EMC 2008: Vol 2: Materials Science 3540852255, 9783540852254

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EMC 2008 14th European Microscopy Congress 1–5 September 2008, Aachen, Germany

Sivia Richter · Alexander Schwedt Editors

EMC 2008 14th European Microscopy Congress 1–5 September 2008, Aachen, Germany Volume 2: Materials Science

123

Dr. Silvia Richter Dr. Alexander Schwedt RWTH Aachen Central Facility for Electron Microscopy Ahornstr. 55 52074 Aachen Germany [email protected] [email protected]

ISBN 978-3-540-85225-4

e-ISBN 978-3-540-85226-1

DOI 10.1007/978-3-540-85226-1 © 2008 Springer-Verlag Berlin Heidelberg This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: digital data supplied by the authors Production: le-tex publishing services oHG, Leipzig, Germany Cover design: eStudioCalamar S.L., F. Steinen-Broo, Girona, Spain Printed on acid-free paper 987654321 springer.com

Preface Volume 2: Materials Science With the 14th European Microscopy Congress the European Microscopy Society (EMS), the German Society for Electron Microscopy (DGE) and the local organizers continue this successful series of conferences. Since the first congress in Stockholm in 1956 (still named European Congress on Electron Miscroscopy - EUREM), this conference series has become a well-accepted platform for academic and industrial scientists not only from Europe, but from all over the world, to discuss and exchange their latest results in the field of electron and other microscopies. The congress is subdivided into the three main areas, “Instrumentation and Methods”, “Materials Science” and “Life Sciences”. This 2nd volume of the conference proceedings collects the contributions related to the application of electron microscopy to the large field of Materials Science, again structured in five symposia covering all kinds of various materials: “Materials for Information Technology”, “Nanomaterials and Catalysts”, “Structural and Functional Materials”, “Soft Matters and Polymers”, and finally “Materials in Mineralogy, Geology and Archaeology”. All in all, this volume contains more than 400 contributions to this wide field of applications. Therefore, at this point we would like to express our deepest thanks to all, who contributed to making this a successful conference: the invited speakers and chairpersons, as well as all authors of contributed papers, may they be presented as oral communication or as poster. We are sure, that by the contributions of all of them the congress will reach an excellent level of scientific quality. Last, but not least, we want to thank all, who assisted in the organization of this conference, i.e. Tobias Caumanns, Achim Herwartz, Helga Maintz, Evi Münstermann, Daesung Park, Thomas Queck, Stefanie Stadler, Sarah Wentz, and especially the staffs of the Eurogress Conference Centre and of the Aachen Congress service. We wish all of you an exciting EMC2008! And after all the days of hard work, don’t forget to enjoy the marvellous city of Aachen. Silvia Richter and Alexander Schwedt Editors, Volume 2 of the EMC 2008 proceedings

Content M

Materials Science

Direct observation of atomic defects in carbon nanotubes and fullerenes ................ 1 K. Suenaga

Atomic studies on ferroelectric oxides by aberration corrected transmission electron microscopy........................................................................................................ 3 K. Urban and C.L. Jia

M1

Materials for Information Technology

M1.1 Si-based semiconductors Dark-field electron holography for the measurement of strain in nanostructures and devices ....................................................................................... 5 M.J. Hÿtch, F. Houdellier, F. Hüe, and E. Snoeck

Some device challenges towards the 22nm CMOS technology................................... 7 F. Andrieu, T. Ernst, O. Faynot, V. Delaye, D. Lafond, and S. Deleonibus

Off-axis electron holography for the analysis of nm-scale semiconductor devices. .............................................................................. 9 D. Cooper, R. Truche, L. Clement, S. Pokrant, and A. Chabli.

Influence of the oxide thickness................................................................................... 11 P. Donnadieu, V. Chamard, M. Maret, J.P. Simon, and P. Mur

Challenges to TEM in high performance microprocessor manufacturing.............. 13 H.J. Engelmann, H. Geisler, R. Huebner, P. Potapov, D. Utess, and E. Zschech

Strain study in transistors with SiC and SiGe source and drain by STEM nano beam diffraction................................................................................. 15 P. Favia, D. Klenov, G. Eneman, P. Verheyen, M. Bauer, D. Weeks, S.G. Thomas, and H. Bender

Cluster growth and luminescence in ion-implanted silica ........................................ 17 H.-J. Fitting, R. Salh, L. Kourkoutis, and B. Schmidt

Coherence Measurements of Bulk and Surface Plasmons in Semiconductors by Diffracted Beam Holography ................................................................................. 19 R.A. Herring

Comparison of 3D potential structures at different pn-junctions in FIB-prepared silicon and germanium samples measured by electron-holographic tomography ......................................................................... 21 A. Lenk, D. Wolf, H. Lichte, and U. Mühle

II

Content

EELS analyses of metal-inserted high-k dielectric stacks......................................... 23 M. MacKenzie, A.J. Craven, D.W. McComb, C.M. McGilvery, S. McFadzean, and S. De Gendt

Low voltage SEM observations of the dopant contrast in semiconductors ............. 25 K. Masenelli-Varlot, S. Luca, G. Thollet, P.H. Jouneau, and D. Mariolle

NiSi2/Si interface chemistry and epitaxial growth mode........................................... 27 S.B. Mi, C.L. Jia, K. Urban, Q.T. Zhao, and S. Mantl

Detailed investigation of a tunnel oxide defect in a flash memory cell using TEM-tomography............................................................................................... 29 U. Muehle, M. Krause, F. Goetze, D. Wolf, and U. Gaebler

Overgrowth of the Mn4Si7 phase on/around the hexagonal SiC and cubic MnSi impurity phases in the Mn4Si7/Si films............................................ 31 A. Orekhov, T. Kamilov, and E.I. Suvorova

HR-STEM EELS analysis of silicon 32 nm technology using a TITAN with a probe Cs corrector ............................................................................................ 33 R. Pantel, J.L Rouvière, E. Gautier, S. Denorme, C. Fenouiller-Beranger, F. Boeuf, G. Bidal, and M. Cheynet.

Tomographic analysis of a FinFET structure............................................................ 35 O. Richard, P. Van Marcke, and H. Bender

STEM EELS/EDX dopant analysis of nm-scale Si devices....................................... 37 G. Servanton, R. Pantel, M. Juhel, and F. Bertin

M1.2 Compound semiconductors Electron beam induced damage: An atom-by-atom investigation with TEAM0.5 .............................................................................................................. 39 C. Kisielowski, R. Erni, and J. Meyer

The atomic structure of GaN-based quantum wells and interfaces ......................... 41 C.J. Humphreys, M.J. Galtrey, R.A. Oliver, M.J. Kappers, D. Zhu, C. McAleese, N.K. van der Laak, D.M. Graham, P. Dawson, A Cerezo, and P.H. Clifton.

Using TEM to investigate antiphase disorder in GaP films grown on Si(001)........ 43 T.B. Adams, I. Nemeth, G. Lukin, B. Kunert, W. Stolz, and K. Volz

TEM characterization of InAs/GaAs quantum dots capped by a GaSb/GaAs layer.................................................................................................. 45 A.M. Beltrán, T. Ben, A.M. Sánchez, D.L. Sales, M.F. Chisholm, M. Varela, S.J. Pennycook, P.L. Galindo, J.M. Ripalda, and S.I. Molina

The microstructure of (0001)GaN films grown by molecular beam epitaxy from a nanocolumn precursor layer ........................................................................... 47 D. Cherns, L. Meshi, I. Griffiths, S. Khongphetsak, S.V. Novikov, N. Farley, R.P. Campion, and C.T. Foxon

Content

III

Compositional and Morphological Variation in GaN/AlN/AlGaN Heterostructures......................................................................... 49 P.D. Cherns, C. McAleese, M.J. Kappers, and C.J. Humphreys

TEM/STEM/EFTEM imaging and Valence Electrons Spectroscopy analysis of Ultra Low-K dielectrics ........................................................................................... 51 M. Cheynet, S. Pokrant, M. Aimadeddine, V. Arnal, and F. Volpi

Epitaxial Orientations of GaN Grown on R-plane Sapphire.................................... 53 J. Smalc-Koziorowska, G.P. Dimitrakopulos, Ph. Komninou, Th. Kehagias, S.-L. Sahonta, G. Tsiakatouras, and A. Georgakilas

Microstructure and growth model of MBE-grown InAlN thin films....................... 55 S.-L. Sahonta, A. Adikimenakis, G.P. Dimitrakopulos, Ph. Komninou, H. Kirmse, E. Pavlidou, E. Iliopoulos, A. Georgakilas, W. Neumann, and Th. Karakostas

Silicon carbide modulated structures as a result of the introduction of 8H bands in a 4H matrix ......................................................................................... 57 N. Frangis, M. Marinova, I. Tsiaoussis, E.K. Polychroniadis, T. Robert, S. Juillaguet, and J. Camassel

HRTEM study of AlN/3C-SiC heterointerfaces grown on Si(001) and Si(211) substrates .................................................................................................. 59 T. Isshiki, K. Nishio, Y. Abe, J. Komiyama, S. Suzuki, and H. Nakanishi

Electron microscopy of GaAs/AlGaAs quantum cascade laser................................ 61 A. Łaszcz, J. Ratajczak, A. Czerwinski, K. Kosiel, J. Kubacka-Traczyk, J. Muszalski, M. Bugajski, and J. Kątcki

Solving the crystal structure of highly disordered Sn3P4 by HRTEM ..................... 63 O.I. Lebedev, A.V. Olenev, and G. Van Tendeloo

Determination of In-distribution in InGaAs quantum dots...................................... 65 D. Litvinov, H. Blank, R. Schneider, D. Gerthsen, and M. Hetterich

Nanoanalytical investigation of the dielectric gate stack for the realisation of III-V MOSFET devices............................................................................................ 67 P. Longo, A.J. Craven, M.C. Holland, and I.G. Thayne

Phase mapping of uncapped InN quantum dots........................................................ 69 J.G. Lozano, M. Herrera, R. García, N.D. Browning, S. Ruffenach, O. Briot, and D. González

STEM investigations of (In,Ga)N/GaN quantum wells............................................. 71 P. Manolaki, I. Häusler, H. Kirmse, W. Neumann, P. Vennéguès, P. De Mierry, and P. Demolon

Defects in m-plane GaN layers grown on (100) γ-LiAlO2 ......................................... 73 A. Mogilatenko, W. Neumann, T. Wernicke, E. Richter, M. Weyers, B. Velickov, and R. Uecker

IV

Content

Improvements on InP epilayers by the use of monoatomic hydrogen during epitaxial growth and successive annealing ................................................................. 75 F.M. Morales, A. Aouni, R. García, P.A. Postigo, C.G. Fonstad, and S.I. Molina

Study of microstructure and strain relaxation on thin InXGa1-xN epilayers with medium and high In contents.............................................................................. 77 F.M. Morales, J.G. Lozano, R. García, V. Lebedev, S. Hauguth-Frank, V. Cimalla, O. Ambacher, and D. González

Convergence of microscopy techniques for nanoscale structural characterization: an illustration with the study of AlInN......................................... 79 A. Mouti, S. Hasanovic, M. Cantoni, E. Feltin, N. Grandjean, and P. Stadelmann

TEM analyses of microstructure and composition of AlxGa1-xN/GaN distributed Bragg reflectors ........................................................................................ 81 A. Pretorius, A. Rosenauer, T. Aschenbrenner, H. Dartsch, S. Figge, and D. Hommel

TEM study of quaternary InGaAsN/GaAs quantum well structures grown by molecular beam epitaxy.......................................................................................... 83 T. Remmele, M. Albrecht, I. Häusler, L. Geelhaar, H. Riechert, H. Abu-Farsakh, and J. Neugebauer

Lattice polarity and capping of GaN dots studied by Z-contrast imaging .............. 85 J.L. Rouviere, C. Bougerol, J. Coraux, B. Amstatt, E. Bellet-Amalric, and B. Daudin

Investigation of swift ions damage in wide band gap wurtzite semiconductors...... 87 S. Mansouri, I. Monnet, H. Lebius, G. Nouet, and P. Ruterana

A TEM analysis of the damage formation in thin GaN and AlN layers during rare earth ion implantation at medium range energy .................................. 89 F. Gloux, M.P Chauvat, and P. Ruterana

Characterization and modelling of semiconductor quantum nanostructures grown by droplet epitaxy ............................................................................................. 91 D.L. Sales, J.C. Hernandez, P.A. Midgley, A.M. Beltran, A.M. Sanchez, T. Ben, P. Alonso-González, Y. Gonzalez, L. Gonzalez, and S.I. Molina

Transmission Electron Microscopy Investigation of Self-Organized InN Nano-columns......................................................................... 93 H. Schuhmann, C. Denker, T. Niermann, J. Malindretos, A. Rizzi, and M. Seibt

Investigations on a dilute magnetic semicondutor (Ga1-xMnxAs) by conventional TEM and EELS ................................................................................ 95 M. Soda, U. Wurstbauer, M. Hirmer, W. Wegscheider, and J. Zweck

About the determination of optical properties using fast electrons ......................... 97 M. Stöger-Pollach

Content

V

M1.3 Data storage/ non-volatile memories Mapping uncompensated spins in exchange-biased systems by high resolution and quantitative magnetic force microscopy.............................. 99 H. J. Hug, M. Marioni, S. Romer, I. Schmid, and S. Romer

Ferroelectric materials and structures suitable for data storage: The role of microscopies in establishing preparation-microstructure-property relations ...................................................... 101 D. Hesse, M. Alexe, K. Boldyreva, H. Han, W. Lee, A. Lotnyk, B.J. Rodriguez, S. Senz, I. Vrejoiu, and N.D. Zakharov

Electronic structures at Magnetic Tunnel Junction interfaces: EELS experiments and FEFF calculations .............................................................. 103 K. March, D. Imhoff, G. Krill, and C. Colliex

Stability and reaction of magnetic sensor materials studied by atom probe tomography ....................................................................................... 105 G. Schmitz, C. Ene, H. Galinski, and V. Vovk

Transmission Electron Microscopy Analysis of Tunnel Magneto Resistance Elements with Amorphous CoFeB Electrodes and MgO Barrier .......................... 107 Michael Seibt, Gerrit Eilers, Marvin Walter, Kai Ubben, Karsten Thiel, Volker Drewello, Andy Thomas, Günter Reiss, and Markus Münzenberg

Study of the intermixing of Fe–Pt multilayers by analytical and high-resolution transmission electron microscopy........................................... 109 W. Sigle, T. Kaiser, D. Goll, N.H. Goo, V. Srot, P.A. van Aken, E. Detemple, and W. Jäger

Exploring structural dependence of magnetic properties in FePt nanoparticle by Cs-corrected HRTEM ....................................................... 111 Z.L. Zhang, J. Biskupek, U. Kaiser, U. Wiedwald, L. Han, and P. Ziemann

M1.4 Nanotubes, nanowires and molecular devices Understanding the Chemistry of Molecules in Nanotubes by Transmission Electron Microscopy .................................................................................................. 113 A.N. Khlobystov, M.W. Fay, and P.D. Brown

Electrical and mechanical property studies on individual low-dimensional inorganic nanostructures in HRTEM....................................................................... 115 D. Golberg, P.M.F.J. Costa, M. Mitome, Y. Bando, and X.D. Bai

Atomic structure of SW-CNTs: correlation with their growth mechanism and other electron diffraction studies....................................................................... 117 R. Arenal, M.F. Fiawoo, R. Fleurier, M. Picher, V. Jourdain, A.M. Bonnot, and A. Loiseau

VI

Content

TEM investigation ofSe nanostructures in/on Acetobacter xylinum cellulose gel-film ......................................................................................................... 119 N. Arkharova, V.V. Klechkovskaya, and E. Suvorova

In-situ electron irradiation studies of metal-carbon nanostructures ..................... 121 L. Sun, Y. Gan, J.A. Rodriguez-Manzo, M. Terrones, A.V. Krasheninnikov, and F. Banhart

Application of 80kV Cs-corrected TEM for nanocarbon materials ...................... 123 A. Chuvilin, U. Kaiser, D. Obergfell, A. Khlobystov, and S. Roth

Control of gold surface diffusion on Si nanowires................................................... 125 M.I. den Hertog, J.-L. Rouviere, F. Dhalluin, P.J. Desré, P. Gentile, P. Ferret, F. Oehler, and T. Baron

Nanowires of Semiconducting Metal-oxides and their Functional Properties...... 127 M. Ferroni, C. Baratto, E. Comini, G. Faglia, L. Ortolani, V. Morandi, S. Todros, A. Vomiero, and G. Sberveglieri

Phase relations in the Fe–Bi–O system under hydrothermal conditions............... 129 A. Gajović, S. Šturm, B. Jančar, and M. Čeh

Dose dependent crystallographic structure of InAs nanowires.............................. 131 F. Gramm, E. Müller, I. Shorubalko, R. Leturcq, A. Pfund, R. Wepf, and K. Ensslin

HRTEM simulations of planar defects in ZnTe nanowires .................................... 133 I. Häusler, H. Kirmse, W. Neumann, S. Kret, P. Dłużewski, E. Janik, G. Kraczewski, and T. Wojtowicz

A universal method for determination of helicities present in unidirectional groupings of graphitic or graphitic-like tubular structures ................................... 135 H. Jiang, D.P. Brown, A.G. Nasibulin, and E.I. Kauppinen

Microstructure of (112) GaAs nanorods grown by MBE ....................................... 137 E. Johnson, S.A. Jensen, L.P. Hansen, C.B. Sørensen, and J. Nygård

Structural characterization of ZnO nanorods grown on sapphire substrate by MOCVD ................................................................................................................. 139 P.-H. Jouneau, M. Rosina, G. Perillat, P. Ferret, and G. Feuillet

Nucleation of Metal Clusters on Carbon Nanotubes............................................... 141 X. Ke, A. Felten, D. Liang, S. Bals, J.J. Pireaux, J. Ghijsen, W. Drube, M. Hecq, C. Bittencourt, and G. Van Tendeloo

EDX and linescan modelling for core/shell GaN/AlGaN nanowire analysis ......... 143 L. Lari, R.T. Murray, T. Bullough, P.R. Chalker, C. Chèze, L. Geelhaar, and H. Riechert

Mo6S9-xIx nanowires: structure studies by aberration corrected high resolution TEM and STEM ....................................................................................... 145 V. Nicolosi, J.N. Coleman, D. Mihailovic, and P. Nellist

Discrete Atom Imaging in Carbon Nanotubes and Peapods Using Cs-Corrected TEM Operated at 100keV.................................................................. 147 Luca Ortolani, Florent Houdellier, and Marc Monthioux

Content

VII

Extended Defects in Semiconductor Nanowires ...................................................... 149 Peter Pongratz, Youn-Joo Hyun, Alois Lugstein, Aaron Andrews, and Emmerich Bertagnolli

Surface chemistry along a single silicon nanowire: Quantitative x-ray photoelectron emission microscopy (XPEEM) of the metal catalyst diffusion ..... 151 O. Renault, A. Bailly, P. Gentile, N. Pauc, T. Baron, L.–F. Zagonel, and N. Barrett

TEM characterization of metallic Ni nanoshells grown on gold nanorods and on carbon nanotubes........................................................................................... 153 J.B. Rodríguez-González, M. Grzelczak, M.A. Correa-Duarte, J. Pérez-Juste, and L.M. Liz-Marzán

Electron Irradiation Effects in Carbon Nanostructures: Surface Reconstruction, Extreme Compression, Nanotube Growth and Morphology Manipulation ................................................................................. 155 M. Terrones, L. Sun, J.A. Rodriguez-Manzo, H. Terrones, and F. Banhart

Crystallographic phase and orientation analysis of GaAs nanowires by ESEM, EDS, TEM, HRTEM and SAED............................................................. 157 A.M. Tonejc, S. Gradečak, A. Tonejc, M. Bijelić, H. Posilović,V. Bermanec, and M. Tambe

3-Dimensional Morphology of GaP-GaAs nanowires ............................................. 159 M.A. Verheijen, R. Algra,M.T. Borgström, G. Immink, E. Sourty, L.F. Feiner, W.J.P. van Enckevort, E. Vlieg, and E.P.A.M. Bakkers

Characteristics of Indium-Catalyzed Si Nanowires ................................................ 161 Z.W. Wang, Z.Y. Li, and F. Iacopi

M2

Nanomaterials and Catalysts

M2.1 Carbon-based HRTEM contribution to the study of extraterrestrial nanocarbons and some earth materials analogues ......................................................................... 163 J.N. Rouzaud and C. Le Guillou

Time resolved in-situ TEM observations of Carbon Nanotube growth................. 165 J. Robertson, S. Hofmann, R. Sharma, C. Ducati, and R. Dunin-Borkowski

Insulator-Metal transition: formation of Diamond Nanowires in n-type Conductive UNCD films ............................................................................ 167 R. Arenal, O. Stephan, P. Bruno, and D.M. Gruen

Field emission from iron-filled carbon nanotubes observed in-situ in the scanning electron microscope ......................................................................... 169 K.J. Briston, Y. Peng, N. Grobert, A.G. Cullis, and B.J. Inkson

Templated ordering of fullerenes on nanostructured oxide surfaces .................... 171 D.S. Deak, B.C. Russell, D.T. Newell, K. Porfyrakis, F. Silly, and M.R. Castell

VIII

Content

Carbon nanostructures produced by chlorination of Cr3C2 and Cr(acac)3 .......... 173 A. Gómez-Herrero, E. Urones-Garrote, D. Ávila-Brande, N.A. Katcho, E. Lomba, A.R. Landa-Cánovas, and L.C. Otero-Díaz

Structural peculiarities of carbon onions, formed by different methods .............. 175 B.A. Kulnitskiy, I.A. Perezhogin, and V.D. Blank

Electron Energy Loss Spectroscopy of La@C82 peapods........................................ 177 R.J. Nicholls, D.A. Eustace, D. McComb, G.A.D. Briggs, D.J.H. Cockayne, and D.G. Pettifor

HRTEM studies of Y-junction bamboo-like CN-nanotubes................................... 179 I.A. Perezhogin, B.A. Kulnitskiy, V.D. Blank, D.V. Batov, and E.V. Polyakov

EF-TEM observation of biological tissue for risk assessment of fullerene nanoparticles .......................................................................................... 181 K. Yamamoto, M. Makino, E. Kobayashi, and Y. Morimoto

M2.2 Nanoparticles and catalysts Looking at the surface of catalysts nanopowders .................................................... 183 J.C. Hernandez, A.B. Hungria, M. Lopez-Haro, J.A. Perez-Omil, S. Trasobares, S. Bernal, P. Midgley, O. Stephan, and J.J. Calvino

Gathering structural and analytical information on catalysts at sub-nanometer level with TEM............................................................................. 185 F.J. Cadete Santos Aires and M. Aouine

Size effect and influence of nanoparticles thickness on order/disorder phenomena in CoPt nanoparticles ............................................. 187 D. Alloyeau, C. Ricolleau, T. Oikawa, C. Langlois, Y. Le Bouar, and A. Loiseau

In situ L10 ordering of FePt nanoparticles ............................................................... 189 P. Bayle-Guillemaud, M. Delalande, V. Monnier, Y. Samson, and P. Reiss

Characterization of indium doped zinc oxide nanorods ......................................... 191 H. Burghardt, H. Schmid, and W. Mader

Adsorbate-induced restructuring on Pt nanoparticles studied by environmental transmission electron microscopy .............................................. 193 M. Cabié, S. Giorgio, and C.R. Henry

EELS in monochromated and Cs probe corrected TEM: ...................................... 195 M. Cheynet, S. Pokrant, and S. Ersen.

Atomic-resolution Electron Microscopy at Ambient Pressure............................... 197 J.F. Creemer, S. Helveg, A.M. Molenbroek, P.M. Sarro, and H.W. Zandbergen

Development of a system for TEM/STEM investigation of air-sensitive materials: Preliminary results on CeO2 reduction behaviour ................................ 199 J.J. Delgado, M. López-Haro, J.D. López-Castro, J.A. Pérez-Omil, S. Trasobares, and J.J. Calvino

Content

IX

Characterization of two new zeolites by combining Electron Microscopy and X-Ray Powder Diffraction analyses .................................................................. 201 E. Di Paola, E. Montanari, S. Zanardi, and A. Carati

Electron beam-induced effects on copper nanoparticles: coarsening and generation of twins........................................................................... 203 D. Díaz-Droguett, V. Fuenzalida, and G. Solórzano

Role of the catalyst and substrate in nucleation and growth of Single Wall Carbon Nanotubes in HFCVD ......................................................... 205 M.-F. Fiawoo, N. Brun, A.-M Bonnot, O. Stephan, J. Thibaultand, and A. Loiseau

PEMFC degradation phenomena studied by electron microscopy........................ 207 L. Guetaz, B. Vion-Dury, and S. Escribano

TEM investigation of magnetite nanoparticles for biomedical applications ......... 209 S. Gustafsson, A. Fornara, F. Ye, K. Petersson, C. Johansson, M. Muhammed, and E. Olsson

Catalytic soot oxidation studied by Environmental Transmission Electron Microscopy .................................................................................................. 211 S.B. Simonsen, S. Dahl, E. Johnson, and S. Helveg

Surface and interface structure of ceria supported ruthenium.............................. 213 J.C. Hernandez, S. Trasobares, J.M. Gatica, D.M. Vidal,M.A. Cauqui, J.J. Calvino, A.B. Hungria, and J.A. Perez-Omil

Characterisation of materials with applications in the photocatalytic activation of water .................................................................. 215 N.S. Hondow, R. Brydson, Y.H. Chou, and R.E. Douthwaite

Complementary EM study on highly active nanodendritic Raney-type Ni catalysts with hierarchical build-up.......................................................................... 217 U. Hörmann, U. Kaiser, N. Adkins, R. Wunderlich, A. Minkow, H. Fecht, H. Schils, T. Scherer, and H. Blumtritt

Structural properties of sol-gel synthesized Li+-doped titania nanowhisker arrays.................................................................................................... 219 U. Hörmann, J. Geserick, S. Selve, U. Kaiser, and N. Hüsing

Quantitative strain determination in nanoparticles using aberration-corrected HREM........................................................................... 221 C.L. Johnson, E. Snoeck, M. Ezcurdia, B. Rodríguez-González, I. Pastoriza-Santos, L.M. Liz-Marzán, and M.J. Hÿtch

Morphological characterization by HRTEM and STEM of Fe3O4 hollow nano-spheres.................................................................................... 223 A. Ibarra, G.F. Goya, J. Arbiol, E. Jr. Lima, H. Rechenberg, J. Vargas, R. Zysler, and M.R. Ibarra

Direct observation of surface oxidation of Rh nanoparticles on (001) MgO......... 225 N.Y. Jin-Phillipp, P. Nolte, A. Stierle, P.A. van Aken, and H. Dosch

X

Content

Characterization of catalyst poisoning in biodiesel and conventional diesel fuelled vehicles ................................................................... 227 T. Kanerva, K. Kallinen, Toni Kinnunen, M. Vippola, and T. Lepistö

TEM Characterisation of Highly Luminescent CdS Nanocrystals ........................ 229 H. Katz, A. Izgorodin, D.R. MacFarlane, and J. Etheridge

Structure and composition of dilute Co-doped BaTiO3 nanoparticles .................. 231 O.I. Lebedev, R. Erni, and G. Van Tendeloo

CoxFe3-xO4 catalytic materials for gaz sensors ......................................................... 233 L. Ajroudi, A. Essoumhi, S. Villain, V. Madigou, N. Mliki, and Ch. Leroux

(S)TEM investigation on the role of alumina dopants to prevent redox activity decay at high temperature in CePrOx /doped-Al2O3 catalysts .................. 235 M. López-Haro, K. Aboussaid, J.M. Pintado, J.J. Calvino, and S. Trasobares

Sulfated Zirconia Catalysts: Structure and Performance Relationship, a TEM Study............................................................................................................... 237 C. Meyer, D. Su, N. Hensel, F.C. Jentoft, and R. Schlögl

A novel procedure for an accurate estimation of the lattice parameter of supported metal nanoparticles from the analysis of plan view HREM images ....................................................................................... 239 C. Mira, J.A. Perez-Omil, J.J. Calvino, and S. Bernal

Microstructure of Pt particles and aggregates deposited on different carbon materials for fuel cells application ............................................................................ 241 D. Mirabile Gattia, E. Piscopiello, M. Vittori Antisari, S. Bellitto, S. Licoccia, E. Traversa, L. Giorgi, R. Marazzi, and A. Montone

Low-loss-energy EFTEM imaging of triangular silver nanoparticles ................... 243 J. Nelayah, L. Gu, W. Sigle, C.T. Koch, L. Pastoriza-Santos, L.M. Liz-Marzan, and P.A. van Aken

Microstructure of cobalt nanocluster arrays fabricated by solid-state dewetting.............................................................................................. 245 Y.-J. Oh, J. Kim, S. Hwang, C.A. Ross, and C.V. Thompson

Size Effect in Gold Nanoparticles Investigated by Electron Holography and STEM ................................................................................................................... 247 L. Ortolani, V. Morandi, and M. Ferroni

Post-Mortem investigation of Fischer Tropsch catalysts using cryo- transmission electron microscopy ......................................................... 249 D. Ozkaya, M. Lok, J. Casci, and P. Ash

TEM Investigations on Cu-impregnated Zeolite Y catalysts via chloride free preparation..................................................................................... 251 M.-M. Pohl, M. Richter, and M. Schneider

Content

XI

Coarsening of mass-selected Au clusters on amorphous carbon at room temperature .................................................................................................. 253 R. Popescu, R. Schneider, D. Gerthsen, A. Böttcher, D. Löffler, and P. Weiss

TEM investigations on Ni clusters electrodeposited on Carbon substrate............ 255 M. Re, M.F. De Riccardis, D. Carbone, D. Wall, and M. Vittori Antisari

Near-surface structure of FePt nanoparticles.......................................................... 257 B. Rellinghaus, D. Pohl, E. Mohn, and L. Schultz

Overgrowth of gold nanorods: From rods to octahedrons ..................................... 259 J.B. Rodríguez-González, E. Carbó-Argibay, I. Pastoriza-Santos, J. Pérez-Juste, and L.M. Liz-Marzán

Reactive Diffusion under Laplace Tension in Spherical Nanostructures.............. 261 C. Ene, C. Nowak, and G. Schmitz

Preparation and characterization of palladium nanoparticles with various size distributions................................................................................... 263 M. Slouf, H. Vlkova, and D. Kralova

Electron microscopy for the characterization of nanoparticles ............................. 265 D. Sommer and U. Golla-Schindler

Titanium dioxide nanoparticles prepared from TiOSO4 aqueous solutions ......... 267 J. Šubrt, J. Boháček, N. Murafa, and L. Szatmáry

Exploring nanoscale ferroelectricity in isolated and interacting colloidal ferroelectric nanocrystals using electron holography ............................................. 269 D. Szwarcman, Y. Lereah, G. Markovich, M. Linck, and H. Lichte

STEM investigation on the one-pot synthesis of nanostructured CexZr1-xO2-BaO·nAl2O3 catalytic materials ............................................................. 271 J.C. Hernandez, J.A. Perez-Omil, J.J. Calvino, S. Bernal, R. di Monte, S. Desinan, J. Kašpar, and S. Trasobares

Enhanced stability against oxidation due to 2D self-organisation of hcp cobalt nanocrystals ......................................................................................... 273 Isabelle Lisiecki, S. Turner, S. Bals, M.P. Pileni, and G. Van Tendeloo

Loaded porous Zn4O(bdc)3 (metal@MOF-5) frameworks characterised by TEM ....................................................................................................................... 275 S. Turner, O.I. Lebedev, F. Schröder, R.A. Fischer, and G. Van Tendeloo

Growth behaviour of sub-nm sized focused electron beam induced deposits ....... 277 W.F. van Dorp, C.W. Hagen, P.A. Crozier, P. Kruit, S. Zalkind, B. Yakshinskiy, and T.E. Madey

Ruthenium deposition on CO2-treated and untreated carbon black investigated by electron tomography........................................................................ 279 M. Wollgarten, R. Grothausmann, P. Bogdanoff, G. Zehl, I. Dorbandt, S. Fiechter, and J. Banhart

XII

Content

Size-dependent crystallinity and relative orientations of nano-Pt/γ-Al2O3 ............ 281 J.C. Yang, L. Li, S. Sanchez, J.H. Kong, Q. Wang, L.L. Wang, Z. Zhang, D.D. Johnson, A.I. Frenkel, and R.J. Nuzzo

Formation of nanometer-sized porous GaSb particles by vacancy clustering induced by electronic excitation ................................................................................ 283 H. Yasuda, A. Tanaka, N. Nitta, K. Matsumoto, and H. Mori

Structural investigations of membrane electrode assemblies in fuel cells via environmental scanning electron microscopy.................................................... 285 S. Zils, N. Benker, and C. Roth

M2.3 Nanostructured materials and Nanolab In situ TEM nanocompression testing ...................................................................... 287 A.M. Minor, J. Ye, and R.K. Mishra

Physical measurements on an individual nanostructure in a TEM nanolaboratory.......................................................................................... 289 M. Kobylko, S. Mazzucco, R. Bernard, M. Kociak, and C. Colliex

TEM study of nanostructured BZO templates in (001)-LAO and (001)-STO substrates for the growth of superconducting YBCO films.................................... 291 P. Abellan, M. Gibert, F. Sandiumenge, M.J. Casanove, T. Puig, and X. Obradors

Hydrothermal synthesis and characterisation of single crystal α-Fe2O3 nanorods ....................................................................................................... 293 T. Almeida, Y.Q. Zhu, and P.D. Brown

GaAs NWs and Related Quantum Heterostructures Grown by Ga-Assisted Molecular Beam Epitaxy: Structural and Analytical Characterization................ 295 J. Arbiol, S. Estradé, F. Peiró, J.R. Morante, C. Colombo, D. Spirkoska, G. Abstreiter, and A. Fontcuberta i Morral

A method for in-situ electrical measurements of thin film heterostructures using TEM and SEM.................................................................................................. 297 J. Börjesson, A. Kalabukhov, K. Svensson, and E. Olsson

Electron Beam Nanofabrication and Characterization of Iron Compounds ........ 299 K. Furuya, M. Shimojo, M. Takeguchi, M. Song, K. Mitsuishi, and M. Tanaka

TEM analysis of the chemical gradient in (Zn,Mn)Te/ZnTe nanowires .............. 301 H. Kirmse, W. Neumann, S. Kret, P. Dłużewski, E. Janik, W. Zaleszczyk, A. Presz, G. Karczewski, and T. Wojtowicz

Structural and morphological characterization of GaN/AlGaN quantum dots by transmission electron microscopy........................................................................ 303 M. Korytov, M. Benaissa, J. Brault, T. Huault, and P. Vennéguès

Structure and stability of core-shell AuAg nanopartciels....................................... 305 Z.Y. Li, R. Merrifield, Y. Feng, J.P. Wilcoxon, R.E. Palmer, A.L. Bleloch, M. Gass, and K. Sader

Content

XIII

In-situ studies on electrical and mass transport in multi-wall carbon and vanadium oxide nanotubes................................................................................. 307 M. Löffler, T. Gemming, R. Klingeler, and B. Büchner

Electron microscopy of nano-magnesium produced by Inert Gas Condensation for hydrogen storage ................................................... 309 E. Piscopiello, E. Bonetti, E. Callini, L. Pasquini, and M. Vittori Antisari

Two Different Structures of Crystalline Mesoporous Indium Oxide Obtained by Nanocasting Process.............................................................................................. 311 E. Rossinyol, E. Pellicer, M. Cabo, O. Castell, and M.D. Baro

Measuring electrical properties of carbon nanotubes using liquid metal immersion, an in situ scanning electron microscopy study..................................... 313 H. Strand, K. Svensson, and E. Olsson

TEM characterization of biogenic metal nanoparticles .......................................... 315 E.I. Suvorova, P.A. Buffat, H. Veeramani, J. Sharp, E. Schofield, J. Bargar, and R. Bernier-Latmani

On the structure of VxOy supported on multiwalled carbon nanotubes................ 317 D. Wang, J.-P. Tessonnier, M. Willinger, C. Hess, D.S. Su, and R. Schlögl

Hexahedral nano-cementites catalysing the growth of carbon nanohelices .......... 319 J.H. Xia, X. Jiang, C.L. Jia, and C. Dong

M2.4 Thin films and interfaces Investigation of organic/inorganic interfaces using nano-analytical transmission electron microscopy ............................................................................. 321 V. Jantou, M.A. Horton, and D.W. McComb

Cationic ordering and interface effects in superlattices and nanostructured materials ................................................................................... 323 P. Boullay, W.C. Sheets, W. Prellier, E.-L. Rautama, A.K. Kundu, V. Caignaert, B. Mercey, and B. Raveau

Strain in SrTiO3 layers embedded in a scandate/titanate multilayer system........ 325 D. Ávila, M. Boese, T. Heeg, J. Schubert, and M. Luysberg

Anisotropic growth of CGO islands on the (001)-LaAlO3 surface ........................ 327 A. Benedetti, M. Gibert, F. Sandiumenge, T. Puig, and X. Obradors

Diffraction contrast imaging and high resolution transmission electron microscopy of multiferroic thin films and heterostructures................................... 329 B.I. Birajdar, I. Vrejoiu, X.S. Gao, B.J. Rodriguez, M. Alexe, and D. Hesse

Imaging of compositional defects at silicide-silicon interfaces using aberration corrected HAADF ...................................................................................................... 331 M. Falke, U. Falke, P. Wang, and A. Bleloch

XIV

Content

Characterization of nanometric oxide particles extracted from a steel surface onto a carbon replica ............................................................... 333 P. Haghi-Ashtiani, A. Ollivier, and M.-L. Giorgi

TEM characterization of textured silicon heterojunction solar cells..................... 335 A. Hessler-Wyser, C. Monachon, S. Olibet, and C. Ballif

Investigation of the change in the microstructure of thin p-type Bi-Sb-Te thermoelectric films after heat treatment ................................................................ 337 F. Heyroth, M. Schade, K. Rothe, H.S. Leipner, and M. Stordeur

EM study on forming Inorganic film with Periodically Organized Mesopores upon Polymer film...................................................................................................... 339 H. Wenqing, Z. Ying, Y. Fang, Zhaoxi, and Y. Wantai

Nanointerface analysis of hard coatings deposited by IBAD.................................. 341 D. Kakas, B. Skoric, A. Miletic, and L. Kovacevic

Transrotational crystals growing in amorphous Cu-Te film.................................. 343 V.Yu. Kolosov, A.V. Kozhin, L.M. Veretennikov, and C.L. Schwamm

TEM investigation of sputtered indium oxide layers on silicon substrate for gas sensors............................................................................................................. 345 Th. Kups, I. Hotovy, and L. Spieß

Microstructure of Sr4Ru2O9 thin films and Bi3.25La0.75Ti3O12/Sr4Ru2O9 bilayers................................................................... 347 R. Chmielowski, V. Madigou, M. Blicharski, and Ch. Leroux

Analysis of the LSM/YSZ interface on micro- and nano-scale by SEM, FIB/SEM and (S)TEM ............................................................................................... 349 Y. Liu, L. Theil Kuhn, and J.R. Bowen

ESI and HRTEM of chemical solution deposited (CSD) ........................................ 351 L. Molina, T. Thersleff, B. Rellinghaus, B. Holzapfel, and O. Eibl

CTEM diffraction contrast of biaxially-textured La2Zr2O7 buffer layers on nickel substrates .................................................................................................... 353 L. Molina, S. Engel, B. Holzapfel, and O. Eibl

TEM sample preparation of YBCO-coated conductors: conventional method and FIB........................................................................................................................ 355 L. Molina, T. Thersleff, C. Mickel, S. Menzel, B. Holzapfel, and O. Eibl

Nucleation and evolution of biepitaxial YBa2Cu3O7-δ thin film grown on SrTiO3 and MgO substrates ................................................................................. 357 H. Pettersson, K. Cedergren, D. Gustafsson, R. Ciancio, F. Lombardi, and E. Olsson

An investigation of Al-Pb interfaces using probe-corrected high-resolution STEM................................................................................................ 359 H. Rösner, S. Lopatin, B. Freitag, and G. Wilde

Content

XV

Spectrometric Full-Color Cathodoluminescence Electron Microscopy Study of Grain Boundaries of ZnO Varistor ...................................................................... 361 H. Saijo, N. Daneu, A. Recnik, and M. Shiojiri

Study of structural properties of Mo/CuInS2/ZnS used in solar cells by TEM..... 363 J. Sandino, G. Gordillo, and H. Lichte

Texture analysis of silicide thin films: combining statistical and microscopical information.................................................................................. 365 H. Schletter, S. Schulze, M. Hietschold, K. De Keyser, C. Detavernier, G. Beddies, A. Bleloch, and M. Falke

Statistical Tomography of 3D Thin Film Structure using Transmission Electron Microscopy .................................................................................................. 367 E. Spiecker, V. Radmilovic, and U. Dahmen

Analytical TEM investigations of Pt/YSZ interfaces............................................... 369 V. Srot, M. Watanabe, C. Scheu, P.A. van Aken, E. Mutoro, J. Janek, and M. Rühle

Microstructure and self-organization of nano-engineered artificial pinning centers in YBa2Cu3O7-x coated conductors................................................. 371 T. Thersleff, E. Backen, S. Engel, C. Mickel, L. Molina-Luna, O. Eibl, B. Rellinghaus, L. Schultz, and B. Holzapfel

The determination of the interface structure between ionocovalent compounds: the general case study of the Al2O3-ZrO2 large misfit system........... 373 G. Trolliard, and D. Mercurio

Simple method to improve quantification accuracy of energy-dispersive X-ray spectroscopy in an analytical transmission electron microscope by specimen tilting...................................................................................................... 375 T. Walther

Comparison of transmission electron microscopy methods to measure layer thicknesses to sub-monolayer precision.................................................................... 377 T. Walther

Determination of interface structure of YBCO/LCMO by a spherical aberration- corrected HRTEM......................................................... 379 Z.L. Zhang, U. Kaiser, S. Soltan, and H.-U. Habermeier

HREM characterization of BST-MgO interface...................................................... 381 O.M. Zhigalina, A.N. Kuskova, A.L. Chuvilin, V.M. Mukhortov, Yu.I. Golovko, and U. Kaiser

M3

Structural and Functional Materials

M3.1 Alloys and Intermetallics TEM investigations on novel shape memory systems with Ni-depletions ............. 383 D. Schryvers, R. Delville, B. Bartova, and H. Tian

XVI

Content

Crystalline-to-amorphous transformation in intermetallic compounds by severe plastic deformation .................................................................................... 385 K. Tsuchiya, T. Waitz, T. Hara, H.P. Karnthaler, Y. Todaka, and M. Umemoto

EELS quantification of complex nitrides in a 12 % Cr steel .................................. 387 M. Albu, F. Méndez Martin, and G. Kothleitner

Formation of ordered solid solution during phase separation in Cu-Ag alloy films.................................................................................................... 389 F. Misják, P.B. Barna, and G. Radnóczi

Precipitates and magnetic domains in an annealed Co38Ni33Al29 shape memory alloy studied by TEM................................................................................................. 391 B. Bartova, D. Schryvers, N. Wiese, and J.N. Chapman

On the gallium accumulation at the boundaries of Al layers in FIB prepared TEM specimens.......................................................................................... 393 P. Favia and H. Bender

Precipitation in an Al-Mg-Ge Alloy.......................................................................... 395 R. Bjorge, C.D. Marioara, S.J. Andersen, and R. Holmestad

Interaction between dislocations and oxide precipitates in an aluminium containing ferritic stainless steel ............................................................................... 397 L. Boulanger, S. Poissonnet, and F. Legendre

Voids Associated with Nano-Particles of Tin in Aluminium .................................. 399 L. Bourgeois, M. Weyland, and B.C. Muddle

Influence of thermal treatments in microstructure and recrystallization peak energy of P/M Al-Mg-X alloys................................................................................... 401 S.J. Buso, A. Almeida Filho, I.M. Espósito, J.R. Matos, and W.A. Monteiro

Analytical TEM of Nb3Sn Multifilament Superconductor Wires .......................... 403 M. Cantoni, V. Abächerli, D. Uglietti, B. Seeber, and R. Flükiger

3D Reconstruction of Ni4Ti3 Precipitates in Ni-Ti by FIB/SEM Slice-and-View...................................................................................... 405 S. Cao, W. Tirry, W. Van Den Broek, and D. Schryvers

Electron microscopy study of Mg78.5Pd21.5: aphase with nanothin 120° rotational twin domains..................................................................................... 407 W. Carrillo-Cabrera, J.P.A. Makongo, Yu. Prots, and G. Kreiner

Analysing small precipitates in a ferritic steel matrix............................................. 409 A.J. Craven and M. MacKenzie

Failure analysis of first stage land-based gas turbine blades.................................. 411 F. Delabrouille, F. Arnoldi, L. Legras, and C. Cossange

TEM investigation of microstructures in low-hysteresis Ti50Ni50-xPdx alloys with special lattice parameters .................................................................................. 413 R. Delville, D. Schryvers, Z. Zhang, S. Kasinathan, and R.D. James

Content

XVII

Evidence of silica layer at the interface between ferrite and the chromium oxide scale in oxidized Fe-Cr-Si alloys ..................................... 415 G. Bamba, P. Donnadieu, Y. Wouters, and A. Galerie

Applying a classical 2 beam diffraction contrast method for measuring nanoprecipitate misfit ....................................................................... 417 L. Lae and P. Donnadieu

Microstructure and interface composition of γ-phase in Co38Ni33Al29 shape memory alloy.......................................................................... 419 R. Espinoza, B. Bartova, D. Schryvers, S. Ignacova, and P. Sittner

Microstructural characterization of the aluminum alloy 6063 after work hardening treatments .............................................................................. 421 I.M. Espósito, S.J. Buso, and W.A. Monteiro

Microstructure- mechanical property relationships in dual phase automotive strip steels................................................................................................ 423 V. Tzormpatzdi and G. Fourlaris

Electron diffraction analysis of nanocrystalline Fe-Al............................................ 425 C. Gammer, C. Mangler, C. Rentenberger, and H.P. Karnthaler

Dual Beam and TEM characterisation of deformation structures in fatigued austenitic stainless steel........................................................................... 427 A. Garcia, L. Legras, M. Akamatsu, and Y. Bréchet

Microstructural characterisation of steel heat-treated by the novel quenching and partitioning process .................................................... 429 K. He, D.V. Edmonds, J.G. Speer, D.K. Matlock, and F.C. Rizzo

Martensite tempering behaviour relevant to the quenching and partitioning process ............................................................................................ 431 K. He, D.V. Edmonds, J.G. Speer, D.K. Matlock, and F.C. Rizzo

Chemical and structural analysis of NiAl-Al2O3 interface by FETEM and STEM ................................................................................................................... 433 W. Hu, T. Weirich, and G. Gottstein

TEM investigations of aluminum precipitate in eutectic Si of A356 based alloys ................................................................................................... 435 Z.H. Jia, L. Arnberg, P. Åsholt, B. Barlas, and T. Iveland

Microstructure of slow-cooled wedge-cast Cu58Co42 alloy with a metastable liquid miscibility gap ................................................................... 437 E. Johnson, S. Curiotto, N. Pryds, and L. Battezzati

TEM investigations of Elektron 21 magnesium alloy after long-term annealing .......................................................................................... 439 A. Kielbus

Microstructure of AJ62 magnesium alloy after long-term annealing.................... 441 A. Kielbus and J. Mizera

XVIII

Content

EELS characterisation of the interface between nanoscaled ODS particles and matrix in advanced fusion steels ........................................................................ 443 M. Klimenkov, R. Lindau, and A. Möslang

Microstructure-mechanical property relationships in a maraging 250 steel ........ 445 P. Kokkonidis, E. Papadopoulou, A. Rizos, T. Koutsoukis, and G. Fourlaris

Microstructure of Co-Ni based superalloys ............................................................. 447 T.J. Konno, T. Tadano, H. Matsumoto, and A. Chiba

Precipitation reactions in superferritic stainless steels ........................................... 449 T. Koutsoukis, K. Konstantinidis, P. Kokkonidis, E. Papadopoulou, and G. Fourlaris

Effect of ageing in cold rolled superaustenitic stainless steels ................................ 451 S. Zormalia, T. Koutsoukis, E. Papadopoulou, P. Kokkonidis, and G. Fourlaris

Structure and properties of P/M material of AlMg – SiO2 system processed by mechanical alloying............................................................................................... 453 A. Kula, L. Błaż, M. Sugamata, J. Kaneko, Ł. Górka, J. Sobota, and G. Włoch

Extrusion of rapidly solidified 6061 + 26 wt% Si alloy ........................................... 455 A. Kula, M. Sugamata, J. Kaneko, L. Błaż, G. Włoch, J. Sobota, and W. Bochniak

TEM and EELS study of carbide precipitation in low alloyed steels..................... 457 C. Leguen, M. Perez, T. Epicier, D. Acevedo, and T. Sourmail

Microstructural analysis of plastically deformed complex metallic alloy κ-AlMnNi ........................................................................................................... 459 M. Lipińska-Chwałek, M. Heggen, M. Feuerbacher, and A. Czyrska-Filemonowicz

Electron microscopy analysis of Mn partitioning in retained austenitemartensite- bainite islands......................................................................................... 461 A. Lis, J. Lis, and P. Wieczorek

TEM characterization of microstructures in a Ni2MnGa alloy.............................. 463 H. Maeda, E. Taguchi, K. Inoue, and A. Sugiyama

Nanocrystalline FeAl produced by high pressure torsion studied by TEM in 3D ............................................................................................................. 465 C. Mangler, C. Rentenberger, and H.P. Karnthaler

HRTEM study of precipitates in Al-Mg-Si-(Ag, Cu) alloys.................................... 467 K. Matsuda, J. Nakamura, T. Kawabata, T. Sato, and S. Ikeno

Martensite structure of non-stoichiometric Co2NiGa ferromagnetic shape memory alloy .............................................................................................................. 469 K. Prusik and M. Morawiec

Electron microscopy of Fe and FeB atomic clusters in the Fe-based amorphous alloys structure ............................................................ 471 E.V. Pustovalov, V.S. Plotnikov, B.N. Grudin, S.V. Dolzhikov, E.B. Modin, O.V. Voitenko, and E.S. Slabzhennikov

Content

XIX

Core/Shell Precipitates in Al-Li-Sc-Zr Alloys.......................................................... 473 V. Radmilovic, M.D. Rossell, A. Tolley, E.A. Marquis, R. Erni, and U. Dahmen

Analysis of basic mechanisms of hardening in ODS EUROFER97 steel using in-situ TEM ....................................................................................................... 475 A. Ramar and R. Schäublin

TEM investigation on the acicular ferrite precipitation in γ’-Fe4N nitride........... 477 X.-C. Xiong, A. Redjaïmia, and M. Gouné

Orientation Relationships between the δ-ferrite Matrix in a Duplex Stainless Steel and its Decomposition Products: the Austenite and the χ and R Frank-Kasper Phases ............................................. 479 A. Redjaïmia, T. Otarola, and A. Mateo

TEM study of localized deformation-induced disorder in intermetallic alloys of L12 structure........................................................................................................... 481 C. Rentenberger, C. Mangler, and H.P. Karnthaler

SEM and TEM study of dynamic recrystallisation of zirconium alloy.................. 483 L. Saintoyant, L. Legras, and Y. Brechet

Effects of solution treatment and test temperature on tensile properties of high strength high Mn austenitic steels ................................................................ 485 K. Phiu-on, W. Bleck, A. Schwedt, and J. Mayer

Microstructure evolution during Ni/Al multilayer reactions ................................. 487 S. Simões, F. Viana, A.S. Ramos, M.T. Vieira, and M.F. Vieira

TEM investigation of severely deformed NiTi and NiTiHf shape memory alloys .................................................................................................. 489 G. Steiner, M. Peterlechner, T. Waitz, and H.P. Karnthaler

TEM studies of nanostructured NiTiCo shape memory alloy for medical applications............................................................................................. 491 D. Stróż and Z. Lekston

TEM investigations of microalloyed steels with Nb, V and Ti after different treatments .......................................................................................... 493 G. Szalay, R. Grill, K. Spiradek-Hahn, and M. Brabetz

Initial Stages of the ω Phase Transformation .......................................................... 495 R. Tewari, K.V. Manikrishna, G.K. Dey, and S. Banerjee

TEM study of the Ni-Ti shape memory micro-wire ................................................ 497 H. Tian, D. Schryvers, and J. Van Humbeeck

Multi-scale observations of deformation twins in Ti6Al4V .................................... 499 W. Tirry, F. Coghe, L. Rabet, and D. Schryvers

Nd:YAG laser joining between stainless steel and nickel-titanium shape memory alloys .................................................................................................. 501 J. Vannod, A. Hessler-Wyser, and M. Rappaz

XX

Content

Focused Ion Beam application on the investigation of tungsten-based materials for fusion application.................................................. 503 L. Veleva, R. Schäublin, A. Ramar, Z. Oksiuta, and N. Baluc

HRTEM of NiTi shape memory alloys made amorphous by high pressure torsion............................................................................................. 505 T. Waitz, K. Tsuchiya, M. Peterlechner, and H.P. Karnthaler

Is the lattice structure of the martensite in nanocrystalline NiTi base centred orthorhombic? .............................................................................................. 507 T. Waitz

TEM study of the NiTi shape memory thin film...................................................... 509 B. Wang, A. Safi, T. Pardoen, A. Boe, J.P. Raskin, X. Wang, J.J. Vlassak, and D. Schryvers

Sub-nano analysis of fine complex carbide in high strength steel with probe Cs (S)TEM ............................................................................................... 511 K. Yamada, E. Hamada, K. Sato, and K. Inoke

Characterization of morphology and microstructure of different kinds of materials at NTNU Mater Sci EM Lab ................................................................ 513 Y.D. Yu, T. Nilsen, M.P. Raanes, J. Hjelen, and J.K. Solberg

Characterization of a Ti64Ni20Pd16 thin film by transmission electron microscopy........................................................................ 515 R. Zarnetta, E. Zelaya, G. Eggeler, and A. Ludwig

Analytical electron microscopy investigations of a microstructure of single and polycrystalline β-Mg2Al3 Samson phase............................................. 517 A. Zielińska-Lipiec, B. Dubie,l and A. Czyrska-Filemonowicz

M3.2 Ceramic materials Grain boundary interfaces in ceramics .................................................................... 519 D.J.H. Cockayne, S.-J. Shih, K. Dudeck, and N. Young

Structure and chemistry of nanometer-thick intergranular films at metal-ceramic interfaces........................................................................................ 521 W.D. Kaplan and M. Baram

Studying nanocrystallization behaviour of different inorganic glasses using Transmission Electron Microscopy ................................................................ 523 Somnath Bhattacharyya, Th. Höche, C. Bocker, C. Rüssel, A. Duran, N. Hémono, F. Muñoz, M.J. Pascual, K. Hahn, and P.A. van Aken

HRTEM and Diffraction Analysis of Surface Phases in Nanostructured LiMn1.5Ni0.5O4 Spinel.................................................................................................. 525 F. Cosandey, N. Marandian Hagh, and G.G. Amatucci

Content

XXI

The structural origin of the antiferroelectric properties and relaxor behavior of Na0.5Bi0.5TiO3 ..................................................................... 527 V. Dorcet, G. Trolliard, and P. Boullay

Electron beam probing of insulators ........................................................................ 529 H.-J. Fitting, N. Cornet, M. Touzin, D. Goeuriot, C. Guerret-Piécourt, D. Juvé, and D. Tréheux

Characterization of Ge-based clathrates oxidized in air by means of TEM and SEM...................................................................................................................... 531 C. Hébert, B. Bartova, M. Cantoni, U. Aydemir, and M. Baitinger

Microstructure analysis of thin Cr2AlC films deposited at low temperature by magnetron sputtering............................................................................................ 533 R. Iskandar, D.P. Sigumonrong, J.M. Schneider, and J. Mayer

Study of structural variation in YBaCo4O7+δ by electron diffraction .................... 535 Y. Jia, H. Jiang, M. Valkeapää, M. Karppinen, and E.I. Kauppinen

Exsolution phenomena in glass-ceramic systems..................................................... 537 I. Tsilika, Ph. Komninou, G.P. Dimitrakopulos, Th. Kehagias, and Th. Karakostas

Transmission Electron Microscopy Studies of Lead-Free Ferroelectrics in the System BNT-BT-KNN ..................................................................................... 539 H.-J. Kleebe, J. Kling, L. Schmitt, S. Lauterbach, and H. Fuess

ReO3-related aluminum tungsten oxides showing a novel type of crystallographic shear structure........................................................................... 541 F. Krumeich and G.R. Patzke

Structural Characterisation by TEM of a New Homologous Series Bi2n+4MonO6(n+1); n=3,4,5 and 6.................................................................................. 543 A.R. Landa-Canovas, J. Hernández-Velasco, E. Vila, J. Galy, and A. Castro

Structural characterisation of a new rich iron layered oxide TlεSr25-εFe30O76-ξ .... 545 C. Lepoittevin, S. Malo, S. Hebert, M. Hervieu, and G. Van Tendeloo

EBSD studies of stress concentrations in ferroelectrics .......................................... 547 I. MacLaren, M.U. Farooq, R. Villaurrutia, T.L. Burnett, T.P. Comyn, A.J. Bell, H. Kungl, and M.J. Hoffmann

High-resolution pictures of nucleation growth triangle of 180° ferroelectric domain wall in a thin film of LiTaO3 obtained by Lorentz DPC-STEM............... 549 T. Matsumoto, M. Koguchi, and Y. Takahashi

Size and structure of barium halide nano-crystals in optically active fluorozirconate-based glasses .................................................................................... 551 P.T. Miclea, B. Ahrens, C. Eisenschmidt, and S. Schweizer

Domain Structure And Microstructure Development of BaTiO3 Doped With Rare-Earth Dopants ......................................................................................... 553 V. Mitic, V.B. Pavlovic, V. Paunovic, M. Miljkovic, B. Jordovic, and Lj. Zivkovic

XXII

Content

SEM and EDS Analysis of BaTiO3 Doped With Yb2O3 and Ho2O3 ....................... 555 V. Mitic, V.B. Pavlovic, V. Paunovic, M. Miljkovic, B. Jordovic, and Lj. Zivkovic

Structure and superconductivity of Pr-Ba-Cu-O crystals prepared by ambient pressure synthesis using citrate pyrolysis method............................... 557 K. Nishio, T. Isshiki, T. Shima, and M. Hagiwara

Electron Diffuse Scattering in epitaxially grown SrTiO3 thin film ........................ 559 F. Pailloux and J. Pacaud

Investigation of the hydration of calciumsulfate hemihydrates with different microscopic methods.......................................................................... 561 C. Pritzel and R. Trettin

Investigation of holes in calciumsulfate-hemihydrate crystals by different microscopic methods ............................................................................. 563 C. Pritzel and R. Trettin

Analytical and high-resolution TEM investigation of Boron-doped CeO2 ............ 565 B. Rahmati, G. Gregori, W. Sigle, C.T. Koch, P.A. van Aken, and J. Maier

Accommodation of the compositional variations in the Ca1-xSrxMnO3-δ (0≤x≤1, 0≤δ≤0.5) system............................................................................................. 567 S. de Dios, J. Ramírez-Castellanos, A. Varela, M. Parras, and J.M. González Calbet

Evidence of SrO(SrTiO3)n Ruddlesden-Popper Phases by High Resolution Electron Microscopy and Holography .................................... 569 M. Reibold, E. Gutmann, A.A. Levin, A. Rother, D.C. Meyer, and H. Lichte

New Barium Antimony Aluminates evidenced by TEM techniques...................... 571 R. Retoux, A. Letrouit, M. Hervieu, and S. Boudin

(Multi-)ferroic domain walls– a combined ab-initio and microscopical investigation ................................................................................ 573 A. Rother, S. Gemming, D. Geiger, and N. Spaldin

Diagnostic of Li battery cathode by EELS, first principles calculation and spectrum-imaging with multi-variate analysis ................................................. 575 K. Tatsumi, Y. Sasano, S. Muto, T. Sasaki, Y. Takeuchi, K. Horibuchi, and Y. Ukyo

Local electronic structure analysis on Ce3+-containing materials by TEM-EELS and first principles calculations...................................................... 577 K. Tatsumi, I. Nishida, and S. Muto

Local chemical inhomogeneities in NaNb1-xTaxO3 as observed by HRTEM and HAADF-STEM.................................................................................................... 579 A. Torres-Pardo, E. García-González, J.M. González-Calbet, F. Krumeich, and R. Nesper

The influence of lanthanum doping on the structure of PbZr0.9Ti0.1O3 ceramics.......................................................................................... 581 R. Villaurrutia, I. MacLaren, and A. Peláiz-Barranco

Content

XXIII

Anomalous absorption of electrons during electron diffraction on BaTiO3 single crystals near phase transition at 120°C ...................................... 583 A. Wall

Template-assisted synthesis and characterization of SrTiO3 nanostructures........................................................................................... 585 K. Žagar, S. Šturm, and M. Čeh

(S)TEM/EELS characterisation of a multilayer C/Cr PVD coating ...................... 587 Z. Zhou, W.M. Rainforth, M. Gass, A. Bleloch, and P.Eh. Hovsepian

M3.3 Magnetic materials High resolution imaging of magnetic structures in a TEM – what is possible? .... 589 J. Zweck

Phase segregation leading to spontaneous outcropping of (Sr,La)Ox dots in La1-xSrxMnO3 films ................................................................................................ 591 P. Abellan, F. Sandiumenge, C. Moreno, M.J. Casanove, T. Puig, and X. Obradors

Microstructure of epitaxially strained LaCoO3 thin films...................................... 593 L. Dieterle, D. Gerthsen, and D. Fuchs

Are the samples really flat? Influence of the supporting membrane on the magnetization of patterned micromagnets ................................................... 595 C. Dietrich and J. Zweck

HRTEM characterization of core-shell Fe@C and Fe@SiO2 magnetic nanoparticles prepared by the arc-discharge plasma method................................ 597 Rodrigo Fernández-Pacheco, Manuel Arruebo, Jordi Arbiol, Clara Marquina, Jesús Santamaría, and M. Ricardo Ibarra

Nanofabrication of ferromagnetic nanotips and nanobridges by 2D and 3D electron-beam cutting ................................................................................... 599 T. Gnanavel, Z. Saghi, Y. Peng, B.J. Inkson, M.R.J. Gibbs, and G. Möbus

An investigation into the crystallization of the MgO barrier layer of a magnetic tunnel junction .................................................................................... 601 V. Harnchana, A.P. Brown, R.M. Brydson, A.T. Hindmarch, and C.H. Marrows

FeCoAlN films with induced magnetic anisotropy .................................................. 603 A. Lančok, M. Klementová, M. Miglierini, F. Fendrych, K. Postava, J. Kohout, and O. Životský

The martensitic microstructure of 5M and NM martensites in off-stoichiometric Ni2MnGa ferromagnetic shape memory alloys..................... 605 Pallavi Sontakke, Amita Gupta, and Madangopal Krishnan

TEM characterization of nanometer-sized Fe/MgO granular multilayer thin films grown by pulsed laser deposition............................................................. 607 C. Magén, E. Snoeck, A. García-García, J.A. Pardo, P.A. Algarabel, P. Štrichovanec, A. Vovk, L. Morellón, J.M. De Teresa, and M.R. Ibarra

XXIV

Content

Structural modification and self-assembly of nanoscale magnetite synthesised in the presence of an anionic surfactant ................................................................... 609 S. Malik, I.J. Hewitt, and A.K. Powell

Electron microscopy phase retrieval of perpendicular magnetic anisotropy (PMA) FePd alloys ..................................................................................................... 611 A. Masseboeuf, C. Gatel, A. Marty, E. Snoek, and P. Bayle-Guillemaud

Magnetic domain wall propagation in nanostructures of alloys with perpendicular magnetic anisotropy.................................................................. 613 A. Masseboeuf, A. Mihaï, J.P. Attané, J.C. Pillet, P. Warin, A.L. Vila, G. Gaudin, M. Miron, B. Rodmacq, E. Gautier, A. Marty, and P. Bayle-Guillemaud

The effect of annealing in the microstructure and magnetic properties of NiCuZn ferrites ...................................................................................................... 615 D. Sakellari, V. Tsakaloudi, V. Zaspalis, and E.K. Polychroniadis

Microstructural and compositional analyses of nano-structured Co-Pt thin films ..................................................................................................................... 617 Z. Samardžija, K. Žužek Rožman, and S. Kobe

L10-type ordered structure of FePd nanoparticles studied by high-resolution transmission electron microscopy ............................................. 619 K. Sato, T.J. Konno, and Y. Hirotsu

Structural and chemical characterization of Co-doped ZnO layers grown on Si and sapphire ...................................................................................................... 621 R. Schneider, L.D. Yao, D. Gerthsen, G. Mayer, M. Fonin, and U. Rüdiger

TEM studies of cobalt-doped zinc oxide films ......................................................... 623 J. Simon, K. Nielsen, M. Opel, S.T.B. Goennenwein, R. Gross, and W. Mader

Nanocrystallization of amorphous Fe40Ni38B18Mo4 alloy ........................................ 625 D. Srivastava, A.P. Srivastava, and G.K. Dey

Structural and compositional properties of Sm-Fe-Ta magnetic nanospheres prepared by pulsed-laser deposition at 157 nm in a N2 atmosphere...................... 627 S. Šturm, K. Žužek Rožman, E. Sarantopoulou, and S. Kobe

Characterization of Ni-Mn-Ga magnetic shape memory alloys using electron holography and Lorentz microscopy ............................................... 629 K. Vogel, M. Linck, Ch. Matzeck, A. Rother, D. Wolf, and H. Lichte

Energy Loss Magnetic Chiral Dichroïsm (EMCD) for magnetic material............ 631 B. Warot-Fonrose, L. Calmels, C. Gatel, F. Houdellier, V. Serin, and E. Snoeck

M3.4 Dislocations, interfaces and other defects Determining the nanoscale chemistry and behavior of interfaces and phases in Al-Si(-Cu-Mg) nanoparticles using in-situ TEM................................................. 633 J.M. Howe, S.K. Eswaramoorthy, and G. Muralidharan

Content

XXV

Dislocations in AlPdMn quasicrystals: contrast in TEM and physical properties .............................................................................................. 635 D. Caillard and F. Mompiou

Characterization of a-plane GaN films grown on r-plane sapphire substrate by electron microscopy .............................................................................................. 637 Y. Arroyo Rojas Dasilva, T. Zhu, D. Martin, N. Grandjean, and P. Stadelmann

A method for atomistic/continuum analysis of defects in large HRTEM images ............................................................................................ 639 A. Belkadi, G.P. Dimitrakopulos, J. Kioseoglou, G. Jurczak, T.D. Young, P. Dluzewski, and Ph. Komninou

High resolution electron microscopy of interfaces in ultrafine microstructures of Zr and Ti based alloys ........................................... 641 G.K. Dey, S. Neogy, R.T. Savalia, R. Tewari, D. Srivastava, and S. Banerjee

Anisotropic strain relaxation in (110) La2/3Ca1/3MnO3 thin films .......................... 643 S. Estrade, I.C. Infante, F. Sanchez, J. Fontcuberta, J. Arbiol, and F. Peiró

Metadislocations in complex metallic alloys: core structures investigated by aberration-corrected scanning transmission electron microscopy ................... 645 M. Feuerbacher, L. Houben, and M. Heggen

TEM of high pressure torsion processed intermetallic Zr3Al................................. 647 D. Geist, C. Rentenberger, and H.P. Karnthaler

Multiscale characterisation of the plasticity of Fe-Mn-C TWIP steels .................. 649 H. Idrissi, L. Ryelandt, K. Renard, S. Ryelandt, F. Delannay, D. Schryvers, and P.J. Jacques

Misfit analysis of the InN/GaN interface through HRTEM image simulations ....................................................................................................... 651 J. Kioseoglou, G.P. Dimitrakopulos, Th. Kehagias, E. Kalessaki, Ph. Komninou, and Th. Karakostas

Application of TEM for Real Structure Determination of Rare Earth Metal Compounds.............................................................................. 653 L. Kienle, V. Duppel, Hj. Mattausch, M.C. Schaloske, and A. Simon

Quantitative Dislocation Analysis of 2H AlN:Si grown on (0001) Sapphire ......... 655 O. Klein, J. Biskupek, U. Kaiser, S.B. Thapa, and F. Scholz

Transrotational crystals in crystallizing amorphous films: new solid state order or novel extended imperfection............................................. 657 V.Yu. Kolosov

Determination of precise orientation relationships between surface precipitates and matrix in a duplex stainless steel................................................... 659 Y. Meng, G. Nolze, W.Z. Zhang, L. Gu, and P.A. van Aken

Interfaces in Cu(In,Ga)Se2 thin film solar cells ....................................................... 661 G. Östberg and E. Olsson

XXVI

Content

In-situ electron beam irradiation of nanopipes in GaN .......................................... 663 F. Pailloux and J.-F. Barbot

The atomic structure of an incommensurate (001)-(110) Si grain boundary resolved thanks to a probe Cs-corrector .................................................................. 665 J.L. Rouviere, F. Lançon, K. Rousseau, D. Caliste, and F. Fournel

Atomic structure and dopant segregation of [0001] tilt grain boundaries in ZnO bicrystals ........................................................................................................ 667 Y. Sato, T. Mizoguchi, J.P. Buban, N. Shibata, T. Yamamoto, T. Hirayama, and Y. Ikuhara

TEM study of strain and defect engineering with diluted nitride semiconductors ......................................................................... 669 J. Schöne, E. Spiecker, F. Dimroth, A.W. Bett, and W. Jäger

Investigation of the Co-Precipitation of Copper and Nickel in Silicon by Means of Transmission Electron Microscopy..................................................... 671 C. Rudolf, L. Stolze, and M. Seibt

Micro-structure analysis of a friction-stir welded 2024 aluminium alloy using electron microscopy.......................................................................................... 673 E. Sukedai, T. Maebara, and T. Yokayama

Deformation defects in a metastable β titanium alloy............................................. 675 H. Xing and J. Sun

Defect generation and characterization in 4H-SiC.................................................. 677 J.P. Ayoub, M. Texier, G. Regula, M. Lancin, and B. Pichaud

Investigation of defects in polymorph B enriched zeolite Beta............................... 679 D. Zhang, J. Sun, S. Hovmöller, and X. Zou

M3.5 Coatings and graded materials Optimizing electron diffraction and EDS for phase identification in complex structures: application to multilayered Ti-Ni-P coatings .................... 681 P.A. Buffat and A. Czyrska-Filemonowicz

Advanced analytical transmission electron microscopy to investigate the nano-graded materials properties ...................................................................... 683 M. Cheynet, S. Pokrant, L. Joly-Pottuz, and J.M. Martin

Characterisation of Nickel Nanocomposites by SEM, TEM and EBSD................ 685 D. Dietrich, Th. Lampke, B. Wielage, D. Thiemig, and A. Bund

Characterisation of Gold Nanocomposites by SEM, TEM and EBSD .................. 687 D. Dietrich, Th. Lampke, B. Wielage, P. Cojocaru, and P.L. Cavallotti

Alumina Coatings as Protection against Corrosive Atmosphere ........................... 689 I. Dörfel, R. Sojref, M. Dressler, D. Hünert, and M. Nofz

Content

XXVII

Advanced Multilayer Systems for X-ray Optics: Quality Assessment by TEM ....................................................................................................................... 691 D. Häussler, W. Jäger, E. Spiecker, B. Ögüt, U. Ross, J. Wiesmann, and M. Störmer

Surface investigation of SU-8 by atomic force and scanning electron microscopy ............................................................................ 693 Th. Kups, Chr. Kremin, M. Hoffmann, and L. Spieß

SEM and TEM investigations of electrophoretical deposited Si3N4 and SiC particles in siloxane of steel substrate ........................................................ 695 Th. Kups, A. Knote, and L. Spieß

Contribution of electron microscopy techniques to the chemical and structural characterization of TiC/a-C nanocomposite coatings .................... 697 C. López-Cartes, D. Martínez-Martínez, J.C. Sánchez-López, and A. Fernández

TEM investigations of the Ti/TiN multilayered coatings deposited on the Ti-6Al-7Nb alloy.............................................................................................. 699 T. Moskalewicz, H.J. Penkalla, and A. Czyrska-Filemonowicz

Microstructural examination of Al and Cr alloyed zinc coatings on low carbon steels.................................................................................................... 701 D. Chaliampalias, G. Vourlias, E. Pavlidou, K. Chrissafis, G. Stergioudis, and S. Skolianos

Study of the structure and high temperature oxidation resistance of high alloyed tool steels ........................................................................................... 703 E. Pavlidou, D. Chaliampalias, G. Vourlias, and K. Chrissafis

A comparative study of NiCrBSi and Al coated steels with thermal spray process in different environments............................................................................. 705 D. Chaliampalias, G. Vourlias, E. Pavlidou, K. Chrissafis, G. Stergioudis, and S. Skolianos

Microscopical study of the influence of zinc addition on the structure of WO3.... 707 K. Nikolaidis, D. Chaliampalias, G. Vourlias, E. Pavlidou, and G. Stergioudis

Microstructural Studies by Electron Microscopy Techniques of TiAlSiN Nanostructured Coatings........................................................................................... 709 V. Godinho, T.C. Rojas, M.C. Jimenez, M.P. Delplancke-Ogletree, and A. Fernández

Structural and interface studies of a nano-scale TiAlYN/CrN/alumina coating ................................................................................... 711 I.M. Ross, W.M. Rainforth, C. Strondl, F. Papa, and R. Tietema

An investigation of SiC-fiber coatings ...................................................................... 713 T. Toplišek, Z. Samardžija, G. Dražić, S. Kobe, and S. Novak

HRTEM-EELS study of atomic layer deposited thin rare earth oxide films for advanced microelectronic devices ....................................................................... 715 S. Schamm, P.E. Coulon, and L. Calmels

XXVIII

Content

New Fullerene like materials for tribological applications: TEM and EELS study................................................................................................ 717 Virginie Serin, Nathalie Brun, and Ch. Colliex

Phase determination of nanocrystalline Al-Cr-O coatings by analytical TEM...................................................................................................... 719 J. Thomas, J. Ramm, B. Arnold, B. Widrig, and T. Gemming

M3.6 Biomaterials Bioinspired synthesis of nanostructures based on S-layer lattices ......................... 721 D. Pum, N. Ilk, and U.B. Sleytr

Direct Imaging of Carbon Nanoparticles inside Human Cells ............................... 723 A.E. Porter, C. Cheng, M. Gass, K. Muller, J. Skepper, P. Midgley, and M. Welland

Micro- and Nano-Textured Surfaces on Ti-Implants Made by Various Methods ................................................................................................... 725 U. Beck, R. Lange, and H.-G. Neumann

Determination of the biocompatibility of biomaterials by scanning electron microscopy (SEM) .................................................................. 727 M. Bovi, N. Gassler, and B. Hermanns-Sachweh

Quantitative evaluation of the long-term marginal behaviour of filling restorations of human teeth using three-dimensional scanning electron microscopy.................................................................................................... 729 W. Dietz, S. Nietzsche, R. Montag, P. Gaengler, and I. Hoyer

The analysis of Si doped hydroxyapatite coatings using FIBSEM, TEM and RHEED ................................................................................................................ 731 H.K. Edwards, S. Coe, T. Tao, M.W. Fay, C.A. Scotchford, D.M. Grant, and P.D. Brown

Electron microscopic investigations of the polymer/mineral composite material nacre............................................................................................................. 733 K. Gries, R. Kröger, C. Kübel, M. Fritz, and A. Rosenauer

Studies on the microstructure of fresh-cut melon ................................................... 735 I. Hernando, L. Alandes, A. Quiles, and I. Pérez-Munuera

Ceramic-loaded mineralizing bioresorbable polymers for orthopaedic applications...................................................................................... 737 L.W. Hobbs, T. Lim, A. Porter, H. Wang, M. Walton, and N.J. Cotton

AFM and TEM study of Ag coated insulin-derived amyloid fibrils ...................... 739 M. Gysemans, J. Snauwaert, C. Van Haesendonck, F. Leroux, B. Goris, S. Bals, and G. Van Tendeloo

Transmission Electron Microscopy studies of bio-implant interfaces using Focused Ion Beam microscopy for sample preparation................................ 741 F. Lindberg, A. Palmquist, L. Emanuelsson, J. Heinrichs, R. Brånemark, F. Ericson, P. Thomsen, and H. Engqvist

Content

XXIX

AFM and SEM of Wax Crystallisation on Artificial Surfaces Controlled by Temperature and Solvents ................................................................................... 743 A. Niemietz, W. Barthlott, K. Wandelt, and K. Koch

Characterization of layer-by-layer microcapsules made of hyaluronic acid by CLSM, SEM and TEM ......................................................................................... 745 I. Pignot-Paintrand, A. Szarpak, and R. Auzely-Velty

Atomic force microscopy analysis of crystalline silicon functionalization with oligonucleotides .................................................................................................. 747 A. Ponzoni, G. Faglia, M. Ferroni, G. Sberveglieri, A. Flamini, G. Andreano, and L. Cellai

Hidden hierarchy of microfibrils within fluorapatite gelatine nanocomposites induced by intrinsic electric dipole fields ..................................... 749 P. Simon and R. Kniep

M4

Soft Matter and Polymers

Self-assembled block copolymer structures studied by transmission electron microtomography ........................................................................................ 751 H. Jinnai, T. Kaneko, C. Abetz, and V. Abetz

Quantitative chemistry and orientation of polymers in 2-d and 3-d by scanning transmission X-ray microscopy............................................................ 753 A.P. Hitchcock, G.A. Johansson, D. Hernández Cruz, E. Najafi, J. Li and and H. Stöver

Characterization of cavitation processes in filled semi-crystalline polymers........ 755 F. Addiego, J. Di Martino, D. Ruch, A. Dahoun, and O. Godard

Quantitative analysis of protein gel structure by confocal laser scanning microscopy .................................................................................................. 757 K. Ako, L. Bécu, T. Nicolai, J.-C. Gimel, and D. Durand

Thermal stability of organic solar cells: the decay in photocurrent linked with changes in active layer morphology ................................................................. 759 S. Bertho, I. Haeldermans, A. Swinnen, J. D’Haen, L. Lutsen, T.J. Cleij, J. Manca, and D. Vanderzande

Determining absorptive potential variation in electron beam sensitive specimens using a single energy-filtered bright-field TEM image ......................... 761 S. Bhattacharyya and J.R. Jinschek

Elemental distribution of soft materials with newly designed 120kV TEM/STEM .................................................................................... 763 C. Hamamoto, N. Endo, H. Nishioka, T. Ishikawa, Y. Ohkura, and T. Oikawa

Preparation of titanate nanotubes and their polymer composites ......................... 765 D. Kralova, N. Neykova, and M. Slouf

XXX

Content

Nanometer size wear debris generated from ultrahigh molecular weight polyethylene in vivo .................................................................................................... 767 M. Lapcikova, M. Slouf, J. Dybal, E. Zolotarevova, G. Entlicher, D. Pokorny, J. Gallo, and A. Sosna

Analysis of nano-composites based on carbon nanoparticles imbedded in polymers.................................................................................................................. 769 Kangbo Lu, Joachim Loos, Sourty Erwan, and Dong Tang

New developments in SEM for in situ tensile tests on polymers............................. 771 P. Jornsanoh, G. Thollet, C. Gauthier, and K. Masenelli-Varlot

A study of the spatial distributions of the carbon blacks in polypropylene composites using TEM-Tomography and quantitative image analysis ................. 773 H. Matsumoto, H. Sugimori, T. Tanabe, Y. Fujita, H. Sano, and H. Jinnai

A study of the chain-folded lamellae structure and its array in the isotactic polypropylene spherulites by HAADF-STEM and HV-TEM Tomography techniques.................................................................... 775 H. Matsumoto, M. Song, H. Sano, M. Shimojo, and K. Furuya

Microstructural analysis of ultra-thin nanocomposite layers fabricated by Cu+ ion implantation in inert polymers............................................................... 777 G. Di Girolamo, E. Piscopiello, M. Massaro, E. Pesce, C. Esposito, L. Tapfer, and M. Vittori Antisari

In-situ experiments on soft materials in the environmental SEM – Reliable results or merely damage?......................................................................................... 779 P. Poelt, H. Reingruber, A. Zankel, and C. Elis

Structural studies on V-amylose inclusion complexes............................................. 781 J.L. Putaux, M. Cardoso, M. Morin, D. Dupeyre, and K. Mazeau

Multilamellar nanoparticles from PS-b-PVME copolymers .................................. 783 C. Lefebvre, J.-L. Putaux, M. Schappacher, A. Deffieux, and R. Borsali

TEM/SEM characterisation of hybrid titanoniobiates used as fillers for thermoplastic nanocomposites ............................................................................ 785 R. Retoux, S. Chausson, L. Le Pluart, J.M. Rueff, and P.A. Jaffres

Phase transitions and ordering in liquid crystals – a case study ............................ 787 A.K. Schaper

Study of degradation and regeneration of silicon polymers using cathodoluminescence........................................................................................ 789 P. Schauer, P. Horak, F. Schauer, I. Kuritka, and S. Nespurek

Orthogonal self-assembly of surfactants and hydrogelators: towards new nanostructures...................................................................................... 791 M.C.A. Stuart, A.M.A. Brizard, E.J. Boekema, and J.H. van Esch

Content

XXXI

Structure of particles formed during Se redox process in aqueous polymer solutions .................................................................................... 793 E.I. Suvorova, V.V. Klechkovskaya, M. Cantoni, and P.A. Buffat

Exploring the 3D organisation of high-performance organic solar cells ............... 795 S. van Bavel, E. Sourty, B. de With, and J. Loos

Morphological study on three kinds of two-dimensional spherulites of PBT ....... 797 T. Yoshioka and M. Tsuji

Solution-Grown Crystals of Optically Active Propene–Carbon Monoxide Copolymer................................................................................................................... 799 T. Yoshioka, N. Kosaka, A. Nakayama, A.K. Schaper, W. Massa, T. Hiyama, K. Nozaki, and M. Tsuji

M5

Materials in Mineralogy, Geology and Archaeology

New insights into ultra-high pressure metamorphism from TEM studies ............ 801 F. Langenhorst and A. Escudero

Characterization of a (021) twin in coesite using LACBED and precession electron diffraction........................................................................... 803 P. Cordier, D. Jacob, and H.-P. Schertl

Rubens in the Prado National Museum: analytical characterization of ground layers.......................................................................................................... 805 M.I. Báez, L. Vidal, M.D. Gayo, J. Ramírez-Castellanos, J.L. Baldonedo, and A. Rodríguez

Development of the FIB-cryo-SEM approach for the in-situ investigations of the elusive nanostructures in wet geomaterials ................................................... 807 G. Desbois and J.L. Urai

TEM applied on the interface characterisation of the replacement reaction chlorapatite by hydroxyapatite ................................................................................. 809 U. Golla-Schindler, A. Engvik, H. Austrheim, and A. Putnis

Quantitative study of valence states of zirconolites ................................................. 811 U. Golla-Schindler and P. Pöml

Study of Organic Mineralogical Matter by Scanning Probe Microscopy ............. 813 Ye.A. Golubev and O.V. Kovaleva

Research of Nanoparticle Aggregates from Water Colloidal Solutions of Natural Carbon Substances and Fullerenes by Atomic Force Microscopy ...... 815 Ye.A. Golubev and N.N. Rozhkova

Diffusion in Synthetic Grain Boundaries ................................................................. 817 K. Hartmann, R. Wirth, R. Dohmen, G. Dresen, and W. Heinrich

XXXII

Content

An examination of Van Gogh’s painting grounds using analytical electron microscopy – SEM/FIB/TEM/EDX .......................................................................... 819 R. Haswell, U. Zeile, and K. Mensch

Amorphisation in fresnoite compounds – a combined ELNES and XANES study....................................................................................................... 821 Th. Höche, F. Heyroth, P.A. van Aken, F. Schrempel, G.S. Henderson, and R.I.R. Blyth

TEM study of Comet Wild 2 pyroxene particles collected during the stardust mission ....................................................................................... 823 D. Jacob, J. Stodolna, and H. Leroux

The mechanism of ilmenite leaching during experimental alteration in HCl-solution ........................................................................................................... 825 A. Janßen, U. Golla-Schindler, and A. Putnis

Microstructure and Texture from Experimentally Deformed Hematite Ore ....... 827 K. Kunze, H. Siemes, E. Rybacki, E. Jansen, and H.-G. Brokmeier

Identifying pigments in the temple of Seti I in Abydos (Egypt) ............................. 829 E. Pavlidou, H. Marey Mahmoud, E. Roumeli, F. Zorba, K.M. Paraskevopoulos, and M.F. Ali

Nanostructural study of ground layers of canvas of Rubens at “El Prado” National Museum ............................................................................... 831 J. Ramírez-Castellanos, J.L. Baldonedo, M.I. Báez, L. Vidal, M.D. Gayo, and M.J. García

Micro- and nano-diamond particles in carbon spherules found in soil samples ............................................................................................................. 833 Z. Yang, D. Schryvers, W. Rösler, N. Tarcea, and J. Popp

The use of FIB/TEM for the study of radiation damage in radioactive/non-radioactive mineral assemblages............................................... 835 A.-M. Seydoux-Guillaume, J.-M. Montel, and R. Wirth

Non-destructive 3D measurements of sandstone’s internal micro-architecture using high resolution micro-CT ................................................................................ 837 E. Van de Casteele, S. Bugani, M. Camaiti, L. Morselli, and K. Janssens

Author Index............................................................................................................... 839 Subject Index .............................................................................................................. 859

1

Direct observation of atomic defects in carbon nanotubes and fullerenes K. Suenaga National Institute of Advanced Industrial Science and Technology (AIST) and the Japan Science and Technology Agency (JST), Tsukuba, 305-8565, Japan [email protected] Keywords: defect, nanotube, fullerene

The diversified properties of carbon nano-structures (nanotubes, fullerenes and their derivatives) are related to their polymorphic arrangement of carbon atoms. Therefore the direct observation of carbon network, such as defects or chirality, is of great consequence in both scientific and technological viewpoints in order to predict the physical and chemical properties. In order to identify the local configuration of pentagons and hexagons in carbon nanostructures, an electron microscope with higher spatial resolution and higher sensitivity is definitively required. Since the spatial resolution of the conventional TEM is limited by the spherical aberration coefficient (Cs) of its objective lens and the wave length (λ) of incident electron beam, the Cs must be minimized to achieve the best performance because the reduction of the λ is detrimental to the high sensitivity to visualize individual carbon atoms. A highresolution transmission electron microscope (HRTEM, JEOL-2010F) equipped with a Cs corrector (CEOS) was operated at a moderate accelerating voltage (120kV). The Cs was set to 0.5 ~ 10 µm in this work. The HRTEM images were digitally recorded under a slightly under-focus condition (Δf = -2 to -7 nm) where the point resolution of 0.14 nm was achieved at 120kV. The spatial resolution of 0.14 nm (a typical C-C bond length) obtained at a moderate accelerating voltage provides us a great advantage because we can realize the visualization of carbon atomic arrangement without massive electron irradiation damage. Here we show some examples for atomic-level characterization of carbon nanostructures. The C60 and C80 fullerene molecule has been successfully identified its structure and orientation at a single-molecular basis (1, 2). Also the active topological defects have been eventually caught red-handed (3, 4). The technique can be widely applicable to visualize a biological activity, at an atomic level, for which any conformation change of the C-C bonds is responsible. The cis-/trans-isomerization of retinal molecules have been successfully visualized (5). 1. 2. 3. 4. 5.

Z. Liu, K. Suenaga and S. Iijima, J. Am. Chem. Soc., 129 (2007) 6666. Y. Sato, K. Suenaga, S. Okubo, T. Okazaki and S. Iijima, Nano Letters, 7 (2007) 3704. K. Suenaga, H. Wakabayashi, M. Koshino, Y. Sato, K. Urita and S. Iijima, Nature Nanotech. 2 (2007) 358. C.-H. Jin, K. Suenaga and S. Iijima, Nature Nanotech. 3 (2008) 17. Z. Liu, K. Yanagi, K. Suenaga, H. Kataura and S. Iijima, Nature Nanotech. 2 (2007) 422.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 1–2, DOI: 10.1007/978-3-540-85226-1_1, © Springer-Verlag Berlin Heidelberg 2008

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6.

The supports of the JST-CREST, JST-ERATO, KAKENHI and JSPS are kindly acknowledged.

Figure 1. a, A 5–7 pair defect found in an SWNT after heat treatment at 2,273 K. b, An enlarged image of the area enclosed by the green line in a) in which the 5–7–7–5 defect can be more clearly seen. c, The black dots indicate the hexagons with six neighbors, the two red dots have seven neighbors, and the two black dots with circles have five neighbors.

Figure 2. a, The Stone-Wales (SW) transformation leading to the 5–7–7–5 defect, generated by rotating a C–C bond in a hexagonal network. b, HR-TEM image obtained for the atomic arrangement of the SW model. c, Simulated HR-TEM image for the model shown in b. (ref. 3)

3

Atomic studies on ferroelectric oxides by aberration corrected transmission electron microscopy K. Urban and C.L. Jia Institute for Solid State Research, Research Centre Jülich, and Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons, D-52428 Jülich, Germany [email protected] Keywords: Oxides, Interfaces, Defects

The advent of aberration-corrected transmission electron microscopy in 1998 [1] has provided materials science with entirely new tools for quantitative investigations. Four key innovations have to be mentioned: (1) The possibility to operate the electron microscope as a variable-sphericalaberration instrument allows to derive a new phase contrast theory optimizing both resolution and point spread [2]. In classical Scherzer phase contrast theory the radius of the point spread disc amounts to three times the Scherzer resolution limit. Besides the fact that information is lost by placing an aperture in the diffraction plane to keep the contrast oscillations in the contrast transfer function from affecting the images this point spread is a second disadvantage of the classical Scherzer approach to phase contrast. Both limitations can be substantially reduced in a new theory in which by both the objective lens defocus Z as well as CS the spherical aberration parameter adopt specific values. As a result the resolution limit coincides with the information limit and the point spread gets reduced to about one half of the latter making it an uncritical parameter in practice. (2) The negative spherical aberration imaging (NCSI) technique leads to enhanced contrast of atoms with low nuclear charge number [3]. It relies on two advantages compared to the classical Zernike technique. The shift of the phase of the diffracted waves is, in contrast to the classical Scherzer technique, in clockwise direction leading to white atom contrast. Furthermore the contrast is enhanced by a dynamic non-linear effect. Oxygen, nitrogen and even boron can be imaged directly even when these atomic species occur in close distance to heavy cations. (3) Essentially point-spread-free atomic images allow to measure occupancies of atomic columns, i.e. local concentrations, with lateral atomic resolution evaluating atomically resolved intensity measurements [4]. This means that high-resolution is not only a structural technique. From now on also local composition maps can be derived which are forming an excellent starting point for ab-initio calculations of interface-, boundary- and defect structures. (4) Measurements of atomic distances can be carried out at an accuracy of a few picometers [5]. This promises to measure structure-dependent physical properties directly on the atomic scale [6]. The technique of choice in ultra-high resolution transmission electron microscopy is to take a focal series of images on the basis of the NCSI technique which is forming the

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 3–4, DOI: 10.1007/978-3-540-85226-1_2, © Springer-Verlag Berlin Heidelberg 2008

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basis of a reconstruction of the electron exit-plane wave function (EPW) [7]. However, in order to arrive at the EPW all major aberrations up to fifth order have to be known or must be compensated. This has to be done by proper diagnostics and adjustment software. The focal series reconstruction allows for additional small corrections of the aberrations but it is by principle not suited to replace aberration correction in general. It should be noted that ultra-high resolution requires modelling of the structure and composition on the computer. The reconstructed EPW is in general not(!) sufficient to carry out high precision measurements since neither the specimen illumination conditions nor the thickness is known a priori. Both seriously affect the EPW. While the latter may permit qualitative interpretation, provided that the projected potential approximation is valid, it is required to do the complete computer fit up to the eventual real structure in order to be able to carry out the picometer-accuracy measurements in the computer. A first example in which the enhanced accuracy of aberration correction has been successfully applied is the investigation of the core structure of Σ3{111} twin boundaries in BaTiO3 [4]. It could be shown that the occupancy of the oxygen sites in the boundary is only 68 %, i.e. 32 % of the sites are left vacant. The corresponding change in the Ti-Ti separation across the boundary of +35 pm and of the Ba-Ba-separation of 17 pm is well described by ab-initio calculations [8]. In a recent study of PbZr0.2Ti0.8O3 (PZT) a new inversion domain boundary was discovered [6]. This longitudinal boundary is charged and presumably formed by the dynamics of domain growth during cooling from above the critical temperature. The boundary could be characterised on the atomic level and the polarisation shifts were measured atom by atom at an accuracy of a few picometers. From these data the polarisation could be calculated as a function of distance from the core of the domain. This is a first example that ferroelectric properties can be measured by ultra-high resolution atomic transmission electron microscopy. 1. 2. 3. 4. 5. 6. 7. 8.

M. Haider, S. Uhlemann, E. Schwan, H. Rose, B. Kabius, and K. Urban, Nature 392 (1998) p. 768. M. Lentzen, Ultramicroscopy 99 (2004) p. 211. C.L. Jia, M. Lentzen and K. Urban, Science 299 (2003) p. 870. C.L. Jia and K. Urban, Science 303 (2004) p. 2001. L. Houben, A. Thust and K. Urban, Ultramicroscopy 106 (2006), p. 200. C.L. Jia, S.B. Mi, K. Urban, I. Vrejoiu, M. Alexe and D. Hesse, Nature mat. 7 (2008) p. 57 K. Tillmann, A. Thust, and K. Urban, Microsc. Microanal. 10 (2004) p. 185. W.T. Geng, Y.J.Zhang & A.J. Freemann, Phys. Rev. B 63 (2000) p. 060101 R

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Dark-field electron holography for the measurement of strain in nanostructures and devices M.J. Hÿtch, F. Houdellier, F. Hüe and E. Snoeck CEMES-CNRS, 29 rue Jeanne Marvig, 31055 Toulouse, France [email protected] Keywords: strain, high-resolution, holography, semiconductors

We present a new method for measuring strain in nanostructures and electronic devices [1]. It is based on a combination of the moiré technique and off-axis electron holography. A hologram is created from the interference between the diffracted beam emanating from an unstrained region of crystal, which serves as the reference, and a beam from the region of interest containing strained crystal. A typical example for these two regions would be the substrate and an active region of a device. The aim is to measure geometric phase differences, from which the deformation can be calculated [2]. Naturally, any other phase contributions should be minimised, notably, dynamic phases due to thickness variations. For this reason, specimens should be prepared with suitably uniform thickness and regions exhibiting bend contours avoided. The technique has a number of advantages over geometric phase analysis (GPA) of high-resolution images for the study of transistors [3]. The specimens do not need to be so thin, being more like those of conventional TEM. Specimens are therefore easier to prepare and the effects of thin-film relaxation reduced. The major advantage, however, is the ability to analyse large regions of crystal at relatively low resolution. Results will be presented for different strained-silicon devices. TEM specimens are prepared by focussed ion beam (FIB) to thicknesses of about 200 nm. Observations are carried out on the SACTEM-Toulouse, a Tecnai (FEI) 200kV TEM equipped with a Cs corrector (CEOS), rotatable biprism and 2k CCD camera (Gatan). Strain fields are extracted using a modified version of GPA Phase 2.0 (HREM Research Inc.), a plug-in for DigitalMicrograph (Gatan). Typical fringe spacings are 1-2 nm and hologram widths from 300-400 nm allowing lengthwise fields of view of several microns. Figure 1 shows an example of a p-MOSFET with recessed Si80Ge20 source and drain [3]. Holograms were formed using the {111}, (004) and (220) diffracted beams (Figure 2a). The corresponding deformation map for the component parallel to the [220] direction, εxx, (Figure 2b) compares favourably with the result from finite element modelling (Figure 2c). In this case, the measurement precision is 0.2% for a spatial resolution of 4 nm. 1. 2. 3. 4.

M.J. Hÿtch, F. Houdellier, F. Hüe and E. Snoeck, Patent Application FR N° 07 06711. M. J. Hÿtch, E. Snoeck, and R. Kilaas, Ultramicroscopy 74 (1998), p. 131. F. Hüe, M.J. Hÿtch, H. Bender, F. Houdellier and A. Claverie, PRL (2008) accepted. F. Hüe is co-funded by the CEA-Leti. The authors thank the European Union for support through the projects PullNano (Pulling the limits of nanoCMOS electronics, IST: 026828)

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 5–6, DOI: 10.1007/978-3-540-85226-1_3, © Springer-Verlag Berlin Heidelberg 2008

6 and ESTEEM (Enabling Science and Technology for European Electron Microscopy, IP3: 0260019), and IMEC for the device material.

Figure 1. Bright-field image of an array of three dummy p-MOSFET strained-silicon channel transistors with Si80Ge20 sources and drains.

Figure 2. Experimental holographic dark-field: (a) hologram of (220) diffracted beam; (b) corresponding deformation map for εxx; (c) finite element modeling.

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Some device challenges towards the 22nm CMOS technology F. Andrieu, T. Ernst, O. Faynot, V. Delaye, D. Lafond, S. Deleonibus CEA-LETI Minatec, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France [email protected] (invited abstract) Keywords: CMOS, integrated circuits

Since the 70’s, the transistor cost decreases exponentially thanks to the CMOS technology scaling down. However, this historical scaling is slowing down. Indeed, the IC’s manufacturers face different issues that the device engineers tend to solve thanks to a combination of both new materials and new architectures. The first (historical) challenge is to proceed the performance improvement while managing the dissipated power. Indeed, to achieve high performance devices, the supply voltage has not been reduced in the same proportion as the feature sizes. This has degraded the dynamic power consumption. The static power has increased even more [1]. At the same time, the performance enhancement has been limited by the difficult scaling of the gate oxide thickness (TOX). Strain has first been used, in order to maintain a good trade-off between performance and dissipated power. Stress Memorization Techniques, Nitride Contact Etch Stop Layers (CESL, see Figure 1), embedded SiGe source/drain [1] were integrated in the 65nm node. Moreover, wafer-level strain [2], (110) oriented substrates or Ge-based channels are currently evaluated in order to boost further the ON state currents of the sub-45nm technology. At the same time, new materials have been assessed to reduce the gate leakage. In particular, a combination of a Hf-based high-k dielectrics and a metal gate was introduced in the 45nm INTEL technology [3]. Finally, new architectures, like Fully Depleted thin films (planar, trigate or FINFETs) are evaluated as a solution to limit the source/drain leakage current (Figure 1-2) of sub-22nm devices. The second challenge is the scaling or, at least, the integration density growth, mainly because of the lithography limits. Moreover, even when the lithography techniques enable to draw aggressively scaled devices, it is found that strain is not necessarily as efficient as for longer ones. Finally, their OFF current is difficult to maintain because of the difficult scaling of all the other device dimensions (especially TOX and the junction depth). The historical scaling of the gate length thus tends to slow down. In the future, this trend will limit the integration density, unless new device architectures take over. Indeed, 3D layouts, like multi-channels or multi-fins structures already demonstrated very promising performance and density ([4], Figure 3-4). The third major concern is the variability issue. It is linked to the statistical technological variations (Line Edge Roughness of the gate, Random Dopant Fluctuation of the channel impurities…) that reduce the working window of the devices (e.g. the Static Noise Margin of the sub-45nm SRAM cells) [5]. To conclude, the slowing-down of the CMOS node shift (from 1.5 to 3 years per node) reflects 3 main technological issues: the more and more challenging trade-off S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 7–8, DOI: 10.1007/978-3-540-85226-1_4, © Springer-Verlag Berlin Heidelberg 2008

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between performance enhancement and dissipated power, the difficult increase of the integration density and the variability issues. Microscopy techniques could help device engineers characterizing new materials and new architectures (where thin films are mandatory, cf. Fig.5 and [6]). However, to be relevant, they have to extract local information (about strain, doping, structure, compound, potential…) because the nanometer-range properties will govern the overall 22nm device performance and variability. 1. 2. 3. 4. 5. 6.

S.E. Thompson et al., IEEE Transactions on Electron Devices, 18, 1, p. 26, 2005. F. Andrieu et al., Micoelec. Eng. 84, p. 2047-53, 2007. K. Mistry et al., IEDM Tech. Dig., pp. 24750, 2007. T. Ernst et al., Proc. of ICICDT, 2008. F. Boeuf et al., VLSI Symp., pp. 24-5, 2007. V. Barral et al., IEDM Tech Dig., pp. 61-4, 2007.

TiN/HfO2

TiN/HfO2

20nm

CESL

9nm thin strained Si channel

Burried Oxide

Figure 1. TEM cross section in the electron transport direction of 25nm short FDSOI MOS with CESL and TiN/HfO2 (TSi=9nm). Si 3.4nm

9nm thin strained Si channel

Figure 2. TEM cross section perpendicularly to the electron transport direction of 40nm narrow FDSOI MOS with TiN/HfO2.

SiO2

4.8nm

Figure 3. Cross section of a silicon nanowire obtained by a self-limited oxidation to obtain a sub-5nm channel.

5nm

TiN HfO2

2.5nm thin strained Si channel

Figure 4. The 3D configuration of staked nanowires compensates the pitch-limited current density observed in planar trigate structures.

Figure 5. Integration of a 2.5nm thin strained Si channel MOS with very good performance [6].

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Off-axis electron holography for the analysis of nm-scale semiconductor devices. D. Cooper1, R. Truche1, L. Clement2, S. Pokrant3, and A. Chabli1. 1. CEA LETI - Minatec, 17 rue des Martyrs, 38054 Grenoble, Cedex 9, France. 2. ST Microelectronics, 860 rue Jean Monnet, 38926 Crolles, France. 3. NXP Semiconductors, 860 rue Jean Monnet, 38926 Crolles, France. [email protected] Keywords: off-axis electron holography, FIB, semiconductors

The reduction in the size of state-of-the-art semiconductors provides challenges for the characterisation of the doped regions during device development [1]. Off-axis electron holography is a promising TEM-based technique that can be used to provide 2D dopant maps with nm-scale resolution [2]. In this paper we will show how specimens containing nm-scale transistors are prepared using focused ion beam (FIB) milling for examination using off-axis electron holography. Parallel-sided specimens have been prepared using combinations of in situ lift out and back-side milling in order to avoid artefacts such as curtaining which can mask the phase measured in electrical junctions. Finally, low-energy FIB cleaning is used to reduce the thickness of the damaged surface regions on the specimens. Electron holograms have been acquired of state-of-the-art device specimens using a probe corrected FEI Titan electron microscope. The unprecedented electrical and mechanical stability of the Titan microscope allows electron holograms to be acquired for time periods of more than one minute allowing phase images of relatively thick, FIB prepared specimens to be reconstructed with a good signal-to-noise ratio [3]. Figure 1 shows reconstructed phase and amplitude images for a 45 nm gate nMOS device. In the amplitude image, no contrast is visible from the presence of the dopants, however, in the phase image the dopants can be clearly seen. The position of the gate is indicated by the white overlays. In this phase image, as well as the heavily doped regions (HDD), the lightly doped source and drain (LDD) regions can be clearly observed either side of the gate which can allow the electrical gate-width to be measured directly if all of the artefacts are understood. In this paper, we will discuss the suitability of using off-axis electron holography on FIB-prepared semiconductor specimens for dopant profiling. We will highlight many of the artefacts that are observed in phase images, including the effects of specimen thickness on the dopant concentration detection limit and the effects of strain in the doped regions. Finally we will show how electron holography has been applied to a range of samples in the semiconductor industry in order to support process development.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 9–10, DOI: 10.1007/978-3-540-85226-1_5, © Springer-Verlag Berlin Heidelberg 2008

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1. 2. 3.

International Technology Roadmap for Semiconductors, 2005 ed. http://public.itrs.net W.D. Rau, P. Schwander, F.H. Baumann, W. Hoppner and A. Ourmazd. Phys. Rev. Lett. 82, 2614 (1999). D. Cooper, R. Truche, P. Rivallin, J. Hartmann, F. Laugier, F. Bertin and A. Chabli. Appl. Phys. Lett. 91, 143501 (2007).

Figure 1. Shows a phase and amplitude image of a 450-nm-thick specimen prepared using FIB milling containing 45 nm gate nMOS devices.

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Influence of the oxide thickness on the SiO2/Si interface structure P. Donnadieu1, V. Chamard2, M. Maret1, J.P. Simon1 and P. Mur3 1. SIMAP, INPGrenoble-CNRS-UJF, BP 75, 38402 Saint Martin d'Hères – France 2. IM2NP, CNRS - Université Paul Cézanne, 13397 Marseille Cedex 20 France 3. CEA-DRT-LETI-Minatec CEA-GRE 17 rue des Martyrs, 38054 Grenoble Cedex 9, France [email protected] Keywords: Interface, HRTEM, geometric phase analysis, x-ray grazing incidence diffraction

A key issue in the elaboration of nanodots deposited on substrates is to be able to control their size, density and organisation. In that perspective, major attention has been given to monitor the substrate strain which may be helpful in some case to induce organization. In that context, we studied a currently used substrate: a Si wafer covered by an oxide layer. The typical thickness for such oxide layer is usually in the nanometer range : namely 1 to 10 nm. To characterize the structure and local chemistry of the oxide layer as well as the Si/oxide interface, TEM provides a large number of possibilities. X-ray surface sensitive techniques like Grazing Incidence Diffraction (GID) and reflectivity can also provide information on strain and electron density profile in the near surface region. We report here on a combined TEM and x-ray study carried out on a series of Si wafers covered with oxide layer of different thicknesses. HRTEM associated to the Geometrical Phase Analysis (GPA) method [1] was used to study the substrate deformation as a function of the oxide layer thickness. The samples were prepared by oxidation of 8 inch (100) CZ P type silicon wafers [2]. Prior to oxidation, the wafers are cleaned with an ozone based process. The oxides were elaborated, using a N2/O2 atmosphere at 800°C in a rapid thermal processing machine. According to ellipsometry measurement, the oxide thickness varies from 1.2 nm to 7 nm within the series we have studied. For each Si wafer, cross section samples have been prepared and examined by HRTEM. The images were further analysed by the GPA method. In the numerical analysis, the g(200) reciprocal vector has been selected to measure the displacement of the (200) planes, i.e. planes parallel the interface. Hence the phase map reported here displays the displacement component normal to the substrate surface. Figure 1a and 1b show a HRTEM image and the related GPA map. The profile in the insert gives the displacement as a function of the position along the AB line indicated in Figure 1b. There is a significant displacement in the vicinity of the surface (about 1-1.5 nm) while at distances larger than 1.5 nm, the almost flat profile indicates a negligible displacement. This behaviour has been observed for all samples, regardless of the oxide thickness between 1.2 and 7 nm. Figure 1c gives the measured displacement amplitude as a function of the oxide layer thickness. Error bars have been estimated from the fluctuations of repeated measurements on the phase maps.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 11–12, DOI: 10.1007/978-3-540-85226-1_6, © Springer-Verlag Berlin Heidelberg 2008

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Figure 1. HRTEM image (Fig. 1a) and phase image for (200) g vector (Fig. 1b) (here the 1.2 nm oxide layer). In insert, the phase profile from A to B. Fig. 1c. plot of the total displacement as a function of thickness (the reported oxide thicknesses are measured by HRTEM which slightly differs from the ellipsometry ones). It comes out that the oxide layer thickness strongly influences the strain in the vicinity of the substrate (approximately 1-1.5 nm). Besides, for increasing thickness, larger displacement are measured (Figure 1c). In terms of deformation, it gives about 1 % for the 1.2 nm oxide thickness up to ~ 3 % for the 7 nm thickness. The relation between the oxide layer thickness and the deformation state of the substrate has been confirmed by observations on a two other samples : one with an extremely thin oxide layer (0.6 nm according to ellipsometry) and one with a thick oxide layer (80 nm). For the 0.6 nm oxide, GPA measurements were within error bars because of a too low strain. For the thick oxide layer, numerous dislocations were observed in the substrate close to the oxide layer which is consistent with the relaxation of a high level of strains. The x-ray GID measurement exhibits a 4-fold modulation of the oxide diffraction peak, which follows the Si[011] and the 3 other equivalent surface directions. This modulation, which shows the preferred orientation of the SiO4 tetrahedra at the interface, decays with increasing oxide thickness. Besides the analysis of x-ray reflectivity measurements emphasizes the presence of a dense interfacial layer (density mismatch ~ 8% for the 0.8 nm layer), which disappears with increasing oxide thickness. This combined TEM and X-ray study points out the complex structure of the oxide layer and the strain in the substrate at the vicinity of the interface. Both the oxide layer structure and the subtrate strain state are sensitive to the oxide thickness. It suggests that further nanostructure deposition may be influenced by the oxide layer thickness. This work has been carried out, in the frame of CEA-LETI / CPMA collaboration, with PLATO Organization teams and tools 1. 2. 3. 4.

M. J. Hytch, E. Snoeck, R. Kilaas, Ultramicroscopy 74, (1998) p. 131 P. Mur, M.-N. Semeria, M. Olivier, A.M. Papon, Ch. Leroux, G. Reimbold, P. Gentile, N. Magnea, T. Baron, R. Clerc, G Ghibaudo, Applied Surface Science 175-176 (2001) p. 726 M. Castro-Colin, W. Donner, S. C. Moss, Z. Islam, S. K. Sinha, R. Nemanich, H. T. Metzger, P. Bösecke and T. Shülli, Phys. Rev. B 71, (2005) p. 045310. We kindly acknowledge the ESRF for allocating beamtime and the ESRF ID1 staff for their help during x-ray experiments.

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Challenges to TEM in high performance microprocessor manufacturing H.J. Engelmann, H. Geisler, R. Huebner, P. Potapov, D. Utess, E. Zschech AMD Saxony LLC & Co. KG, CCA, MS E23-MA, D-01109 Dresden, Germany [email protected] Keywords: Electron Tomography, EELS, Strain Analysis, Dark-Field Diffraction

Smaller structures and new materials require the application of advanced TEM techniques for process control and failure analysis in 45 nm CMOS technology node and beyond. Both imaging TEM and analytical TEM techniques have to be modified or adapted to special questions. There are several reasons for that: A) Device structures that have to be characterized are often located completely within a TEM lamella. For example, typical gate lengths of 45 nm technology node transistors are in the range between 40 and 45 nm. The diameters of respective contacts are smaller than 80 nm. Assuming a standard lamella thickness of 60…80 nm, not all details of a 3D structure can be seen in the 2D projection image anymore. A possible approach to solve this problem is the application of Electron Tomography. While tomographic image acquisition and data treatment have already become a standard technique, sample preparation is still a challenge, especially in case of failure analysis. As an example, Figure 1 shows the 3D reconstruction of a defect in the contact area. Missing silicide caused an increased electrical resistance in that case. B) The application of new materials requires the characterization of their properties in dependence on deposition and treatment parameters. For example, low-k dielectric materials which are used to reduce the cross-talk between Cu interconnects show changes in chemical composition caused by plasma etch processes. The resulting kvalue increase has to be measured in the direct neighbourhood of etched structures like trenches and vias, with a spatial resolution better than 5 nm. While changes in chemical composition are analyzed by EELS, direct measurement of the k-value can be done by Valence EELS. A procedure was developed which allows determining the 1014 Hzfrequency dielectric permittivity [1]. Even though this is not the k-value corresponding to the GHz-frequency range used in microprocessors, relative changes in the dielectric constant can be detected very precisely (Figure 2). Ultra low-k (ULK) materials that are expected to be introduced for the 32 nm CMOS technology node will contain pores. Local pore size/pore distribution characterization will be another challenge for TEM. C) The introduction of ‘strained silicon’ into the channel region of transistors requires advanced characterization techniques. Mechanical stress results in a distortion of the silicon lattice which affects the electronic band structure, allowing improvements in carrier mobility. For process control and next technology node transistor development, local strain measurements in the Si MOSFET channel are needed. Nano Beam Diffraction (NBD) is an analysis technique that uses a small probe electron beam with reduced convergence angle to produce diffraction patterns with smaller spots than in CBED patterns [2]. The lattice parameter can be determined from the positions of the S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 13–14, DOI: 10.1007/978-3-540-85226-1_7, © Springer-Verlag Berlin Heidelberg 2008

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spots which allows strain quantification. The challenge in this technique is the NBD pattern analysis for very precise lattice spacing determination which is needed for strain quantification. Figure 3 shows the relative change of the Si lattice spacing in direction in the channel region of a tensile strained NMOS transistor. D) With shrinking of structure sizes new questions arise regarding product reliability. For example, the Cu microstructure becomes more and more important with decreasing dimensions of the interconnect lines. Grain size, grain orientation and twin formation can influence the stability against electromigration/stress migration to a high degree. So far, the EBSD technique has been used to characterize the Cu microstructure. Since agglomerates of small Cu grains are expected to be a reliability concern for the 32 nm CMOS technology, grains with sizes below 40 nm have to be analyzed which requires a TEM-based technique. Dark-Field Diffraction Circular Scanning with subsequent diffraction pattern reconstruction can be used to produce grain orientation maps. As an example, Figure 4 shows a [001] inverse pole figure map of a Cu interconnect stack. Further challenges exist in the field of sample preparation: Quality/precision, target preparation for failure analysis/defects and sample throughput. 1. 2. 3.

P. Potapov, H.J. Engelmann, E. Zschech, M. Stöger-Pollach, submitted to Micron. H.J. Engelmann, S. Heinemann, E. Zschech, Proc., IMC 16, Sapporo, Sept. 3-8, 2006. We kindly acknowledge the financial support by the German BMBF, FKZ 13N9431

Figure 1. 3D reconstruction of a defect in the contact area

Figure 2. Relative change in dielectric constant in surface-plasma treated low-k material (covered with a Cr layer).

Figure 3. Relative change of Si lattice spacing in NMOS channel region

Figure 4. Inverse pole figure map of a Cu interconnect stack

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Strain study in transistors with SiC and SiGe source and drain by STEM nano beam diffraction P. Favia1, D. Klenov2, G. Eneman1,3, P. Verheyen1, M. Bauer4, D. Weeks4, S.G. Thomas4 and H. Bender1 1. IMEC, Kapeldreef 75, 3001 Leuven, Belgium 2. FEI, Achtseweg Noord 5, 5651 GG Eindhoven, The Netherlands 3. K U Leuven, ESAT/INSYS, and Fund for Scientific Research-Flanders, Belgium 4. ASM America, 3440 E. University Dr., Phoenix, AZ 85034, USA [email protected] Keywords: nano-beam diffraction, strain, SiGe, SiC

Strain is introduced in the fabrication of complementary metal-oxide-semiconductor devices to enhance their channel region carrier mobility [1]. Epitaxial Si1-xGex (1530at% Ge) or Si1-xCx (1-2at% C) are typical stressor materials. As Ge has a 4% larger lattice constant (0.566 nm) than Si (0.543 nm), Si1-xGex deposited in the source/drain (S/D) regions will induce compressive strain in the Si channel, while Si1-xCx in the S/D will induce tensile strain in the channel [2]. Nano-beam diffraction (NBD) is a TEM-based technique that allows to obtain a diffraction pattern from small regions and, as a result, to measure directly local lattice parameter and thus to quantify 2-D strain. NBD uses a small diameter electron probe which determines the lateral resolution ( Ce0.62Zr0.38O2). The electron microscopy studies (HREM,

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HAADF, XEDS and EELS) of the high-temperature treated catalysts showed that the Ru particles keep the same epitaxial relationship already observed after reduction at low temperature, defined by Ru(002) || Ce0.8Tb0.2O2(1-11) and Ru[-2-10] || Ce0.80Tb0.20O2 [2-11]. Likewise such studies also evidenced that the chemical composition in the pedestals, i.e. in the regions of the oxide close to the metallic nanoparticles, was comparable to that observed in other areas of the support, Figure 2. 1. 2. 3. 4.

D. L. Trimm, Z. I. Onsan, Catalysis Reviews-Science and Engineering 43 (2001), 31. R. Lanza, S.G. Järås and P. Canu, Applied Catalysis A: General 325 (2007), 57. S. Bernal, G. Blanco, J.J. Calvino, C. López-Cartes, J.A. Pérez-Omil, J.M. Gatica, O. Stephan and C. Colliex, Catalysis Letters 76 (3–4) (2001), 385. We acknowledge the financial support from Ministry of Education and Science of Spain (MAT2005-00333) and Junta de Andalucia (FQM334, FQM110). Electron microscopy imaging was carried out in the Central Service of Science and Technology from Universidad de Cadiz.

[010] (002) 61º (002)

61º

(101)

(100)

(101)

(101)

[110] (111)

2 nm Figure 1. HREM image of a Ru(1%)/Ce0.62Zr0.38O2 catalyst reduced under H2 at 1173K. The structural analysis shows an epitaxial relationship between the metallic phase and the support defined by Ru(002) || Ce0.62Zr0.38O2(-111) and Ru[010]|| Ce0.62Zr0.38O2[110]. 1000

800 Ru

Ce

O

600

Tb Tb 400

Ce

pedestal

Ce Tb

O

Cu

Tb

Ce Ce

Tb Tb

200

Cu

particle

Ce Tb

support

Cu

Tb

0 0

2

4

keV

6

8

10

Figure 2. (Left) HREM image of a Ru(1%)/Ce0.8Tb0.2O2 catalyst reduced under H2 at 1173K showing pedestal-like nanostructures. Note the epitaxial relationship between the metallic phase and the support. (Center) XEDS compositional analysis showing similar chemical composition in the pedestal areas and the support. (Right) HREM image showing the distance between the metal and the oxide in the interface.

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Characterisation of materials with applications in the photocatalytic activation of water N.S. Hondow1, R. Brydson1, Y.H. Chou2 and R.E. Douthwaite2 1. Institute for Materials Research, University of Leeds, Leeds, LS2 9JT, United Kingdom 2. Department of Chemistry, University of York, York, YO10 5DD, United Kingdom [email protected] Keywords: photocatalyst, TEM, STEM

The requirement for the development of alternative fuel sources is highlighted by the limited supplies of fossil fuels and the environmental impact caused by their extensive use. The conversion of solar energy is a particularly desirable option, with the photocatalytic conversion of water into hydrogen and oxygen representing an attractive source of fuel. An ideal material suitable for this type of reaction has yet to be reported, though several promising developments have been made. An ideal photocatalyst would exhibit certain characteristics, such as long term stability, optimum absorption of the solar spectrum, and the ability to oxidise and reduce water to O2 and H2 respectively. Stable oxide semiconductors have shown the best results, with the possibility of manipulating the valence and conduction bands of the materials through alteration of the composition and structure allowing the required redox reactions. However, the materials developed at present generally have an overall low efficiency as they only utilise the high energy UV periphery of the solar spectrum [1]. This therefore creates the need for either the development of new materials, or the further improvement of these known systems. In either case, the application of alternative synthetic methods may lead to the formation of new phases and novel materials. One such synthetic route currently being investigated is that of using microwave-induced plasma promoted dielectric heating [2]. Materials currently being made include titanates, niobates and tantalates. The morphology and crystallinity of the samples can directly affect the performance of the materials as photocatalysts. It is important that sites for the oxidation and reduction reactions are separated so as to prevent recombination. The morphology of the materials has been examined by field emission SEM and the crystalline structure of the materials has been confirmed using conventional high resolution phase contrast TEM and selected area diffraction. This has been examined at several points throughout the catalyst development, including before and after catalytic testing, enabling observations as to the stability of the materials. Attempts to increase the catalytic performance has led to the introduction of further elements into the systems being investigated, with particular interest in the formation of metal or nitrogen/oxynitride rich surface regions [3,4]. The key factors in how these materials will perform as photocatalysts for the splitting of water include the

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distribution and composition of these added particles. This has been analysed by high angle annular dark field STEM imaging in combination with EDX mapping. Initial studies have found that some of the conditions the materials are subjected to leads to phase separation of the metals present, rather than the desired surface doping (Figure 1). Further elemental composition, including lighter elements, has also been determined using EELS, and supporting chemical bonding information has been obtained by the surface sensitive technique XPS. 1. 2. 3. 4.

A. Kudo, H. Kato and I. Tsuji, Chemistry Letters 33 (2004), p. 1534. R.E. Douthwaite, Dalton Transactions (2007), p 1002. A. Kudo, R. Niishiro, A. Iwase and H. Kato, Chemical Physics 339 (2007), p 104. Y. Lee, H. Terashima, Y. Shimodaira, K. Teramura, M., Hara, H. Kobayashi, K. Domen and M. Yashima, Journal of Physical Chemistry C 111 (2007), p. 1042.

Figure 1. High angle annular dark field STEM image (left) and EDX maps (right) of NiTa2O6 after attempts at nitrogen doping by reduction in ammonia at 750 oC. EDX maps of Ni (top right) and Ta (bottom right) show that phase separation of the metals has occurred in some particles.

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Complementary EM study on highly active nanodendritic Raney-type Ni catalysts with hierarchical build-up U. Hörmann, U. Kaiser1, N. Adkins2, R. Wunderlich3, A. Minkow3, H. Fecht3, H. Schils3, T. Scherer4 and H. Blumtritt5 1. Ulm University, Electron Microscopy Group of Materials Science, Albert-Einstein-Allee 11, 89081 Ulm, FRG 2. Ceram, Queens Road, Penkhull, Stoke-on-Trent, ST4 7LQ, Great Britain 3. Ulm University, Institute of Micro- and Nanomaterials, Albert-Einstein-Allee 47, 89081 Ulm, FRG 4. Forschungszentrum Karlsruhe, Institute of Nanotechnology, PO Box 3640, 76021 Karlsruhe, FRG 5. Max-Planck-Institut für Mikrostrukturphysik, Weinberg 2, 06120 Halle/Saale, FRG [email protected] Keywords: Raney-type Ni, dendrites, structure, Cs-corrected HRTEM, gas atomisation, slicing view

Nanostructured Raney-type Ni catalysts have been used in industry since the 1920s for the production of a wide range of chemicals. [1] In the EU supported project IMPRESS it has been shown that by using gas atomisation processing high surface area particles with significantly increased catalytic activity in hydrogenation reactions can be produced. [2,3] Structural investigations with complementary methods of electron microscopy in combination with X-ray powder diffractometry have enabled the link between processing, structure and catalytic activity to be explored. [4] Raney-type Ni catalysts were produced from alloy powder prepared by gas atomisation. After activation by leaching with NaOHaq and prior to the structural investigations the samples were passivated with oxygen. Size selected microparticles of ca. 100 µm size, grown from different melt compositions were chosen for this study. The microstructure of the samples was characterised in 2D by light microscopy and by SEM, see Fig. 1, and SEM EDX mappings. The nanostructure was investigated with HRTEM and Energy filtered TEM for elemental mappings (Ni, Al) using a Cs-corrected FEI 80-300 Titan microscope operated at 300kV. The use of a dual-beam FIB SEM for sample preparation allowed the investigation of one particular nanodendrite on different scales, first within the microparticle by SEM and hereafter as a single cut lamella in the TEM. In order to correlate the local structure with integral measurements, X-ray powder diffractometry was also carried out. The 3D interconnection of the nanodendrites, which build up the whole particle was imaged with slicing view by using a FIB SEM. The resulting porous particles were found to be built-up of nanodendrites. The thickness of the dendrites decreases with increasing Al content. The samples with the finest dendrites were obtained from Ni-75%Al alloy powder, i.e. from an alloy with a higher Al content than the one which is used to produce the standard commercial catalysts. The dendrites consist of two adjacent phases, from which one after leaching and passivation is transformed into NiO. This phase is located at the dendrite tips, and S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 217–218, DOI: 10.1007/978-3-540-85226-1_109, © Springer-Verlag Berlin Heidelberg 2008

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might offer the reactive sites for the catalytic reaction. The complex structure was characterised by Cs-corrected HRTEM. On the mesoscale it shows a polycrystalline framework structure with filled mesopores. The nanocrystals within the mesopores clearly reveal texture. The outer surface of the dendrite tips shows nanosteps, which increase significantly the surface area provided for the catalytic reaction, see Fig. 2. 1. 2. 3. 4.

M. Raney: US patent 1563587 (1925) A.M. Mullis, N.J. Adkins, Z. Huang, R.F. Cochrane, Proc. 3rd International Conference on Spray Deposition & Melt Atomization, 2006, Bremen, Germany, CD proceedings F. Devred et al., to be published. U. Hörmann, U. Kaiser, N.J.E. Adkins, R. Wunderlich, A. Minkow, H. Fecht, H. Schils, F. Devred, B. Nieuwenhuys, H. Blumtritt, submitted to 9th International Conference on Nanostructured Materials, Nano 2008, Rio de Janeiro, Brazil (2008)

Figure 1. Left: Light microscopy image of a microparticle from the 75 – 106 µm size fraction with a high inner porosity due to the nanodendritic structure. Right: SEM image of a single dendrite with capped tips (light grey), see arrows.

Figure 2. Left: Dark field micrograph of the interface between the caps and the dendrite backbone. Right: Cs-corrected energy-filtered HRTEM micrograph of the mesopores at the outer rim of the capped dendrite tips, showing the pores and the surface steps.

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Structural properties of sol-gel synthesized Li+-doped titania nanowhisker arrays U. Hörmann1, J. Geserick2, S. Selve1, U. Kaiser1, and N. Hüsing2 1. Ulm University, Electron Microscopy Group of Materials Science, Albert-Einstein-Allee 11, 89081 Ulm, FRG 2. Ulm University, Institute of Inorganic Chemistry I, Albert-Einstein-Allee 11, 89081 Ulm, FRG [email protected] Keywords: titania, anatase, rutile, nanowhiskers, mesoporous material, HRTEM, sol-gel synthesis

Nanostructured titania is of particular interest for applications in photo-catalysis due to its high catalytic activity. Moreover, these structures are of particular interest for many applications due to their electronic properties, e.g. anti-reflection layers, sensors, vacuum microelectronics. The band gap of the nanoscaled semiconducting anatase is size dependent. The band gap increases in the size range of 15 nm to 3.9 eV [1], compared to the bulk value of 3.2 eV [2], suggesting already a quantum confinement effect. Nanowhiskers, grown in even smaller dimensions as in this study are prospective candidates for showing a transition to the quantum confinement effect. Sol-gel synthesis of mesoporous oxides relies on the self-assembly of the structure directing agents, the surfactants which rule the solidification or crystallisation of the inorganic oxide. Mesoporous ordered solids produced by sol-gel processing are e.g. monolithic SBA-15 type silica networks or the highly catalytically active mesoporous titania powders. In this study titania nanowhisker arrays with a high surface area were produced. Anatase nanowhiskers were grown in a sol-gel process [3] using ethylene glycol modified titanium(IV) (EGMT) as the titania precursor and Lithiumdodecyl sulphate (LDS) as a structure directing agent. The LDS simultaneously delivers the Li+ as a dopant. After synthesis the samples were dried and calcined in order to remove the surfactant. The samples were characterised by X-ray powder-diffractometry. The dried samples were found to consist of an approximately proportionate equal mixture of rutile and anatase. The high temperature phase of titania grows thus even under room temperature processing. After calcination at 400 °C for 4 h, the intensity of the anatase peak grew significantly, indicating a higher anatase ratio. After calcination nitrogen sorption measurements were performed in order to determine the average pore sizes as well as the specific surface areas. The resulting samples were investigated by HRTEM. The samples showed a strong growth anisotropy, i.e. the whiskers revealed a high aspect ratio. The diameter of the whiskers measures approximately 3 – 4 nm and the length up to 50 nm even after calcination. The titania crystals grew as whiskers with a preferential orientation. These needles are aggregated to radial bunches, thus forming nanowhisker arrays.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 219–220, DOI: 10.1007/978-3-540-85226-1_110, © Springer-Verlag Berlin Heidelberg 2008

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Calcination caused the formation of roundish nanoparticles on top of the whisker tips. These crystalline particles are associated with an amorphous phase and were attributed to the anatase phase. 1. 2. 3.

T. Toyoda, Ikumi Tsuboya, Rev. Sci. Instrum. 74 (1) (2003), p. 782 W. Wunderlich, L. Miao, M. Tanemura, S. Tanemura, P. Jin, K. Kaneko, A. Terai, N. Nabatova-Gabin, R. Belkada, Int. J. Nanoscience 3 (4&5) (2004), p. 439. J. Geserick, N. Hüsing, R. Roßmanith, C.K. Weiß, K. Landfester, Y. Denkwitz, R.J. Behm, U. Hörmann, U. Kaiser MRS Spring Meeting 2007

Figure 1. Left: Survey of nanowhisker arrays in the sample after calcination for 4 h at 400 °C. Right: HRTEM micrograph showing the whiskers with some roundish particles.

d(101) = 0.35nm Figure 2. Left: Roundish particles observed after calcination for 4 h at 400 °C. Right: HRTEM micrograph. Detail of one particle of Fig. 2 left, identified as anatase with 0.35 nm d-spacing of the (101) plane.

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Quantitative strain determination in nanoparticles using aberration-corrected HREM C.L. Johnson1, E. Snoeck1, M. Ezcurdia1, B. Rodríguez-González2, I. Pastoriza-Santos2, L.M. Liz-Marzán2 and M.J. Hÿtch1 1. CEMES-CNRS, 29, rue Jeanne Marvig, 31055 Toulouse, France 2. Departamento de Quimica Fisica, CSIC, University of Vigo, 36310 Vigo, Spain [email protected] Keywords: strain, nanoparticles, aberration correction, high-resolution electron microscopy

Metallic nanoparticles exhibit exceptional optoelectronic properties that are strongly size and shape dependant and locally variable. Recently, novel synthesis techniques have enabled precise control over the growth of metallic nanoparticles, occasionally resulting in morphologies that cannot be characterized using standard techniques [1]. One example is five-fold-twinned decahedral Au nanoparticles. Owing to the decahedral geometry, these nanoparticles must be strained or contain defects and models have been proposed to predict their strain states. We examined the internal structures of decahedral Au nanoparticles using a combination of aberration-corrected HREM, strain mapping, and finite-element analysis [2,3]. HREM images (Figure 1) were obtained using the SACTEM-Toulouse, a Tecnai F20 ST (FEI) equipped with an imaging aberration corrector (CEOS), rotatable electron biprism and a 2K CCD camera (GATAN). Strain analysis was done using DigitalMicrograph (GATAN) and the GPA Phase 2.0 (HREM Research) software. Microscope distortions were calibrated to obtain highly accurate (< 0.1% strain), highspatial-resolution (< 1 nm) maps of the lattice strain and rotation in the decahedral nanoparticle. Aberration correction provides high-contrast images necessary for accurate high-resolution strain determination. The strain mapping revealed that internal rigid-body rotations (Figure 2a) combined with shear strains (Figure 2b) accommodate the geometric constraints imposed by the decahedral geometry. Our measurements confirm, for the first time, the existence of a disclination. Furthermore, comparison of the results to finite-element analyses revealed that shear strains, which are not predicted by the commonly accepted strain models for decahedral particles, result from elastic anisotropy. The internal structure of these complex nanoparticles will determine their growth and stability as well as affect their surface structures, and, therefore, will be of great importance for engineering their electronic and optical properties. 1. 2. 3. 4.

A. Sánchez-Iglesias et al, Advanced Materials 18 (2006) p. 2529. M.J. Hÿtch et al, Ultramicroscopy 74 (1998), p. 131. C.L. Johnson et al, Nature Materials 7 (2008) p. 120. We thank the EU Integrated Infrastructure Initiative ESTEEM (Ref. 026019 ESTEEM) and the Spanish Ministerio de Educacion y Ciencia (Grants No. MAT2004-02991 and NAN2004-08843-C05-03) for support.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 221–222, DOI: 10.1007/978-3-540-85226-1_111, © Springer-Verlag Berlin Heidelberg 2008

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Figure 1. Aberration-corrected HREM image of decahedral Au nanoparticle. (a) The image shows the 5-fold rotational symmetry marked by twin boundaries that intersect at the centre of the particle. (b, c) Enlarged views of the core and edge of the particle.

Figure 2. (a) Internal rigid-body rotation of the crystallographic lattice and (b) shearstrain distributions in the decahedral Au nanoparticle. The lattice rotation combined with the shear strains, which result from elastic anisotropy, accommodate the unique geometry of the decahedral particle.

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Morphological characterization by HRTEM and STEM of Fe3O4 hollow nano-spheres Alfonso Ibarra1, Gerardo F. Goya1, Jordi Arbiol3, Enio Lima Jr.4, Hercílio Rechenberg4, Jose Vargas5, Roberto Zysler5 and M. Ricardo Ibarra1,2 1. Aragon Nanoscience Institute (INA), 2. Materials Science Institute of Aragon (CSICZaragoza University), University of Zaragoza, 50009 Zaragoza, (Spain), 3. TEM-MAT, Serveis Cientificotecnics, UB, 08028 Barcelona, (Spain) 4. LMM, University of São Paulo (Brazil), 5. Centro Atomico Bariloche, 8400, S. C. Bariloche (Argentina) [email protected] Keywords: Fe3O4 nanoparticles, HRTEM, STEM, HAADF, EELS, EFTEM

Morphology, surface and finite size effects in magnetic nanoparticles have been the subject of growing interest in recent years from both experimental and theoretical point of view [1]. The magnetic properties are strongly associated with the morphological and structural homogeneity of the nanoparticles [2]. Interparticle interactions also play an important role in the magnetic behaviour of an ensemble of nanoparticles, which differs from that of non-interacting systems [3]. The aim of this work is the characterization, by means of transmission electron microscopy (TEM), of the morphology and structure of Fe3O4 nanoparticles prepared by chemical route [4] in order to understand their magnetic behaviour. TEM specimens were prepared dispersing the nanoparticles in toluene and dropping this colloidal solution onto a carbon-coated copper grid. TEM analyses were performed in a JEOL 1010 (200 kV). Interesting enough is to point out that a deeper High Resolution TEM (HRTEM) and STEM analysis combined with Energy Filtered TEM (EFTEM) as well as high angular annular dark field (HAADF or Z-contrast) show that magnetite nanoparticles interact creating hollow nano-spheres, and thus affecting the magnetic behaviour of the sample. Figure 1 shows a general view of the sample where the projection reveals a toroidallike shape nanostructures with a weak interaction between them. Electron energy loss spectroscopy (EELS) analyses show that the nanostructures are constituted by Fe3O4, which is corroborated by a chemical analysis where the ~60 % wt. of the final powder corresponds to the Fe3O4 nanoparticles, and ~40 % wt. corresponds to the organic cap of oleic acid that covers the particles and avoid their agglomeration. A more detailed analysis by HRTEM, Figure 2, shows that depending on defocus; new crystallographic planes appear “inside” the projected toroids, indicating that the observed nanostructured may correspond to hollow spheres instead of toroids. In order to confirm this assumption, EFTEM Fe Maps (Figure 3), were obtained showing the homogeneity of the Fe around the whole surface of the sphere. The inferred morphology of hollow spheres is reported here for the first time in magnetic nanoparticles, and it is intimately related to novel magnetic properties displayed by these samples.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 223–224, DOI: 10.1007/978-3-540-85226-1_112, © Springer-Verlag Berlin Heidelberg 2008

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1. 2. 3. 4. 5.

D. Fiorani., Surface effects in magnetic nanoparticles, Springer, New York (2005). C. B. Murray, C. R. Kagan and M. G. Bawendi, Annu. Rev. Mater. Sci. 30, 545 (2000). J. L. Dormann, E. D'Orazio, F. Lucari, E. Tronc, P. Prené, J. P. Jolivet, D. Fiorani, R. Cherkaoui and M. Nogués, Phys. Rev. B 53, 14291 (1996). J. M. Vargas and R. D. Zysler, Nanotech. 16, 1474 (2005); J. M. Vargas, W. C. Nunes, L. M. Socolovsky, M. Knobel and D. Zanchet, Phys. Rev. B 72, 184428 (2005). This work has been supported by the Spanish Projects Nanoscience Action NAN200409270C3-1/2 and Consolider Ingenio CSD2006-00012. GFG acknowledges support from the Spanish MEC through the Ramon y Cajal program

Figure 1. TEM micrograph of the sample where the projection of nanoparticles seems toroidal structures.

b)

c) 2 nm

a) 5 nm

Figure 2. a) HRTEM micrograph where crystalline planes are observed forming hollow spheres. b) FFT of the area. Welldefined rings show the polycrystalline character of the sample. c) Magnified image of a nanoparticle where the Fe3O4 microstructure is observed.

Figure 3. EFTEM Fe map. The presence of Fe forming the hollow sphere is observed.

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Direct observation of surface oxidation of Rh nanoparticles on (001) MgO N.Y. Jin-Phillipp, P. Nolte, A. Stierle, P.A. van Aken, and H. Dosch Max Planck Institute for Metal Research, Heisenbergstr.3, D-70569 Stuttgart, Germany [email protected] Keywords: surface oxidation, nanoparticles, HRTEM, EELS, Rhodium

The late transition metals have been studied extensively for decades because of their catalytic applications. Understanding the oxidation behaviour and the structure of the oxides of these metals are essential in order to raise the efficiency of the catalysts [1]. In the present contribution we investigate surface structure of Rhodium (Rh) nanoparticles grown on (001) MgO and oxidized at oxygen (O2) pressure of 2x10-5 mbar by highresolution transmission electron microscopy (HRTEM) in both (110) and (100) crosssections, and by spatially-resolved electron energy-loss spectroscopy (EELS). Surface layer with a structure different from Rh fcc-structure may be clearly seen at the Rh (1 1 1) surface at the top-right side of the particle. As indicated in Figure 1 the measured spacing between the surface layer and the Rh (1 1 1) top layer is 0.28nm, markedly higher than d111,Rh of 0.220nm, measured from the core of the particle. The distance between the image points in the surface layer along Rh is 0.27nm. Similar measurements have been carried out for particles without any surface layer, and it is found that even for the very small Rh particles of a size of ~ 2nm the error is within ±0.005nm. This confirms, that our observation of larger spacing of the surface layer is not due to the deviation of the lattice spacing measurement found in the case of randomly oriented small particles [2]. Spatially-resolved EELS line-scans were performed across {111} surfaces of Rh particles free of epoxy. Figure 2(a) illustrates one of such line scans. Figure 2(b) shows the background subtracted energy-loss near-edge structure (ELNES) of the Rh-M edge of selected spectra. A small extra peak, marked with an arrow, is detected in the spectrum 3 taken at the surface. This small peak lies at the energy position of ~532eV, 11eV distant from Rh-M2 peak, and is therefore the O-K edge. This result suggests that the surface layer observed by HRTEM is surface oxide formed during oxidation. Image simulation using a theoretical model of the surface oxide obtained by density functional theory (DFT) [3] suggests a hexagonal trilayer of O-Rh-O at the Rh (111) surface of the nanoparticles. 1. 2. 3.

H. Over, Y.D. Kim, A.P. Seitsonen, S. Wendt, E. Lundgren, M. Schmid, P. Varga, A. Morgante, and G. Ertl, Science 287 1474 (2000). J.-O. Malm and M.A. O’Keefe, Ultramicroscopy, 68, 13 (1997). J. Gustafson, A. Mikkelsen, M. Borg, E. Lundgren, L. Köhler, G. Kresse, M. Schmidt, P. Varga, J. Yuhara, X. Torrelles, C. Quirós, and J.N. Andersen, Phys. Rev. Lett. 92, 126102 (2004).

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4.

Financial support from the European Union under Contract No. NMP3-CT-2003-505670 (NANO2) is acknowledged.

Figure 1. High-resolution micrograph of a Rh nanoparticle on the (110) cross-section, showing the surface oxide layer at Rh (1 1 1) surface.

Figure 2. (a) EELS line-scan across the {111} surface of a Rh nanoparticle with a spacing between the spectra of 0.3nm. The scan started at vacuum (spectrum 1) and ended inside the particle (spectrum 7), (b) Selected EELS spectra (3-5) are shown, and an O-K peak is found at the surface (spectrum3).

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Characterization of catalyst poisoning in biodiesel and conventional diesel fuelled vehicles T. Kanerva1, K. Kallinen2, Toni Kinnunen2, M. Vippola1 and T. Lepistö1 1. Tampere University of Technology, Department of Materials Science, P.O.Box 589, FIN-33101 Tampere, Finland 2. Ecocat Oy, Typpitie 1, FIN-90650 Oulu, Finland [email protected] Keywords: TEM, catalyst, biodiesel, poisoning

Demand for lower and lower emissions in road transportation has promoted the development of more efficient exhaust emission catalysts. On the same time the fight against the impact of transportation on climate change has opened the way for the use of biofuels, e.g. biodiesel. Deactivation of catalytic surfaces is a serious problem in the design of more efficient automotive exhaust catalysts. Deactivation of catalysts can be classified in three types: chemical (e.g. poisoning), mechanical (e.g. fouling) and thermal (e.g. ageing). In the long run these deactivation processes can cause nearly total loss of catalytic activity in the catalyst material. In biodiesel fuelled vehicles these processes can lead to notably different effects in catalyst efficiency compared to those of conventional diesel vehicles [1]. In this study typical diesel catalyst with noble metals Pt and Pd was vehicle-aged using two different fuels: conventional diesel (EN590) and biodiesel (RME, rapeseed methyl ester). Samples were studied with analytical transmission electron microscope (TEM) and field emission scanning electron microscope (FEG-SEM), both equipped with energy dispersive x-ray spectrometer (EDS). Catalyst poisons from vehicle-ageing were analysed after conventional diesel and biodiesel use. Characterization included EDS-mapping, spot analyses and imaging. According to the results different types and contents of poisons were found in the samples depending on the fuel used. Poisons and their contents are presented in tables 1 and 2. In conventional diesel sample typical poisons were S and K with contents of around 0.5 wt%. In biodiesel samples the highest contents were for poisons S, K and Zn, with much higher proportions. Also overall number of poisons was higher in biodiesel sample. Locations of some EDS-spot analyses for RME and EN590 is presented in figures 1 and 2 respectively. In this vehicle-ageing microstructural effects were minor and no detectable effects were found. In this study the conventional diesel samples were less poisoned and there was not any effect on the performance of this catalyst. The vehicle-ageing using RME caused significant loss of efficiency in the catalyst. Higher contents of poisons and higher number of poisons in vehicle-aged samples using biodiesel rises questions of the quality of biodiesels. There is a lot of research going on to gain more knowledge on the properties and behaviour of biodiesels in automotive engines. Further studies in the

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effects of biodiesel use on the catalyst components is required to meet the future demands of international energy policies [2]. 1. 2.

J.B. Butt and E.E. Petersen, Activation, Deactivation and Poisoning of Catalysts (Academic Press Inc., 1988). M. Lapuerta, O. Armas and J. Rodriguez-Fernadez, Progress in Energy and Combustion Science 34 (2007), p. 198.

Table 1. Poisons detected in vehicle-aged RME-sample. Contents in wt%. RME

EDS 1 EDS 2 EDS 3 EDS 4 EDS 5 EDS 6 EDS 7 EDS 8

S

0.8

0.2

0.6

0.9

0.1

1.5

1.3

0.2

K

2.4

0.3

4.3

3.7

0.5

2.5

0.9

0.3

0.3

0.1

Ca

0.1

Cr

0.2

0.1

Fe

0.1

0.1

6.2

0.4

0.1

0.3

0.3

Zn

0.5

0.1

0.5

1.1

0.1

0.7

0.9

0.1

Table 2. Poisons detected in vehicle-aged EN590-sample. Contents in wt%. EN590 EDS 1 EDS 2 EDS 3 EDS 4 EDS 5 EDS 6 EDS 7 EDS 8 S

0.5

K Fe Zn

0.2

0.4

0.6

0.4

0.4

0.2

0.1

0.3

0.1

0.1 0.2

Figure 1. Area of RME EDS 1.

0.1

0.1 0.2

0.1

Figure 2. Locations of EN590 EDS 4,5 and 6.

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TEM Characterisation of Highly Luminescent CdS Nanocrystals Hadas Katz1, Alexey Izgorodin2, Douglas R. MacFarlane2, Joanne Etheridge1,3 1. Dept of Materials Engineering, Monash University, Clayton, Victoria, 3800, Australia 2. ARC Centre of Excellence for Electromaterials Science, Monash University, Clayton, Victoria, 3800, Australia 3. Monash Centre of Electron Microscopy, Monash University, Clayton, Victoria, 3800, Australia [email protected] Keywords: TEM, Cadmium Sulphide, nanocrystal, electroluminescence.

Luminescent II-VI semiconductor nanocrystals have been the focus of many studies in recent years due to their low energy consumption, wide variety of electroluminescence properties and a large number of combinations of core/shell materials that can be synthesized by the simple and cost efficient reverse micelle method [1]. The size of the nano-crystal determines its surface to volume ratio [2], which affects the band gap and hence the luminescence properties of the crystal. The crystal structure and defect structure, such as point defects and dislocations, also affect band gap energy [3] and hence wavelength of the emitted light as well as the stability of the luminescence materials over time. Characterizing composition, nanocrystals size, crystal structure, defect structure and atomic bonding in the atomic and even subatomic level by electron microscopy will enable us to understand how their size and atomic structure would affect the wavelength of the emitted light and stability of the luminescence materials over time. Those are important factors in the engineering of luminescence materials with desired properties. This work presents an electron microscopy and diffraction study of the crystal structure of highly luminescence CdS nanocrystals produced using the reverse micelles method. Energy-dispersive X-ray spectroscopy (EDX), selected area diffraction (SAD) and atomic resolution imaging using an analytical JEOL 2011 TEM fitted with a LaB6 filament were used to determine the CdS nanocrystal’s composition, crystallographic structure, defect structures and size with a view to understanding how these affect the stability, band gap energy and luminescence properties. Nanoparticles were observed both aggregated in clusters and distributed across the carbon film. The size of the nanoparticles is typically between 3-13nm and was determined by counting of atomic planes in atomic resolution images. Selected area diffraction (SAD) patterns taken from filtered solution indicate the presence of hexagonal CdS and cubic CdS only. However, in unfiltered solutions cubic

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CdO and cubic Na2S nanocrystals were also observed and are assumed to be byproducts. Careful measurement of a SAD pattern of numerous particles distributed across the carbon film shows a 4% difference in the nominal cubic 220 and -220 spacing, suggesting the cubic CdS structure is distorted. This could have an affect on band gap and electroluminescence properties. Using high resolution images and their Fourier transforms, it was conformed that both cubic and hexagonal CdS nanocrytals and a cubic CdO by–product are produced using the reverse micelle process (e.g. figure 1). In addition, a high resolution image of a small cluster containing 3 cubic CdS nanocrystals shows that these particles share a common atomic plane and might had inter-grown during growth process. 1. 2. 3.

D. R. Vij, Handbook of Electroluminescent Materials, Institute of Physics Publishing, (2004). S. J. Rosenthal, J. McBride, S. J. Pennycook, L.C. Feldman, Surface Science Reports, 62 (2007) 111-157. Ronghui Xu, Yongxian Wang, Guangqiang Jia, Wanbang Xu, Sheng Liang, Duanzhi Yin,. Journal of Crystal Growth, 299 (2007) p. 28-33.

Figure 1. (a) HRTEM Image of A small cluster of 4 CdS nanocrystals supported on a carbon film. (b) Fourier transform taken of the image. 3 nanoparticles have cubic structure and are oriented down the and zone axis and share the {31-1} atomic plane (fig. b1). The fourth nanoparticle has hexagonal CdS structure (fig. b2). (c) Inverse of the Fourier transform with diffuse background masked to enhance atomic contrast. The orientations of the 3 cubic CdS nanocryatls sharing the {31-1} atomic plane (fig c1) and of the hexagonal CdS nanocrystal atomic plane (fig. c2) are marked. The cluster diameter is ~7 nm.

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Structure and composition of dilute Co-doped BaTiO3 nanoparticles O.I. Lebedev, R. Erni and G. Van Tendeloo EMAT, University of Antwerp, Groenenborgerlaan 171, B2020 Antwerpen, Belgium [email protected] Keywords: nanoparticles, edge dislocation, vacancies, EFTEM, HRTEM

Dilute ferromagnetism in semiconductors with Curie temperatures (Tc) above 300 K are materials of high technological interest due to their potential use in spin based electronic devices operable at room temperature. Additionally, the current technological trends towards device miniaturization are driving the development of materials research strongly in the direction of functional nanomaterials. Therefore, fabrication of well characterized nano dilute magnetic semiconductor systems is becoming increasingly important. Nanoparticles of 5% Co-doped BaTiO3 (Co-BTO) with nominal composition BaTi1¡xCoxO3 were synthesized following an established solvothermal drying route with additional cobalt(II) nitrate hexahydrate as Co precursor in stoichiometric quantities. Detailed TEM and ED studies confirm that the samples are indeed single phase Codoped BaTiO3, devoid of other impurity phases or Co metal clusters. HRTEM investigation indicates the presence of Ba vacancies in varying concentrations. Figure 1 shows a HRTEM image from a single Co-BTO nanoparticle along the [111]C zone axis. There is a clear reduction of contrast of the lattice fringes within 1-2 nm size areas. Such local variation in HRTEM contrast can be attributed to clusters of Ba vacancies. Moreover, exceeding a certain vacancy concentration leads to internal stress that can be reduced by the formation of edge dislocations (Fig.2a). The existence of dislocations is particularly surprising in case of nanoparticles where the energy stability of a dislocation is not a priori warranted. The closure failure of the Burgers circuit in the HRTEM image (Fig.2b) determines the Burgers vectors as b1 and b2 =a√2 [110]C (a being the lattice parameter of cubic BaTiO3). In order to clarify the origin of these contrast variations, EFTEM and Z- contrast imaging have been employed. The EFTEM Ti and Co map (Fig 2d,e) clearly confirms a quite narrow Ti-Co distribution inside the nanoparticles while the Z-contrast imaging (Fig.2c) indicates that the bright spots correspond to pore-like structures in the nanoparticles, and are not related to any chemical inhomogeneity or metal clustering effects. The elemental maps and the plasmon-loss image reveal that the regions with brighter contrast in the HRTEM image do not correlate with increased concentrations of Ti or Co. This leads to the conclusion that physical voids within the particles have to be present. Electron Microscopy results indicate that we have formed Co-doped cubic BTO nanocrystals in which the presence of vacancies and relative defect concentrations regulate the occurrence/absence of ferromagnetism.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 231–232, DOI: 10.1007/978-3-540-85226-1_116, © Springer-Verlag Berlin Heidelberg 2008

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Figure 1. [111] HRTEM image of Co-doped BaTiO3 nanoparticle and corresponding FT pattern. Filtered HRTEM image from selected region marked by white frame notice variation of the contrast ( marked by white arrow)

Figure 2. (a) - [111] HRTEM image of a highly defected Co-doped BaTiO3 nanoparticle and corresponding FT pattern; (b)-filtered HRTEM image showing presence of core dislocations. The associated Burgers circuits are indicated. (c) - Z contrast image of an agglomerate of nanoparticles exhibiting inhomogenities and EFTEM images of selected nanoparticles at Co-M edge(65 eV energy loss) (d) and TiM edge (45 eV energy loss) (e)

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CoxFe3-xO4 catalytic materials for gaz sensors L. Ajroudi1,2, A. Essoumhi1, S. Villain1, V. Madigou1, N. Mliki2, and Ch. Leroux1 1. IM2NP (UMR-CNRS 6242), South University Toulon-Var (USTV), Bat.R, B.P.20132, 83957 La Garde Cedex, France 2. LMOP, Physics Department, University Tunis El-Manar, 2092 Tunis, Tunisia [email protected] Keywords: nanoparticles, ferrites, catalysis

Nanomaterials based on spinel ferrites have already numerous applications, mainly based on their magnetic properties. Recently, catalytic properties of nickel, copper and cobalt ferrites in the conversion of CO and CH4 were evidenced, opening a new field of applications for these materials [1]. Magnetic properties of nanoparticles, as well as catalytic properties, will depend on their size, but also on their shape and size distribution. These parameters are linked to the elaboration method. The properties of transition metal spinel oxides depend also on the nature of the transition metal and on his site occupation in the structure. The location of the cations in the spinel structure is related to their octahedral or tetrahedral sites preference, but also to the synthesis method. For magnetite Fe3O4, which adopts the inverse spinel structure, the tetrahedral sites are fully occupied by Fe3+ ions, whereas octahedral sites are occupied by Fe3+ and Fe2+. For Co3O4, the octahedral and tetrahedral sites are respectively occupied by Co3+and Co2+ (normal spinel structure). Intermediate situations occur for CoxFe3-xO4 ,. Thus, three different compositions were prepared CoFe2O4, Co0.6 Fe2.4O4, Co1.4 Fe1.6O4. In order to synthesize chemical homogeneous powders, we used a co-precipitation method, and a non aqueous elaboration technique developed by Pinna [2]. For the coprecipitation method, the starting iron and cobalt salts were FeCl3.6H2O, FeSO4.7H2O and CoSO4.7H2O. Two different co-precipitations were realised. The proportions and nature of the salts changed, but the rest of the procedure was the same. The salts were dissolved in distilled water, and the solution was then mixed to a solution of NaOH, heated at 70°C. Since Fe3O4 was obtained by co-precipitation of FeCl3.6H2O and FeSO4.7H2O, a co-precipitation was realised with FeCl3.6H2O, FeSO4.7H2O, and CoSO4.7H2O, (sample A FC 17). Another attempt with FeCl3.6H2O and CoSO4.7H2O, was also done (sample B FC16). The precipitates were annealed at different temperatures (250°C,300° and 500°C). For the second method, iron acetylacetonate and cobalt 2,4-pentanedionate were mixed in various proportion in benzyl alcohol. The mixture was stirred and put into a steel autoclave. After two days in a furnace, one obtains a dark suspension, which was ultrasonicated and centrifuged. The precipitates were thoroughly washed and subsequently dried in air. This procedure was applied to the elaboration of CoFe2O4 (sample C), Co0.6 Fe2.4O4,(sample D) and Co1.4 Fe1.6O4 (sample E). Whatever the elaboration method, CoxFe3-xO4 nanoparticles were obtained. The spinel nanoparticles, obtained by co-precipitation method, have irregular shapes (Figure 1a) and mean sizes ranging from 8 nm (sample B, 300° C) to 12 nm (sample A, 500 °C).

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 233–234, DOI: 10.1007/978-3-540-85226-1_117, © Springer-Verlag Berlin Heidelberg 2008

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Sample B is chemically homogeneous, but sample A contains Co3O4 in form of platelets and needles (Figure 1b). TEM studies of samples annealed at lower temperatures showed that the platelets result from the decomposition of cobalt hydroxide, as needles come from the initial cobalt sulphate. Spinel nanoparticles obtained by the non aqueous method are very regular in shape and well dispersed (Figure 2a). They are also chemically homogeneous and very homogeneous in size (Figure 2b). The chemical composition was tested by nanoprobe analysis. 1. 2.

D. Fino, S. Solaro, N.Russo, G. Saracco, V. Specchia, Topics in Catalysis 42, (2007), p.454 N. Pinna, S. Grancharov, P. Beato,| P. Bonville, M. Antonietti and M. Niederberger, Chem. Mater. 17 (2005), p. 3044.

Figure 1. a) HREM of one CoFe2O4 particle, with a [110] zone axis. b) Sample A, annealed at 500°C. The powder consists in a mixture of CoFe2O4 nanoparticles, and Co3O4, in form of platelet and needles.

Figure 2. a) CoFe2O4 nanoparticles (sample C). b) Histogram of the size distribution.

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(S)TEM investigation on the role of alumina dopants to prevent redox activity decay at high temperature in CePrOx /doped-Al2O3 catalysts M. López-Haro, K. Aboussaid, J.M. Pintado, J.J. Calvino, S. Trasobares Departamento de Ciencias de los Materiales, Ingeniería Metalúrgica y Química Inorgánica. Universidad de Cádiz, 11510-Puerto Real (Cádiz). Spain [email protected] Keywords: CePrOx Catalysts, STEM, doped-alumina

CePrOx mixed oxides, which present extraordinary redox properties, have a wide range of potential applications in environmental catalysis [1]. A good dispersion of these oxides over a high surface area material, like alumina, increases their specific surface and, hence, their oxygen handling capabilities. Moreover if the alumina support is modified with a doping agent, their textural stability can be improved and their deactivation by solid-state reaction with the support inhibited [2]. In this work, Transmission Electron Microscopy Imaging Techniques (HREM and HAADF) have been combined with spectroscopic techniques, (EELS and X-EDS), to investigate the influence of the dopant nature (SiO2, La2O3) on the chemical and structural properties of CePrOx particles supported on modified aluminas.. A mechanism to explain the differences observed [3] in the resistance against high temperature deactivation of a Ce0.8Pr0.2O2-x supported on Si-doped alumina (Ce0.8Pr0.2O2-x/Al2O3- 3.5% SiO2) and a La-doped alumina (Ce0.8Pr0.2O2-y/Al2O3 -4% La2O3) system is proposed. To reveal the effects of high temperature aging, samples of the two catalysts were studied after treatments under reducing conditions at low, 350ºC, and high temperature, 900ºC. HREM indicates the presence in both materials of a fluorite-like structure on the samples treated at 350ºC. Neatly different results are observed at the highest temperature. Thus, two different crystalline phases have been detected in the Si-doped material: a lanthanide hidroxycarbonate (Bastnesite-type) (figure 1.A) and a fluorite-like structure. In the case of La-doped sample, only a perovskite phase, LnAlO3 (Ln=Ce, Pr) (figure 1.B) is observed. The formation of the redox-inactive perovskite phase would explain the greater deactivation behaviour observed in the La-doped sample. To investigate further the role of the dopant in these solid state chemistry differences, the samples were characterised by STEM-XEDS and STEM EELS. These techniques provide a more accurate, high spatial resolution, description of the elements distribution. In the Si-doped samples (both at 350ºC and 900ºC) EELS studies indicated the simultaneous presence of small (a few nanometers) PrOx crystallites and, much larger (100-200 nm), Ce-rich, CePrOx crystals over the support. In contrast, in the La dopedsample, Pr is homogeneously distributed all over the catalyst, not only in the form of Ce-rich CePrOx mixed oxide particles (at low temperature) or as LnAlO3 (at high temperature) but also into/over the alumina particles (figure 2).

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 235–236, DOI: 10.1007/978-3-540-85226-1_118, © Springer-Verlag Berlin Heidelberg 2008

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These results suggest that the addition of SiO2 as dopant prevents the formation of the redox-inactive LnAlO3 perovskite phase by blocking the diffusion of the lanthanide ions into the alumina crystallites, which allows maintaining the lanthanide ions within crystalline phases which still present a high enough Ln4+/Ln3+ exchange capability.

Figure 1.- Experimental HREM images acquired on (a) the Si-doped material and (b) the La-doped material reduced at 900ºC. Ce M5,4 La M5,4

Pr M5,4

1050

0

950

50

Distance (nm)

100

850

Energy Loss (eV)

Figure 2.- EELS 3D representation of a collection of 50 spectra acquired on the Ladoped material after treatment at 900ºC. Similar results were observed at 350ºC. 1. 2. 3. 4.

M. Shelef, G.W. Graham, R.W. McCabe, Catalysis by Ceria and Related Materials A. Trovarelli,Imperial College Press, London 343-374 (2002). H. Schaper, E. B. M. Doesburg, L.L. van Reijen, Appl. Catal. 7, 211 (1983). K. Aboussaid, S. Bernal, G. Blanco, G.A. Cifredo, A. Galtayries, J.M. Pintado Mohamed Soussi el Begrani. Surface and Interface Analysis, 40, 3-4 ,250-253 (2008) We acknoledge the financial support from Ministry of Education and Science of Spain (Proyto MAT2005-00333) Junta de Andalucía (Grupos FQM-110 y FQM-334), and Programa Ramón y Cajal 2003. The electron microscopy work was carried out at the Electron Microscopy Division of Central Services of Science and Technology at the University of Cádiz.

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Sulfated Zirconia Catalysts: Structure and Performance Relationship, a TEM Study C. Meyer1, D. Su1, N. Hensel1, F.C. Jentoft1 and R. Schlögl1 1. Department of Inorganic Chemistry, Fritz-Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany [email protected] Keywords: Sulfated zirconia, structure, heterogeneous catalysis, HR-TEM

Sulfated Zirconia (SZ) is an important and suitable catalyst for heterogeneous nalkane isomerization that experiences braod industrial application. Zirconia in tetragonal phase that is stabilized at low temperature in the form of nanosized particles [1] proved a high activity and selectivity for this reaction [eg. 2]. A key issue in elucidating parameters relevant for catalytic performance is the observation of processes occurring during the calcination process, in which the precursor material is transformed to the active catalyst [3]. During calcination exothermic crystallization of the amorphous zirconia precursor produces a specific overshoot in the temperature known as the glow phenomenon. Once this event has occurred, the material exhibits significant activity as opposed to the inactive precursor. This study is focused on the correlation of structural characteristics and activity or selectivity of SZ nano powder catalyst. A series of quenching experiments at different stages of the calcination process has been conducted. Sulfated hydrous zirconia (MEL Chemicals XZ0 682/01) was used as starting material. Calcination was performed in flowing air at 823 K in batches of 20 g. Temperature was held for 3 h, applying a temperature ramp for heating and cooling of 15 K / min. Quenching in liquid nitrogen was done before, during and after the glow phenomenon as well as at completion of the temperature program. Isomerisation of nbutane (1 % n-butane in He at atmospheric pressure) at 373 K was used as a test reaction. Activity and selectivity of the catalyst samples were monitored as a function of time by on-line gas chromatography. Further characterization included XRD, UV-VIS and BET measurements. Systematic TEM investigations reveal sample properties with a high degree of spatial resolution. Electron diffraction and Fourier transformation are used for phase characterization, EDX and EELS for chemical analysis and HR TEM for morphology and grain size measurements. Further, detailed structures of single grains are investigated. Figure 1 exhibits features of interest using a tetragonal grain of zirconia with a maximum diameter of 30 nm as an example. Line of sight is parallel to [100], (011) and (002) are projected. Surface steps (1), bending of projected lattice traces (2) and intra grain porosity (3) are observable. This sample is taken after the glow phenomenon and shows high activity. Figure 2 shows for comparison a sample with little catalytic activity. Lattice spacings

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 237–238, DOI: 10.1007/978-3-540-85226-1_119, © Springer-Verlag Berlin Heidelberg 2008

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prove the tetragonal nature of the zirconia. A difference lies for example in the smoothness of the surface termination denoting energetic differences.

Figure 1. HR TEM micrograph of SZ catalyst. Projection of (011) and (002), line of sight is [100]. The arrows indicate exemplarily structural features, for details see text.

Figure 2. HR TEM micrograph of SZ catalyst. (011) planes of tetragonal zirconia are projected. The arrows indicate porosity (1) and a smooth surface termination (2). 1. 2. 3.

R.C. Garvie, J. of Phys. Chem., 82 (1965), p. 218 – 224. M. Benaissa, J.G. Santiesban, G. Dias, C.D. Chang, M. Jose-Yacaman, J. of Catalysis, 161 (1996), p. 694 - 703. A.H.P. Hahn, R.E. Jentoft, T. Ressler, G. Weinberg, R. Schlögel, F.C. Jentoft, J. of Catalysis, 236 (2005), p. 324 - 334.

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A novel procedure for an accurate estimation of the lattice parameter of supported metal nanoparticles from the analysis of plan view HREM images C. Mira, J.A. Perez-Omil, J.J. Calvino and S. Bernal Dep. Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica. Universidad de Cádiz. c/ Rep. Saharaui s/n. 11510 Puerto Real (Cádiz) - SPAIN [email protected] Keywords: HREM, plan view, nanoparticle lattice parameter

The lattice parameter of metal nanoparticles supported on a carrier material, as are those present in a large variety of catalysts, can suffer small modifications from the value expected for the bulk materials. Thus, dilatation or contraction of the lattice constant of supported metal has been related to effects like incorporation of support elements into the particles in the form of alloys; incorporation of small atoms of other elements, like H, O, or C, into the metal lattice; pseudomorphic growth; surface stress or encapsulation of the metal under a large compressive stress by the substrate. The observed modifications of the lattice parameter are frequently smaller than 5%. A precise quantification of this effect could help to understand their precise origin. The measure of lattice parameters by X-ray diffraction is quite extended. In spite of its accuracy this technique provides only an average value of all the particles under analysis. Likewise, the analysis becomes very unreliable with diffraction patterns with a low signal to noise ratio as are those obtained in systems with very small particles. In the case of HREM images, errors higher than 5% can be expected in direct measurement of lattice spacings [1]. In fact, the accuracy with this measurement technique depends on several experimental factors [2]. SAED patterns allow estimations with high relative errors (2-3%). An statistical approach, considering a large number of particles, improves the accuracy of HREM or SAED measurements [3], but in this case we are not characterising a single particle but an ensemble of them. We have developed a procedure to increase the accuracy in the determination of the lattice spacings of supported metal particles based on the detailed analysis of Moiré type fringes observed in plan view HREM images. These Moiré fringes correspond to linear combinations between the characteristic metal and support reflections. With particles of only a few nanometers a large number of Moiré spots can be detected in the corresponding image diffractograms. Using the lattice fringes of the bulk support as a reference, the measurement of each Moiré reflection in reciprocal space allows an estimation of metal lattice spacings. The error obtained in these individual determinations is lower than that expected for the direct measurement of the metal spacing, the exact value of the error depending on the specific Moiré reflection selected. Nevertheless, a much better estimation can be obtained if all the information present in the diffractogram is used simultaneously.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 239–240, DOI: 10.1007/978-3-540-85226-1_120, © Springer-Verlag Berlin Heidelberg 2008

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If we record an intensity profile of the image diffractogram we can try to fit it to a theoretical curve in which the metal structure is the parameter to be refined. We have developed a software to apply this approach. This program allows us fitting simultaneously all the visible peaks in the intensity profile, which includes not only the metal and support peaks but also a set of Moiré reflections. The positions of the different peaks in the theoretical curve are very sensitive to subtle modifications of the metal lattice spacings. Thus, the correlation coefficient between the theoretical and experimental curves shows a maximum for a precise metal spacing value, usually corresponding to situations of slight lattice contractions or expansions. In the figure below a planar view of a CeO2-supported Pd particle (a) and its diffractogram (b) are shown. Different Moiré reflections can be identified, which result from the combination of (111) CeO2 and (111) Pd reflections. The experimental intensity profile and its theoretical fitting are also shown. Two possible metal lattice modifications have been considered (c). A 0.6% contraction shows a better correlation (r) than that characteristic of a 0.4% expansion. By applying this procedure to the analysis of HREM images simulated for a set of models which consider exact metal lattice expansions/contractions we have estimated the precision of the method to be of the order of 0.2%. This new procedure has been applied to Pd/CeO2 images to detect, in single particles, variations in the metal lattice parameters lower than 1% with high reliability. 1. 2. 3. 4.

J.-O. Malm, M.A. O´Keefe; Ultramicroscopy 68 (1997) 13-23. W.J. DE Ruijter, R. Sharma, M.R. McCartney, D.J. Smith; Ultramicroscopy 57 (1995) 409422 S.-C.Y. Tsen, P.A. Crozier, J. Liu; Ultramicroscopy 98 (2003) 63-72 MEC/FEDER (MAT2005-00333) and JA (FQM-110, FQM-334) are acknowledged

a

b CeO2 Pd

Figure 1. (a) HREM image of a Pd/CeO2 catalyst ; (b) image diffractogram; (c) fitting of the experimental intensity profile to -0.6% and 0.4% variations in the lattice parameter. 300

300

-0,6%

r = 99,2%

250

r = 98,3%

250

+0,4%

calculado Calc.

200

intensity intensidad

intensity Intensidad

exptal.

150 100

150 100 50

50

0

0

c

200

0

20

40 pixel

60

80

0

20

40 pixel

60

80

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Microstructure of Pt particles and aggregates deposited on different carbon materials for fuel cells application D. Mirabile Gattia1, E. Piscopiello1*, M. Vittori Antisari1, S. Bellitto2, S. Licoccia2, E. Traversa2, L. Giorgi1, R. Marazzi1, A. Montone1 1. FIM Department, ENEA – C.R. Casaccia, Via Anguillarese 306, 00123 Rome, Italy *C.R.Brindisi, Via Appia Km 702, 72100 Brindisi, Italy 2. Department of Chemical Science and Technology, University of Roma “Tor Vergata”, Via della Ricerca Scientifica, 00133 Rome, Italy [email protected] Keywords: carbon nanostructures, fuel cell, catalyst

PEM (polymer electrolyte membrane fuel cells) and DMFC (direct methanol fuel cells) have demonstrated to be suitable devices in order to realize a widespread diffusion of electrical-H2 fed vehicles in the near future [1]. In recent years several research efforts were on the study of Pt clusters deposited on different kinds of nanostructured carbon, besides the classical carbon black, with the purpose of reducing the Pt loading by the optimization of the catalyst performances during electrochemical reactions at the cell electrodes. In this work Pt clusters have been deposited by an impregnation process on three carbon supports: Multi-Wall carbon Nanotubes (MWNT), Single-Wall carbon Nanohorns (SWNH) and Vulcan XC-72. MWNT and SWNH have been home synthesized by a DC [2] and an AC arc discharge process [3] respectively. The Pt particles, deposited on the three carbon supports, have been characterized by Scanning and Transmission Electron Microscopy, X-ray diffraction and cyclic voltammetry measurements. Electron microscopy investigations, revealed the presence of nanostructured aggregates with different diameters: 50-100 nm and 20-50 nm in Pt/SWNH and Pt/MWNT samples respectively, while in the case of Pt/Vulcan single nanoparticles were deposited. In this last sample the process resulted in a strongly inhomogeneous microstructure with several sample regions free from deposited particles. Electrochemical characterization showed that the Pt nanostructures deposited on MWNT were particularly efficient in the methanol oxidation reaction, even if the Pt active surface area on the Vulcan substrate is larger. This shows that particle aggregates can be more efficient respect to single particles, probably owing to the particular particle shape and to the presence of grain boundaries. The comparison between the two nanostructured substrates evidences furthermore a role for the small size of aggregates. The details of the microstructure, as evidenced by the high resolution TEM analyses, are reported in the insets (figure 1). The agglomerates deposited on the nanotubes appear to be constituted by single crystal region larger than the single leafs so that the structure appears quite complex and requires further analyses for a complete description.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 241–242, DOI: 10.1007/978-3-540-85226-1_121, © Springer-Verlag Berlin Heidelberg 2008

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a)

b)

c)

d)

Figure 1. Low magnification (a) and high magnification (b) TEM images of Pt particles deposited on Vulcan XC-72. In the inset a high resolution image is reported. In (c) and (d) Pt aggregates deposited on MWNT are shown with a high resolution detail in the inset. 1. 2. 3.

S. Gottersfield and T. Zawodzinski, Adv. Electrochem. Sci. Eng. 5 (1997), p. 195. D. Mirabile Gattia, M. Vittori Antisari, R. Marazzi, L. Pilloni, V. Contini and A. Montone, Materials Science Forum 518 (2006), p. 23. D. Mirabile Gattia, M. Vittori Antisari and R. Marazzi, Nanotechnology 18 (2007), p. 255604.

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Low-loss-energy EFTEM imaging of triangular silver nanoparticles J. Nelayah1, L. Gu1, W. Sigle1, C.T. Koch1, L. Pastoriza-Santos2, L.M. Liz-Marzan2, and P.A. van Aken1 1. Max Planck Institute for Metals Research, Stuttgart Center for Electron microscopy, Heisenbergstr. 3, D-70569 Stuttgart, Germany 2. Departemento de Quimica Fisica, Universidade de Vigo, 36310, Vigo, Spain [email protected] Keywords: EFTEM, EELS, metallic nanoparticles, surface plasmon mapping

Understanding how light interacts with matter at the nanometer scale is a fundamental issue in optoelectronics and nanophotonics. It is known that the optical properties of nanoparticles are entirely dependent on collective excitations of their valence electrons, known as "surface plasmon resonances" (SPR´s), under electromagnetic illumination. Measuring these properties locally at the level of the individual nano-object constitutes a challenging issue for linking of the global response of the nanoparticles and the underlying structure and morphology. The high-energy electron beam in a transmission electron microscope (TEM) is an excellent tool for this application. In particular, it has been recently shown that low-loss electron energy-loss spectroscopy (EELS) in the context of a scanning transmission electron microscope (STEM) enables the optical properties of metallic nanoparticles in the ultraviolet–near-infrared (UV–NIR) domain to be probed with nanometer resolution via the mapping of SPR´s [1]. With the advent of recent instrumental improvements such as electron monochromators and in-column energy filters, it is expected that the understanding of these optical properties can be further improved through the gain in both energy and spatial resolution. In this contribution, we present energy-filtered transmission electron microscope (EFTEM) studies of the optical properties in the UVNIR regime of individual triangular silver nanoparticles.. Triangular silver nanoprisms have been synthesized as described in [2]. The prisms have edge lengths in the range between 100 and 300 nm and are typically between 5 and 10 nm thick. The instrument used for this investigation was the new 200 kV SESAM FEG-TEM (Zeiss) fitted with an electrostatic monochromator and a high-dispersion and high-transmissivity in-column MANDOLINE filter [3]. The energy resolution was set to 0.25 eV for these experiments. The EFTEM series were acquired on a 2k × 2k CCD camera (8 × 8 binning) using a 0.2 eV energy selecting slit. Energy-filtered images were recorded from 0.5 eV to 4 eV (17 images) with an acquisition time of 20 s/image. Figure 1 shows a series of EFTEM images of a triangular nanoparticle with 210 nm edge length recorded at energy losses of (a) 0 eV, (b) 1.0 eV, (c) 1.6 eV, and (d) 2.2 eV, respectively. The two-dimensional images in Figures 1(b)-(d) represent the intensity distributions of the first three main SPR´s of the silver nanoprism as already observed with STEM-EELS in [1]. But, compared to the latter data, our EFTEM images display

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increased spatial sampling and are obtained with shorter acquisition time and without post-acquisition data processing. These results clearly demonstrate that low-energy-loss EFTEM imaging in the SESAM microscope provides a fast and precise analytical tool for investigating the optical properties of single metallic nanoparticles in the visible range. This tool enables both unprecedented spatial and energy resolution which will provide new information about the optical properties of nanomaterials. 1. 2. 3. 4.

J. Nelayah, M. Kociak, O. Stephan, F.J.G. de Abajo, M. Tencé, L. Henrard, D. Taverna, I. Pastoriza-Santos, L.M. Liz-Marzan, and C. Colliex., Nature Physics 3 (2007) 348. V. Bastys, I. Pastoriza-Santos, B. Rodriguez-Gonzalez, R. Vaisnoras and L.M. Liz-Marzan, Adv. Funct. Mater. 16 (2006) 766. C.T. Koch, W. Sigle, R. Höschen, M. Rühle, E. Essers, G. Benner, and M. Matijevic, Micoscopy and. Microanalysis 12 (2006) 506. We acknowledge financial support from the European Union under the Framework 6 program under a contract for an Integrated Infrastructure Initiative. Reference 026019 ESTEEM

(a)

(b)

(c)

(d)

Figure 1. EFTEM images of a triangular silver nanoparticle with 210 nm edge length imaged at energy losses of (a) 0 eV, (b) 1.0 eV, (c) 1.6 eV and (d) 2.2 eV. Images were taken with a slit width of 0.2 eV centred on the specific energy loss. Scale bar and colour level are common for all images. The bright pixels indicate maximum intensity.

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Microstructure of cobalt nanocluster arrays fabricated by solid-state dewetting Yong-Jun Oh1, Junghwan Kim1, Sukhun Hwang1, Caroline A. Ross2, Carl V. Thompson2 1. Advanced Materials Science and Engineering Div., Hanbat University, Korea 2. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 [email protected] Keywords: nanoclusters, dewetting, cobalt phases

Cobalt nanocluster arrays have recently attracted considerable attention due to their applications as patterned magnetic recording media as well as catalyst arrays for growing carbon nanotubes [1,2]. The processes to fabricate nanocluster arrays are mostly based on direct lithography of thin films using coatings of photo resist and their selective removal. Since the resultant clusters formed by this technique retain the microstructure of the original thin films, we need to control the microstructure of thin films before lithography to obtain clusters with specific crystal property. Recently, one of the authors developed a self-assembling technique to fabricate gold nanoparticle arrays by dewetting a thin metal film on topographic templates at elevated temperatures [3]. The technique was also characterized by crystal reorientation during agglomeration of the thin film by dewetting. In this study, we investigate the changes in phase, crystallography, and microstructure of cobalt before and after dewetting by thermal annealing. The topographic templates consisted of 200-nm-period square arrays of inverted pyramidal pits on (100) silicon wafers. Interference lithography using a laser beam was used to create patterns on the wafers. The templates were oxidized to prevent the reaction between the substrate silicon and the cobalt thin film. The cobalt films were deposited on the templates using ion-beam sputtering and were annealed in forming gas to induce dewetting. The ordered cobalt clusters at a high temperature were mostly in the fcc phase (Figure 1), while the films annealed at a low temperature showed a mixture of hcp and fcc cobalt phases (Figure 2). The dewetted clusters were almost single crystal when twin boundaries were disregarded. The orientation of more than a quarter of the observed particles was such that the (111) plane of the Co particles was parallel to a pair of the inverted pyramidal faces of the silicon template. The dewetting process is believed to be a promising technique to fabricate single-crystal nanocluster arrays for high-density magnetic recording media and carbon nanotube growth. 1.

J.I. Martin, J. Nogues, K. Liu, J.L. Vicent, I.K. Schuller, Journal of Magnetism and Magnetic Materials 256 (2003), p.449.

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3. 4.

C.A. Ross, M. Hwang, M. Shima, J.Y. Cheng, M. Farhoud, T.A. Savas, Henry I. Smith, W. Schwarzacher, F.M. Ross, M. Redjdal, F.B. Humphrey, Physical Review B, 65 (2002), p.144417. A.L. Giermann, C.V. Thompson, Applied Physics Letters 86 (2005), p.121903. We thank H.I. Smith and K. Berggren at MIT for interference lithography. (a)

(b)

Zfcc-Co=[110]

100 nm

100 nm

Figure 1. (a) Scanning and (b) transmission electron microscope (SEM and TEM) images showing the dewetted clusters. The SAD pattern on the top right was taken from the particles in pits.

fcc[100]

fcc[110]

hcp[1213]

5 nm

Figure 2. High-resolution TEM image of the as-sputtered cobalt film. The arrows indicate the grains of fcc-Co and hcp-Co phases showing the atomic images along zone axis with low indices.

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Size Effect in Gold Nanoparticles Investigated by Electron Holography and STEM L. Ortolani1,2, V. Morandi2 and M. Ferroni3 1. University of Bologna, Dept. of Physics, v.le B. Pichat, 6/2, 40127 Bologna, Italy 2. CNR-IMM Bologna, v. Gobetti, 101, 40129 Bologna, Italy 3. INFM-CNR SENSOR and Dept. of Chemistry and Physics, Brescia University, v. Valotti, 9, 25133 Brescia, Italy [email protected] Keywords: Gold Nanoparticles, Electron Holography, HAADF-STEM

Gold clusters are extremely interesting nanosystems with a high catalytic activity, exploited for sensing applications and to promote the growth of nanostructures [1,2]. All these potential applications motivated numerous structural studies on Au nano-clusters. The mean electrostatic potential (MIP) is a fundamental quantity and its value is crucial for accurate evaluation and simulation of experimental data from TEM imaging and electron diffraction. Recently, a dependence of the MIP on particle size has been reported, measured by electron holography (EH): the increase of the MIP over the bulk value for particle sizes lower than 5 nm has been shown, suggesting a correlation with the catalytic behaviour of gold [3,4]. Despite these very promising results, a similar effect was observed in amorphous carbon films as the result of a thickness independent phase shift [5]. EH is capable of providing a quantitative determination of this surface phase shift since it depends on the projected sample thickness. Unfortunately, gold particles are reported to change their contact angle with the substrate reducing their dimension, as a result of a size-dependent change in the particle-support interaction [3]. To overcome these limitations, and to determine unambiguously information on surface phase effects in gold clusters, a combination of High Angle Annular Dark Field STEM (HAADF-STEM) and electron holography has been used, exploiting the local sample thickness dependence of the HAADF-STEM signal. HAADF intensity depends also on the imaging conditions, on the atomic number and of the density of the observed material. By keeping fixed all these parameters, it is possible to directly correlate image intensity to sample thickness variations. From the holographic reconstructed phase map of gold clusters over an amorphous carbon film, like the one shown in Fig. 1a), it is possible to fit the induced phase shift and the projected radius of the particle, as reported in the linescan of Fig. 1b). From a HAADF-STEM image of the same clusters it is possible to fit the projected radius and the HAADF intensity, as shown in Fig. 2a). By keeping constant all the imaging parameters, intensity variation in the image only depends on changes in the particles shape. The fit of the data of Fig. 2b) shows that the smaller particles are thinner than the larger ones, as shown in the model of Fig. 3a). From these results it is possible to correct the electron holography phase shift measurements, obtaining the plot of Fig. 3b). Numerical fitting of the data reveals, for gold clusters dispersed over a carbon film, a thickness independent phase shift of 0.45

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rad. Additional studies are needed to find the origin of these surface electrostatic effects, which could be addressed to surface strain at cluster interfaces. Nonetheless, the synergy of EH and HAADF-STEM provides an insight into the interactions between the constituents of nanostructured systems. 1. 2. 3. 4. 5.

R Andres, T. Bein and M. Dorogi, Science, 272 (1996), p. 1323. M. Haruta, Catal. Today, 36 (1996) p.153. S. Ichikawa, T. Akita and M. Okamura, JEOL News, 38 (2003), p. 6. L. Ortolani et al., J. Eur. Ceram. Soc., 27 (2007), p. 4131 M. Wanner et al., Utramicroscopy, 106 (2006), p. 341.

Figure 1. a) Reconstructed phase map of three gold nanoparticles. b) Linescan profile and result of the numerical fit.

Figure 2. a) Linescan profile from HAADF image of a gold nanoparticles and result of the fit. b) Plot of the HAADF intensity for different particles and numerical fit.

Figure 3. a) Model for gold particles shape of decreasing dimension. b) Plot of the holographic phase shift and numerical fit showing a surface phase effect of 0.45 rad.

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Post-Mortem investigation of Fischer Tropsch catalysts using cryo- transmission electron microscopy Dogan Ozkaya1, Martin Lok2, John Casci2 and Peter Ash1 1. Johnson Matthey Technology Centre Blounts Court Sonning Common Reading RG4 9NH UK 2. Johnson Matthey Technology Centre, PO Box1 Belasis Avenue Billingham TS231LB UK [email protected] Keywords: GTL, Fischer Tropsch, Cryo- microscopy

Co/Al2O3 catalysts are widely used in the Fischer-Tropsch, gas to liquids (GTL), catalytic reaction where syngas (CO2 and H2) is converted into higher hydrocarbon wax products. One important use of the wax product is through cracking to produce clean diesel fuel. In most production routes the catalyst is initially in the form of highly dispersed Co-oxide particles on a high surface area gamma alumina with up to 1 wt% addition of a precious metal promoter. The catalyst can then be reduced to its active state in-situ in the FT reactor or supplied in pre-reduced form. In the case of the prereduced catalyst the material is encapsulated in a wax product to prevent re-oxidation of the cobalt. Post reaction the catalyst is suspended in the wax product of the FT reaction. It is of paramount importance to analyse the initial state and the final state of a catalyst in order to understand how the reaction has progressed. Any pre or post-reactor analysis therefore needs to deal with the wax but leave the catalyst unchanged. However, the dewaxing procedures traditionally applied to the catalyst, (Soxhlet extraction and calcination at 350°C) before examination, not only partially oxidize the Co but also cause some changes in the microstructure. Consequently, the combination of Cryoelectron microscopy and cryo-microtomy offer a straightforward, but unique, route to analyse the catalyst within its original wax environment. The sample (spent catalyst had operated for 1000 hours in a slurry reactor at 210 C and 20 bar using a H2/CO ratio of 2.1) was prepared as follows: wax sample was stuck to a microtome stub using sucrose solution at liquid nitrogen temperatures and microtomed using a Leica FC-6 cryo-ultramicrotome. The slices were placed on a holey carbon coated Cu TEM grid and transferred to a Tecnai F20 field emission transmission electron microscope using a Gatan cryo-transfer system. Direct analysis of the catalyst is demonstrated with high-resolution images and analysis from the TEM. The catalyst analysed was produced using the high dispersion Catalyst (HDC) technique [1,2] rather than the more usual nitrate route. The material generated using HDC route was then reduced, generating Cobalt metal on the support, and encapsulated in wax An example of a microtomed wax on a TEM grid is shown in figure 1a. The marks from a diamond knife can be seen on the wax and this illustrates the difficulties of handling wax at low temperatures. Figure1b shows a part of the catalyst embedded

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within the wax. It shows that diamond knife marks do not necessarily prevent the analysis of the catalyst. Figure 2a shows a region of the catalyst close up. The particle size analysis from a region like this is shown in figure 2b with catalyst as prepared (fresh) and after it has been through the reaction (spent). The changes in the particle size reflect directly the conditions that the reactor has been through and possible to correlate it with reactivity. 1. 2.

1- Lok C. M. Studies in Surface Science and Catalysis 147 (2004) 283 2- Bonne R. and Lok C. M. US patent 5, 874 (1999) 381

Figure 1. Low magnification image of the wax slice on a TEM grid (fig 1a) and a catalyst piece within a wax surround.

Figure 2. The Co metal particles on alumina support (fig 2a) with particle size distributions for a fresh catalyst and spent catalyst.

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TEM Investigations on Cu-impregnated Zeolite Y catalysts via chloride free preparation M.-M. Pohl, M. Richter, M. Schneider Leibniz-Institute for Catalysis e.V.(branch Berlin), Richard-Willstätter-Str. 12, D-12489 Berlin, Germany [email protected] Keywords: catalysis, impregnated zeolite, Cu dispersion

Copper-containing zeolites are potential catalysts for the oxidative carbonylation of methanol to DMC [1,2] but have a minor activity without chloride. The catalyst used for this study was a chloride-free system which combines high performance with the attractiveness of a process that abandons any halogens during catalyst preparation and process operation [3]. In all those zeolite catalyst systems the question of the distribution of the copper particulary at high loading is crucial. The investigation of the complex morphologies of zeolites by microscopy is a challenge due to their beam sensitivity. Ion exchanged zeolites decrease the beam stability further. The metals leave the zeolite matrix as particles and the zeolite structures are destroyed. As ultimate consequence nanowires can be formed, shown by Mayoral and Anderson [4]. For HRTEM on zeolites the use of Cs-corrected microscopes is a suitable way Tesche [5] showed this opportunity by imaging metal clusters inside ordered pores without any loss of the 3D-Structure. Since the access on Cs-corrected microscopes are limited most microscopists have to deal with conventional TEM. The here analyzed zeolite Y with 14wt% Cu load shows the typical growth of nanoparticles under electron beam at 200kV. Even in the first seconds with intact lattice planes Cu-seeds are visible which grow further under electron bombardment. Parallel the lattice plane disappear under shrinkage of the zeolite as shown in Figure 1. Additional Cu containing particles were detected both by XRD and TEM as CuO differ considerable from the beam grown Cu features (Figure 2.). Since damage could appear within the first seconds within the microscope, no secure interpretation on fine structures of these systems should be interpreted with care . 1. 2. 3. 4. 5. 6.

S. T. King, J. Catal. 161 (1996) 530. S. T. King, Catal. Today 33 (1997) 173 M. Richter, M. Faith, R. Eckelt, E. Schreier, M. Schneider, M.-M. Pohl, R. Fricke, Applied Catalysis B.: Environmental 73(2007) 269-281 A. Mayoral, PA Anderson, Nanotechnology 18 (2007)165708(6pp) B. Tesche, F.C. Jenthoft, R. Schlögl, S. R. Bare, L.T. Nemeth, S. Valencia, A. Corma, 41. Jahrestreffen deutscher Katalytiker, Weimar 2008, P43 We kindly acknowledge the financial support by the Federal Ministry for Education and Research of the FRG, the Senate of Berlin and the European Union (project 03X2002).The sample preparation is acknowledged to Mr. R. Eckelt.

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Within 20 sec

After 1 minute

After 3 minutes

Figure 1. High-resolution at 200kV of a Cu impregnated zeolite Y (1,4 nm lattice planes) with increasing beam damage and development of Cu nano particles

Relative Intensity (%)

Zeolite Y with 14wt%Cu

100.0

CuO

* 0.0

10.0

20.0

30.0

* 40.0

50.0

2Theta

Figure 2. CuO at high Cu load detected by XRD and TEM image with CuO and beginning electron damage within the zeolite Y matrix and first Cu seeds

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Coarsening of mass-selected Au clusters on amorphous carbon at room temperature R. Popescu1, R. Schneider1, D. Gerthsen1, A. Böttcher2, D. Löffler2 and P. Weiss2 1. Laboratorium für Elektronenmikroskopie and Center for Functional Nanostructures, Universität Karlsruhe, 76128 Karlsruhe, Germany 2. Institut für Physikalische Chemie, Universität Karlsruhe, 76128 Karlsruhe, Germany [email protected] Keywords: Au clusters growths, transmission electron microscopy, surface Ostwald ripening.

Mass-selected Aun (n=4,6,13 and 20) clusters and clusters with an initial distribution of Aum (10≤m≤20) clusters were deposited on amorphous carbon (a-C) thin films by low-energy-beam cluster deposition. The samples were stored at room temperature under ambient conditions over more than two years to analyse the stability of the cluster sizes. The cluster-size distributions were investigated by transmission electron microscopy (TEM) in regular time intervals. Several hundred Au clusters were analysed for each sample and time interval. The cluster radii were assessed by measuring the projected cluster area, which is in a good approximation a circular one. Size histograms were derived and the average radii at a given time t R (t ) were determined. Figure 1 shows the measured R (t ) values which increase strongly over a period of more than two years although the samples were not exposed to elevated temperatures. The coarsening process is best described by a least-square fit of the experimental R (t ) based on R 4 (t ) = R 4 (0) + K d t (t: time, Kd: constant), which corresponds to surface diffusion-limited Ostwald ripening (OR) with the mass transport taking place through the cluster-substrate contact line [1,2]. Coalescence of clusters caused by Brownian motion can be excluded for the given experimental conditions. The values of the surface mass-transport diffusion coefficient Ds' can be calculated using the 45 K d ln( L) ϕ (θ ) k B T , where DS' is given by Kd values and the relation Ds' = 4 ω 2 γ n0 Ds' = Ds c Au with the surface-diffusion coefficient of single Au atoms Ds on a-C and the number of single Au ad-atoms on sites of the a-C substrate cAu. ω=1.7⋅10-29 m3 denotes the volume of gold atoms, γ=1.5 Jm-2 the Au surface energy [3], n0=1.1⋅1019 m-2 the density of sites on the cluster surface [4], kB the Boltzmann constant and T=298 K the temperature. L=2.5 is the screening distance, which is taken to be constant [1]. The parameter ϕ (θ ) = 0.45 depends on the contact angle θ between the Au cluster and the a-

C substrate [4]. The Ds' values are between (1.1±0.1) and (3.8±0.4)⋅10-25 m2s-1. Values for cAu between 0.8 and 2.4⋅1017 atoms⋅m-2 can be derived for our samples as outlined in detail elsewhere [5]. The surface-diffusion coefficient of single Au atoms on a-C is

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given by Ds (T ) = D0 exp(− Ed k BT ) with D0=1.6⋅10-8 m2s-1. Using the relation Ds' = Ds c Au with the values for cAu and Ds' , an activation energy for the surface diffusion of single Au atoms Ed=0.87±0.05 eV is determined in good agreement with a previous theoretical value of Ed=1.0 eV [6]. We show that the cAu values depend - besides on the temperature and the average distance between clusters - also on the initial Au-cluster size distribution on the substrate. They are not particularly sensitive (within our error limit) with respect to the initial size of the Aun (n=4,6,13 and 20) clusters in the case of mass-selected deposition. Moreover, the coarsening process for mass-selected Au clusters (even in case of an initial limited Au-cluster distribution) is quite different from that observed for the deposition of non mass-selected Au clusters on a-C at room temperature as reported in Ref. [7].

1. 2. 3. 4. 5. 6. 7. 8.

B. K. Chakraverty, J. Phys. Chem. Solids 28 (1967), 2401. M. Zinke-Allmang, L. C. Feldman and M. H. Grabow, Surf. Sci. 16(8) (1992), 377. W. R. Tyson and W. A. Miller, Surf. Sci. 62 (1977), 267. R. Popescu, E. Müller, M. Wanner, D. Gerthsen, M. Schowalter, A. Rosenauer, A. Böttcher, D. Löffler and P. Weis, Phys. Rev. B 76 (2007), 235411. R. Popescu, D. Gerthsen, M. Wanner, A. Böttcher, D. Löffler and P.Weiss, to be published. A. A. Schmidt, H. Eggers, K. Herwig and R. Anton, Surf. Sci. 349 (1996), 301. M. Wanner, R. Werner, G. Schneider and D. Gerthsen, Phys. Rev. B 72 (2005), 045426. This work has been performed within the project C4 of the DFG Research Center for Functional Nanostructures (CFN). It has been further supported by a grant from the Ministry of Science, Research and the Arts of Baden-Württemberg (Az: 7713.14-300).

Figure 1. a) Average radii of Au clusters as a function of storage time R (t ) . The

symbols represent the measured R for samples prepared by deposition of: Au4 (Y), Au6 ( ), Au13 (V), Au20 with 1.5⋅1012 clusters (U), Au20 with 0.75⋅1012 clusters ( ) and Aum (10≤m≤20) cluster distribution ( ). The solid lines with the corresponding colour represent fits of the data for diffusion-limited kinetics of surface OR under steady-state condition with the mass transport through the cluster-substrate contact line (see text); b) magnified section inside the dashed rectangle of a) up to 2.5 107 s .

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TEM investigations on Ni clusters electrodeposited on Carbon substrate M. Re1, M.F. De Riccardis1, D. Carbone1, D. Wall2 and M. Vittori Antisari1* 1. ENEA, FIM Department, C.R.Brindisi, Via Appia Km 702, 72100 Brindisi- Italy * C.R.Casaccia , Via Anguillarese 301, 00123 Roma – Italy. 2. FEI, Building AAE Achtseweeg Noord 5, Acht – Eindohven 5651GG [email protected] Keywords: catalysts, nanostructures, Ni clusters

The role of catalysts in the growth of carbon nanostructures by CVD is particularly critical, since the nano-carbon shape can depend on the catalyst composition and structure besides the deposition parameters [1-3]. In the synthesis of metal catalyzed carbon nanofilaments the performances of the catalyst particles can dramatically depend on both physical and chemical interaction with the substrate. In particular, a good adherence of the clusters to the substrate is necessary to avoid coalescence phenomena during the growth process generally carried out at relatively high temperature. The study of catalyst-substrate microstructure is particularly relevant for the optimization of the whole growth process. In this work Ni clusters were synthesized by electrodeposition, a versatile, rapid and inexpensive technique which, by a specific control of the process parameters, can allow the deposition of continuous metallic films or of nanoparticles, also on complex and convoluted substrates. The Ni clusters were electrodeposited on different C substrates, and have been successful used to assist the CVD growth of carbon nanofibres, having a particularly good adhesion with the substrate [4-5]. The experimental electrodeposition conditions are reported elsewhere [6]. Particularly interesting results were obtained in the case of Carbon Fibres (PAN fibres, produced by controlled pyrolysis of Polyacrylonitrile) [4-6] which were, by this method, decorated with carbon nanofibres grown at the electrodeposited Ni clusters. Transmission Electron Microscopy, with a TECNAI G2 F30 operated at 300 kV, was used to characterize the morphology and microstructure of the electrodeposited Ni and to study in detail the interface between the metal and the substrate in order to better understand the adhesion mechanism of Ni clusters to the C substrates. Considering the cylindrical shape of the Carbon Fibres, cross sectional samples for TEM observations were prepared by FIB with a FEI Strata 400 dual beam instrument. Conventional bright field and high resolution TEM images show that the Ni clusters have a globular shape, with a width in the range of 60–90 nm and a height between 50 and 80 nm (Figure 1 a). The clusters, on the contrary of a commonly observed situation, are polycrystalline and have a grain size of the order of 10 nm (Figure 1 c). The structure of the interface between the carbon substrate and the cluster is not particularly evident in the high resolution images (Figure 1 b), despite the favourable observation geometry. In order to characterize the carbon-cluster interface, EDS spectra were

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collected with a focused electron beam. The analyses, carried out on different clusters, showed systematically a higher O content at this interface. This finding, in agreement with SIMS experiments not reported, can bring another piece of information on the interface structure and indicating the way for the interpretation of the strong bonding of the Ni clusters with the substrate. 1. 2. 3. 4. 5. 6. 7.

I. Martin-Gullon, J. Vera, J. A. Conesa, J. L. . Gonzales, C. Merino, Carbon, 44 (2006), 1572-1580 F.H. Kaatz, M.P.Siegel, D.L. Overmyer; P.P. Provencio, D.R. Talland, Appl. Phys. Lett., 89 (2006), 241915 A. de Lucas, P. B. Garcia, A. Garrido, A. Romero, J.L. Valverde, Appl. Cat. A, 301 (2006), 123-132 Th. Dikonimos Makris, R. Giorgi, N. Lisi, L. Pilloni, E. Salernitano, M.F. De Riccardis and D. Carbone, Fullerenes, Nanotubes and Carbon Nanostructures, vol 13, supplement 1 , 2005, 383-392 M. F. De Riccardis, D. Carbone, Th. Dikonimos Makris, R. Giorgi, N. Lisi, E. Salernitano, Carbon, 44 (2005) 671 M. F. De Riccardis, D.Carbone, Appl. Surf. Sci. 252 (2006), 5403-5407, We kindly acknowledge the technical support of F. Tatti, Application Specialist of FEI Italy.

Figure 1. a: a BF TEM image of the longitudinal cross section of the sample; b: a HRTEM image of the interface between a Ni cluster and the substrate; c: a HRTEM image of a small area of the Ni cluster.

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Near-surface structure of FePt nanoparticles B. Rellinghaus1, D. Pohl1, E. Mohn1, and L. Schultz1 1. IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden, Germany [email protected] Keywords: FePt, Nanoparticles, Aberration corrected TEM.

Stoichiometric FePt nanoparticles in the chemically ordered tetragonal L10 phase have gained significant interest in the past decade, since their huge magneto-crystalline anisotropy makes them promising materials for future ultra-high density magnetic data storage media. However, simulations of the equilibrium structure of FePt nanoparticles imply that the formation of the L10 phase may be impeded by a segregation of Pt atoms to the particle surface. Recently, an increase of the lattice constant towards the particle surface – as expected for Pt-enriched surfaces – was reported for FePt nanoparticles [1]. We have therefore systematically investigated the structure of FePt nanoparticles by aberration corrected TEM utilizing a FEI Titan3 80-300 microscope equipped with an image CS corrector (CEOS). FePt nanoparticles were prepared from the gas phase [2,3] and deposited onto amorphous carbon support films. Owing to the clean preparation process, the particle surfaces are free of any stabilizing organics. Particle morphologies and structures range from icosahedral or deceahedral multiply twinned particles (MTPs) to truncated octahedra which are often single crystals. The mean particle diameter is roughly 7 nm. Two typical FePt icosahedra are depicted in Fig. 1 where the phase of the reconstructed exit wave as obtained from the evaluation of a focus series of TEM images is shown. A detailed analysis does not reveal any systematic increase of the lattice spacing upon approaching the particle surface, but a rather statistic variation of any inter-atomic distances (not only the radial spacings). Increased lattice parameters close to the particle surface were only observed, when the particles were terminated by incomplete layers of atoms, or in the vicinity of pronounced (near-surface) defects. The latter is illustrated in Fig. 2 which shows exemplarily a truncated FePt octahedron with a near-surface edge dislocation. As can be seen from the magnification of the defected area in Fig. 2b, the spacing between the last complete (though bent) surface layer to the atoms of an additional incomplete surface layer as manifested by the faint contrast marked by the white arrows is larger than in the depth of the particle. Such defects are more likely to occur in un-equilibrated particles (see, e.g., the twin boundary in the vicinity of the sintering neck to a neighboured particle). The effect of thermal equilibration of the particles by short-time in-flight annealing will be discussed. 1. 2.

R.M. Wang, O. Dmitrieva, M. Farle, G. Dumpich, H.Q. Ye, H. Poppa, R. Kilaas and C. Kisielowski, Phys. Rev. Lett. 100 (2007) 017205. S. Stappert, B. Rellinghaus, M. Acet and E.F. Wassermann, J. Cryst. Growth 252 (2003) 440.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 257–258, DOI: 10.1007/978-3-540-85226-1_129, © Springer-Verlag Berlin Heidelberg 2008

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B. Rellinghaus, E. Mohn, L. Schultz, T. Gemming, M. Acet, A. Kowalik, and B.F. Kock, IEEE Trans. Magn. 42 (2006) 3048.

Figure 1. (a) Reconstructed exit wave (phase image) of two icosahedral FePt nanoparticles lying with their two-fold symmetry axes parallel to the electron beam. (b) Magnification of the area marked by the dashed rectangle in fig. (a). (c) Line profiles as obtained from the areas indicated in fig. (b).

Figure 2. (a) Reconstructed exit wave of a [110]-oriented truncated FePt octahedron at a focus where a near-surface edge dislocation becomes visible. The dashed line indicates a twin boundary (TB) close the sintering neck to an adjacent particle (only partly shown, bottom left corner). (b) Blow-up of the area marked in fig. (a). Dashed lines highlight the dislocation. Arrows indicate incomplete layers of surface atoms.

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Overgrowth of gold nanorods: From rods to octahedrons J.B. Rodríguez-González, E. Carbó-Argibay, I. Pastoriza-Santos, J. Pérez-Juste and L.M. Liz-Marzán Departamento de Química Física, Unidad Asociada CSIC-Universidade de Vigo, 36310 Vigo, Spain. [email protected] Keywords: TEM, gold, nanorods.

In this work, we use transmission electron microscopy (TEM), and selected area electron diffraction (SAED) to study the growth of previously synthesized monocrystalline gold nanorods (NRs) [1]. When HAuCl4 was reduced on the rods by DMF in the presence of PVP, preferential growth on the sides was obtained, together with sharpening of the tips. TEM images of one original NR, two intermediate particles, and the final stage particle, as well the corresponding SAED patterns, are shown in Figure 1. The starting single-crystal Au NRs, are enclosed within eight {110} and {100} alternating lateral facets, whereas the rod tips are terminated by {100}, {110}, and {111} facets [2]. The SAED analysis (Figure 1) reveals that the tips of the intermediate particles are composed of four {111} facets and indicates that the lateral facets are {110}. The final particles display an octahedral shape whit all facets type {111}, while maintaining a single-crystalline structure [3]. We propose a growth mechanism as sketched in Figure 2. Transformation of the initial rods (Figure 2a) into particles with four {110} lateral facets and sharp tips enclosed by four {111} facets should involve disappearance of the {100} side facets through preferential addition of Au atoms on them (Figure 2b). The morphological transition produced by further growth of the sharp NRs will accordingly be determined by the ratio between the growth rates along the [110] and the [111] directions, this is schematically shown in Figure 2c by the red spheres closing the {110} facet and forcing the {111} facets to join, one with each other, in the final octahedral structure. The described mechanism, based on preferential growth of certain crystalline facets should correlate with a sequence of surface energies in the order {100}>{110}>{111}, which is not in full agreement with the general sequence of surface energies for the different crystallographic Au fcc planes γ(111)< γ (100) 0.1) .

Figure 2. EBSD results of the Fe-18.9%Mn-0.62%C-0.02%Ti-0.005%B-0.11%N steel after hot rolling, 1000°C/30min solution treatment and tensile test at -40°C. Image sequence and legend as in Fig. 1.

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Microstructure evolution during Ni/Al multilayer reactions S. Simões1, F. Viana1, A.S. Ramos2, M.T. Vieira2 and M.F. Vieira1 1. Dep. de Engenharia Metalúrgica e Materiais, GMM/IMAT, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200–465 Porto, Portugal 2. ICEMS, Dep. de Engenharia Mecânica, Faculdade de Ciências e Tecnologia, Universidade de Coimbra, R. Luís Reis Santos, 3030-788 Coimbra, Portugal [email protected] Keywords: nickel aluminides, multilayer, exothermic reaction

Heating of thin multilayer systems can lead to stable or metastable phase formation. The structural evolution is known to depend on processing pathways and/or nominal composition; interdiffusion or intermixing prior to phase transformation, play a key role in determining the phase formation kinetics. The reaction of Ni and Al multilayer to form NiAl has been the subject of some investigations over the past two decades. The first phase to form depends on sample processing, bilayer thickness and annealing conditions. In the literature the first phase to form has been reported to be Al3Ni [1], AlNi [2], or Al9Ni2 [3]. Ni/Al multilayer is an interesting system since it is known to transform to NiAl in a rapid, exothermic, self sustained reaction. The heat is released locally and progress through the multilayer until all the Al and Ni has reacted. This system has potential for use as heat source for joining temperature-sensitive materials, like microelectronic components. Thin films with nanometric Ni and Al alternated layers were deposited by d.c. magnetron sputtering using nickel and aluminium pure targets. In our experiments, we use periods, or bilayer thicknesses, of 5, 14 and 30 nm and a total film thickness ranging from 2 to 5 μm. The structural evolution of the Ni/Al multilayer with temperature was studied by differential scanning calorimetry (DSC), scanning electron microscope (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). DSC experiments were performed on freestanding films, from room temperature to 700 °C at 10 and 40 °C/min. Two exothermic reactions were detected in DSC curves of the film with 30 nm period, with peak temperatures at 230 and 330 ºC while for the 5 and 14 nm period film we only observed one exothermic peak at 190 and 250ºC, respectively. To identify the reaction products, DSC samples were examined by XRD. For the asdeposited condition only Al and Ni were detected by XRD. The films with 30 nm period were heated at 300ºC (temperature between the two peaks), 450ºC (temperature after the second peak) and 700ºC. For the 300ºC sample, the XRD patterns identified Al3Ni and Ni phases. For the 450ºC sample, Al3Ni and NiAl were the detected phases. Only after heating up to 700ºC, Ni and Al react completely to form NiAl. For the 5 and 14 nm periods films, the formation of NiAl occurs in one single step. The structural evolution was followed by SEM and TEM to observe the morphological changes occurring during reaction. Figure 1 shows SEM images for as-deposited and DSC samples treated at 300ºC and 700ºC. With the formation of NiAl the multilayer morphology is no longer present. S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 487–488, DOI: 10.1007/978-3-540-85226-1_244, © Springer-Verlag Berlin Heidelberg 2008

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E. Ma, C.V. Thompson, L.A. Clevenger, J Appl Phys 69 (1991) p. 2211 C. Michaelsen, G. Lucadamo, K. Barmak, J Appl Phys 80 (1996) p. 6689. M.H. Silva Bassani, J.H. Perepezko, A.S. Edelstein, R.K. Everett, Scripta Mat 37 (1997) p. 227.

This work was supported by “Fundação para a Ciência e a Tecnologia” through the project PTDC/CTM/69645/2006 and the Grant SFRH/BD/30371/2006 financed by POS_C. a

b

c

NiAl

Figure 1. Schematic illustration and SEM images of the structural evolution of Ni/Al multilayer samples: a) as-deposited, b) annealed at 300ºC and c) annealed at 700ºC.

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TEM investigation of severely deformed NiTi and NiTiHf shape memory alloys G. Steiner, M. Peterlechner, T. Waitz and H.P. Karnthaler Physics of Nanostructured Materials, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria [email protected] Keywords: TEM, amorphization, nanocrystalline, NiTi, NiTiHf

NiTi shape memory alloys show a martensitic phase transformation from a cubic high temperature phase (B2 austenite) to a monoclinic structure (B19´ martensite). A crystalline to amorphous phase transformation can be obtained by methods of severe plastic deformation such as cold rolling and high pressure torsion (HPT) [1]. Deformation at a temperature below the martensitic finish temperature (Mf) promotes the amorphization [2]. A NiTi alloy and a NiTiHf alloy that are martensitic at room temperature (RT) but have different values of Mf (~30 and 110°C, resp.) were subjected to HPT at RT and analysed by transmission electron microscopy (TEM). Discs (8mm ø, 0.8 mm thick) were deformed by HPT (4 GPa, 12 turns). TEM specimens were punched out at a distance of 2.7 mm from the centre of the HPT discs corresponding to a deformation of 250. TEM was carried out at 200 kV. The phase structure was analysed by selected area diffraction pattern (SADP) methods. The TEM bright field image of Fig. 1a shows the heterogeneous microstructure of NiTi obtained by HPT. Band shaped areas of highly strained and fragmented martensitic grains (cf. A in Fig. 1a and the corresponding SADP in Fig. 1b). Martensite was observed containing nanoscale (001) compound twins; these deformation twins could facilitate the amorphization acting as obstacles and causing dislocation accumulation [3]. Amorphous phase occurs near A since in Fig. 1b diffuse rings superimpose the diffraction spots of the crystalline lattice. Areas that contain a mixture of a nanocrystalline and an amorphous phase are observed near B in Fig. 1a (cf. the corresponding SADP of Fig. 1c showing a ring pattern containing diffraction spots of the nanocrystals and broad diffuse rings of the amorphous phase). Diffraction rings were observed that correspond to B2 and B19´. Therefore, in some of the nanograins a reverse transformation from the martensite to the austenite was induced during the HPT. Compared to NiTi, considerably less nanocrystalline and amorphous phase is observed in NiTiHf after HPT (cf. Fig. 2). B2 austenite is not observed in SADP of NiTiHf. NiTiHf contains rather large grains (> 300 nm) with relatively few dislocations leading to moderate lattice strains only. A stripe like contrast is frequently observed that might arise by a twinned martensitic lattice. The present results indicate that dynamical recovery hinders dislocation accumulation and therefore the formation of a nanocrystalline structure and the transition to an amorphous phase. 1. 2.

T. Waitz, V. Kazykhanov, H.P. Karnthaler, Acta Mater. 52 (2005) p. 137. S.D. Prokoshkin et al., Acta Mater. 53 (2005) p. 2703.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 489–490, DOI: 10.1007/978-3-540-85226-1_245, © Springer-Verlag Berlin Heidelberg 2008

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H. Nakayama et al., Mater. Trans. 42 (2001) p. 1987. The authors thank the group of Prof. R. Pippan for the kind help with the HPT deformation. Support by the research project "Bulk Nanostructured Materials" within the research focus "Materials Science" of the University of Vienna and the I.K. "Experimental Materials Science – Nanostructured Materials" a college for Ph.D. students is acknowledged.

Figure 1. HPT NiTi (a) TEM bright field image showing highly deformed and fragmented grains (near A) and a mixture of nanograins and amorphous phase (near B). (b) and (c) SADP of the areas marked by A and B, resp., in (a).

Figure 2. HPT NiTiHf. (a) TEM bright field image of twinned grains containing relatively few dislocations. (b) SADP of the area encircled in (a) showing diffraction spots and weak diffuse rings caused by a small volume fraction of amorphous phase.

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TEM studies of nanostructured NiTiCo shape memory alloy for medical applications D. Stróż and Z. Lekston Institute of Material Science, University of Silesia, Bankowa 12, 40-007 Katowice Poland [email protected] Keywords: shape memory effects, nanocrystalline microstructure, interface structure

The NiTi shape memory alloys have been widely studied over the last 50 years as they show the best functional properties and find applications in many different fields of industry and medicine. Recently, seeking for still improved properties of these alloys, the attentions was focussed on the opportunity of controlling the alloy structure by adjusting their crystallisation conditions. The alloys are subjected to severe plastic deformation - leading to their amorphization - and then annealed at relatively low temperatures that produces nanocrystalline structure of the required grain size [1-4]. It was found that if the grains size is less than 60 nm only the R phase transformation can occur in the alloy, while the grains larger then 150 nm contained the B19’ martensite only that showed a unique “herring-bone” structure [3]. In the recent work the binary NiTi alloy was modified by addition of 1.3 at.% of Co substituting nickel that improved the alloy workability [5]. It was designed for producing implants in form of clamps used in surgical treatment of mandibular fractures. In order to ensure the recovery temperatures close to the human body temperature and optimise its functional properties, the alloy was subjected to different thermo-mechanical treatment, one of which was cold-rolling and annealing. Samples in form of 2 mm wire were cold rolled by 30% and then annealed at the temperature range 350oC – 600oC. It was found that annealing at 350oC and 400oC produced nanocrystalline structure where the grain sizes varied from about 50 – 200 nm (Figure 1). The specimens showed a very good superelasticity effect caused by the R-phase transformation. The B19’ martensite was not formed in these samples – as could be seen at the DSC curves. The TEM observation carried out at room temperature showed mainly the B2 phase in the sample, occasionally in same grains the R-phase was found. The HREM studies of the grain boundaries structure revealed that many of them were coherent twin boundaries (Figure 2). Often small angle boundaries were also observed. This could be the reason of the good functional properties of these samples. 1. 2. 3. 4. 5.

C. Rentenberger, T. Waitz, H.P. Karnthaler, Scripta Materialia 51 (2004), p.789 T.Waitz, H.P.Karnthaler, Acta Materialia 52 (2004), p. 5461 T. Waitz, Acta Materialia 53 (2005), p. 2273 X.Wang, J.J. Vlassak, Scripta Materialia 54 (2006), p. 925 J. Drugacz, Z. Lekston, H. Morawiec, K. Januszewski, J. Oral Maxillofac.Sur. 53 (1995), p. 665

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 491–492, DOI: 10.1007/978-3-540-85226-1_246, © Springer-Verlag Berlin Heidelberg 2008

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a

b

Figure 1. Nanocrystalline structure of the cold-rolled and then annealed at 350oC/1h NiTiCo alloy – bright field (a) and dark field (b) images

a

b

c

Figure 2. High resolution image of a grain boundary between the nanograins (a) and the processed image (b) showing the twin relationship between both grains obtained by filtering the FFT (c)

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TEM investigations of microalloyed steels with Nb, V and Ti after different treatments G. Szalay1, R. Grill2, K. Spiradek-Hahn1, and M. Brabetz1 1. Austrian Research Centers GmbH- ARC, Advanced Materials and Aerospace Technology, Alloy Development Group, 2444 Seibersdorf, Austria 2. voestalpine Grobblech GmbH, Voestalpine-Str. 3, 4020 Linz, Austria [email protected] Keywords: low carbon steel, heat treatment, carbides

The low carbon steel microalloyed with Nb, V, and Ti has been thermomechanically rolled with subsequent accelerated cooling (TM+DIC). This results in a homogeneous fine grain microstructure which leads to high strength and ductility [1]. Additionally a part of this material has been quenched and tempered (TM+DIC+QT). For the analysis of the microstructure a FEI CM-20 STEM Transmissionelectronmicroscope at an acceleration voltage of 200kV was used. The TEM is equipped with a secondary electron detector (SE) for scanning the foil surface and a energy dispersive X-ray spectrometer (EDX) for chemical analysis. For the analysis of the crystal structure of the precipitates electron diffraction was used. The chemical composition of the particles was analysed by EDX. HRTEM investigations on ultra-fine precipitates were carried out with a FEI Tecnai F20 at 200kV. The initial state (TM+DIC) exhibits fine long and narrow grains as a result of thermomechanical rolling with a lathlike substructure inside the grains. At the grain boundaries and lath interfaces a very low density of cementite precipitates was observed (cf. Fig 1a). Layers of retained austenite were present at the lath interfaces (cf. Fig 1b). Inside the laths a low density of cementite (50-80nm in size) and near cubic TiC or (Ti,Nb)C precipitates (50-100nm in size) were inhomogeneous distributed (cf. Fig 1c). Contrary to this the additionally quenched and tempered steel (TM+DIC+QT) shows a high density of homogeneous distributed precipitates at laths interfaces and grain boundaries (cf. Fig 2a) identified by electron diffraction as cementite. No more retained austenite at lath interface has been observed. Inside the laths coarse cementite (50300nm) and (Ti,Nb) carbides (50-100nm), with near cubic morphology and fine (filling) of the baseline varied from +7.7µm (marginal excess) to -20.3µm (negative ledge), average value -2.0µm (Figure 2). After 5 or 10 years at the latest, the maximum loss of the filling material above the interface was estimated between -7.2 and -48.4µm, depending on the baseline situation, average value: -27.0µm after 10 years. A fifteen-year use of most of the restorations showed reduced negative ledges of between -9.0 and -46.8, average value: –22.0µm. These investigations proved an increasing marginal filling material loss during the first five years (Figure 1a, b) causing negative enamel-filling ledges. Between 5 and 10 years, the margin near abrasion of enamel and filling was nearly the same (Figure 2). Between 10 and 15 years, the lowering of the negative ledges (Fig 1c, 2) was a result of the preponderance of the enamel abrasion. The quantitative long-term 3-D SEM evaluation of Visio Molar filling restorations of human teeth proved that the margin near loss of the filling material is limited and does not importantly affect the longevity of these restorations nor the secondary caries at the hard tissue-filling interface. This method is a valuable addition to the clinical and usual micromorphological evaluations. S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 729–730, DOI: 10.1007/978-3-540-85226-1_365, © Springer-Verlag Berlin Heidelberg 2008

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J.F. Roulet, B. Salchow and M. Wald, Dent. Mater. 7 (1991), 44. P. Gaengler, I. Hoyer, R. Montag and P. Gaebler, J. Oral Rehabil. 231 (2004), 991 R. Stoll, M. Gente, M. Palichleb and V. Stachniss, Dental Materials 23 (2007), 145 W. Dietz, S .Meineber, U. Kraft, I. Hoyer and E. Glockmann in Proceedings of the Microscopy Conference 2005, Davos Switzerland 28.8.-2.9.2005, ISSN1019-6447

100µm Pl

1a

E F

1b

1c Figure 1. Profile reconstruction of an enamel-filling (Visio Molar) margin. 1 (1a), 5 (1b) and 15 (1c) years after application. Pl: profile-line, E: enamel, F: filling.

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-10,0 -15,0

-12,7

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Figure 2. Long-term marginal filling material loss of dental fillings (Visio Molar): development of negative enamel-filling ledges (µm) over 15 years.

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The analysis of Si doped hydroxyapatite coatings using FIBSEM, TEM and RHEED H.K. Edwards1, S. Coe1, T. Tao1, M.W. Fay2, C.A. Scotchford1, D.M. Grant1 and P.D. Brown1 1. School of Mechanical, Materials and Manufacturing Engineering, 2. University of Nottingham Nanotechnology and Nanoscience Centre, both at the University of Nottingham, University Park, Nottingham, NG7 2RD, UK. [email protected] Keywords: FIBSEM, RHEED, EELS, EFTEM, hydroxyapatite, biomaterial

Silicon doping has been found to enhance the in vitro and in vivo bioactivity of hydroxyapatite (HA) [1,2], a bioceramic widely used in orthopaedic implants. The atomic arrangement of the Si within the HA structure and the exact role of the dopant on bioactivity are not completely understood [3]. Therefore, the effect of Si dopant levels on the HA thin film structure and chemistry has been examined using the combined techniques of transmission electron microscopy (TEM), selected area electron diffraction (SAED), scanning TEM (STEM), electron energy loss spectroscopy (EELS), energy filtered TEM (EFTEM) and energy dispersive X-ray (EDX) mapping, along with complementary scanning electron microscopy (SEM), X-ray diffraction (XRD) and reflection high energy electron diffraction (RHEED). Si-HA/Ti samples containing 0, 1.8, 4.2 and 13.4 wt.% Si were prepared by plasma assisted RF sputtering of HA (~200 nm thickness) using a multiple target unbalanaced magnetron configuration onto 10 mm by 1 mm Ti discs, followed by heat treatment at 600 ºC under flowing Ar. Due to the composite nature of the Si-HA/Ti samples, focused ion beam scanning electron microscopy (FIBSEM) has been employed for the preparation of cross sectional TEM samples. Specimens were prepared using an FEI Quanta 200 3D FIBSEM fitted with a Quorum cryo-transfer unit, an Omniprobe micromanipulator and an INCA Oxford Instruments EDX analysis system. Following deposition of a protective W coating, FIBSEM milling for lift-out was carried out using sequential ion beam currents of 20 nA down to 30 pA. Electron transparent specimens were inspected using a JEOL 2100f TEM and a liquid nitrogen cooled sample holder. Reference TEM and SAED results found that the pure HA thin film (0 wt % Si) had a polycrystalline structure (Figure 1). RHEED and XRD results indicated that a high concentration of Si destabilises the HA structure, causing the coatings to exhibit smaller HA crystallites and become increasingly amorphous. Preliminary STEM-EELS investigations showed a homogeneous Si, Ca and P dispersion throughout a 13.4 wt % Si - HA thin film on Ti, indicating that Si does not preferentially segregate to HA grain boundaries (Figure 2).

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 731–732, DOI: 10.1007/978-3-540-85226-1_366, © Springer-Verlag Berlin Heidelberg 2008

732 1. 2. 3. 4. 5.

I. Gibson, S. Best and W. Bonfield, J. Biomedical Materials Research, 44 (1999) p. 422. I. Gibson et al., Key Engineering Materials, 218 (2002) p. 203. D. Arcos et al., J. Biomedical Materials Research, 78A (2006) p. 762. This work was supported by the EPSRC under grant EP/E015379/1. The authors kindly acknowledge Joanne Hampshire at Teer Coatings Ltd. for the deposition of the HA thin films.

Figure 1. Bright field TEM image and SAED patterns of a pure (0 wt % Si) HA thin film on Ti and the protective W coating laid down during FIB preparation. The Ti and W coating were found to be crystalline while the HA thin film was polycrystalline.

Figure 2. Elementally sensitive maps derived from STEM-EELS analysis of a 13.4 wt % Si - HA thin film on Ti, showing a homogeneous distribution of Si, Ca and P within this coating on the 10 nm scale.

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Electron microscopic investigations of the polymer/mineral composite material nacre K. Gries1,2, R. Kröger3, C. Kübel4, M. Fritz1 and A. Rosenauer2 1. University of Bremen, Institute of Biophysics, Otto-Hahn-Allee 1, 28359 Bremen, Germany 2. University of Bremen, Institute of Solid State Physics, Otto-Hahn-Allee 1, 28359 Bremen, Germany 3. University of York, Department of Physics, Heslington, York YO10 5DD, United Kingdom 4. Fraunhofer Institute for Manufacturing Technology and Applied Materials Research (IFAM), Wiener Straße 12, 28359 Bremen, Germany [email protected] Keywords: nacre, TEM, mineral bridge

Nacre of the mollusc Haliotis laevigata was investigated using transmission electron microscopy (TEM). Nacre, the inner iridescent layer of mollusc shells, is a typical example for a material which is formed by biomineralization processes. It is composed of the CaCO3-polymorph aragonite and a small amount of about 5wt% organic matter [1]. The polygonal shaped aragonite platelets show a width which ranges from 5μm to 10μm and a thickness of about 500nm [2]. They are laterally arranged in layers and vertically in stacks. The aragonite crystal structure can be described by the space group Pmcn 62 with the c-axis perpendicular to the face of the platelets and thus to the surface of the shell [3]. The platelets are separated by layers of organic material, the organic matrix. This arrangement resembles a brick and mortar like structure. The combination of stiff crystalline material and soft organic material, as well as the layered structure increase the fracture toughness in comparison with pure (geological) aragonite. In TEM investigations structures which are located within the organic layer between stacked aragonite platelets were observable (marked in Figure 1 by a white arrow). Electron tomography investigations showed that these structures connect the stacked platelets. High resolution TEM allowed a detailed analysis of these structures, the socalled mineral bridges, and revealed that they consist of aragonite which exhibits a constant crystallographic orientation. During the process of growing the orientation of the aragonite might be transferred through the organic matrix via the mineral bridges. To check if stacked platelets exhibit a similar orientation, the tilt of these aragonite platelets against each other was determined from selected area diffraction patterns. It could be shown that the platelets show small relative tilt angles of 700 in both cases.

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Analysis of nano-composites based on carbon nanoparticles imbedded in polymers Kangbo Lu1, Joachim Loos1, Sourty Erwan2, Dong Tang2 1.Laboratory of Materials and Interface Chemistry and Soft Matter Cryo-TEM Research Unit, Eindhoven University of Technology, 5600 MB Eindhoven, the Netherlands. 2. FEI Company, Achtseweg Noord 5, 5600 KA Eindhoven/Acht, the Netherlands. [email protected] Keywords: STEM, electron tomography, quantification, polymer nanocomposites

Nowadays, polymer nano-composite is one of the most interesting research topics of polymer science and materials engineering, especially, when the nano-filler can bring polymer matrix special multifunctional properties. In this case, carbon nano-fillers such as carbon nanotubes (CNTs) and carbon black(CB) are excellent candidates for manufacturing high performance and conductive polymer nano-composites due to their unique properties. Controlling the distribution of carbon nano-fillers in polymer matrix is the key point of improving the material properties. Conventional Transmission Electron Microscopy (CTEM) is the main tool to investigate nanofillers’ distribution. Recently, we have introduced High-Angle Annular Dark Field (HAADF) Scanning Transmission Electron Microscopy (STEM) as a versatile tool for investigation of purely carbon-based functional polymer systems [1]. Due to contrast and sharpness enhancement in HAADF-STEM imaging, morphology details are revealed that are not observable or not as clear in CTEM (Figure 1). Main origin for the contrast achieved in STEM is the density difference between the components of the polymer systems under investigation. As an additional issue, changing the camera length, and hence the minimum scattering angle collected on the HAADF detector, is a way to dosing diffraction contrast in carbon-based crystalline materials. Commonly, polymer materials are electron beam sensitive. In this respect, one advantage of STEM is that the electron dose is low when compared with CTEM. However, in CTEM low dose operation modes are implemented that allow ultimate reduction of the actual dose and thus apply doses that are orders of magnitude lower than for STEM. As consequence, electron beam damage is a critical issue that has to be addressed when applying STEM on polymer systems. Another aspect we like to discuss is the application of tomography for better understanding the local organisation of nano-composites. Commonly, two-dimensional (2D) images are used to provide structure information of the sample. However, 2D images represent a projection of the three-dimensional (3D) volume of the sample, which has a thickness of about 100 nm, which may cause that separated MWCNTs or well distributed CB seem to overlap in the projection. Thus 3D volume information is very helpful in our study to better understand nano-scale organization of polymer composites [2].

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 769–770, DOI: 10.1007/978-3-540-85226-1_385, © Springer-Verlag Berlin Heidelberg 2008

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The 3D structure and morphology information can be acquired after reconstruction a series of 2D projections – acquired for both CTEM and HAADF-STEM – which were obtained by tilting the specimen around the tilt axis. The 3D reconstruction of CB/PE composites cross sections are shown in Figure 2. CB is good distributed and forms a conductive network in the polymer matrix. We critically discuss advantages and drawbacks of both CTEM and HAADF-STEM tomography for obtaining quantitative volume data. 1. 2. 3.

Erwan Sourty, Svetlana van Bavel, Kangbo Lu, Ralph Guerra, Georg Bar, Joachim Loos, accepted Ultramicroscopy J. Yu, K. Lu, E.D. Sourty, N. Grossiord, C.E. Koning, J. Loos, Carbon 45, 2897-2903, (2007). The authors would like to thank Erwan Sourty for his help with HAADF-STEM data interpretation. Further, we like to thank Ralph Guerra, Georg Bar and Bob Vastenhout from The Dow Chemical Company, Dow Olefinverbund GmbH, and Dow Benelux B.V., respectively, for their help with the CB/polymer nanocomposite materials. The work forms a part of the Dutch Polymer Institute (DPI) program on quantify polymer nano-composites.

Figure 1. Carbon black embedded in polymer, CTEM (left) vs. HAADF-STEM (right).

Figure 2. Snapshot from 3D reconstruction of the carbon black (gray) imbedded in the polymer matrix.

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New developments in SEM for in situ tensile tests on polymers P. Jornsanoh1, G. Thollet1, C. Gauthier1 and K. Masenelli-Varlot1 1. Université de Lyon, MATEIS UMR 5510, INSA-Lyon, 7 avenue Jean Capelle, 69621 Villeurbanne, France [email protected] Keywords: tensile tests, STEM, SEM, ESEM

Investigations of the microscopic deformation and damage mechanisms give access to very useful information to understand the macroscopic mechanical behaviour of materials. However for non conductive materials, specimens need to be coated with a conductive layer and in some cases the specimen surface has to be chemically prepared to reveal a contrast between the different phases. In situ mechanical testing in a SEM of these materials has been limited to small strain deformation since at larger strain, cracks in the conductive coating induce charging effect and thus hinders the observation of the samples. Moreover in any case and whatever the detection mode - i.e. backscattered electrons (BSE) or secondary electrons (SE) - SEM restricts so far to observations of the sample surface. Conversely to conventional SEM, controlled pressure SEM enables the investigation of non conductive samples without any coating, due to the presence of gaseous molecules in the microscope chamber. This offers the possibility to perform in situ mechanical tests even on non-conductive samples. Moreover, it has previously been shown, during wet-STEM experiments, that the detection of the incident electrons diffused at large angles (HAADF-like mode, further called transmission mode), enables the observation of samples up to a few µm thick with a good contrast [1]. This work presents a new procedure for in situ tensile tests in a SEM, using simultaneously classical detectors and a HAADF-like detector. Both imaging systems were used to explore the changes in the structure of a PVC-based nanocomposite. SE images illustrate the crack initiation and propagation through the specimen (Figure1). Images of crack tips obtained in transmission mode (STEM) show microdeformation and cavitation around the filler particles (Figure2A). The STEM contrast makes obvious the presence of filler particles all along crack paths (Figure 2B). From the images, the local deformation can be completely determined using digital image processing based on images correlation that gives access to the whole deformation field in the sample. 1.

A. Bogner, G. Thollet, D. Basset, P. Jouneau, C. Gauthier, Ultramicroscopy 2005, 104, 290.

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Figure 1. SE image of crack initiation on surface defects

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Figure 2. STEM images of a crack tip (a) and filler particles along the crack path (b)

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A study of the spatial distributions of the carbon blacks in polypropylene composites using TEM-Tomography and quantitative image analysis H. Matsumoto1, H. Sugimori2, T. Tanabe2, Y. Fujita3, H. Sano1 and H. Jinnai2 1. Mitsubishi Chemical Gr. Science and Technology Research Center Inc. 1000 Kamoshida, Aobaku, Yokohama-city, 227-8502, JAPAN 2. Dep. of Macromolecular Science and Engineering, Kyoto Inst. of Technology 3. Japan Polypropylene Co., JAPAN [email protected] Keywords: Transmission electron micro-tomography, Quantitative image analysis, Carbon black / polypropylene electron conductive composites

It is well known that nanometer scale carbon materials such as carbon black (CB) and carbon nanotube were applied for filler of electron conductive polymer composites. However, it seems the knowledge of local structure of those networks is limited, but is imperative for understanding the physical mechanism and for controlling those distributions. It is necessary for us to create innovative methods. In this research, 3D imaging based on TEM of CB aggregates surrounding polymer were carried out. And the algorism, quantitative analysis of interconnecting particles in 3D, was developed by our group. The polymer used in this work was CB/iPP system (Japan Polypropylene, Japan). Concentration of CB in iPP is 5 wt %, and its content volume is above the percolation threshold. The TEM used in this work was a 200kV-TEM ( TECNAI G2 F20, FEI Company, USA) which was equipped field emission gun and post column type imaging filter (GATAN, USA). Alignment and reconstruction of tilt images for tomogram were carried out using gold marker tracking method and filter back projection method, respectively. The used software of computed tomography was IMOD imaging software[1]. Figure 1 shows CB aggregations surrounding iPP matrix. From this result, it was impossible to explain an absolute quantity of interconnecting CB particles, because of the projection principle of TEM. Therefore, TEM-T experiment was carried out, and then, quantitative image analysis developed in our group was applied. Figure 2 shows results of quantitative image analysis at the same area of Fig.1. In this image analysis, interconnecting aggregations were classified each other using the packing particles algorithm developed by H. Jinnai [2] after segmentation of reconstruction images, and all interconnecting pathway of CB particles were calculated. From these processes, CB aggregations in Fig.1 could be separated 5. In Fig.2(a), the biggest one was visualized as orange solid circles. In view of electron charge transfer pathway, if it is capable to assume that the pathway of charge transfer is minimum length between one side and the other side of a CB aggregation, the minimum interconnecting pathway from the network was calculated by the algorism of warshall-floyd method [3]. The pathway of each S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 773–774, DOI: 10.1007/978-3-540-85226-1_387, © Springer-Verlag Berlin Heidelberg 2008

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aggregation were visualized as yarrow and red lines in Figure 2 (b), respectively. The pathway of orange one in Figure 2(a) was measured ca. 1.31 μm (indicating a black arrow). 1. 2. 3.

J.R. Kremer, D.N. Mastronarde and J.R. McIntosh, J. Struct. Biol. 116(1996) p.71; D.N. Mastronarde, J. Struct. Biol. 120(1997) p.343; Also://http://bio3d.colorado.edu/imod/. H.Jinnai et al., Macromolecules, 40(2007) p.6758. C. Thomas, L. Charles and R. Ronaid, Introduction of algorithms, first edition. MIT press and McGrawHil, US, (1990).

500 nm Figure 1. Bright field TEM image of aggregated CB surrounding iPP matrix.

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Figure 2. the results of quantitative image analysis of CB aggregates in Fig.1. (a) A segmented digital slice image. Each color-label indicates interconnecting CB aggregates, and (b) a volume rendering image.

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A study of the chain-folded lamellae structure and its array in the isotactic polypropylene spherulites by HAADF-STEM and HV-TEM Tomography techniques H. Matsumoto1, M. Song2, H. Sano1, M. Shimojo2,3 and K. Furuya2 1. Mitsubishi Chemical Gr. Science and Technology Research Center Inc. 1000 Kamoshida-cho, Aoba-ku, Yokohama, 2278502, Japan 2. High-Voltage Electron Microscopy Station, Dep. of Materials Infrastructures, National Inst. for Materials Science, sakura 3-13, Tsukuba, Ibaragi, 3050003 Japan 3. Saitama Inst. of Technology, Fusaiji 1690, Fukaya, Saitama, 3690293, Japan [email protected] Keywords: HAADF-STME and HV-TEM tomography / isotactic polypropylene, 3D array of chain-folded lamellae structures

It seems that the knowledge of the morphologies of chain-folded lamellae structure in the bulk crystalline polymers is limited, however, in industry, is out of necessary to understand increasing mechanical properties. Why had not TEM investigations been advanced? In this answer, two reasons can be thought as follows; 1) Misfit between wide length scales of crystalline polymer, which is classified 3 scales; unit cell (subnanometer), chain-folded lamellae (thickness: 10 nm, lateral dimensions: several um), and finally, spherulites (from μm to mm), and the penetration power of convergent TEM. 2) The lamellae structures in a TEM image are only that of edge-on type in the specimen because of 2D projection principle. In view of wide length scales of lamellae structures, new methods; 3D and high penetration power of HV-TEM observation are very appropriate techniques. In this research, HAADF STEM and HV-TEM tomographic investigation of 3D lamellae structure in isotactic polypropylene spherulites (iPP, Japan Polypropylene Co., Japan) were carried out. The stained specimens for HAADF-STEM and HV-TEM tomography were prepared using the ultra-microtorm-sectioning and the focused-ion-beam techniques, respectively. Those tilt series for tomography were alimented and reconstructed using IMOD software developed by Mastronarde et al [1]. Figure 1 shows a 3D surface rendering image of a cross-section of a spherulite reconstructed from HAADF-STEM tilt series. Multi lamellae structures were visible and classified mother (red) and daughter (green) lamellae structures. Almost the all lamellae structural entities in spherulites were built up by daughter lamellae structure, which were explained growth from mother lamellae by Lotz[2]. However the sample thickness for HAADF-STEM was limited and lateral length of lamellae could not be measured.

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Figure 2 shows bright field HV-TEM images of iPP at different tilt angles. The Rodshape specimen in diameter 1.2 μm could be obtained by the HV-TEM, and lamellae structures were visible at each tilt angles as white lines. In this presentation, the shape of lamellae structure and its array in a iPP spherulites based on HV-TEM tomography will be discussed. 1. 2.

1. J.R. Kremer, D.N. Mastronarde and J.R. McIntosh, J. Struct. Biol. 116(1996) p.71; D.N. Mastronarde, J. Struct. Biol. 120(1997) p.343; Also://http://bio3d.colorado.edu/imod/. 2. B. Lotz, J.C. Wittman: J.Polym.Sci., Ed., 24(1986), p. 1541.

Figure 1 A surface rendering image of lamellae structure in iPP. Mother lamellae and daughter lamellae were identified by the pre-observation of nucleated area. The tiltseries for HAADF-STME tomography was obtained from -75 degrees to +75 degrees, and dual axis method was carried out in order to reduce missing zone.

Figure 2 Bright field HV-TEM images of lamellae structure in iPP. The rod shape specimen was prepared parallel to the redial direction of an iPP spherulete. Mother lamellae was nearly parallel to the rod axis.

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Microstructural analysis of ultra-thin nanocomposite layers fabricated by Cu+ ion implantation in inert polymers G. Di Girolamo1, E. Piscopiello1, M. Massaro1, E. Pesce1, C. Esposito1, L. Tapfer1, M. Vittori Antisari2 ENEA, Dept. Adv. Phys. Technol. and New Materials (FIM), 1.Brindisi Research Center, Strada Statale “Appia” km 713, 72100 Brindisi, Italy 2.Casaccia Research Center, Via Anguillarese 301, 00123 Rome, Italy [email protected] Keywords: TEM, ion implantation, polycarbonate

Ion implantation was used to fabricate ultra-thin nanocomposite subsurface layers in inert polymers for applications in mechanics, optics and electronics [1]. Amorphous polycarbonate substrates were implanted at room temperature with low energy Cu+ ions of 60 keV, at 1 μA/cm2 and with doses in a range from 1x1016 to 1x1017 ions/cm2. The nanocomposite surfaces were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), optical absorption spectroscopy and electrical conductivity. Cross-section transmission electron microscopy (XTEM) was used to analyze the microstructure and morphology of the Cu-implanted region. TEM experiments show that nanocrystals are formed at ion doses of 1x1016 ions/cm2 (Figure1). The ionimplanted nanocrystals are located at about 50nm-80nm below the polymer surface, in accordance with TRIM calculations (projected range of 75nm and straggling of 20nm). However, at higher ion doses (5x1016 ions/cm2) a continuous thin nanocrystalline copper films is produced. Figure 2 (b) shows the grazing-incidence XRD patterns (incidence angle = 1°) recorded prior and after Cu-implantation in polycarbonate as well as the corresponding diffraction difference curve. The observed diffraction peaks correspond to copper (cubic phase) in accordance with the ICDD (card no. 851326; JCPDS-ICDD 2000). The XTEM image (Figure 2a) shows a continuous polycrystalline copper films below the polycarbonate surface; the lattice fringes are well observed in the Cu film. Optical absorption spectra show a surface plasmon resonance at 2eV suggesting the formation of nanocrystalline Cu films. This characteristic SPR peak is well pronounced for doses of 5x1016 ions/cm2, while at higher doses the SPR peak is smeared out. This finding is in agreement with the XRD and TEM results that indicate a damaged and structurally disordered film for doses of 1x1017 ions/cm2. In addition, electrical conductivity measurements clearly show a reduced electrical resistance for the samples implanted with a doses of 5x1016 ions/cm2, in accordance with the formation of a continuous metallic film (Figure 2). However, no electrical conductivity could be measured for doses of 1x1016 ions/cm2, since only isolated nanocrystals (no continuous films) are formed. Also higher doses (1x1017 ions/cm2) are detrimental for the electrical properties due to the induced ion radiation damage. 1.

D. Fink, Transport Processes in Ion-Irradiated Polymers, Springer-Verlag (2004)

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Figure 1. – XTEM image of Cu-implanted polycarbonate with 60 keV Cu+ and dose of 1x1016 ions/cm2. Cu nanoparticles (diameter Ø=4-10nm) are located at about 40nm from the surface. Images (a) and (b) are taken from the same sample but at different magnification.

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Figure 2. – (a) XTEM image of Cu-implanted polycarbonate showing the formation of a continuous nanocrystalline copper film below the polycarbonate surface. (b) Grazingincidence X-ray diffraction patterns of the polycarbonate prior and after the Cuimplantation; the diffraction difference curve exhibits the characteristic Bragg peaks of the cubic copper.

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In-situ experiments on soft materials in the environmental SEM – Reliable results or merely damage? P. Poelt1, H. Reingruber2, A. Zankel1 and C. Elis1 1. Institute for Electron Microscopy, Graz University of Technology, Steyrerg. 17, A-8010 Graz, Austria 2. Institute of Experimental Physics, Graz University of Technology, Petersg. 16, A-8010 Graz, Austria [email protected] Keywords: environmental SEM, soft materials, irradiation damage

The conventional high vacuum scanning electron microscope is an instrument which is mainly used for the analysis of solid materials. In contrast, the environmental scanning electron microscope (ESEM) is also ideally suited for the operation and control of a great variety of dynamic experiments. Since the type of gas in the specimen chamber, the relative humidity in case of water vapour as gas, the gas pressure and the specimen temperature can be varied over a broad range, an ESEM forms a sort of micro reactor, where the wetting, melting, recrystallization, corrosion … of materials can be investigated. Additionally, no coating of non-conductive materials is necessary to prevent charging. All this seems to make the ESEM an excellent tool for the investigation of soft materials and also their behaviour in a wet environment. But several shortcomings make these experiments much more difficult and the results less reliable than one would predict beforehand. Firstly, soft materials are mainly carbonaceous and therefore give notoriously poor contrast. In the low vacuum the contrast decreases additionally with increasing pressure. Although this could be compensated for by an increase in the probe current, a concurrent increase in the irradiation damage makes this very often impossible [1]. But in many cases a thin coating of the material with e.g. chromium or gold suffices to substantially reduce the damage. Moreover, the presence of water can strongly increase the amount of the irradiation damage due to the formation of highly mobile and reactive free radicals [2, 3]. It can also change the wetting behaviour of the material. Figure 1 shows that both the wetting of a material and its drying-up can be affected by the electron irradiation. But the Figures 2 and 3 prove that despite all these shortcomings the ESEM can be a very valuable tool for in-situ experiments of soft materials. A new and exciting application is automated ultra microtomy in the ESEM and the 3D-representation of the internal structure of materials [4]. Other applications are for example the fracture behaviour of textile fibres in dependence on the relative humidity in the specimen chamber or the imaging of the transport of fluids through porous media [5]. 1. 2.

G.D. Danilatos, Adv. Electronics and El. Phys. 71 (1988), p. 109. C.P. Royall, B.L. Thiel and A.M. Donald, J. Microsc. 204 (2001), p. 185.

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3. 4. 5. 6.

L.M. Jenkins and A.M. Donald, SCANNING 19 (1997), p. 92. W. Denk and H. Horstmann, PLoS. Biol. 2(11) (2004), e329. H. Reingruber, P. Poelt and B. Holst, Proc. 5th World Congress on Industrial Process Tomography, Bergen, Norway (2007), p. 23. We thank Gatan GmbH and Mr. B. Kraus for making the ultra microtome 3VIEWTM available and Mrs. M. Schaffer for creating the 3D-representation.

Figure 1. Wetting and drying-up of a cellulose nitrate membrane (10 nm Au-coating). Left: Before recording the image, mainly the marked area had been irradiated. Contrary to the surrounding, many of the pores in this area are not filled / fully filled with water (image width: 100 µm). Centre and right: Drying-up is delayed in the irradiated areas (centre) compared to other areas (right). In the irradiated areas strong damage is visible (image width: 42 µm).

Figure 2. 3D-representation of EPR (ethylene propylene rubber) modified iPP (isotactic polypropylene) after a tensile test, stopped at 25% yield and stained with RuO4 (160 slices, slice thickness: 100 nm); black: EPR particles; grey: cracks.

Figure 3. Wetting of a polyethersulfon membrane (nominal pore size: 450 nm) with water in dependence on time (width of the images: 45 µm). Some of the big pores remain partially filled / unfilled. The water was provided by condensation at a Peltier cooling stage.

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Structural studies on V-amylose inclusion complexes J.L. Putaux1, M. Cardoso2, M. Morin1, D. Dupeyre1 and K. Mazeau1 1. Centre de Recherches sur les Macromolécules Végétales, ICMG-CNRS, BP 53, F-38041 Grenoble cedex 9, France 2. Brazilian Synchrotron Light Laboratory, P.O. Box 6192, Campinas, ZIP Code 13083-970, Brazil [email protected] Keywords: amylose, single crystals, inclusion complexes, electron diffraction, HREM, modeling

Amylose, the linear homopolymer of α-D-glucose found in native starch, can be crystallized from dilute solutions by addition of a large variety of organic guests (alcohols, lipids, aromas, etc.) [1,2]. The morphology and structure of the resulting V-type crystals depend on the nature of the complexing molecule and parameters such as degree of polymerization (DP), concentration and crystallization temperature [3]. We have used DP 100 amylose biosynthesized in vitro with phosphorylase [4] to prepare single crystals whose morphology and structure were characterized by scanning and transmission electron microscopy, electron diffraction and molecular modeling [5]. Lamellar V-type complexes prepared in the presence of isopropanol and linalool exhibited a rectangular shape (Figures 2a,b). The electron diffraction patterns recorded perpendicularly to the crystal base plane suggested an orthorhombic unit cell containing 6-fold amylose single helices and guest molecules entrapped inside and/or in-between helices [5,6]. Square single crystals of V-amylose complexed with α-naphthol (Figure 2a) yielded exceptional base-plane electron diffraction patterns, up to a resolution of 0.13 nm (Figure 2b). Lattice images at a resolution of 0.39 nm confirmed that amylose was crystallized as 8-fold single helices, in a tetragonal space group (Figure 2c) [7]. The crystal structure was further investigated by molecular modeling to determine the helical conformation and the location of the α-naphthol guest molecules (Figure 2c). Pseudo-spherocrystals made of lamellar subunits were prepared by recrystallizing concentrated (2 wt% ) amylose solutions. Figure 3 shows two examples of peculiar flower-shaped complexes, crystallized in the presence of quinoline (Figure 3a) and α-naphthol (Figure 3b), respectively. 1. 2. 3. 4. 5. 6. 7.

Y. Yamashita, K. Monobe, J. Appl. Polym. Sci. Part A2 9 (1971), 1471. W. Helbert, Doctoral thesis (1994), Université Joseph Fourier Grenoble I, France. A. Buléon, G. Potocki-Véronèse, J.-L. Putaux, Aust. J. Chem. 60 (2007), 706. S. Kitamura S., Yunokawa H., Mitsuie S., Kuge T. Polym. J. 14 (1982), 93. A. Buléon, M.M. Delage, J. Brisson, H. Chanzy, Int. J. Biol. Macromol. 12 (1990), 25. J. Nuessli, J.-L. Putaux, P. Le Bail, A. Buléon, Int. J. Biol. Macromol. 33 (2003), 227. M.B. Cardoso, J.L. Putaux, Y. Nishiyama, W. Helbert, M. Hÿtch, N.P. Silveira, H. Chanzy, Biomacromolecules 8 (2007), 1319.

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Figure 1. TEM micrographs of single crystals of synthetic amylose complexed with isopropanol (a) and linalool (b); c) base-plane electron diffraction pattern of a Visopropanol amylose single crystal.

Figure 2. Single crystals of synthetic amylose complexed with α-naphthol : a) TEM image of lamellar crystals in plan view ; b) base-plane electron diffraction pattern of one crystal; c) translational average of a HREM image of the crystal lattice recorded along the helical axis. Inset : projection of a tentative molecular model, indicating the position of α-naphthol molecules inside and in-between the 8-fold single helices.

Figure 3. SEM images of pseudo-spherocrystals prepared by recrystallizing synthetic amylose in the presence of quinoline (a) and α-naphthol (b).

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Multilamellar nanoparticles from PS-b-PVME copolymers C. Lefebvre1, J.-L. Putaux2, M. Schappacher1, A. Deffieux1 and R. Borsali1,2 1. Laboratoire de Chimie des Polymères Organiques, CNRS-ENSCPB, 16 Av. Pey Berland, F-33600 Pessac, France 2. Centre de Recherches sur les Macromolécules Végétales, ICMG-CNRS, BP 53, F-38041 Grenoble cedex 9, France [email protected] Keywords: block copolymers, micelles, cryo-TEM, cryo-negative staining

Linear poly(styrene-b-vinylmethylether) (PS-b-PVME) has been synthesized using anionic (PS block) and cationic (PVME block) polymerization [1]. The copolymer was first dissolved in THF, a good solvent for both blocks, and water, a selective solvent of the PVME block, was slowly added. Care was taken to operate at a temperature below the low critical solution temperature (LCST) of PVME in water (about 30°C). The copolymer chains self-assembled and formed micelles. Solutions at concentrations from 0.2 to 1 mg/mL were observed by cryo-transmission electron microscopy (cryo-TEM) using a Philips CM200 'Cryo' microscope [1]. PS56-b-PVME126 (PS volume fraction of 0.44) formed two types of micellar assemblies (Figure 1a). The solutions mostly contained cylinders made of an electron-dense PS core (13 nm) and a hardly visible PVME corona. The tubular aspect of the core suggested that residual THF might be entrapped. Images recorded after cryo-negative staining [2] showed wider wormlike micelles (35 nm), indicating that the embedding stain outlined the corona of the cylinders without penetrating in it (Figure 1b). More remarkable was the presence of multilamellar vesicles made of a varying number of uniformly-spaced concentric layers (Figure 2). PS56-b-PVME126 "onions" consisting of up to 13 layers were observed. By extension of the model proposed to explain the contrast of cylindrical micelles in vitreous ice, we assumed that the electron-dense bilayers (6 nm) of the vesicles were formed by the PS blocks and were regularly spaced by two adjacent PVME coronas. Images recorded with a larger defocus revealed the presence of the outer PVME corona (Figure 2b). Work is in progress to determine if the multilamellar vesicles are built by shearing of larger lamellar assemblies [3,4] or through a layer-by-layer mechanism [5,6]. Such PS-b-PVME "solid onions" may constitute interesting multicompartmented nanovectors for encapsulation and controlled release of active molecules. 1. 2. 3. 4. 5. 6.

C. Lefebvre. Doctoral thesis, Bordeaux University (2007). S. De Carlo, C. El-Bez, C. Alvarez-Rúa, J. Borge, J. Dubochet, J. Struct. Biol. 138 (2002), 216. F. Gauffre and D. Roux, Langmuir 15 (1999), 3738. O. Regev and F. Guillemet, Langmuir, 15 (1999), 4357. M. R. Talingting, P. Munk, S. E. Webber, Z. Tuzar, Macromolecules 32 (1999), 1593. H. Shen and A. Eisenberg, Angew. Chem. Int. Ed. 39 (2000), 3310.

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Figure 1. Cryo-TEM (a) and cryo-negative staining (b) images of wormlike micelles formed by PS56-b-PVME126 in water.

Figure 2. Cryo-TEM images of multilamellar particles formed by PS56-b-PVME126 in water. The particles are made of 1 and 2 (a), 4 (b) and 6 (c) concentric vesicles.

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TEM/SEM characterisation of hybrid titanoniobiates used as fillers for thermoplastic nanocomposites R. Retoux1, S. Chausson1, L. Le Pluart2, J.M. Rueff1 and P.A. Jaffres3 1. CRISMAT, UMR CNRS 6508, ENSICAEN, and 2. LCMT, UMR CNRS 6507 6 Bd du Maréchal Juin, 14050 Caen cedex France 3. CEMCA, UMR 6521, Faculté des Sciences et Techniques, Université de Bretagne Occidentale, 6 Av. Le Gorgeu, 29238 Brest France [email protected] Keywords: TEM, STEM SEM, nanocomposite, hybrid layered materials, titanoniobates

Layered-silicates such as montmorillonite (MMT) have been widely studied as nanofillers to improve the physical properties of polymers (strength, thermal and barrier effects) [1]. Thermoplastic nanocomposites have been characterized combining X ray diffraction and Electron Microscopy techniques. Here we present the results obtained on hybrid nanocomposites where a modified layered titanoniobate has been used to fill two types of polymers, polyethylene (PE) and polyamide 12 (PA12) [2,3]. This mineral oxide, parent of KTiNbO5 [4], presents the advantage of having a well-defined structure at an atomic scale compared to layered silicate clays [5]. It also allows obtaining particles with a high degree of purity, leading to an easier characterisation of the layers by XRD and a greater regularity of the hybrid structures. Electron Microscopy is here used to establish structure-properties relationships of the nanocomposites at nanoscale. First we showed that the intercalation of N-alkyl amines in the interlayer space of the pristine titanoniobate KTiNbO5 (Fig. 1) improve the dispersion and the exfoliation of the oxide in the both polymer matrixes (PE and PA12). Second, the type of matrix strongly influences the exfoliation degree of the nanofiller in the hybrid nanocomposite. Contrary to PA12, in PE, the nanofiller presents tactoids ranging from a few sheets to numbered thicker particles made of several sheets. Figure 2 present respectively (a) the partially exfoliated sheets in an apolar PE and the full exfoliation in a polar PA12 (b). The figure 3 shows the SEM and STEM EDS mappings of these sheets showing that during the melt intercalation of the filler in the matrix no chemical modification of the filler occurs. There is no diffusion of the Ti and Nb atoms in the matrix. One of the main aims of this study is to improve properties like, here for example, thermomechanical properties. This is illustrated in figure 4 for PE and PA12 filled with pristine KTiNbO5 modified by octadecylamine compared to the neat polymers. 1. 2. 3. 4. 5.

A. Okada, O. Kawasumi, A. Usuki, Y. Kojima et al., Mater. Res. Soc. Proc. 171 (1990). S. Chausson, V. Caignaert, R. Retoux, J.M. Rueff et al l, Polymer, 49, 2, (2008), p. 488. S. Chausson, R. Retoux, J.M. Rueff, L. Le Pluart, and P.A. Jaffres, to be submitted. A. Grandin, M.M. Borel and B. Raveau, Journal of Solid State Chemistry 60 (1985), p. 366. A. Beigbeider, S. Bruzaud, P. Médéric, T. Aubry, Y. Grohens, Polymer, 46 (2005), p. 12279.

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(a) (b) Figure 1. SEM images showing the increase of the interlayer space in the amine intercalated oxide (a) compared to the pristine compound KTiNbO5 (b) . 50 nm

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Nb L

G' (MPa)

(b) (a) Figure 3. SEM and STEM images and EDS mappings of PE-C18 5% (a) and PA-C18 5% (b) showing that in both cases the modified titanoniobate has not been deteriorated by the exfoliation process. Table I Improvement of the thermomechanical properties. 1x1 0

9

1x1 0

9

9x1 0

8

8x1 0

8

7x1 0

8

6x1 0

8

5x1 0

8

4x1 0

8

3x1 0

8

2x1 0

8

1x1 0

8

T° at G'100 km. Burgers vectors of dislocations in coesite are [100], [001], and [110] (i.e., a, c, and a+b). The (110) plane could be identified as a slip plane. Small prismatic dislocation loops with Burgers vector [010] are also observed and possibly represent water-related defects. The presence of fluids is also obvious from numerous bubbles occurring on {101} Brazil twin boundaries in surrounding quartz. At great depth, the water was probably dissolved in coesite and was then liberated by the back transformation to quartz occurring during exhumation. Metamorphic diamonds from UHP gneisses of the Erzgebirge occur as inclusions in garnet, too and are surrounded by a number of other phases. TEM-EDX analyses show that the mineral assemblage around diamond is composed of intercalated sheet silicates (potassic and sodic micas, chlorite), anatase, quartz, plagioclase, apatite and other rare earth element phosphates (Figure 1). Since most of these phases are hydrous, it was concluded that diamond formed from supercritical C-O-H fluids [4,5], which reacted with surrounding garnet. In order to resolve the question of the redox reaction that led to the precipitation of elemental carbon as diamond, the iron oxidation state of sheet silicates was measured by electron energy loss spectroscopy (EELS). The sheet silicates are anomalously enriched in Fe3+, suggesting an oxidation of iron, compensated by the reduction of the carbon-bearing precursor (possibly CO2).

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The α-PbO2-structured TiO2 high-pressure phase was recently observed as nanosized slab in a twinned rutile from a diamondiferous gneiss of the Erzgebirge, as well [6]. This TEM study suggests a formation of the TiO2 high-pressure phase by martensitic shear deformation. Our reinvestigation of TiO2 phases from diamondiferous gneiss of the Erzgebirge reveals, however, a completely different microstructure. Rutile crystals contain only few dislocations and are devoid of planar defects. The difference in the observed microstructures may be explained by heterogeneity in deviatoric deformation component. Altogether, the TEM observations suggest that subducted crustal rocks can be exhumed from depths up to 150 km. At this depth, supercritical fluids are liberated by decomposition of volatile-bearing minerals in the subducted slab. These fluids influence the transformation kinetics of high-pressure minerals and result into mineral-forming redox reactions. 1. 2. 3. 4. 5. 6.

C. Chopin, Contrib. Mineral. Petrol. 86 (1984), p. 107-118. N.V. Sobolev, V.S. Shatsky, Nature 343 (1990), p. 742-745. F. Langenhorst, J.P. Poirier, Earth Planet. Science Lett. 203 (2002), p. 793-803. B. Stöckert, J. Duyster, C. Trepmann, H.J. Massonne, Geology 29 (2001), p. 391-394. F. Langenhorst, Mitt. Österr. Miner. Ges. 148 (2003), p. 401-412. Hwang S.L., Shen P., Chu H.T., Yui T.F., Science 288 (2000), p. 321-324.

C

Si

K

Na

P

Ti

Garnet

Diamond

Paragonite

Monazite

Figure 1. STEM image and corresponding element maps of a diamond-bearing inclusion in garnet from the Erzgebirge, Germany.

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Characterization of a (021) twin in coesite using LACBED and precession electron diffraction P. Cordier1 and D. Jacob1 and H.-P. Schertl2 1. Université des Sciences et Technologies de Lille Laboratoire de structure et propriétés de l’état solide – UMR CNRS 8008 59655 Villeneuve d’Ascq Cedex, France 2. Institut für Geologie, Mineralogie und Geophysik, Ruhr-Universität Bochum, D44780 Bochum, Germany [email protected] Keywords: precession electron diffraction, LACBED, twin, dislocations

Coesite is a high-pressure polymorph of silica stable in the pressure range 2.5-9 GPa, which corresponds to a minimum depth in Earth of ca. 90 km. Given the ubiquity of silica at the surface of the Earth, coesite represents a good marker of high-pressure processes. Coesite exhibits a monoclinic symmetry with space group C12/c1. Cell parameters are a = 0.71356, b = 1.23692 and c = 0.71736 nm, with β = 120.34°. While monoclinic in symmetry, the coesite lattice has almost hexagonal dimensions with a chex/ahex ratio of 1.73. It is thus possible to describe the coesite structure within a pseudohexagonal cell. In this study, electron diffraction has been used to characterize a (021)-twin in a metamorphic coesite from Parigi, Dora Maira Massif, Western Alps. Due to the quasihexagonal dimensions of coesite, indexation of spot patterns obtained in conventional diffraction is impossible. Two techniques have been used to characterize this defect: large angle convergent beam electron diffraction (LACBED) and precession electron diffraction (PED). In LACBED, the large number of hkl Bragg lines which can be observed enables the determination of absolute orientations (Figure 1). With PED, the absolute indexation of the patterns is made possible through the possibility of measuring spots intensities (Figure 2). In both cases, the orientation relationships between adjacent parts of the twin are characterized unambiguously. The twin is described as a rotation of 89.94° around the [100] axis of the monoclinic C12/c1 coesite. This microscopic description is fully consistent with original descriptions of twinning in synthetic coesite.

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Figure 1. LACBED patterns taken on one side of the twin (variant A) (a), on the twin area (b) and on the other side of the twin (variant B) (c). In (b), the trace of the twin plane is visible and parallel to (021)A and (02-1)B Bragg lines. The mirror symmetry induced by the twin is clearly seen in the enlarged areas of the patterns in (b) and not present in patterns from either the A or B variants.

Figure 2. Experimental patterns taken on each part of the twin for [110] (a and c) and [101] (b and d) orientations.

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Rubens in the Prado National Museum: analytical characterization of ground layers M.I. Báez1, L. Vidal1, M.D. Gayo2, J. Ramírez-Castellanos3, J.L. Baldonedo4 and A. Rodríguez4 1. Dpto. Pintura-Restauración. Universidad Complutense de Madrid (España) 2. Laboratorio Química. Museo Nacional del Prado (España) 4. Dpto. Química Inorgánica. Universidad Complutense de Madrid (España) 5. Centro Microscopía y Citometría. Universidad Complutense de Madrid (España) [email protected] Keywords: Rubens, scanning electron microscopy, artist materials.

The artistic presence of Rubens in Spain is notable and the National Museum of the Prado has an important number of works his. Some of them were made in Spain during their two stays in the Royal court; others come from Ambers (Belgium), where he used to work usually. The peculiar characteristics in the painting method that he used may additionally be useful in dating or authentication of his artworks. Nevertheless, it is important to note that he painted many canvases during his second visit to Spain in a very short time (1628-29). Furthermore, he always used the painting style of his time, such as, reddish ochre grounds from natural colored earths that have a complex chemical composition, (e.g., different aluminosilicates with different ratio of iron oxides). It is proposed to study the grounds that Rubens used in works executed during his time in Spain and at Ambers. The data thus gathered will serve to compare the materials used with one another and with others of the author’s works, also located at the Prado National Museum, regarding which there are reasonable doubts as to whether they were executed in Spain, during his second travel [1]. For the analysis, estratigraphic sections microsamples have been studied, using scanning electron microscopy (SEM), high transmission electron microscopy (HRTEM) and light microscopy (LM), but here we present only the results of SEM examination. For SEM work, samples are included in epoxy resin and prepared in a thin layer on a sample-holder of the same material; the sections must contain all the particles in the microsample unaltered. The obtained results of the study of several microsamples from the canvas entitled “Filopómenes reconocido por unos ancianos en Megara” (1609) (Ambers) (Figure 1), lead to identify the characteristics and nature of the inorganic materials that were used by Rubens. In this occasion, the date and place of the painting are both perfectly dating. Numerous results of the morphologic analysis of the inorganic materials used by Rubens are discussed; moreover, physic-chemical characteristics and chemical distribution (depending on their granulometry, morphology and electronic density) are shown.

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The SEM images of the micro sample sections reveal a number of common general characteristics: considerable compacting in the internal structure of the ground and highly uniform granulometry (Figure 2). Numerous qualitative and semi-quantitative microanalyses by EDS have been performed to locate the pigments and additives used by the artist. The results shows the main and secondary components, such as aluminosilicates containing iron and magnesium, which seem to be an umber earth (Figure 2.a), mixed with different micas (Figure 2.b) and animal-origin calcium carbonate (chalk) (Figure 2.c). Also regular amounts of lead appear; possibly it is the drying used by the artist. 1. This work has been carried forward with funding from the Ministry of Science and Technology under the National Plan for Scientific Research and Technological Development Projects (R&D) (Ref.: HUM2006-01847/ARTE).

Figure 1. Filopómenes reconocido por unos ancianos en Megara (1609). Oil on canvas. Prado National Museum (Madrid).

Figure 2. Ground layer. SEM backscattering sample. a) Aluminosilicate containing iron and magnesium (*). b) Micas (*). c) Chalk (*).

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Development of the FIB-cryo-SEM approach for the in-situ investigations of the elusive nanostructures in wet geomaterials G. Desbois1, J.L. Urai1 1. Structural Geology, Tectonics and Geomechanics, Geological Institute, RWTH Aachen University, Lochnerstrasse 4-20, 52062 Aachen, Germany [email protected] Keywords: FIB-cryo-SEM, geomaterials, halite, clay, elusive structures, grain boundary, porosity

In fluid-filled porous geomaterials, fluid-rock interactions have important effects on their physical and chemical properties. Though the bulk expression of these properties are relatively well known for a number of geomaterials, the relation between nanostructures and macroproperties are poorly understood for a complete understanding of the fluid-rock interactions. Thus, one of the present challenges in experimental geosciences is to directly characterize the structures of the porous media at the nano scale. However, some geomaterials are so fluids-sensitive that investigations on dried samples, required for conventional electron microscopy imaging, are proscribed. For instance, one new alternative for geosciences is to use the cryo-SEM technology which combines the vitrification of the in-situ fluids to stabilize the microstructures and the SEM imaging at high resolution. In addition, the development of ion milling tools, like FIB, directly embedded into the SEM chamber allows the preparation of high quality polished cross-sections suitable for high-resolution imaging. The FIB-cryo-SEM therefore offers a powerful combination for direct and in-situ investigations of the elusive structures in geomaterials at pore scale. We are developing the use of the FIB-cryo-SEM for the study of halite and clays rocks [1,2,3], which are two very important and widespread geomaterials of which the investigations remain difficult due to their high fluid-sensivity. Halite from salt glaciers is much softer than halite in the deep subsurface, and it deforms to very large strains by solution precipitation creep activated by the small grain size and traces of water in the grain boundaries. The role of the small amounts of water in the grain boundaries during this process is not known in any detail. Yet, the use of the FIB-cryo-SEM is suitable to freeze the deformed grain boundary structures which tend to relax fast after removing the active stress, to overcome the problems of dissolutionrecrystallisation artifacts in grain boundary that occurs on dried samples and to give direct evidence of the fluid distribution. In the long term, this will allow us to test the different models for grain boundary structures in solution-precipitation creep, which have been subject of much controversy for the past twenty years. For clays, the morphology of the porosity has a strong effect on many mechanical and transport properties, but its characterization has been mostly indirect until now. On one hand, none of conventionnal approaches is able to directly describe the in-situ porosity at the pore scale, they are limited due to the poor quality of the surfaces which make it difficult to observe and interpret the nanostructures. On the other hand, all of S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 807–808, DOI: 10.1007/978-3-540-85226-1_404, © Springer-Verlag Berlin Heidelberg 2008

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the conventional methods require dried samples in which the natural structure of the pores could be damaged due to the desiccation and dehydration of the clay minerals. We have started to study fine grained Boom clays (Belgium) which are of special interest because it is considered as a potential host formation for the geological disposal of highlevel and long-lived radioactive waste. This study will be the basis for models of transport and chemical reactions in fine grained materials. Our first investigations on wet halite and wet clay materials are very promising and show that it is possible to stabilize the in-situ fluids in grain boundaries or pores by rapid cooling, preserve the natural structures at nano scale, use the FIB milling tool for producing high quality polished cross-sections and for serial-sectioning to reconstruct accurately the grain boundary and the pore space networks in 3D. Thus, we have validated the use of the FIB-cryo-SEM technology for the in-situ investigations of the elusive structures in wet geomaterials without any damages or artifacts. This opens a new field of applications in geosciences. 1. 2. 3.

Desbois G. and Urai J.L. (In submission). In-situ morphology of the meso-porosity in Boom clay (Mol site, Belgium) inferred by the innovative FIB-cryo-SEM method. Geology. Desbois G., Urai J.L., Burkhardt C., Drury M.R., Hayles M. and Humbel B. (2008). Cryogenic vitrification and 3D serial sectioning using high resolution cryo-FIB SEM technology for brine-filled grain boundaries in halite: first results. Geofluids 8 (1), 60–72. Schenk O., Urai J.L. and Piazolo S. (2006). Structure of grain boundaries in wet, synthetic polycrystalline, statically recrystallizing halite – evidence from cryo-SEM observations. Geofluids, 6: 93-104.

Figure 1. I. SEM picture (BSE) of cryo-stabilized brine film in grain boundary close to a triple junction located in a natural polycrystalline salt sample. The surface has been prepared by using the FIB. II. 3D reconstruction of the pore space by FIB serial crosssectioning around a quartz grain in Boom-clay. The thickness of each cross-section is 500 nm. (a) Initial SE pictures and, (b) equivalent segmented pictures.

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TEM applied on the interface characterisation of the replacement reaction chlorapatite by hydroxyapatite U. Golla-Schindler1, A. Engvik2, H. Austrheim3 and A. Putnis1 1. Institute for Mineralogy, University of Muenster, Corrensstr. 24, 48149 Muenster, Germany 2. Geological Survey of Norway, N-7491 Trondheim, Norway 3. Institute for geoscience/PGP, University of Oslo, N-0316 Oslo, Norway [email protected] Keywords: HRTEM, STEM DF, FIB, apatite, replacement reaction

The aim of this work is to understand the mineral replacement mechanism occurring in the transformation from originally Cl-rich apatite and to hydroxyapatite found in south Norway. The hypothesis is that a fluid-mediated mineral replacement mechanism based on interface-coupled dissolution re-precipitation [1] was inducing the phase transformation. For the TEM studies selected apatite grains were chosen, which show nice alteration interfaces (Figure 1a). The TEM samples were prepared with a dual beam microscope (Zeiss CrossBeam 1540EsB). This machine is equipped with a Kleindiek in situ lift out facility and an EsB inlens detector, which enables the detection of the interface in a similar manner than a BSE detector and allows the precise cutting of the TEM Lamella across the interface. The aim was to obtain images of both phases and to yield structural information from the interface between the chlorapatite and the hydroxyapatite. The TEM analysis were performed using two kinds of transmission electron microscopes a JEOL 3010 and a ZEISS LIBRA 200 FE, where conventional diffraction, STEM and high resolution images were obtained. Figure 1b shows a dark field image of the prepared TEM Lamella, where the chlorapatite and hydroxyapatite regions are clearly visible and additionally the sharp interface between both. The electron diffraction pattern Figure 1 c, d, e taken in the chlorapatite, hydroxyapatite region and at the interface on the position 1, 2, 3 in Figure 1b yield identical diffraction pattern except the sharpness of the diffraction spots. The identical orientation and structures for the studied [1-21] zone axis of both phases gives an indication for a topotactical exchange mechanism. This is confirmed by the HRTEM images taken in the chlorapatite and hydroxyapatite region Figure 1f, g that obtained the same lattice spacing. However, there are obvious differences in both images: on the one hand the chlorapatite high resolution image has a lower signal to noise ratio than the hydroxyapatite, and on the other hand the hydroxyapatite has additional contrast related to a small sized porosity. The difference in the quality and sharpness of the diffraction spots and also the difference in the attainable signal to noise ratio of the high resolution images gives the idea that the chlorapatite phase present less long range order and has more destroyed regions, whereas the hydroxyapatite shows a more recovered crystal structure but with

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an additional small sized porosity. All these TEM results fulfill the criteria for an interface-coupled dissolution re-precipitation reaction mechanism. 1.

A. Putnis and C.V. Putnis Solid State Chemistry 180 (2007), p. 1783-1786

Figure 1. TEM analysis of a selected apatite grain. (a) FIB-SEM image with a clear contrast between the chlor- and hydroxyapatite phases (b) STEM dark field image recorded in the LIBRA 200FE. (c-e) diffraction pattern across the interface at position 1, 2, 3 shown in (b) in the chlorapatite phase, on the interface and in the hydroxyapatite phase recorded with the JEOL 3010 (f, g) high resolution images of the chlorapatite and hydroxyapatite phase, respectively.

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Quantitative study of valence states of zirconolites U. Golla-Schindler1, P. Pöml1 1. Institute for Mineralogy, University of Muenster, Corrensstr. 24, 48149 Muenster, Germany [email protected] Keywords: beam damage, valence states, EELS, zirconolite

Minerals that have mixed valence states are widespread and form in many different rock types. On the one hand, the oxidation state can reflect the redox conditions under which the host materials crystallised and is therefore important for answering fundamental questions about Earth’s evolution and structure. On the other hand, in metamorphic and altered rocks, the oxidation state gives important information about the rock forming and alteration processes. The new generation of electron microscopes equipped with an energy filter enables excellent spatial as well as energy resolution, allowing the acquisition of detailed information about the atomic structure, the chemical composition and the local electronic states of the object. This opens new avenues for advanced applications, like establishing the correlation of macroscopic with microscopic and nanoscopic properties in the field of mineralogy. To apply the new facilities and quantitative EELS and ELNES to study these fundamental questions two main problems have to be overcome. These are: artifact-free specimen preparation and the necessity to require spectra free of electron beam damage effects [1,2]. The dose rate has been found to be a decisive factor in enabling the artifact-free study of beam sensitive material. We have shown that with a dose rate of approximately 1.8 x 102 e/nm2s [3] beam damage effects can be avoided for long exposure times and high electron beam doses. For our studies we selected a homogeneous specimen area with t/λ=0.5, resulting in an absolute specimen thickness of approximately 43 nm [4]. The zirconolite mineral system plays an important role in the development of ceramic waste forms (e.g. synroc [5]) for actinides, especially Pu. To analyse the influence of hydrothermal alteration, zirconolites with Ce as an analogue for Pu have been synthesised with varied chemistry. The difference in the ELNES for different valence states shown in Figure 1 can be used for a quantitative study of the valence state of Ce . The ionic radius of Ce3+ and Ce4+ is significantly different therefore it can be expected that they will occupy different crystal sites. The knowledge of the valence state will consequently enable to yield essential information on the site occupancy. The investigations were performed using two different TEM’s. One is a LIBRA 200FE operating at 200 kV, equipped with a field emission gun, a 4 K slow-scan CCD Camera, and a corrected 90° in-column Omega energy filter and the second is the SATEM operating at 200 kV equipped with a monochromator a Cs-Corrector, a corrected 90° in-column Omega energy filter and a 1 K slow-scan CCD camera. S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 811–812, DOI: 10.1007/978-3-540-85226-1_406, © Springer-Verlag Berlin Heidelberg 2008

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1. 2. 3. 4. 5.

L.A.J. Garvie and P.R. Buseck Journal of Physics and Chemistry of solids 60 (1999), p.1943. L.A.J. Garvie et al. American Mineralogist 89 (2004), p.1610. U. Golla-Schindler, R. Hinrichs, P. Pöml., C. Putnis and A. Putnis Quantitative study of valence states of beam sensitive minerals. Microsc. Microanal. 13 Suppl. 2 (2007), p.12661267. R.F. Egerton, Electron Energy-Loss Spectroscopy in the Electron Microscope 2nd ed., Plenum Press, New York, 1996. G.R. Lumpkin, Elements 2 (2006), p.365.

Figure 1. EELS spectra of Monazite and Cerianite. a), b) recorded with the LIBRA 200FE demonstrating the differences in the ELNES for the different valence states Ce3+ and Ce4+. c) recorded with the SATEM showing the improvement due to the enhanced energy resolution and d) a x-ray absorption spectrum for comparison [5].

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Study of Organic Mineralogical Matter by Scanning Probe Microscopy Ye.A. Golubev, O.V. Kovaleva Institute of Geology of Komi SC of RAS, Pervomaiskaya St., 54, 167982, Syktyvkar, Russia [email protected] Keywords: solid bitumens, amber, scanning probe microscopy

Among products of geological processes in the context of occurrence and variety of nanosize structural elements of natural, roentgenoamorphous, organic substances are most interesting objects [1, 2]. Nanosize structures of such substances are named supermolecular structures. In this work, the results of supermolecular structure researches of natural solid bitumens (hydrocarbons) and fossil resins (ambers) are resulted. These substances concern to the most widespread in lithosphere and practically significant of organic mineralogical substances. The supermolecular structures of natural bitumens of the thermal consequent row asphaltites – lower kerites (albertites) – higher kerites (impsonites) – average anthraxolites – higher anthraxolites from the Timan-Pechora petroleum province and Karelian shungite rocks, Russia, were studied in details [2]. Fossil resin samples for our researches transparent grains and grain fragments of the Baltic amber (Kaliningrad region, Russia) with diameter 5-10 cm have used. The used experimental technique were scanning tunneling (STM) and atomic force (AFM) microscopy, following fracture preparation. It should be noted that natural solid bitumens have a mineral multiphase composition. Therefore, the composition of the surfaces under study should be controlled. The analysis of the element distribution on the surfaces under study was performed by an X-ray spectrometer "Link ISIS", combined with SEM JSM6400 (Jeol). Using X-ray spectral analysis, it was shown that mineral impurities were mainly located as scattered inclusions (from one up to several tens of micrometers in size) in a hydrocarbon matrix. So, the nanometer objects found many times on the AFM-images, can be interpreted as bitumen supermolecular structure particles. In this work, we characterized the supermolecular evolution of natural solid bitumens in the carbonization sequence by quantitative parameters. The types of supermolecular structures and sizes of their initial particles have been determined (ex., Fig. 1, a, b). The transfer from fiber structure to globular-fiber structure with the increase of bitumen metamorphism degree from asphaltites up to average anthraxolites has been observed. The sizes of fibers decrease from 250 up to 30 nm from asphaltites up to average anthraxolites. Higher anthraxolites have globular supermolecular structure. It is shown, that the Baltic amber is mainly make-up of incoherent accumulations of densely aggregated globule-like particles of the sizes from 50 to 120 nm (Fig. 1, c). The

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prevailing form of particles is not determined, they represent a row of the forms varying from ellipsoidal globules up to short fibres. Supermolecular particles do not form homogeneous substances, they are associated in various aggregates. 1. 2.

V.F. Pen'kov Genetic mineralogy of carbonaceous substances. Moscow: Nedra Press; (1996), 356 p. Ye.A. Golubev, O.V. Kovaleva, N.P. Yushkin, Fuel, V. 87. (2008). pp. 32–38.

a)

c)

b)

Figure 1. AFM image of globular structure of shungite’s carbon from Karelia, Russia (a), “brain”-like structure of average anthraxolites fron Lena River, Siberia, Russia (b), globular-fibrous structure of Baltic amber (c).

815

Research of Nanoparticle Aggregates from Water Colloidal Solutions of Natural Carbon Substances and Fullerenes by Atomic Force Microscopy Ye.A. Golubev1, N.N. Rozhkova2 1. Institute of Geology of Komi SC of RAS, Pervomaiskaya St., 54, 167982, Syktyvkar, Russia 2. Institute of Geology of Karelian SC of RAS, Pushkinskaya St., 11, 185000, Petrozavodsk, Russia [email protected] Keywords: shungite, carbon nanoparticles, atomic force microscopy

At the present time interest to geological fullerene-like substances grows. The wellknown natural fullerene-like substance is the anthraxolite of shungite rocks (further – shungite) of Karelia, Russia [1]. Interest to research of colloidal solutions of disaggregated shungite substances is determined by an opportunity of the characteristic of aggregation mechanisms of nanoparticles [2]. In addition, films from colloidal solutions represent also independent value as laboratory model of fine-grained geological materials with the peculiar physical and chemical properties testifying to its activation [2]. The films from water colloidal solutions of С60–С70 were investigated in virtue of structural and morphological similarity of structural elements of shungite carbon and fullerene for comparison. In this work the results of studying of morphological features aggregates of carbon nanoparticles, deposited from fine-grained shungite and fullerene water dispersions is carried out by atomic force and electron microscopy. [3]. For formation films the shungite were dispersed by mechanical and ultrasonic means [4]. High-oriented pyrolitic graphite was used as substrates. Drops of suspensions on substrates were drayed. It is shown, that fullerene water dispersions form at drying a thin films from particle aggregates of tens nanometers size. Aggregates form single, double and multijointed chains. Their orientation is chaotic, some microns long. In addition, single particles are observed. Particles can be divided into two types: i) spherical or ellipsoidal globules (Figure 1, a); ii) cup-like particles (Figure 1, b). Globules have height 70 nm, cup-like particles up to 30 nm. The average diameter of particles in fullerene films is 150 nm, distribution similar to normal (Gaussian). Received from shungite water colloids thin film is a set of a multilayered particle deposits, frequently connected and forming "networks" (Figure 2, a). Particles have form of ellipsoidal globules, their average size makes 60 nm. Fullerene films of particle distribution on the sizes is logarithmically normal. The lognormal form of size distribution is typical for aggregates of colloidal particles. The film, received from shungite water dispersions, are generated from units which average size is similar to sizes of carbon globules of shungite rocks (Figure 2, b). Thus,

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the possibility of shungite globule separation is shown by transformation of carbon shungite rocks in water dispersion. 1. 2. 3. 4.

P.R. Buseck, L.P. Galdobina, V.V. Kovalevski, N.N. Rozhkova, J.W. Valley, and A.Z. Zaidenberg, Canadian Mineralogist. V. 35. (1997). pp. 1363–1378. N.N. Rozhkova in “Perspectives of Fullerene Nanotechnology” ed. E. Osawa, (Dordrecht: Kluwer Academic Pub.), (2002), рр. 237-251. Ye.A. Golubev, N.N. Rozhkova, V.N. Filippov, Surface, V. 10. (2007). pp. 47–52. G.V. Andrievsky, V.K. Klochkov, E.L. Karyakina, N.O. Mchedlov-Petrossyan, Chemical Physics Letters. V. 300. (1999). pp. 392–397.

a)

b)

Figure 1. AFM-images of particles of fullerene aggregates.

a)

b)

Figure 2. AFM-images of shungite nanostructure (a) and individual shungite globules (b).

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Diffusion in Synthetic Grain Boundaries K. Hartmann1, R. Wirth1, R. Dohmen2, G. Dresen1 and W. Heinrich1 1. GeoForschungsZentrum Potsdam, Section 4.1, Telegrafenberg, 14473 Potsdam, Germany 2. Ruhr-Universität Bochum, Institut für Geologie, Mineralogie und Geophysik, Universitätsstr. 150, 44780 Bochum [email protected] Keywords: Thin film Diffusion, Grain Boundary, Interface

Grain and phase boundaries usually represent only a small volume fraction of a rock. However, their physical and chemical properties strongly influence the macroscopic properties of rocks, such as elasticity, strength, electrical conductivity, and the efficiency of diffusive mass transport. Grain boundary diffusion is normally estimated to be several orders of magnitude higher compared to volume diffusion [1]. Yttrium-Aluminium-Garnet (YAG) bicrystal samples were synthesised for the first time with the wafer direct bonding method [2]. The highly polished and ultra clean crystal surfaces are saturated with pure adsorbed water and are brought into contact at no force. Upon initial contact, hydrogen bonds of the opposing crystal surfaces are expected to form. The adsorbed water readily evaporates at elevated annealing temperatures leaving a synthetic grain boundary behind. Synthetic garnet is used to investigate the grain boundary structure and grain boundary diffusion in a relatively simple system, as a major practical problem with natural materials is the difficulty in controlling their purity as well as stoichiometry. High-Resolution Transmission Electron Microscopy (HREM) and analytical TEM combined with Focussed Ion Beam (FIB) sample preparation was used to investigate the grain boundary structure and its width. Figure 1 shows a straight grain boundary in YAG where the lattice fringes of the two crystals are directly connected, no noncrystalline material is observed. Diffusion experiments are designed in thin-film geometry, such that the grain boundary is perpendicular to the surface covered with the thin-film. Pulsed Laser Deposition (PLD) [3] was used to deposit Nd or Yb doped YAG on the bicrystal. The thin-films were initially amorphous, but during annealing they crystallized using the structure of the bicrystal. Therefore the grain boundary continues within the epitaxially grown thin-film (Figure 2). After diffusion annealing of the bicrystals diffusion profiles were measured with analytical TEM and/or Rutherford Backscattering (RBS). Cherniak [4] measured volume diffusion profiles with Rutherford Backscattering (RBS) of approx. 50 nm after annealing the sample for 2 h at 1300°C. Even though, we choose the same T-tparameters and analytical techniques we could not detect any volume diffusion at all, grain boundary diffusion could not be observed either. After annealing for 17 h at 1300°C, grain boundary diffusion was measured with EDX in TEM, whereas volume diffusion was still undetectable. The diffusion length between the different experimental S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 817–818, DOI: 10.1007/978-3-540-85226-1_409, © Springer-Verlag Berlin Heidelberg 2008

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approaches strongly differs. This may be caused by different defect structures in the substrate, different water activity or a different contact between substrate and source for the diffusing element. More experiments at different temperatures, diffusion times, and thin-film compositions are planned. 1. 2. 3. 4.

Gleiter H., Chalmers B., Progress in Materials Science 16, (1972) p: 77 Heinemann S., Wirth R., Gottschalk M., Dresen G., Physics and Chemistry of Minerals 32 (2005), p: 229 Dohmen, R., Becker, H.-W., Meissner, E., Etzel, T. & Chakraborty, S., European Journal of Mineralogy 14, (2002), p: 1155 Cherniak, D.J., Physics and Chemistry of Minerals 26, (1998), p: 156

Figure 1. Energy-filtered HREM image of the grain boundary in YAG. The inset shows its diffraction pattern, indices are marked with ‘l’ for left ‘r’ for the right crystal site.

Figure 2. Bright field (BF) TEM image of the thin-film diffusion geometry.

819

An examination of Van Gogh’s painting grounds using analytical electron microscopy – sem/fib/tem/edx R. Haswell1, U. Zeile2, K. Mensch1 1. Shell Global Solutions International B.V., 1030 BN Amsterdam, The Netherlands 2. Carl-Zeiss NTS GmbH, D-73446 Oberkochen, Germany [email protected] Keywords: TEM, FIB, SEM, EDX, pigments, ground, Van Gogh

In this paper we report the results of an analytical electron microscopy study of the microstructure of the grounds used by Van Gogh. In an initial study we examined samples from three paintings [1] and tentatively concluded that the nature of the barium sulphate used in the grounds was different in each painting. In order to confirm these initial findings we have prepared additional samples from both the original three paintings plus two new ones. The five paintings were all from the French period dating from 1886-1888. The aim of the work was to determine whether the barium sulphate was the same in closely associated works. To this end we have investigated whether the variations in strontium concentration, both between and with-in individual barium sulphate crystals might help answer this question. The inter-particle characterisation of the barium sulphate was made using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) while Transmission Electron Microscopy (TEM) and EDX was employed for the intra-particle examination. The thin sections for the TEM were prepared using the Focused Ion Beam (FIB) from barium sulphate crystals selected using the SEM/EDX results. Typical SEM backscatter electron (BSE) images from polished cross-section samples from two of the paintings being investigated are shown in Figure 1. In two of the paintings (F377/4 and F546/9) barium sulphate is the only phase present in the ground as illustrated in Figure 1 (a). In the other three paintings the barium sulphate was one of a number phases present in multiple layers of paint. An example is shown in Figure 1 (b). We have found differences in both the overall strontium concentration in the barium sulphate crystals from different paintings as well as variation within a painting itself using SEM/EDX. However the most striking differences were in the intra-particle variation of the FIB sections measured with TEM/EDX using 0.5 μm diameter spots, as shown in Figure 2. These results indicate that - contrary to our initial conclusions - the barium sulphate can actually be divided into two types, namely: type I which has barium sulphate crystals with large intra-particle variation in the strontium concentration (paintings F244/4, F 297 a/2 and F546/9); and type II which has barium sulphate crystals with uniform strontium concentrations although there is a large difference between individual particles (paintings F297/1 and F377/4). These results did not agree with our prior expectations.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 819–820, DOI: 10.1007/978-3-540-85226-1_410, © Springer-Verlag Berlin Heidelberg 2008

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The ability to classify the barium sulphate into different types is being used to add to our knowledge of the methods and materials used by van Gogh, which is helping in the reconstruction of Van Gogh’s oeuvre and attribution. 1. 2.

R. Haswell1 , U. Zeile and K. Mensch, accepted for publication Microchimica Acta, 2008 This work was possible due to the financial support of Shell Netherlands B.V. This work also benefited from fruitful discussions with Ella Hendriks (Van Gogh Museum, Amsterdam) who also helped in the selection of the Van Gogh grounds.

(a)

(b)

atomic Sr concentration normalised to Ba

Figure 1. Figure 1 (a) and (b): SEM backscatter images from paint samples from portrait of Gauguin (F546/9) and basket with pansies (F244/4), respectively. In Figure 1(b) barium sulphate particles are indicated with arrows. 10.0 8.0 6.0 4.0 2.0 0.0 0

1 F244/4

2 F377/4

3 F546/9

4 F297/1

5 F297 a/2 6

Figure 2. The variation in the atomic Sr concentration normalised to Ba measured using TEM/EDX, spot size 0.5 μm’s, from various FIB sections from individual barium sulphate particles from each of the five paintings. Note: the F. numbers used to identify the paintings correspond to the catalogue numbers in Bart de la Faille’s catalogue

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Amorphisation in fresnoite compounds – a combined ELNES and XANES study Th. Höche1, F. Heyroth2, P.A. van Aken3, F. Schrempel4, G.S. Henderson5, and R.I.R. Blyth6 1. Leibniz-Institut für Oberflächenmodifizierung e.V., D-04103 Leipzig, Germany 2. Martin-Luther-Universität Halle-Wittenberg, IZ für Materialwissenschaften, Heinrich-Damerow-Str. 4, D-06120 Halle, Germany 3. Max-Planck-Institut für Metallforschung, Stuttgart Center for Electron Microscopy, Heisenbergstr. 3, D-70569 Stuttgart, Germany 4. Friedrich-Schiller-Universität Jena, Institut für Festkörperphysik, Max-Wien-Platz 1, D-07743 Jena, Germany 5. Department of Geology, University of Toronto, 22 Russell Street, Toronto, M5S 3B1, Canada 6. Canadian Light Source, 101 Perimeter Road, University of Saskatchewan, Saskatoon S7N OX4, Canada [email protected] Keywords: ELNES, XANES, fresnoite

The fresnoite family of minerals (including Ba2TiSi2O8, Ba2TiGe2O8, Sr2TiSi2O8, as well as Ba2VSi2O8, K2V3O8, and Rb2V3O8) has attracted scientific interest not only for its remarkable piezoelectric [1] and optical properties [2] but also due to the occurrence of pentahedrally coordinated Ti4+ and V4+, respectively. L2,3 electron energy-loss near-edge structure (ELNES) and X-ray absorption nearedge structure (XANES) spectra of the latter elements possess particularly wellpronounced peaks due to the narrow natural line width caused by core-hole life-time broadening. While ELNES spectra are typically averaged over a specimen thickness of 50 to 100 nm (but can be excited by a sub-nm probe), two types of XANES spectra, with very different probing depths, are commonly acquired in parallel: total electron yield (TEY) and fluorescence yield (FY) data. TEY XANES spectra probe some 4 nm [3] while FY XANES spectra are estimated to contain information down to a depth of about 50 nm. In the present contribution, we compare XANES spectra of fresnoite compounds recorded at the SGM beamline of the Canadian Light Source (energy resolution below 0.1 eV) with ELNES spectra obtained in a dedicated STEM (VG HB 501) equipped with a cold field-emisison gun and a Gatan Enfina 1000 spectrometer (spectral resolution ~ 0.4 eV). Samples were exposed to ion irradiation of 300 eV, 6 keV, as well as 200 keV. As shown in the cross-sectional TEM micrograph depicted in Fig. 1, the latter acceleration voltage causes superficial amorphisation down to a depth of around 150 nm [4]. The extent of the amorphisation layer decreases with decreasing ion energy and hence the

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 821–822, DOI: 10.1007/978-3-540-85226-1_411, © Springer-Verlag Berlin Heidelberg 2008

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various probing depths of ELNES and XANES spectra can be utilised to get deeper insights into coordination changes associated with amorphisation. Moreover, the advantages of enhanced spectral resolution for the investigation of coordination changes are clearly demonstrated. For transition metal-L3 edges, e.g. the Ti-L3 and the V-L3 ELNES, the conclusion is drawn, based on the XANES data, that it is advantageous to study amorphisation processes at a spectral resolution below 100 meV. 1. 2. 3. 4.

S.A. Markgraf, A. Halliyal, A.S. Bhalla, et al. Ferroelectrics 62 (1985) p. 17. Y. Takahashi, K. Kitamura, Y. Benino, et al., Appl. Phys. Lett., 86 (2005) Art.-No. 091110. B.H. Frazer, B. Gilbert, B.R. Sonderegger, G. De Stasio, Surf. Sci., 537 (2003) p. 161. Th. Höche, F. Schrempel, M. Grodzicki, P.A. van Aken, and F. Heyroth, Chem. Mater., 18 (2006), p. 5351.

Ba2TiSi2O8 Glass

Ba2TiSi2O8 Single Crystal 455

460

465

470

Energy Loss [eV]

Figure 1. Ti-L2,3 ELNES spectra of amorphised (by irradiation with 200 keV Ar+) single-crystalline Ba2TiSi2O8 recorded at different depths beneath the surface. For comparison, a spectrum of the identically composed glass is also shown.

823

TEM study of Comet Wild 2 pyroxene particles collected during the stardust mission D. Jacob, J. Stodolna and H. Leroux Laboratoire de Structure et Propriétés de l’Etat Solide - UMR CNRS 8008, Université des Sciences et Technologies de Lille – Bât. C6, 59655 Villeneuve d’Ascq, France. [email protected] Keywords: Stardust, TEM, pyroxene

In January 2006, the NASA Stardust spacecraft successively returned to Earth dust from comet 81P/Wild 2, captured in a low-density SiO2 aerogel. Samples of three collected pyroxene-rich particles have been investigated by transmission electron microscopy (TEM). They are coarse-grained Ca-poor pyroxenes with compositions and structures ranging from orthorhombic enstatite to monoclinic pigeonite. The samples originate from terminal particles of two neighbouring tracks (Figure 1). Details about extraction, manipulation and preparation for TEM by ultramicrotomy can by found in [1]. Results were acquired using LaB6 filaments Philips CM30 (300 keV) and FEI Tecnai G2-20 twin (200 kV) microscopes, equipped with Thermo-Noran and EDAX Si-detectors respectively for Energy Dispersive X-ray Spectroscopy (EDX) (see [2] for a full description of the analytical procedure). The general aspect of the ultramicrotomed samples consists of a central part made of crystalline shards, surrounded by a more or less thin and discontinuous rim of dense amorphous SiO2-rich material. Among the three samples, two exhibit very similar and homogeneous compositions and microstructures (C2027,2,69,2,2 and C2027,3,32,2,3). Their composition corresponds to enstatite within the range En94-97Wo2-5Fs2-5. Selected area electron diffraction patterns reveal an orthorhombic Pbca space group. In most of the shards, planar faults parallel to (100) are observed. Lattice fringe images (Figure 2) reveal that they consist in the insertion of one or more clinoenstatite lamellae (fringe spacing ~ 9 Å) in the orthoenstatite matrix (fringe spacing ~ 18 Å). The third sample (C2027,2,69,1,1) is made of clinopyroxene with composition in the range En73-78Wo36Fs18-23. Diffraction patterns indicate a pigeonite monoclinic P121/c1 space group. The dominant microstructure consists in a high density of (100) lamellae (figure 3). Diffraction patterns show that these lamellae are associated with twinned domains. A few chromite exsolutions were detected, in topotactic relationship to the pigeonite host. The sample also contains small olivine grains (Fa21) in inclusion within the pyroxene matrix. In the three samples, dislocations in glide configuration have also been found. In conclusion, the three studied terminal particles are coarse-grained pyroxene which survived to the strong heating associated with the collect (i.e. a full deceleration from 6 km/s along a ~1cm track). They appear relatively undamaged in comparison to the thermally modified grains frequently found in samples extracted from the wall tracks [1, 2]. The microstructure of the studied samples may have been formed by shock deformation, probably prior to the capture into aerogel. Nevertheless the exceptional S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 823–824, DOI: 10.1007/978-3-540-85226-1_412, © Springer-Verlag Berlin Heidelberg 2008

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physical conditions of the collect include a possible intense thermal pulse. A thermal shock as responsible for the observed microstructure cannot be ruled out. 1. 2. 3.

M. E. Zolensly et al, Science 314 (2006), p.1735. H. Leroux et al., Meteoritics & Planet. Sci. (2008), in press. We thank the French Space Agency CNES for their support. Keiko Nakamura Messenger is gratefully acknowledged for the preparation of the ultramicrotomed samples.

Figure 1. Optical photography (credit: NASA/JSC) of the tracks associated with the three studied terminal particles a)

b)

Figure 2. (a) TEM bright-field image of enstatite in C2027,2,69,2,2. The clinoenstatite lamellae parallel to (100) are clearly visible by the 9 Å lattice spacing, whereas the 18 Å lattice spacing corresponds to orthoenstatite. (b) Diffraction pattern. a)

b)

Figure 3. (a) TEM dark-field image showing the (100) twins in pigeonite, sample C2027,2,69,1,1. (b) Diffraction pattern corresponding to the superposition of the P121/c1 [010] and [01 0] zone axes.

825

The mechanism of ilmenite leaching during experimental alteration in HCl-solution A. Janßen1, U. Golla-Schindler, A. Putnis 1. WWU Münster, Institut für Mineralogie, Corrensstraße 24, 48149 Münster, Germany [email protected] Keywords: ilmenite, alteration mechanism, dissolution-reprecipitation

Ilmenite (FeTiO3) is an important mineral being the raw material for the production of titanium for the high-tech industries. The production process typically involves acid treatment, which oxidises and removes the Fe, leaving a TiO2-rich phase, generally rutile. In naturally weathered ilmenite, Grey and Reid (1975) first proposed a two-stage alteration mechanism and remains the generally accepted model [1]. In the first stage ilmenite undergoes weathering through oxidation and removal of Fe to form an apparently continuous series of compositions from ilmenite to pseudorutile (ideally Fe2Ti3O9). The Fe is assumed to diffuse out through the unaltered oxygen lattice. Pseudorutile is a transitional phase and undergoes incongruent dissolution to form rutile, hematite and goethite [2]. Understanding the structural and chemical relationships at the nanometre scale between ilmenite to pseudorutile to rutile is essential because it can be help to understand the exact alteration mechanism of ilmenite, and hence optimise the industrial process. A hard rock ilmenite from the Manvers granite pegmatite dike (Canada) with starting composition Fe0.94Mn0.06Ti0.99O3 was used in this study. The mineral was cut into cubes with length of 3 mm. The dissolution experiments were carried out in 0.1 M HCl at 150 °C for 31 days and in 3 M HCl solution at 150 °C for 4 and 5 days. The resulting products were studied by X-ray diffraction, electron microprobe, scanning and transmission electron microscopy. The first results indicate that the alteration proceeds in two distinct stages, each with a sharp interface between the parent phase and the product. The alteration begins at the original ilmenite crystal surface and along cracks through which the fluid can migrate. The first alteration product is pseudorutile – no phases intermediate between ilmenite and pseudorutile were detected. The textural relationship between ilmenite and pseudorutile suggests a coupled dissolution-reprecipitation mechanism rather than a solid-state continuous oxidation and Fe diffusion mechanism. The second stage involves a further dissolution-reprecipitation step to form rutile. Throughout the alteration process the original morphology of the ilmenite is preserved although the product is highly porous. The rutile inherits crystallographic information from the parent ilmenite, resulting in a triply twinned rutile microstructure Figure 1. A fine scale veining in the ilmenite after the experiment was found Figure 2. Characterization of these veins with HRTEM is still in progress. Electron energy loss

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 825–826, DOI: 10.1007/978-3-540-85226-1_413, © Springer-Verlag Berlin Heidelberg 2008

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spectroscopy (EELS) will be use to determine the oxidation state of Fe in the starting material and the resulting alteration products. 1. 2.

I.E. Grey and A.F. Reid, The American Mineralogist 60 (1975), p. 898-906. P.A. Schroeder, J.J. Le Golvan and M.F. Roden, American Mineralogist 87 (2002), p. 16161625.

Figure 1. SE – Image of the treated ilmenite surface. Preservation of the crystallographic information: triply twinned rutile after ilmenite.

Figure 2. TEM – image of the vein structure in the ilmenite after the experiment. New crystals grew in the structure .The characterizations of these crystals are still in progress.

827

Microstructure and Texture from Experimentally Deformed Hematite Ore K. Kunze1, H. Siemes2, E. Rybacki3, E. Jansen4, H.-G. Brokmeier5 1. Electron Microscopy ETH Zurich (EMEZ), 8093 Zurich, Switzerland 2. Institut f. Mineralogie u. Lagerstättenlehre, RWTH Aachen, 52056 Aachen, Germany 3. Geoforschungszentrum Potsdam, 14473 Potsdam, Germany 4. Mineralogisches Institut, Uni Bonn and FZ Jülich, 52425 Jülich, Germany 5. Institut f. Werkstoffkunde u. Werkstofftechnik, TU Clausthal and FZ Geesthacht, 21502 Geesthacht, Germany [email protected] Keywords: deformation mechanism, dynamic recrystallisation, electron backscatter diffraction, orientation contrast

Relationships between microstructure and texture (crystallographic preferred orientations, CPO) have been reported by several studies on banded hematite ore from Brasil [1, 2]. Pole figure maxima of basal planes are located about normal to foliation, those of prism planes are within the foliation with highest density towards the lineation. This study aims at further understanding of the deformation mechanisms and texture forming processes in experimentally deformed hematite ore. Microstructural observations were performed using reflected light microscopy and SEM orientation contrast imaging, texture measurements were obtained from neutron diffraction [3,4] and from SEM-EBSD orientation mapping [5,6]. Cylindrical samples of fine grained natural hematite ore (diameter 14mm, length 10mm) have been deformed in torsion using a high pressure – high temperature deformation apparatus [7]. Samples were isolated from the pressure medium (argon gas) by a jacket of iron or copper, and separated from this jacket by a thin (0.5mm) Ag-Pd foil in order to minimize the formation of magnetite. Deformation experiments were performed at temperatures between 700°C and 1000°C, a confining pressure of 400MPa, at twist rates corresponding to a maximum shear strain rate of 0.4e-5s-1 and 4.7e-5s-1 , respectively, and to a maximum shear strain of gamma=4.7. After all of the experiments, hematite has dynamically recrystallised and developed a homogeneous polygonal grain fabric with little shape preferred orientation. The average grain size is larger at higher deformation temperature and shows also a gradient across the sample radius, with a remarkable increase near the central axis (Figure 1). The CPO also records a development with increasing shear strain, where an elliptical caxis (0001) maximum forms slightly off the shear plane normal, and where the CPO strength (texture index) increases monotonously with shear strain (Figure 2). The distributions of (11-20) and (10-10) prism poles follow girdles close to the shear plane, with maxima towards the shear direction. It is concluded from the similar microstructures and textures in nature and experiments that the hematite deformed in both cases primarily by dislocation creep accompanied by dynamic recrystallisation.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 827–828, DOI: 10.1007/978-3-540-85226-1_414, © Springer-Verlag Berlin Heidelberg 2008

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C.A. Rosière, H. Siemes, H. Quade, H.-G. Brokmeier and E.M. Jansen, J. Struct. Geol. 23(2001), 1429-1440. J. Bascou, M.I.B. Raposo, A. Vauchez and M. Egydio-Silva, Earth & Planetary Science Letters 198(2002), 77-92. E. Jansen, W. Schäfer and A. Kirfel, J. Struct. Geol. 22(2000), 1559-1564. H.-G. Brokmeier, U. Zink, R. Schnieber and B. Witassek, Materials Science Forum 273275(1998), 277-282 K. Kunze, S.I. Wright, B.L. Adams & D. Dingley, Textures & Microstruct. 20(1993), 41-54. B.L. Adams, S.I. Wright and K. Kunze, Mat. Trans. 24A (1993), 819-831 M.S. Paterson and D. Olgaard, J. Struct. Geol. 22(2000), 1341-1358.

r = 7mm (outside)

(inside) r = 0mm

Figure 1. Orientation mapping of central cut through torsion sample ST27. Color key according to IPF for torsion axis. A gradient of crystal preferred orientations and in grain size evolved from inside (right) to outside (left) of the torsion cylinder.

r = 5mm 4mm 3mm 2mm 1mm 0mm Figure 2. CPO evolution (sample ST04) with distance (r) from torsion axis and therefore with finite shear strain. Pole figure projections onto the shear plane, CPO strength represented by texture index J (random CPO means J=1).

829

Identifying pigments in the temple of Seti I in Abydos (Egypt) E. Pavlidou1, H. Marey Mahmoud2, E. Roumeli1, F. Zorba1, K.M. Paraskevopoulos1, M.F. Ali2 1. Physics Department, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece 2. Conservation Department, Faculty of Archaeology, Cairo University, 12613 Giza, Egypt [email protected] Keywords: Egypt, SEM, FTIR, Pigment

The temple of Seti I in Abydos, a sacred city noted as the most venerated place in Egypt, was built by the 19th dynasty (ca.1294-1279 BCE). The temple is famous for its remarkably unique design; it is in the shape of an “L” and its wall paintings are decorated with the most complete series of Kings and Gods in Egypt, which virtually helped to decode Egyptian history. Our first results concern to samples from these wall paintings which are examined by SEM-EDS and FTIR microscopy in order to identify the used pigments. The dimensions of the samples were about 3x6mm, with blue, green, yellow and red colors on the surfaces. For the FTIR measurements tiny species from the painted surface of the samples were removed and placed on a freshly prepared KBr pellet. The transmittance IR spectra, were obtained with a Perkin-Elmer FTIR microscope, i-series. A database of FTIR spectra from reference materials was used. The above samples along with crosssectioned specimens, were analyzed also by SEM-EDS, using a Jeol 840A Scanning Microscope with an Energy Dispersive Spectrometer attached by Oxford, model ISIS 300. From the EDS analysis of the blue colored surface of the wall-painting specimens (Fig. 1a) are detected Ca (12%), Cu (15%) and Si (33%), while the FTIR spectra that are collected from the same specimens, present characteristic peaks lying mainly between 1280 and 1000cm-1 that are attributed to Si-O-Si stretching vibrations. The comparison of the FTIR spectra (Fig. 2a) with these from our spectral library and the literature [1], leads to the conclusion that the blue color is Egyptian blue (CaCuSi4O10). Additionally, the peak at 1319cm-1 is a strong indication of the presence of calcium oxalate derived from biodegradation process. Studying the green pigment by EDS (Fig. 1b,d) are observed areas with great amounts of Si (43%) and areas with Ca (11%), Cu (13%) and Si (29%). The FTIR spectra from the green specimens (Fig. 2a) are similar with these from blue, presenting mainly a broader peak in the area 850-1250cm-1, indication of a glassy phase. The combination of the above results guide to the conclusion that the used green pigment is Green Frit [2, 3], a material consisted of cuproan wollastonite with large quantity of a glass phase and few bronze residues. Finally the FTIR spectra of yellow and red samples (Fig. 2b) reveal, except of the

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 829–830, DOI: 10.1007/978-3-540-85226-1_415, © Springer-Verlag Berlin Heidelberg 2008

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peaks of calcite, the characteristic bands of ochre, which are attributed to aluminosilicate materials such as kaolin. Additionally the presence of Fe (19-30%) in great amounts in EDS analysis (Fig. 1c), affirms the consideration that the used pigments are yellow and red ochre respectively. The pigments are used in thin layers, as it is observed from the optical examination of the specimen and are common in this period of time. 1. 2. 3.

G. A. Mazzocchin, D. Rudello, C. Bragato, F. Agnoli, J. Cul.Her 5 (2004) p. 129 S. Schiegl, K.L. Weiner, A. El Goresy, Naturwissenschaften 76 (1989) p. 393 P. Bianchetti, F. Talarica, M.G. Vigliano, M.F. Ali, J. Cul.Her 1 (2000) p. 179

Figure 1. Cross Section SEM micrographs of blue (a) green (b), red (c) and chemical mapping of green segment (d) 80

90 80 70

Transmittance (%)

Transmittance (%)

70 60 50 40

50 40 30 20

B lue Green

30

60

10

R ed R ed O ch re, referen ce

0

20 750

1000

125 0

150 0 -1

W avenum ber (cm )

(a)

17 50

20 00

1000

1500

2000

2500

3000 -1

W av en u m b er (cm )

(b)

Figure 2. FTIR blue and green area (a), spectra from red area (b).

1 2 3 4 5

Code AB B2 GR R Y5

Table I. List of analyzed samples Color Materials identification Blue Egyptian blue, calcium oxalate Blue Egyptian blue Green Green frit, gypsum Red Red ochre, calcite, gypsum Yellow Yellow ochre, calcite, gypsum

3500

4000

831

Nanostructural study of ground layers of canvas of Rubens at “El Prado” National Museum J. Ramírez-Castellanos1, J.L. Baldonedo2, M.I. Báez3, L. Vidal3, M.D. Gayo4 and M.J. García3 1. Dpto. de Química Inorgánica. Universidad Complutense de Madrid (España). 2. Centro Miscoscopía y Citometría. Universidad Complutense de Madrid (España). 3. Dpto. de Pintura-Restauración. Universidad Complutense de Madrid (España). 4. Laboratorio de Química. Museo Nacional del Prado (España) [email protected] Keywords: Rubens, high resolution transmission electron microscopy, artist materials.

The authors are members of an inter-disciplinary investigation team working in the field of Cultural Heritage Conservation. The aim of this project is the comparative study of grounds of works in the Prado National Museum by Rubens, during his time in Spain and at Ambers (Belgium), due to the peculiar characteristics of the materials used in the coloured grounds -which are of a complex and varied nature- and specifically the peculiarities that they present in Rubens’ canvases, require a detailed nanostructural characterization by means of high-resolution transmission electron microscopy (HRTEM), by using a 300 FEG JEOL electron microscope and an Energy Dispersive Xray Spectroscopy (EDS) microanalysis, in order to determine the nanostructure and chemical composition of the particles forming the pictorial materials [1]. The final properties of crystallized materials depend on different structural and chemical aspects. Furthermore, the presence of defects, crystal size, chemical composition, stechiometry, cationic substitutions and impurities, all lead to chemical and physical property changes. The data thus gathered will serve to compare the materials used with one another and with others of the author’s works, also located at “El Prado” National Museum, regarding which there are reasonable doubts as to whether they were executed in Spain during his second visit (1628-29). This study is made from estratigraphic microsamples taken from works examination object, following a methodology in the preparation that allows maintaining the pictorial layers and as they were applied by the author. This process is complex, because the ultra-thin sections must be stable under the electron beam and, in addition, the sections must contain all the unaltered particles of the microsample. To achieve this, they were included in a suitably fluid, hard after chemical and thermal treatment and chemically neutral Spurr epoxy resin. The ultra-thin sections (50-100 nm thick) were cutted using an ultramicrotome equipped with a diamond knife and a carbon film was evaporated on to their surface [2]. In this contribution, we present the first obtained results corresponding to the work entitled “Filopómenes descubierto por unos ancianos en Megara” by Rubens at Ambers (1609), in collaboration with Frans Snyders (Figure 1). The possible relations

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 831–832, DOI: 10.1007/978-3-540-85226-1_416, © Springer-Verlag Berlin Heidelberg 2008

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between the nanostructural features of the used materials and some related aspects, such as origin, elaboration, manufacture, manipulation, etc. will be discussed. Figure 1. Filopómenes reconocido por unos ancianos en Megara (1609). Oil on canvas. Prado National Museum (Madrid). (Sample place is marked as a red circle).

The SAED pattern (Fig. 2a) shows broad diffused scattering and rings at low angles indicate the amorphous nature of the sample (marked as a red circle in Fig. 1). Moreover, the intensity and discrete spots suggest the presence of randomly oriented grains of very small dimensions. The corresponding HRTEM images (Fig. 2b) reveals a complex microstructure, a glassy matrix containing some crystallized domains were found. EDS microanalysis shows the existence of Si, Al, Fe, Mg, Ca, K and Na. In these sense, data seem to confirm that the used grounds by Rubens are mainly composed by Fealuminosilicates, related to feldespast structure. Figure 2. SAED pattern (a) and corresponding HTEM image (b) of the used materials in the coloured grounds.

1. This work has been carried forward with funding from the Ministry of Science and Technology under the National Plan for Scientific Research and Technological Development Projects (R&D) (Ref.: HUM2006-01847/ARTE). 2. M. San Andrés, M.I. Báez, J.L. Baldonedo and C. Barba, Journal of Microscopy 188 (1997), p. 42-50.

833

Micro- and nano-diamond particles in carbon spherules found in soil samples Z. Yang1*, D. Schryvers1, W. Rösler2, N. Tarcea3, J. Popp3 1. EMAT, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium 2. Institute for Pre- and Early History, University of Mainz, Schillerstrasse 11, D-55116 Mainz, Germany 3. Institute of Physical Chemistry, University of Jena, Helmholtzweg 4, D-07743, Jena, Germany * now at College of Materials Science and Engineering, Hunan University, Changsha, Ch-410082, China [email protected] Keywords: diamond, nanoparticles, microflakes, impact

Carbonaceous spherules of millimeter size diameter and found in the upper soils throughout Europe are investigated by TEM, including SAED, HRTEM and EELS, and Raman spectroscopy. The spherules consist primarily of carbon and have an open celllike internal structure. Most of the carbon appears in an amorphous state, but different morphologies of nano- and microdiamond particles have also been discovered including flake shapes. The latter observation, together with the original findings of some of these spherules in crater-like structures in the landscape and including severely deformed rocks with some spherules being embedded in the fused crust of excavated rocks, points towards unique conditions of origin for these spherules and particles, possibly exogenic [1]. Optical microscopy and SEM reveal mainly cenospheres exhibiting foam-, sponge-, or cell-like internal structures with cell sizes approximately ranging from 10 to 40 micron, as shown in Figure 1. Elemental analyses using EDX show a high portion of C but also considerable amounts of O and no heavy elements. The matrix of the spherules consists of amorphous carbon, with in many cases embedded monocrystalline nanoparticles or defected polycrystalline nanograins, an example of the first shown in Figure 2. Diffraction rings correspond with an fcc-based structure with a lattice parameter of 0.360 nm (adiamond = 0.356 nm). The appearance of the 200 ring, extinct for the perfect diamond structure, can be attributed to the existence of multiple lattice defects in the nanograins or a deviation from the perfect diamond lattice in the nanoparticles. In some specimens, micrometer-sized, flake-shaped diamonds could be identified inside the cell-like structures: an example is shown in Figure 3 together with a set of SAED patterns revealing diamond extinctions in the expected positions. In Figure 4 the characteristic diamond ELNES shape of the C K-edge obtained from such a microflake is shown (the small π* edge originates from amorphous C surface material) together with the plasmon peak at 33 eV, the latter shifting to 24 eV for the nanoparticles. The existence of micrometer sized diamonds in some particles was supported by the observation of the characteristic sharp diamond band at 1332.3 cm-1 in Raman spectroscopy, as shown in Figure 5 [2]. S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 833–834, DOI: 10.1007/978-3-540-85226-1_417, © Springer-Verlag Berlin Heidelberg 2008

834

1. 2. 3.

V. Hoffmann, W. Rösler, A. Patzelt, B. Raeymaekers, P. Van Espen, Meteoritics & Planetary Science 40 (2005) A69 Z.Q. Yang, J. Verbeeck, D. Schryvers, N. Tarcea, J. Popp and W. Rösler, (2008) (in press) doi:10.1016/j.diamond.2008.01.104 We kindly acknowledge support of the GOA project on EELS of the University of Antwerp

1.)

2.)

Figure 1. SEM showing foam-like structure in the interior of the spherules. Figure 2. Monocrystalline diamond nanoparticle viewed along cubic zone.

3.) Figure 3. Several diamond microflakes alongside amorphous carbon support together with some SAED patterns with extinctions indicated by crosses in [001] zone.

4.)

5.)

Figure 4. C K-edge ELNES revealing characteristic diamond σ* shape plus plasmon peak at 33 eV in inset. Figure 5. Raman spectrum with diamond peak at 1332.3 cm-1.

835

The use of FIB/TEM for the study of radiation damage in radioactive/non-radioactive mineral assemblages A.-M. Seydoux-Guillaume1, J.-M. Montel1 and R. Wirth2 1. LMTG, UMR 5563 CNRS, UPS, 14 avenue Edouard Belin, 31400 Toulouse, France 2 GFZ, Telegrafenberg, PB 4.1, 14473 Potsdam, Germany [email protected] Keywords: radiation damage, minerals, FIB/TEM

Radiation damage in radioactive minerals has been studied in geosciences for two main reasons. First, U-Th-rich minerals are used for U-Th-Pb datation, and it is essential to understand the effects of radiation damage on lead retentivity. Second, the effect of long term accumulation of radiation damage is a key parameter for assessing the durability of ceramics that could be used for nuclear-waste storage. One strategy typically used is to study naturally radioactive minerals in specific geological contexts by various analytical methods. In contrast to the numerous studies on radiation effects within radioactive minerals, e.g. zircon, monazite, thorite-group…, i.e. “self-damage”, very few have been done on radiation damage effects in Non Radioactive (NR) host minerals. Damage due to irradiation typically appears as concentric structures named "radiohaloes", and are very familiar to petrologists who use them to identify the presence of radioactive minerals in metamorphic or plutonic rocks. Recently, only two papers investigated radiohaloes, in biotite [1] and in chlorite and cordierite [2]. These studies demonstrated that radiohaloes are created by α-particles and correspond only to modifications of optical characteristics of the host mineral. Furthermore, these authors found intensive damage (i.e. amorphous domains visible in the TEM) only in cordierite over a distance of a few tens of nanometers around radioactive inclusions, and assigned them to recoil nuclei. Alternatively the radiohalo may consist of a "large" radioactive (R) /non-radioactive (NR) interface (Figure 1, in Diopside; [3]), between R and NR host mineral, made of completely different minerals. In some case there can also be almost no radiohalo (Figure 1, in Calcite). In this study we present various examples of “radiohaloes” in mineral pairs (thorite/monazite [4], uranothorianite/diopside, uranothorianite /calcite [3]). Most radioactive minerals in rocks are 10-100 µm in size, and the radiohalo thicknesses only 1-30 µm. It is therefore necessary to adapt the techniques to the size of the areas to be investigated. Samples will be characterised by conventional microscopy, SEM, and TEM associated with FIB preparation. This last method is essential because in-situ measurements are needed in order to study the interface between R/NR minerals (Figure 2). 1.

L. Nasdala, M. Wenzel, M. Andrut, R. Wirth, P. Blaum. The nature of radiohaloes in biotite: experimental studies and modeling. American Mineralogist 86, 2001, p. 498-512.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 835–836, DOI: 10.1007/978-3-540-85226-1_418, © Springer-Verlag Berlin Heidelberg 2008

836

2. 3. 4.

L. Nasdala, M. Wildner, R. Wirth, N. Groshopf, D.C. Pal, A. Möller. Alpha particle haloes in chlorite and cordierite. Mineralogy and Petrology 86, 2006, p. 1-27. A.-M. Seydoux-Guillaume, J.-M. Montel, R. Wirth, and B. Moine, Radiation damage in diopside and calcite crystals surrounding uranothorianite, in press in Chemical Geology. A.-M. Seydoux-Guillaume, R. Wirth, and J. Ingrin. Contrasting response of ThSiO4 and monazite to natural irradiation. European Journal of Mineralogy 19, 2007, p. 7-14.

Figure 1. Optical microscope image from two examples of radiohaloes in the Tranomaro skarns (Madagascar). Note the presence of cracks around the uranothorianites (UTh) grains within Cpx, and the difference between the radiohaloes in diopside (Cpx) and in calcite (Cc). After [3]

Figure 2. A-C: SEM images of the UTh / Cpx + Cc interface in figure 1A with FIB locations. D-E: TEM images of Cc1-UTh and Cpx-ϕ boundaries. Note the presence of an amorphous phase (~200 nm thick) between Cc1 and UTh. After [3].

837

Non-destructive 3D measurements of sandstone’s internal micro-architecture using high resolution micro-CT E. Van de Casteele1, S. Bugani2, M. Camaiti3, L. Morselli2 and K. Janssens4 1. SkyScan, Belgium 2. Department of Industrial Chemistry and Materials, University of Bologna, Italy 3. CNR – Institute for Conservation and Enhancement of Cultural Heritage, Italy 4. Department of Chemistry, University of Antwerp, Belgium [email protected] Keywords: X-ray micro-CT, sandstone characterization, 3D analysis

Calcareous stones such as Lecce stones have a high porosity which results in a readily uptake of rainwater. Due to the atmospheric pollutants dissolved in the water these stones, used in a lot of historical buildings, are constantly under attack which leads to a decay of the stone [1]. Different kind of organic hydrophobic products such as Paraloid B72 (PB72) and fluorinated rubber (NH) are often applied as protectives with the aim to reduce the corrosion of the material. In order to study the manner in which these treatment products fill the pores a desktop X-ray microtomography system was used. This technique allows the 3D investigation of the internal structure of the stone in a non-destructive way [2,3]. In this research morphological parameters such as the total porosity (as a percentage of the enclosed empty spaces on the volume of interest), pore size distribution, surface-to-volume ratio (which gives an idea of the complexity of the internal structures) and structure model index (SMI) (giving an estimation of the average shape of the pores (0 = ideal plate, 3 = cylinder and 4 = sphere)) were calculated before and after treatment in order to evaluate the changes induced by the polymer application. The 2D reconstructed cross-sections, shown in Figure 1, confirm that Lecce stone has a very complex internal structure. Several different inclusions such as shells with different shapes and sizes (from a few µm up to 1mm, foraminifera in Figure 1) can be clearly distinguished. The 3D rendering of a small portion of the pores network (Figure 2) gives an idea of the complexity and interconnectivity of the internal structure. The pore size distribution (Figure 2) shows that almost 90% of the pores range from 8 to 29µm. The results of the porosity calculation before and after treatment can be found in Table 1. In both cases the variation of the porosity due to the conservation treatments is significant, but very small. The treatments give very high water repellence to the stone, as reported in [4], but they do not drastically change its natural porosity. X-ray micro-CT is a powerful tool for the investigation of the internal structure of sandstone. The reconstructed cross-sections and 3D rendering of the pores network are able to show, qualitatively the shape and quantitatively the dimension of the pores. Moreover, the data processing allows calculating different morphological parameters useful to characterize the stone. Because µCT is a non-destructive technique and it has a high repeatability, the samples can be monitored during the conservation treatments following the changes in porosity of the specimens that may occur.

S. Richter, A. Schwedt (Eds.): EMC 2008, Vol. 2: Materials Science, pp. 837–838, DOI: 10.1007/978-3-540-85226-1_419, © Springer-Verlag Berlin Heidelberg 2008

838

Figure 1. Left: Reconstructed cross-section of a Lecce stone sample scanned with micro-CT at a pixel size of 2.5µm. Right: A zoom of a reconstructed cross-section of a Lecce stone, including the orthogonal views made through the shell in the middle.

Figure 2. Left: 3D rendering of the pore network of a Lecce stone. Right: Pore size distribution calculated with the sphere fitting method [5] Table 1. Porosity calculated before and after the treatment

1. 2. 3. 4. 5.

Product

Before

After

Decrease

PB72

33.1%

29.5%

3.6%

NH

29.4%

26.5%

2.9%

M. Camaiti, S. Bugani, E. Bernardi, L. Morselli and M. Matteini, Applied Geochemistry 22 (2007): p.1248-1254. A. Sasov, Journal of Microscopy, 147(2) (1987): p.169-192. A. Sasov and D. Van Dyck, Journal of Microscopy, 191(2) (1998): p.151-158 S. Bugani, Study of the interactions between nitrogen oxides (NOx) and stone materials treated with conservation products, Master thesis, University of Bologna, Italy, 2004. T. Hildebrand and P. Ruegsegger, Journal of Microscopy, 185 (1997): p.67-75.

Author Index A Abächerli, V. 403 Abe, Y. 59 Abellan, P. 291, 591 Abetz, C. 751 Abetz, V. 751 Aboussaid, K. 235 Abstreiter, G. 295 Abu-Farsakh, H. 83 Acevedo, D. 457 Adams, T.B. 43 Addiego, F. 755 Adikimenakis, A. 55 Adkins, N. 217 Ahrens, B. 551 Aimadeddine, M. 51 Ajroudi, L. 233 Akamatsu, M. 427 Ako, K. 757 Alandes, L. 735 Albrecht, M. 83 Albu, M. 387 Alexe, M. 101, 329 Algarabel, P.A. 607 Algra, R. 159 Ali, M.F. 829 Alloyeau, D. 187 Almeida Filho, A. 401 Almeida, T. 293 Alonso-González, P. 91 Amatucci, G.G. 525 Ambacher, O. 77 Amstatt, B. 85 Andersen, S.J. 395 Andreano, G. 747 Andrews, A. 149 Andrieu, F. 7 Aouine, M. 185 Aouni, A. 75 Arbiol, J. 223, 295, 597, 643

Arenal, R. 117, 167 Arkharova, N. 119 Arnal, V. 51 Arnberg, L. 435 Arnold, B. 719 Arnoldi, F. 411 Arroyo Rojas Dasilva, Y. 637 Arruebo, M. 597 Aschenbrenner, T. 81 Ash, P. 249 Åsholt, P. 435 Attané, J.P. 613 Austrheim, H. 809 Auzely-Velty, R. 745 Ávila, D. 325 Ávila-Brande, D. 173 Aydemir, U. 531 Ayoub, J.P. 677

B Backen, E. 371 Báez, M.I. 805, 831 Bai, X.D. 115 Bailly, A. 151 Baitinger, M. 531 Bakkers, E.P.A.M. 159 Baldonedo, J.L. 805, 831 Ballif, C. 335 Bals, S. 141, 273, 739 Baluc, N. 503 Bamba, G. 415 Bando, Y. 115 Banerjee, S. 495, 641 Banhart, F. 121, 155 Banhart, J. 279 Baram, M. 521 Baratto, C. 127 Barbot, J.-F. 663 Bargar, J. 315

840

Barlas, B. 435 Barna, P.B. 389 Baro, M.D. 311 Baron, T. 125, 151 Barrett, N. 151 Barthlott, W. 743 Bartova, B. 383, 391, 419, 531 Batov, D.V. 179 Battezzati, L. 437 Bauer, M. 15 Bayle-Guillemaud, P. 189, 611, 613 Beck, U. 725 Bécu, L. 757 Beddies, G. 365 Belkadi, A. 639 Bell, A.J. 547 Bellet-Amalric, E. 85 Bellitto, S. 241 Beltrán, A.M. 45, 91 Ben, T. 45, 91 Benaissa, M. 303 Bender, H. 15, 35, 393 Benedetti, A. 327 Benker, N. 285 Bermanec, V. 157 Bernal, S. 183, 239, 271 Bernard, R. 289 Bernier-Latmani, R. 315 Bertagnolli, E. 149 Bertho, S. 759 Bertin, F. 37 Bett, A.W. 669 Bhattacharyya, S. 523, 761 Bidal, G. 33 Bijelić, M. 157 Birajdar, B.I. 329 Biskupek, J. 111, 655 Bittencourt, C. 141 Bjorge, R. 395 Blank, H. 65 Blank, V.D. 175, 179 Błaż, L. 453, 455 Bleck, W. 485 Bleloch, A.L. 305, 331, 365, 587 Blicharski, M. 347

Author Index

Blumtritt, H. 217 Blyth, R.I.R. 821 Bochniak, W. 455 Bocker, C. 523 Boe, A. 509 Boekema, E.J. 791 Boese, M. 325 Boeuf, F. 33 Bogdanoff, P. 279 Bohácek, J. 267 Boldyreva, K. 101 Bonetti, E. 309 Bonnot, A.M. 117, 205 Borgström, M.T. 159 Börjesson, J. 297 Borsali, R. 783 Böttcher, A. 253 Boudin, S. 571 Bougerol, C. 85 Boulanger, L. 397 Boullay, P. 323, 527 Bourgeois, L. 399 Bovi, M. 727 Bowen, J.R. 349 Brabetz, M. 493 Brånemark, R. 741 Brault, J. 303 Bréchet, Y. 427, 483 Briggs, G.A.D. 177 Briot, O. 69 Briston, K.J. 169 Brizard, A.M.A. 791 Brokmeier, H.-G. 827 Brown, A.P. 601 Brown, D.P. 135 Brown, P.D. 113, 293, 731 Browning, N.D. 69 Brun, N. 205, 717 Bruno, P. 167 Brydson, R.M. 215, 601 Buban, J.P. 667 Büchner, B. 307 Buffat, P.A. 315, 681, 793 Bugajski, M. 61 Bugani, S. 837

Author Index

Bullough, T. 143 Bund, A. 685 Burghardt, H. 191 Burnett, T.L. 547 Buso, S.J. 401, 421

C Cabié, M. 193 Cabo, M. 311 Cadete Santos Aires, F.J. 185 Caignaert, V. 323 Caillard, D. 635 Caliste, D. 665 Callini, E. 309 Calmels, L. 631, 715 Calvino, J.J. 183, 199, 213, 235, 239, 271 Camaiti, M. 837 Camassel, J. 57 Campion, R.P. 47 Cantoni, M. 79, 403, 531, 793 Cao, S. 405 Carati, A. 201 Carbó-Argibay, E. 259 Carbone, D. 255 Cardoso, M. 781 Carrillo-Cabrera, W. 407 Casanove, M.J. 291, 591 Casci, J. 249 Castell, M.R. 171 Castell, O. 311 Castro, A. 543 Cauqui, M.A. 213 Cavallotti, P.L. 687 Cedergren, K. 357 Čeh, M. 129, 585 Cellai, L. 747 Cerezo, A 41 Chabli, A. 9 Chaliampalias, D. 701, 703, 705, 707 Chalker, P.R. 143 Chamard, V. 11 Chapman, J.N. 391

841

Chausson, S. 785 Chauvat, M.P. 89 Cheng, C. 723 Cherns, D. 47 Cherns, P.D. 49 Cheynet, M. 33, 51, 195, 683 Chèze, C. 143 Chiba, A. 447 Chisholm, M.F. 45 Chmielowski, R. 347 Chou, Y.H. 215 Chrissafis, K. 701, 703, 705 Chuvilin, A.L. 123, 381 Ciancio, R. 357 Cimalla, V. 77 Cleij, T.J. 759 Clement, L. 9 Clifton, P.H. 41 Cockayne, D.J.H. 177, 519 Coe, S. 731 Coghe, F. 499 Cojocaru, P. 687 Coleman, J.N. 145 Colliex, C. 103, 289, 717 Colombo, C. 295 Comini, E. 127 Comyn, T.P. 547 Cooper, D. 9 Coraux, J. 85 Cordier, P. 803 Cornet, N. 529 Correa-Duarte, M.A. 153 Cosandey, F. 525 Cossange, C. 411 Costa, P.M.F.J. 115 Cotton, N.J. 737 Coulon, P.E. 715 Craven, A.J. 23, 67, 409 Creemer, J.F. 197 Crozier, P.A. 277 Cullis, A.G. 169 Curiotto, S. 437 Czerwinski, A. 61 Czyrska-Filemonowicz, A. 459, 517, 681, 699

842

D Dahl, S. 211 Dahmen, U. 367, 473 Dahoun, A. 755 Daneu, N. 361 Dartsch, H. 81 Daudin, B. 85 Dawson, P. 41 de Dios, S. 567 De Gendt, S. 23 De Keyser, K. 365 De Mierry, P. 71 De Riccardis, M.F. 255 De Teresa, J.M. 607 de With, B. 795 Deak, D.S. 171 Deffieux, A. 783 Delabrouille, F. 411 Delalande, M. 189 Delannay, F. 649 Delaye, V. 7 Deleonibus, S. 7 Delgado, J.J. 199 Delplancke-Ogletree, M.P. 709 Delville, R. 383, 413 Demolon, P. 71 den Hertog, M.I. 125 Denker, C. 93 Denorme, S. 33 Desbois, G. 807 Desinan, S. 271 Desré, P.J. 125 Detavernier, C. 365 Detemple, E. 109 Dey, G.K. 495, 625, 641 D’Haen, J. 759 Dhalluin, F. 125 Di Girolamo, G. 777 Di Martino, J. 755 di Monte, R. 271 Di Paola, E. 201 Díaz-Droguett, D. 203 Dieterle, L. 593 Dietrich, C. 595

Author Index

Dietrich, D. 685, 687 Dietz, W. 729 Dimitrakopulos, G.P. 53, 55, 537, 639, 651 Dimroth, F. 669 Dłużewski, P. 133, 301, 639 Dohmen, R. 817 Dolzhikov, S.V. 471 Dong, C. 319 Donnadieu, P. 11, 415, 417 Dorbandt, I. 279 Dorcet, V. 527 Dörfel, I. 689 Dosch, H. 225 Douthwaite, R.E. 215 Dražić, G. 713 Dresen, G. 817 Dressler, M. 689 Drewello, V. 107 Drube, W. 141 Dubiel, B. 517 Ducati, C. 165 Dudeck, K. 519 Dunin-Borkowski, R. 165 Dupeyre, D. 781 Duppel, V. 653 Duran, A. 523 Durand, D. 757 Dybal, J. 767

E Edmonds, D.V. 429, 431 Edwards, H.K. 731 Eggeler, G. 515 Eibl, O. 351, 353, 355, 371 Eilers, G. 107 Eisenschmidt, C. 551 Elis, C. 779 Emanuelsson, L. 741 Endo, N. 763 Ene, C. 105, 261 Eneman, G. 15 Engel, S. 353, 371 Engelmann, H.J. 13

Author Index

Engqvist, H. 741 Engvik, A. 809 Ensslin, K. 131 Entlicher, G. 767 Epicier, T. 457 Ericson, F. 741 Erni, R. 39, 231, 473 Ernst, T. 7 Ersen, S. 195 Erwan, S. 769 Escribano, S. 207 Escudero, A. 801 Espinoza, R. 419 Esposito, C. 777 Espósito, I.M. 401, 421 Essoumhi, A. 233 Estradé, S. 295, 643 Eswaramoorthy, S.K. 633 Etheridge, J. 229 Eustace, D.A. 177 Ezcurdia, M. 221

F Faglia, G. 127, 747 Falke, M. 331, 365 Falke, U. 331 Fang, Y. 339 Farley, N. 47 Farooq, M.U. 547 Favia, P. 15, 393 Fay, M.W. 113, 731 Faynot, O. 7 Fecht, H. 217 Feiner, L.F. 159 Felten, A. 141 Feltin, E. 79 Fendrych, F. 603 Feng, Y. 305 Fenouiller-Beranger, C. 33 Fernández, A. 697, 709 Fernández-Pacheco, R. 597 Ferret, P. 125, 139 Ferroni, M. 127, 247, 747 Feuerbacher, M. 459, 645

843

Feuillet, G. 139 Fiawoo, M.F. 117, 205 Fiechter, S. 279 Figge, S. 81 Fischer, R.A. 275 Fitting, H.-J. 17, 529 Flamini, A. 747 Fleurier, R. 117 Flükiger, R. 403 Fonin, M. 621 Fonstad, C.G. 75 Fontcuberta i Morral, A. 295 Fontcuberta, J. 643 Fornara, A. 209 Fourlaris, G. 423, 445, 449, 451 Fournel, F. 665 Foxon, C.T. 47 Frangis, N. 57 Freitag, B. 359 Frenkel, A.I. 281 Fritz, M. 733 Fuchs, D. 593 Fuenzalida, V. 203 Fuess, H. 539 Fujita, Y. 773 Furuya, K. 299, 775

G Gaebler, U. 29 Gaengler, P. 729 Gajović, A. 129 Galerie, A. 415 Galindo, P.L. 45 Galinski, H. 105 Gallo, J. 767 Galtrey, M.J. 41 Galy, J. 543 Gammer, C. 425 Gan, Y. 121 Gao, X.S. 329 Garcia, A. 427 García, M.J. 831 García, R. 69, 75, 77 García-García, A. 607

844

García-González, E. 579 Gass, M. 305, 587, 723 Gassler, N. 727 Gatel, C. 611, 631 Gatica, J.M. 213 Gaudin, G. 613 Gauthier, C. 771 Gautier, E. 33, 613 Gayo, M.D. 805, 831 Geelhaar, L. 83, 143 Geiger, D. 573 Geisler, H. 13 Geist, D. 647 Gemming, S. 573 Gemming, T. 307, 719 Gentile, P. 125, 151 Georgakilas, A. 53, 55 Gerthsen, D. 65, 253, 593, 621 Geserick, J. 219 Ghijsen, J. 141 Gibbs, M.R.J. 599 Gibert, M. 291, 327 Gimel, J.-C. 757 Giorgi, L. 241 Giorgi, M.-L. 333 Giorgio, S. 193 Gloux, F. 89 Gnanavel, T. 599 Godard, O. 755 Godinho, V. 709 Goennenwein, S.T.B. 623 Goetze, F. 29 Goeuriot, D. 529 Golberg, D. 115 Goll, D. 109 Golla-Schindler, U. 265, 809, 811, 825 Golovko, Yu.I. 381 Golubev, Ye.A. 813, 815 Gómez-Herrero, A. 173 González Calbet, J.M. 567, 579 González, D. 69, 77 Gonzalez, L. 91 Gonzalez, Y. 91 Goo, N.H. 109 Gordillo, G. 363

Author Index

Goris, B. 739 Górka, Ł. 453 Gottstein, G. 433 Gouné, M. 477 Goya, G.F. 223 Gradečak, S. 157 Graham, D.M. 41 Gramm, F. 131 Grandjean, N. 79, 637 Grant, D.M. 731 Gregori, G. 565 Gries, K. 733 Griffiths, I. 47 Grill, R. 493 Grobert, N. 169 Gross, R. 623 Grothausmann, R. 279 Grudin, B.N. 471 Gruen, D.M. 167 Grzelczak, M. 153 Gu, L. 243, 659 Guerret-Piécourt, C. 529 Guetaz, L. 207 Gupta, A. 605 Gustafsson, D. 357 Gustafsson, S. 209 Gutmann, E. 569 Gysemans, M. 739

H Habermeier, H.-U. 379 Haeldermans, I. 759 Hagen, C.W. 277 Haghi-Ashtiani, P. 333 Hagiwara, M. 557 Hahn, K. 523 Hamada, E. 511 Hamamoto, C. 763 Han, H. 101 Han, L. 111 Hansen, L.P. 137 Hara, T. 385 Harnchana, V. 601 Hartmann, K. 817

Author Index

Hasanovic, S. 79 Haswell, R. 819 Hauguth-Frank, S. 77 Häusler, I. 71, 83, 133 Häussler, D. 691 He, K. 429, 431 Hébert, C. 531 Hebert, S. 545 Hecq, M. 141 Heeg, T. 325 Heggen, M. 459, 645 Heinrich, W. 817 Heinrichs, J. 741 Helveg, S. 197, 211 Hémono, N. 523 Henderson, G.S. 821 Henry, C.R. 193 Hensel, N. 237 Hermanns-Sachweh, B. 727 Hernández Cruz, D. 753 Hernandez, J.C. 91, 183, 213, 271 Hernández-Velasco, J. 543 Hernando, I. 735 Herrera, M. 69 Herring, R.A. 19 Hervieu, M. 545, 571 Hess, C. 317 Hesse, D. 101, 329 Hessler-Wyser, A. 335, 501 Hetterich, M. 65 Hewitt, I.J. 609 Heyroth, F. 337, 821 Hietschold, M. 365 Hindmarch, A.T. 601 Hirayama, T. 667 Hirmer, M. 95 Hirotsu, Y. 619 Hitchcock, A.P. 753 Hiyama, T. 799 Hjelen, J. 513 Hobbs, L.W. 737 Höche, Th. 523, 821 Hoffmann, M. 693 Hoffmann, M.J. 547 Hofmann, S. 165

845

Holland, M.C. 67 Holmestad, R. 395 Holzapfel, B. 351, 353, 355, 371 Hommel, D. 81 Hondow, N.S. 215 Horak, P. 789 Horibuchi, K. 575 Hörmann, U. 217, 219 Horton, M.A. 321 Hotovy, I. 345 Houben, L. 645 Houdellier, F. 5, 147, 631 Hovmöller, S. 679 Hovsepian, P.Eh. 587 Howe, J.M. 633 Hoyer, I. 729 Hu, W. 433 Huault, T. 303 Hüe, F. 5 Huebner, R. 13 Hug, H. J. 99 Humphreys, C.J. 41, 49 Hünert, D. 689 Hungria, A.B. 183, 213 Hüsing, N. 219 Hwang, S. 245 Hÿtch, M.J. 5, 221 Hyun, Y.-J. 149

I Iacopi, F. 161 Ibarra, A. 223 Ibarra, M.R. 223, 597, 607 Idrissi, H. 649 Ignacova, S. 419 Ikeno, S. 467 Ikuhara, Y. 667 Iliopoulos, E. 55 Ilk, N. 721 Imhoff, D. 103 Immink, G. 159 Infante, I.C. 643 Inkson, B.J. 169, 599

846

Inoke, K. 511 Inoue, K. 463 Ishikawa, T. 763 Iskandar, R. 533 Isshiki, T. 59, 557 Iveland, T. 435 Izgorodin, A. 229

J Jacob, D. 803, 823 Jacques, P.J. 649 Jaffres, P.A. 785 Jäger, W. 109, 669, 691 James, R.D. 413 Jančar, B. 129 Janek, J. 369 Janik, E. 133, 301 Jansen, E. 827 Janßen, A. 825 Janssens, K. 837 Jantou, V. 321 Jensen, S.A. 137 Jentoft, F.C. 237 Jia, C.L. 3, 27, 319 Jia, Y. 535 Jia, Z.H. 435 Jiang, H. 135, 535 Jiang, X. 319 Jimenez, M.C. 709 Jinnai, H. 751, 773 Jin-Phillipp, N.Y. 225 Jinschek, J.R. 761 Johansson, C. 209 Johansson, G.A. 753 Johnson, C.L. 221 Johnson, D.D. 281 Johnson, E. 137, 211, 437 Joly-Pottuz, L. 683 Jordovic, B. 553, 555 Jornsanoh, P. 771 Jouneau, P.H. 25, 139 Jourdain, V. 117 Juhel, M. 37 Juillaguet, S. 57

Author Index

Jurczak, G. 639 Juvé, D. 529

K Kaiser, T. 109 Kaiser, U. 111, 123, 217, 219, 379, 381, 655 Kakas, D. 341 Kalabukhov, A. 297 Kalessaki, E. 651 Kallinen, K. 227 Kamilov, T. 31 Kaneko, J. 453, 455 Kaneko, T. 751 Kanerva, T. 227 Kaplan, W.D. 521 Kappers, M.J. 41, 49 Karakostas, Th. 55, 537, 651 Karczewski, G. 301 Karnthaler, H.P. 385, 425, 465, 481, 489, 505, 647 Karppinen, M. 535 Kasinathan, S. 413 Kašpar, J. 271 Katcho, N.A. 173 Kątcki, J. 61 Katz, H. 229 Kauppinen, E.I. 135, 535 Kawabata, T. 467 Ke, X. 141 Kehagias, Th. 53, 537, 651 Khlobystov, A.N. 113, 123 Khongphetsak, S. 47 Kielbus, A. 439, 441 Kienle, L. 653 Kim, J. 245 Kinnunen, T. 227 Kioseoglou, J. 639, 651 Kirmse, H. 55, 71, 133, 301 Kisielowski, C. 39 Klechkovskaya, V.V. 119, 793 Kleebe, H.-J. 539 Klein, O. 655 Klementová, M. 603

Author Index

Klenov, D. 15 Klimenkov, M. 443 Kling, J. 539 Klingeler, R. 307 Kniep, R. 749 Knote, A. 695 Kobayashi, E. 181 Kobe, S. 617, 627, 713 Kobylko, M. 289 Koch, C.T. 243, 565 Koch, K. 743 Kociak, M. 289 Koguchi, M. 549 Kohout, J. 603 Kokkonidis, P. 445, 449, 451 Kolosov, V.Yu. 343, 657 Komiyama, J. 59 Komninou, Ph. 53, 55, 537, 639, 651 Kong, J.H. 281 Konno, T.J. 447, 619 Konstantinidis, K. 449 Korytov, M. 303 Kosaka, N. 799 Kosiel, K. 61 Kothleitner, G. 387 Kourkoutis, L. 17 Koutsoukis, T. 445, 449, 451 Kovacevic, L. 341 Kovaleva, O.V. 813 Kozhin, A.V. 343 Kraczewski, G. 133 Kralova, D. 263, 765 Krasheninnikov, A.V. 121 Krause, M. 29 Kreiner, G. 407 Kremin, Chr. 693 Kret, S. 133, 301 Krill, G. 103 Krishnan, M. 605 Kröger, R. 733 Kruit, P. 277 Krumeich, F. 541, 579 Kubacka-Traczyk, J. 61 Kübel, C. 733 Kuhn, L.T. 349

847

Kula, A. 453, 455 Kulnitskiy, B.A. 175, 179 Kundu, A.K. 323 Kunert, B. 43 Kungl, H. 547 Kunze, K. 827 Kups, Th. 345, 693, 695 Kuritka, I. 789 Kuskova, A.N. 381

L Lae, L. 417 Lafond, D. 7 Lampke, Th. 685, 687 Lancin, M. 677 Lančok, A. 603 Lançon, F. 665 Landa-Cánovas, A.R. 173, 543 Lange, R. 725 Langenhorst, F. 801 Langlois, C. 187 Lapcikova, M. 767 Lari, L. 143 Łaszcz, A. 61 Lauterbach, S. 539 Le Bouar, Y. 187 Le Guillou, C. 163 Le Pluart, L. 785 Lebedev, O.I. 63, 231, 275 Lebedev, V. 77 Lebius, H. 87 Lee, W. 101 Lefebvre, C. 783 Legendre, F. 397 Legras, L. 411, 427, 483 Leguen, C. 457 Leipner, H.S. 337 Lekston, Z. 491 Lenk, A. 21 Lepistö, T. 227 Lepoittevin, C. 545 Lereah, Y. 269 Leroux, Ch. 233, 347

848

Leroux, F. 739 Leroux, H. 823 Letrouit, A. 571 Leturcq, R. 131 Levin, A.A. 569 Li, J. 753 Li, L. 281 Li, Z.Y. 161, 305 Liang, D. 141 Lichte, H. 21, 269, 363, 569, 629 Licoccia, S. 241 Lim, T. 737 Lima, E. 223 Linck, M. 269, 629 Lindau, R. 443 Lindberg, F. 741 Lipińska-Chwałek, M. 459 Lis, A. 461 Lis, J. 461 Lisiecki, I. 273 Litvinov, D. 65 Liu, Y.-L. 349 Liz-Marzán, L.M. 153, 221, 243, 259 Löffler, D. 253 Löffler, M. 307 Loiseau, A. 117, 187, 205 Lok, M. 249 Lomba, E. 173 Lombardi, F. 357 Longo, P. 67 Loos, J. 769, 795 Lopatin, S. 359 López-Cartes, C. 697 López-Castro, J.D. 199 López-Haro, M. 183, 199, 235 Lotnyk, A. 101 Lozano, J.G. 69, 77 Lu, K. 769 Luca, S. 25 Ludwig, A. 515 Lugstein, A. 149 Lukin, G. 43 Lutsen, L. 759 Luysberg, M. 325

Author Index

M MacFarlane, D.R. 229 MacKenzie, M. 23, 409 MacLaren, I. 547, 581 Mader, W. 191, 623 Madey, T.E. 277 Madigou, V. 233, 347 Maebara, T. 673 Maeda, H. 463 Magén, C. 607 Mahmoud, H.M. 829 Maier, J. 565 Makino, M. 181 Makongo, J.P.A. 407 Malik, S. 609 Malindretos, J. 93 Malo, S. 545 Manca, J. 759 Mangler, C. 425, 465, 481 Manikrishna, K.V. 495 Manolaki, P. 71 Mansouri, S. 87 Mantl, S. 27 Marandian Hagh, N. 525 Marazzi, R. 241 March, K. 103 Maret, M. 11 Marinova, M. 57 Marioara, C.D. 395 Mariolle, D. 25 Marioni, M. 99 Markovich, G. 269 Marquina, C. 597 Marquis, E.A. 473 Marrows, C.H. 601 Martin, D. 637 Martin, J.M. 683 Martínez-Martínez, D. 697 Marty, A. 611, 613 Masenelli-Varlot, K. 25, 771 Massa, W. 799 Massaro, M. 777 Masseboeuf, A. 611, 613 Mateo, A. 479

Author Index

Matlock, D.K. 429, 431 Matos, J.R. 401 Matsuda, K. 467 Matsumoto, H. 447, 773, 775 Matsumoto, K. 283 Matsumoto, T. 549 Mattausch, Hj. 653 Matzeck, Ch. 629 Mayer, G. 621 Mayer, J. 485, 533 Mazeau, K. 781 Mazzucco, S. 289 McAleese, C. 41, 49 McComb, D.W. 23, 177, 321 McFadzean, S. 23 McGilvery, C.M. 23 Méndez Martin, F. 387 Meng, Y. 659 Mensch, K. 819 Menzel, S. 355 Mercey, B. 323 Mercurio, D. 373 Merrifield, R. 305 Meshi, L. 47 Meyer, C. 237 Meyer, D.C. 569 Meyer, J. 39 Mi, S.B. 27 Mickel, C. 355, 371 Miclea, P.T. 551 Midgley, P.A. 91, 183, 723 Miglierini, M. 603 Mihaï, A. 613 Mihailovic, D. 145 Miletic, A. 341 Miljkovic, M. 553, 555 Minkow, A. 217 Minor, A.M. 287 Mira, C. 239 Mirabile Gattia, D. 241 Miron, M. 613 Mishra, R.K. 287 Misják, F. 389 Mitic, V. 553, 555 Mitome, M. 115

849

Mitsuishi, K. 299 Mizera, J. 441 Mizoguchi, T. 667 Mliki, N. 233 Möbus, G. 599 Modin, E.B. 471 Mogilatenko, A. 73 Mohn, E. 257 Molenbroek, A.M. 197 Molina, L. 351, 353, 355 Molina, S.I. 45, 75, 91 Molina-Luna, L. 371 Mompiou, F. 635 Monachon, C. 335 Monnet, I. 87 Monnier, V. 189 Montag, R. 729 Montanari, E. 201 Monteiro, W.A. 401, 421 Montel, J.-M. 835 Monthioux, M. 147 Montone, A. 241 Morales, F.M. 75, 77 Morandi, V. 127, 247 Morante, J.R. 295 Morawiec, M. 469 Morellón, L. 607 Moreno, C. 591 Mori, H. 283 Morimoto, Y. 181 Morin, M. 781 Morselli, L. 837 Moskalewicz, T. 699 Möslang, A. 443 Mouti, A. 79 Muddle, B.C. 399 Muehle, U. 29 Muhammed, M. 209 Mühle, U. 21 Mukhortov, V.M. 381 Müller, E. 131 Muller, K. 723 Muñoz, F. 523 Münzenberg, M. 107 Mur, P. 11

850

Murafa, N. 267 Muralidharan, G. 633 Murray, R.T. 143 Muszalski, J. 61 Muto, S. 575, 577 Mutoro, E. 369

N Najafi, E. 753 Nakamura, J. 467 Nakanishi, H. 59 Nakayama, A. 799 Nasibulin, A.G. 135 Nelayah, J. 243 Nellist, P. 145 Nemeth, I. 43 Neogy, S. 641 Nesper, R. 579 Nespurek, S. 789 Neugebauer, J. 83 Neumann, H.-G. 725 Neumann, W. 55, 71, 73, 133, 301 Newell, D.T. 171 Neykova, N. 765 Nicholls, R.J. 177 Nicolai, T. 757 Nicolosi, V. 145 Nielsen, K. 623 Niemietz, A. 743 Niermann, T. 93 Nietzsche, S. 729 Nikolaidis, K. 707 Nilsen, T. 513 Nishida, I. 577 Nishio, K. 59, 557 Nishioka, H. 763 Nitta, N. 283 Nofz, M. 689 Nolte, P. 225 Nolze, G. 659 Nouet, G. 87 Novak, S. 713 Novikov, S.V. 47 Nowak, C. 261

Author Index

Nozaki, K. 799 Nuzzo, R.J. 281 Nygård, J. 137

O Obergfell, D. 123 Obradors, X. 291, 327, 591 Oehler, F. 125 Ögüt, B. 691 Oh, Y.-J. 245 Ohkura, Y. 763 Oikawa, T. 187, 763 Oksiuta, Z. 503 Olenev, A.V. 63 Olibet, S. 335 Oliver, R.A. 41 Ollivier, A. 333 Olsson, E. 209, 297, 313, 357, 661 Opel, M. 623 Orekhov, A. 31 Ortolani, L. 127, 147, 247 Östberg, G. 661 Otarola, T. 479 Otero-Díaz, L.C. 173 Ozkaya, D. 249

P Pacaud, J. 559 Pailloux, F. 559, 663 Palmer, R.E. 305 Palmquist, A. 741 Pantel, R. 33, 37 Papa, F. 711 Papadopoulou, E. 445, 449, 451 Paraskevopoulos, K.M. 829 Pardo, J.A. 607 Pardoen, T. 509 Parras, M. 567 Pascual, M.J. 523 Pasquini, L. 309 Pastoriza-Santos, I. 221, 259 Pastoriza-Santos, L. 243 Patzke, G.R. 541

Author Index

Pauc, N. 151 Paunovic, V. 553, 555 Pavlidou, E. 55, 701, 703, 705, 707, 829 Pavlovic, V.B. 553, 555 Peiró, F. 295, 643 Peláiz-Barranco, A. 581 Pellicer, E. 311 Peng, Y. 169, 599 Penkalla, H.J. 699 Pennycook, S.J. 45 Perez, M. 457 Perezhogin, I.A. 175, 179 Pérez-Juste, J. 153, 259 Pérez-Munuera, I. 735 Perez-Omil, J.A. 183, 199, 213, 239, 271 Perillat, G. 139 Pesce, E. 777 Peterlechner, M. 489, 505 Petersson, K. 209 Pettersson, H. 357 Pettifor, D.G. 177 Pfund, A. 131 Phiu-on, K. 485 Pichaud, B. 677 Picher, M. 117 Pignot-Paintrand, I. 745 Pileni, M.P. 273 Pillet, J.C. 613 Pintado, J.M. 235 Pireaux, J.J. 141 Piscopiello, E. 241, 309, 777 Plotnikov, V.S. 471 Poelt, P. 779 Pohl, D. 257 Pohl, M.-M. 251 Poissonnet, S. 397 Pokorny, D. 767 Pokrant, S. 9, 51, 195, 683 Polyakov, E.V. 179 Polychroniadis, E.K. 57, 615 Pöml, P. 811 Pongratz, P. 149 Ponzoni, A. 747

851

Popescu, R. 253 Popp, J. 833 Porfyrakis, K. 171 Porter, A.E. 723, 737 Posilović, H. 157 Postava, K. 603 Postigo, P.A. 75 Potapov, P. 13 Powell, A.K. 609 Prellier, W. 323 Presz, A. 301 Pretorius, A. 81 Pritzel, C. 561, 563 Prots, Y. 407 Prusik, K. 469 Pryds, N. 437 Puig, T. 291, 327, 591 Pum, D. 721 Pustovalov, E.V. 471 Putaux, J.L. 781, 783 Putnis, A. 809, 825

Q Quiles, A. 735

R Raanes, M.P. 513 Rabet, L. 499 Radmilovic, V. 367, 473 Radnóczi, G. 389 Rahmati, B. 565 Rainforth, W.M. 587, 711 Ramar, A. 475, 503 Ramírez-Castellanos, J. 567, 805, 831 Ramm, J. 719 Ramos, A.S. 487 Rappaz, M. 501 Raskin, J.P. 509 Ratajczak, J. 61 Rautama, E.-L. 323 Raveau, B. 323 Re, M. 255 Rechenberg, H. 223

852

Recnik, A. 361 Redjaïmia, A. 477, 479 Regula, G. 677 Reibold, M. 569 Reingruber, H. 779 Reiss, G. 107 Reiss, P. 189 Rellinghaus, B. 257, 351, 371 Remmele, T. 83 Renard, K. 649 Renault, O. 151 Rentenberger, C. 425, 465, 481, 647 Retoux, R. 571, 785 Richard, O. 35 Richter, E. 73 Richter, M. 251 Ricolleau, C. 187 Riechert, H. 83, 143 Ripalda, J.M. 45 Rizos, A. 445 Rizzi, A. 93 Rizzo, F.C. 429, 431 Robert, T. 57 Robertson, J. 165 Rodmacq, B. 613 Rodríguez, A. 805 Rodriguez, B.J. 101, 329 Rodríguez-González, J.B. 153, 221, 259 Rodriguez-Manzo, J.A. 121, 155 Rojas, T.C. 709 Romer, S. 99 Rosenauer, A. 81, 733 Rosina, M. 139 Rösler, W. 833 Rösner, H. 359 Ross, C.A. 245 Ross, I.M. 711 Ross, U. 691 Rossell, M.D. 473 Rossinyol, E. 311 Roth, C. 285 Roth, S. 123 Rothe, K. 337 Rother, A. 569, 573, 629

Author Index

Roumeli, E. 829 Rousseau, K. 665 Rouvière, J.L. 33, 85, 125, 665 Rouzaud, J.N. 163 Rozhkova, N.N. 815 Rožman, K.Ž. 617, 627 Ruch, D. 755 Rüdiger, U. 621 Rudolf, C. 671 Rueff, J.M. 785 Ruffenach, S. 69 Rühle, M. 369 Rüssel, C. 523 Russell, B.C. 171 Ruterana, P. 87, 89 Rybacki, E. 827 Ryelandt, L. 649 Ryelandt, S. 649

S Sader, K. 305 Safi, A. 509 Saghi, Z. 599 Sahonta, S.-L. 53, 55 Saijo, H. 361 Saintoyant, L. 483 Sakellari, D. 615 Sales, D.L. 45, 91 Salh, R. 17 Samardžija, Z. 617, 713 Samson, Y. 189 Sánchez, A.M. 45, 91 Sanchez, F. 643 Sanchez, S. 281 Sánchez-López, J.C. 697 Sandino, J. 363 Sandiumenge, F. 291, 327, 591 Sano, H. 773, 775 Santamaría, J. 597 Sarantopoulou, E. 627 Sarro, P.M. 197 Sasaki, T. 575 Sasano, Y. 575 Sato, K. 511, 619

Author Index

Sato, T. 467 Sato, Y. 667 Savalia, R.T. 641 Sberveglieri, G. 127, 747 Schade, M. 337 Schaloske, M.C. 653 Schamm, S. 715 Schaper, A.K. 787, 799 Schappacher, M. 783 Schäublin, R. 475, 503 Schauer, F. 789 Schauer, P. 789 Scherer, T. 217 Schertl, H.-P. 803 Scheu, C. 369 Schils, H. 217 Schletter, H. 365 Schlögl, R. 237, 317 Schmid, H. 191 Schmid, I. 99 Schmidt, B. 17 Schmitt, L. 539 Schmitz, G. 105, 261 Schneider, J.M. 533 Schneider, M. 251 Schneider, R. 65, 253, 621 Schofield, E. 315 Scholz, F. 655 Schöne, J. 669 Schrempel, F. 821 Schröder, F. 275 Schryvers, D. 383, 391, 405, 413, 419, 497, 499, 509, 649, 833 Schubert, J. 325 Schuhmann, H. 93 Schultz, L. 257, 371 Schulze, S. 365 Schwamm, C.L. 343 Schwedt, A. 485 Schweizer, S. 551 Scotchford, C.A. 731 Seeber, B. 403 Seibt, M. 93, 107, 671 Selve, S. 219 Senz, S. 101

853

Serin, V. 631, 717 Servanton, G. 37 Seydoux-Guillaume, A.-M. 835 Sharma, R. 165 Sharp, J. 315 Sheets, W.C. 323 Shibata, N. 667 Shih, S.-J. 519 Shima, T. 557 Shimojo, M. 299, 775 Shiojiri, M. 361 Shorubalko, I. 131 Siemes, H. 827 Sigle, W. 109, 243, 565 Sigumonrong, D.P. 533 Silly, F. 171 Simões, S. 487 Simon, A. 653 Simon, J. 623 Simon, J.P. 11 Simon, P. 749 Simonsen, S.B. 211 Sittner, P. 419 Skepper, J. 723 Skolianos, S. 701, 705 Skoric, B. 341 Slabzhennikov, E.S. 471 Sleytr, U.B. 721 Slouf, M. 263, 765, 767 Smalc-Koziorowska, J. 53 Snauwaert, J. 739 Snoeck, E. 5, 221, 607, 631 Snoek, E. 611 Sobota, J. 453, 455 Soda, M. 95 Sojref, R. 689 Solberg, J.K. 513 Solórzano, G. 203 Soltan, S. 379 Sommer, D. 265 Song, M. 299, 775 Sontakke, P. 605 Sørensen, C.B. 137 Sosna, A. 767

854

Sourmail, T. 457 Sourty, E. 159, 795 Spaldin, N. 573 Speer, J.G. 429, 431 Spiecker, E. 367, 669, 691 Spieß, L. 345, 693, 695 Spiradek-Hahn, K. 493 Spirkoska, D. 295 Srivastava, A.P. 625 Srivastava, D. 625, 641 Srot, V. 109, 369 Stadelmann, P. 79, 637 Steiner, G. 489 Stephan, O. 167, 183, 205 Stergioudis, G. 701, 705, 707 Stierle, A. 225 Stodolna, J. 823 Stöger-Pollach, M. 97 Stolz, W. 43 Stolze, L. 671 Stordeur, M. 337 Störmer, M. 691 Stöver, H. 753 Strand, H. 313 Štrichovanec, P. 607 Strondl, C. 711 Stróż, D. 491 Stuart, M.C.A. 791 Šturm, S. 129, 585, 627 Su, D.S. 237, 317 Šubrt, J. 267 Suenaga, K. 1 Sugamata, M. 453, 455 Sugimori, H. 773 Sugiyama, A. 463 Sukedai, E. 673 Sun, J. 675 Sun, J. 679 Sun, L. 121, 155 Suvorova, E.I. 31, 119, 315, 793 Suzuki, S. 59 Svensson, K. 297, 313 Swinnen, A. 759 Szalay, G. 493

Author Index

Szarpak, A. 745 Szatmáry, L. 267 Szwarcman, D. 269

T Tadano, T. 447 Taguchi, E. 463 Takahashi, Y. 549 Takeguchi, M. 299 Takeuchi, Y. 575 Tambe, M. 157 Tanabe, T. 773 Tanaka, A. 283 Tanaka, M. 299 Tang, D. 769 Tao, T. 731 Tapfer, L. 777 Tarcea, N. 833 Tatsumi, K. 575, 577 Terrones, H. 155 Terrones, M. 121, 155 Tessonnier, J.-P. 317 Tewari, R. 495, 641 Texier, M. 677 Thapa, S.B. 655 Thayne, I.G. 67 Thersleff, T. 351, 355, 371 Thibault, J. 205 Thiel, K. 107 Thiemig, D. 685 Thollet, G. 25, 771 Thomas, A. 107 Thomas, J. 719 Thomas, S.G. 15 Thompson, C.V. 245 Thomsen, P. 741 Tian, H. 383, 497 Tietema, R. 711 Tirry, W. 405, 499 Todaka, Y. 385 Todros, S. 127 Tolley, A. 473 Tonejc, A. 157 Tonejc, A.M. 157

Author Index

Toplišek, T. 713 Torres-Pardo, A. 579 Touzin, M. 529 Trasobares, S. 183, 199, 213, 235, 271 Traversa, E. 241 Tréheux, D. 529 Trettin, R. 561, 563 Trolliard, G. 373, 527 Truche, R. 9 Tsakaloudi, V. 615 Tsiakatouras, G. 53 Tsiaoussis, I. 57 Tsilika, I. 537 Tsuchiya, K. 385, 505 Tsuji, M. 797, 799 Turner, S. 273, 275 Tzormpatzdi, V. 423

U Ubben, K. 107 Uecker, R. 73 Uglietti, D. 403 Ukyo, Y. 575 Umemoto, M. 385 Urai, J.L. 807 Urban, K. 3, 27 Urones-Garrote, E. 173 Utess, D. 13

V Valkeapää, M. 535 van Aken, P.A. 109, 225, 243, 369, 523, 565, 659, 821 van Bavel, S. 795 Van de Casteele, E. 837 Van Den Broek, W. 405 van der Laak, N.K. 41 van Dorp, W.F. 277 van Enckevort, W.J.P. 159 van Esch, J.H. 791 Van Haesendonck, C. 739 Van Humbeeck, J. 497

855

Van Marcke, P. 35 Van Tendeloo, G. 63, 141, 231, 273, 275, 545, 739 Vanderzande, D. 759 Vannod, J. 501 Varela, A. 567 Varela, M. 45 Vargas, J. 223 Veeramani, H. 315 Veleva, L. 503 Velickov, B. 73 Vennéguès, P. 71, 303 Veretennikov, L.M. 343 Verheijen, M.A. 159 Verheyen, P. 15 Viana, F. 487 Vidal, D.M. 213 Vidal, L. 805, 831 Vieira, M.F. 487 Vieira, M.T. 487 Vila, A.L. 613 Vila, E. 543 Villain, S. 233 Villaurrutia, R. 547, 581 Vion-Dury, B. 207 Vippola, M. 227 Vittori Antisari, M. 241, 255, 309, 777 Vlassak, J.J. 509 Vlieg, E. 159 Vlkova, H. 263 Vogel, K. 629 Voitenko, O.V. 471 Volpi, F. 51 Volz, K. 43 Vomiero, A. 127 Vourlias, G. 701, 703, 705, 707 Vovk, A. 607 Vovk, V. 105 Vrejoiu, I. 101, 329

W Waitz, T. 385, 489, 505, 507 Wall, A. 583 Wall, D. 255

856

Walter, M. 107 Walther, T. 375, 377 Walton, M. 737 Wandelt, K. 743 Wang, B. 509 Wang, D. 317 Wang, H. 737 Wang, L.L. 281 Wang, P. 331 Wang, Q. 281 Wang, X. 509 Wang, Z.W. 161 Wantai, Y. 339 Warin, P. 613 Warot-Fonrose, B. 631 Watanabe, M. 369 Weeks, D. 15 Wegscheider, W. 95 Weirich, T. 433 Weiss, P. 253 Welland, M. 723 Wenqing, H. 339 Wepf, R. 131 Wernicke, T. 73 Weyers, M. 73 Weyland, M. 399 Widrig, B. 719 Wieczorek, P. 461 Wiedwald, U. 111 Wielage, B. 685, 687 Wiese, N. 391 Wiesmann, J. 691 Wilcoxon, J.P. 305 Wilde, G. 359 Willinger, M. 317 Wirth, R. 817, 835 Włoch, G. 453, 455 Wojtowicz, T. 133, 301 Wolf, D. 21, 29, 629 Wollgarten, M. 279 Wouters, Y. 415 Wunderlich, R. 217 Wurstbauer, U. 95

Author Index

X Xia, J.H. 319 Xing, H. 675 Xiong, X.-C. 477

Y Yakshinskiy, B. 277 Yamada, K. 511 Yamamoto, K. 181 Yamamoto, T. 667 Yang, J.C. 281 Yang, Z. 833 Yao, L.D. 621 Yasuda, H. 283 Ye, F. 209 Ye, J. 287 Ying, Z. 339 Yokayama, T. 673 Yoshioka, T. 797, 799 Young, N. 519 Young, T.D. 639 Yu, Y.D. 513 Žagar, K. 585

Z Zagonel, L.-F. 151 Zakharov, N.D. 101 Zaleszczyk, W. 301 Zalkind, S. 277 Zanardi, S. 201 Zandbergen, H.W. 197 Zankel, A. 779 Zarnetta, R. 515 Zaspalis, V. 615 Zehl, G. 279 Zeile, U. 819 Zelaya, E. 515 Zhang, D. 679 Zhang, WZ. 659 Zhang, Z. 281, 413

Author Index

Zhang, Z.L. 111, 379 Zhao, Q.T. 27 Zhaoxi 339 Zhigalina, O.M. 381 Zhou, Z. 587 Zhu, D. 41 Zhu, T. 637 Zhu, Y.Q. 293 Zielińska-Lipiec, A. 517 Ziemann, P. 111

857

Zils, S. 285 Zivkovic, Lj. 553, 555 Životský, O. 603 Zolotarevova, E. 767 Zorba, F. 829 Zormalia, S. 451 Zou, X. 679 Zschech, E. 13 Zweck, J. 95, 589, 595 Zysler, R. 223

Subject Index 1 2024 Al alloy 673 2411 371 2-beam conventional TEM 417 3D analysis 837 3D array of chain-folded lamellae structures 775 3D reconstruction 405

A ab initio structure determination 571 aberration corrected TEM 257 aberration correction 221, 331, 619 aberration-corrected electron microscopy 39 absorption 305 acicular ferrite 477 ADF-STEM 395 adhesion 415 AEM 627 α-Fe2O3 293 AFM 79, 87, 617, 693, 713 AFM-TEM 115 a-GaN 637 Ag-Cu alloy 389 ageing 445 air sensitive materials 199 AJ62 441 Al – Si alloys 455 AlGaAs 61 AlGaN 49, 143 AlGaN/GaN DBRs 81 AlInN 79 alloy 79 alloying elements 701 Al-Mg-Ge alloy 395 AlN 59, 87 AlPdMn 635 alteration mechanism 825 alternating copolymer 799

alumina 529, 689, 711 aluminate 571 aluminium alloy 399, 401, 421, 435, 467 aluminium nitride 655 aluminum matrix composite 453 amber 813 amorphization 489, 505 amorphous alloys 471 amorphous carbon 697 amorphous/crystalline interface 107 amorphous-crystalline transformations 657 amylose 781 analysis 461 analytical TEM 301, 565, 719 anatase 219 antiphase boundaries 481 apatite 321, 809 apatite-gelatine 749 artificial pinning centers 371 artist materials 805, 831 atom probe tomography 105, 261 atomic force microscopy 747, 815 atomic layer deposition 715 atomic structure 117, 639 atom-probe-tomography (APT) 473 Au clusters growths 253 austenite- martensite- bainite islands 461 austenitic stainless steel 427

B bacterial cellulose gel-film 119 β-Al3Mg2 517 band gap smearing 87 barium chloride nano-crystals 551 bariumtitanat 583 basal stacking faults 89 BaTiO3 553, 555 B-doped CeO2 565

860

beam damage 811 bend contours 343 β-FeOOH 293 biocompatibility 741 bio-composites 749 biodiesel 227 bio-implant interfaces 741 biomaterial 729, 731, 739 biomineralisation 721, 749 bioresorbable polymers 737 biosensor 127 bismuth ferrite 129 bismuth oxide 129 bismuth-molybdenum oxides 543 block copolymers 751, 783 bond-orientational ordering 787 BOPP 339 bright-field contrast 635 BZO 291

C C 39 C/Cr PVD coating 587 cadmium sulphide 229 Cahn-Hilliard-theory 105 calciumsulfate 561 calciumsulfate-hemihydrate 563 carbide 431, 457, 493, 511 carbide-derived carbon 173 carbon 121 carbon black / polypropylene electron conductive composites 773 carbon materials 123 carbon nanohelices 319 carbon nanomaterials 177 carbon nanoparticles 163, 723, 815 carbon nanostructures 241 carbon nanotube 141, 147, 165, 169, 179, 205, 313, 317 catalysis 211, 233, 251, 317 catalyst 165, 183, 185, 205, 227, 241, 255, 609 cathodoluminescence 17, 361, 789 cation disorder 539

Subject Index

cavitation 755 CdS 39 Ce3+ 577 CeO2 reduction 199 CePrOx Catalysts 235 ceramics 581 ceria mixed oxides 213 CeZrO2 catalysts 271 CGO 327 channeling 681 charge injection 529 chemical 683 chemical composition 467 chemical interaction 141 chemical order 619 chemical solution deposition 327 chemistry 433 CIGS 661 clathrates 531 clay 807 CMOS 7 coated conductors 351, 353, 355 coating 389, 681, 699, 701, 705, 709, 719 coating materials 697 cobalt phases 245 Co-doped ZnO 621 CoFeB/MgO/CoFeB 601 coherence 19 collagen 321 colloids 263 columnar grains 509 complex metallic alloys 459, 517, 645 composites 755 compositional analysis 67, 83 compositional gradient 497 confocal 757 Co-Ni alloy 447 CoNiAl shape memory alloy 391 copper 203 co-precipitation 671 CoPt nanoparticles 187 CoPt thin films 617 core and low loss spectra of TiO2 anatase 195

Subject Index

core shell nanospheres 261 core/shell precipitates 473 core-shell 597 core-shell nanoparticles 305 Cr and U oxides nanoparticles 315 Cr2AlC 533 crack 411 creep 483 cross section polisher 341 cryo-electron microscopy 791 cryo-microscopy 249 cryo-negative staining 783 cryo-TEM 783 crystal defects 73 crystal growth 47 crystal structure 63, 131, 467 crystallization 601 crystallographic boundaries 647 Cs Corrected TEM 147 Cs correction 123 Cs probe corrected TEM 195 Cs-corrected HRTEM 217 Cs-corrector 111, 379 CSD 291 CSL and DSC lattices 479 Cu dispersion 251 Cu-Co alloys 437 Cu-O chain 557 cuprate superconductor 557 Cu-Te amorphous condensates 343 CVD deposition 165

D dark-field diffraction 13 dedicated specimen holders 289 defect 1, 3, 43, 679 deformation 451 deformation defect 675 deformation mechanism 827 deformation twinning 485, 499 degradation 207, 285, 575, 759 dendrites 217 dental fillings 729 dewetting 245

861

DFT 573 diamond 833 diesel engine 211 differential phase microscopy 589 diffraction 525, 559, 681 diffraction contrast 191 diffuse intensity 495 diffuse interfaces 521 diffuse scattering 559 diffusion 151 diffusion couple 501 dilute nitride 43, 669 diopside 537 dislocation 79, 397, 459, 475, 635, 637, 639, 649, 655, 663, 803 dislocation blocking 669 dislocation core 677 dislocation core structure 645 dislocation reduction 47 dislocations structures 427 disordered carbon 173 disordering 63 disordering of ordered structures 481 dissolution-reprecipitation 825 domain texture 323 domain wall 549 domain wall propagation 613 doped-alumina 235 doping contrast 25 double helical structure 751 Dual Beam 427 dual phase 423 duplex (δ+γ) stainless steel 479 duplex stainless steel 659 dynamic recrystallisation 827

E earth analogues 163 EBID 277 EBSD (electron backscatter diffraction) 365, 485, 547, 649, 827 edge dislocation 231 EDS 393, 555, 681, 727, 763 EDS analysis 673

862

EDX (energy-dispersive X-ray spectroscopy) 109, 143, 191, 337, 369, 375, 377, 403, 671, 819 EELS (electron energy loss spectroscopy) 13, 23, 33, 67, 95, 97, 103, 167, 177, 223, 225, 243, 265, 295, 321, 369, 387, 409, 443, 457, 631, 683, 711, 715, 717, 731, 811 EFTEM 49, 51, 181, 223, 231, 243, 587, 597, 621, 623, 731 Egypt 829 electric fields 749 electrocatalyst 207 electroluminescence 229 electrolytic plasma 725 electron beam degradation 789 electron beam nanofabrication 299 electron beam sensitive specimen 761 electron diffraction 117, 135, 333, 425, 535, 539, 583, 653, 781 electron holography 19, 247, 269, 611, 629 electron irradiation 155 electron irradiation damage 663 electron microscopy 213, 401, 421, 435, 471, 473, 695, 703, 707, 713 electron tomography 13, 35, 91, 187, 275, 279, 471, 599, 769 electronic and mechanical investigations 683 electronic excitation 283 electronic properties 51 electrophorese 695 electroplating 685, 687 Elektron 21 439 ELNES 23, 497, 577, 715, 821 elusive structures 807 EMCD 631 emission control 211 energy-filtered TEM 723 environmental SEM 157, 285, 771, 779 environmental TEM 165, 193, 197, 211 epitaxial strain 329

Subject Index

epitaxy 53, 373, 591 EPMA 513 etching 725 exchange bias effect 99 exothermic reaction 487 exsolution 537 extended crystal imperfection 657 extended defects 149 extraterrestrial carbon 163 extreme compression 155

F fatigue 427 Fe3O4 nanoparticles 223 FEBIP 277 Fe-N 477 FePt 257 FePt nanoparticles 189 ferrites 233, 615 ferroelectric materials 101, 381, 527, 547, 549, 579, 581 ferroelectric nanocrystals 269 ferromagnetism 621 FETEM 433 FIB 9, 371, 393, 403, 419, 503, 509, 741, 809, 819 FIB milling 321 FIB preparation 671 FIB/SEM 349, 405, 731 FIB/TEM 835 FIB-cryo-SEM 807 field emission 169 films 381 fin field effect transistor 35 first principles calculation 577 Fischer Tropsch 249 flash memory cell 29 fluorite structure 543 fluorozirconate glass ceramic 551 Frank-Kasper phases 479 fresh-cut 735 fresnoite 821 friction 697 friction-stir welding 673

Subject Index

FSMA 469 FTIR 829 fuel cell 241 fullerene 1, 113, 171, 181

G Ga in Al 393 GaAs (gallium arsenide) 61, 67, 137 GaAs nanowires 157, 295 γ-Al2O3 281 GaMnAs 95 GaN (gallium nitride) 41, 47, 55, 73, 79, 87, 89, 143, 663 gas atomisation 217 GaSb 45 gas-solid interactions 197 gate dielectrics 715 gate oxide 29 Ge 39 gel structure 757 geomaterials 807 geometric phase analysis 11, 691 glass-ceramics 537 GMR sensors 105 goethite 129 gold 259 gold and palladium nanoparticles 263 gold diffusion 125 gold nanoparticles 247 γ-phase 469 γ-polyketone 799 graded materials 683 grain boundary 665, 667, 807, 817 grain boundary width 377 grain refining 455 granular materials 607 ground 819 group theory 479 growth 205 growth kinetics 83 growth mechanism 117, 165, 319 GTL 249

863

H HAADF 223, 295, 303, 331 HAADF-STEM 247, 541, 579, 667, 795 HAADF-STME and HV-TEM tomography / isotactic polypropylene 775 halite 807 hardness 421, 697 heat treatment 493 helical dislocation 673 helicity 135 hematite 129 hemihydrate 561 HEMT 55 heterogeneous catalysis 197, 237, 281 heterojunction 335 heterostructure 103, 295, 323 hexahedral nano-cementites 319 high dielectric constant 715 high manganese austenitic steel 485 high pressure 175 high resolution 519 high resolution electron microscopy 57, 221, 569 high tensile strength steel 511 high-k dielectric 23 high-pressure minerals 801 high-resolution 5 HO2O3 555 hole drilling 599 holography 5, 569, 573 HREM 239, 641, 781 HR-STEM 33, 359 HRTEM (high resolution transmission electron microscopy) 11, 59, 63, 69, 77, 111, 145, 167, 201, 219, 223, 225, 231, 237, 265, 303, 323, 335, 345, 379, 395, 447, 457, 467, 505, 507, 521, 525, 541, 579, 597, 639, 653, 667, 679, 715, 809, 831 HRTEM and X-ray EDS analysis 315 HRTEM simulation 133, 651 hyaluronic acid 745

864

hybrid layered materials 785 hybrid thin film 339 hydrogen storage 309 hydrothermal synthesis 129, 293 hydroxyapatite 731

I IBAD 341 III nitrides 79 ilmenite 825 impact 833 implants 741 impregnated zeolite 251 impurity phases 31 in situ microscopy 289 in situ optical microscopy 561 in situ TEM 287, 657 (In,Ga)N 71 In2O3 39, 345 InAlN 79 InAs nanowires 131 InAs QDs 45 inclusion complexes 781 incommensurate 581, 665 Inconel 738LC 411 indium 55, 161 indium nitride 69 indium oxide 69, 127, 311 In-doped zinc oxide nanorod 191 inert gas condensation 309 InGaAs 65 InGaAsN 83 InGaN 39, 77 InN 87, 93 InP on GaAs 75 in-situ 307 in-situ electron microscopy 121 in-situ SEM 297 in-situ TEM 297, 633 integrated circuits 7 interdiffusion 109 interface 3, 11, 27, 41, 331, 349, 351, 353, 355, 379, 381, 419, 443, 519, 661, 817

Subject Index

interface structure 59, 373, 433, 491 intermetallic 449 internal crystal lattice bending 343 intrinsic electrostatic potential 21 ion implantation 17, 89, 777 ion tracks 87 ionic conductors 543 iron 169 iron antenna 299 iron oxide 545 iron oxide nanostructures 299 irradiation damage 779

L L10 ordering 189 La@C82 177 LACBED 803 LaCoO3 593 Laplace tension 261 laser welding 501 lattice constants 799 layered structures 545 LCMO 643 lead-free ferroelectrics 539 LiMn1.5Ni0.5O4 525 LiNiO2 575 liquid crystals 787 liquid immiscibility gap 437 liquid metal 313 local atomic and electronic structure 577 long-term annealing 439, 441 Lorentz DPC-STEM 549 Lorentz microscopy 391, 589, 595, 629 low carbon steel 493 low hysteresis 413 LSMO films 591 LVSEM 337, 727

M magnesium 309 magnesium alloy 439, 441

Subject Index

magnetic domains 391 magnetic force microscopy 99 magnetic imaging 589, 595 magnetic materials 631 magnetic nanoparticles 597, 609 magnetic properties 615 magnetic shape memory alloys 629 magnetic tunnel junction 601 magnetite 209 magnetostriction 463 maraging 250 445 martensite 383, 385, 423, 469, 507, 605 materials science 717 MBE 55, 75, 295, 303 MCM-41 339 mechanical alloying 453 mechanical properties 287, 423, 445 melon 735 membrane electrode assembly 285 MEMS 197 mesoporous 311 mesoporous material 219 metadislocations 645 metal contact 141 metal gate 23 metal@MOF-5 275 metal-ceramic interfaces 369 metallic glass 641 metallic nanoparticles 243 Mg78.5Pd21.5 407 MgO 357 micelles 783 microanalysis 375, 617 microbial reduction 315 microcapsules 745 microelectromechanical systemts 197 microflakes 833 microscopies 101 microstructure 27, 383, 423, 429, 437, 439, 441, 445, 447, 463, 553, 615, 685, 687, 689, 709, 735 micro-wire 497 mineral bridge 733 mineralization 737

865

minerals 835 misfit 417 misfit dislocation 359, 651 Mn partitioning 461 Mn4Si7/Si films 31 MOD 591 modeling 781 modulated structure 57, 535 Moiré 371 monochromator 195 morphology 159, 795 morphology of wear particles 767 MOSFET 67 Mössbauer spectroscopy 603 MOVPE 43 MRAM 107 multicompartment nanostructures 791 multiferroics 329, 573 multilayer 109, 487, 691, 699 multi-metal silicides 671 multiple scattering calculation 103

N nacre 733 nano-beam diffraction 15 nanobelts 115 nanobridges 599 nanocasting 311 nanoclusters 245 nano-columns 93 nanocomposite 697, 709, 765, 785 nanocrystal 197, 229, 273, 625, 641 nanocrystalline materials 425 nanocrystalline microstructure 491 nanocrystallinity 465, 489, 719 nanocrystallization 89, 523 nanodiamond 167 nanodots 87 nanofabrication 599 nano-filaments 117 nanohuts 327 nanointerface 341 nanomagnetism 627 nanometer scale 277

866

nanometer size wear debris 767 nanoparticle 111, 203, 221, 225, 231, 233, 257, 265, 267, 281, 283, 603, 619, 685, 687, 739, 833 nanoparticle arrays 721 nanoparticle lattice parameter 239 nanorod 139, 259, 293 nanospheres 627 nanostructures 101, 255, 349, 585, 595, 725 nanotips 599 nanotube 1, 113, 115, 117, 121, 135, 307, 753 nanotube growth 155 nano-twinning 593 nanowhiskers 219 nanowire 115, 133, 137, 139, 143, 145, 149, 151, 159, 167, 301 NBT 527 NEXAFS 753 Ni clusters 255 Ni2MnGa 463 Ni4Ti3 405 nickel 153 nickel aluminides 487 Ni-Mn-Ga 605 NiTi 489, 505, 507 NiTiHf 489 nitride 55, 85, 457 nitride interfaces 651 nitride precipitates 387 nitride semiconductors 87 NMR 603 non-conductive samples 529 nonpolar Gallium Nitride 53 non-stoichiometry 567 nucleation 357, 633 nuclei 205

O octahedral tilting 539 ODS steels 443 off-axis electron holography 9 off-stoichiometric alloy 463

Subject Index

oligonucleotide 747 one-pot synthesis 271 onion 175 optical properties 87, 97 order 521 order/disorder phenomena 187 ordered solid solution 389 organic solar cells 759 orientation contrast 827 orientation relationship 479, 659 orthopaedic implants 737 oxidation 415, 703 oxide 3, 475 oxide electrode 347 oxide layer (or oxidation) 531

P pack cementation 701 particles 695 PE 339 peak broadening 425 peapods 147 pearlite 477 PEMFC 207, 285 perovskite 323, 567, 593 perovskite-solid solution 579 perpendicular magnetic anisotropy 611, 613 phase identification 681 phase mapping 69 phase segregation 591 phase separation 389, 523 phase transformation 479, 495 phase transition 527, 583, 787 phason walls 635 photoactive layer 795 photocatalyst 215, 267 piezoresponse force microscopy 269 pigment 819, 829 plan view 239 plasma-jet deposition 603 plasmon loss electrons 19 plastic deformation 459 PLD 371

Subject Index

PMPSi 789 p-n junction 21 poisoning 227 polarity 47, 85 poly(butylene terephthalate) (PBT) 797 poly[methyl(phenyl)silylene] 789 polyamide 765 polycarbonate 777 polyethylene 755 polymer crystallization 797 polymer nanocomposites 769 polymer stabilised nanoparticles 119 polymers 753 porosity 807 potential mapping 565 powder metallurgy 503 precession electron diffraction 803 precipitate 391, 397, 409, 417, 435, 467 precipitation 383, 395, 449, 451, 457, 673 precipitation crystallography 659 prismatic stacking faults 89 probe Cs corrector 33, 359, 665 projected potential 761 protection layers 689 protein assembly 721 Pt 281 Pt catalysts 193 pulsed laser deposition (PLD) 347, 607, 699 PVD 345 pyroxene 823

Q quantification 387, 769 quantitative 757 quantitative electron microscopy 729 quantitative image analysis 773 quantum cascade laser 61 quantum dot 65, 85, 91, 303 quantum rings 91 quantum wells 41, 71

867

quasi in-situ structure research 285 quasicrystals 635 quenching and partitioning 429

R radiation damage 37, 39, 835 Raney-type Ni 217 rapid solidification (RS) 455 rare earth doping 89, 553 rare earth oxides 715 reactive diffusion 261 recrystallization 401, 483 redox process 793 replacement reaction 809 replica TEM preparation 333 retardation 97 RHEED 731 rhodium 225 risk assessment 181 rotational twinning 407 Rubens 805, 831 Ruddlesden Popper phases 569 ruthenium catalysts 213, 279 rutile 219

S Samson phase 517 sandstone characterization 837 sapphire 655 scanning probe microscopy 813 Se/polymer particles 793 segregation 623, 667 selective oxidation 333 selenium nanowires 119 self assembly 273, 743, 791 SEM (scanning electron microscopy) 25, 79, 201, 265, 313, 365, 501, 503, 513, 555, 693, 701, 705, 727, 745, 771, 805, 819, 829 semiconductor silicon 33 semiconductors 5, 9, 25, 37 severe plastic deformation 465, 481, 647

868

shape memory 605 shape memory alloys 413, 419, 515 shape memory effects 491 shear band 385, 465 shells 153 short range ordered cubic phases 567 shungite 815 Si As/P doped 37 Si nanowire 161 SiC (silicon carbide) 15, 57, 677 SiC buffer layer 59 SiC fibers 713 SiGe 15 silica 415, 529 silica layers 17 silicon 37, 151, 747 silicon nanowires 125 silicon oxide 453 silicon polymers 789 simulation 495 single atom detection 39 single crystals 781 slicing view 217 SMA 501 soft materials 763, 779 softmagnetic material 625 sol-gel electrophoretic deposition 585 sol-gel synthesis 219 solid bitumens 813 solid-liquid interface 633 solution treatment 485 soot oxidation 211 specimen preparation 393 specimen surface 21 specimen tilt 375 spectrum imaging 409 spherulite 797 spin torque 107 spintronic 103 Sr4Ru2O9 347 SrTiO3 171, 325, 357, 585 stacking faults 637, 677 stacking sequence 557 stainless steel 415, 501

Subject Index

Stardust 823 steel 409, 429, 431, 457 STEM (scanning transmission electron microscopy) 49, 67, 71, 81, 85, 125, 145, 199, 215, 223, 235, 265, 271, 305, 349, 433, 453, 455, 665, 763, 769, 771 STEM and EDS 793 STEM DF 809 STEM EELS/EDX 37 STEM SEM 785 STEM/EELS 575, 587 STEM-simulation 81 STM (scanning tunnelling microscopy) 171, 297, 307 STM-TEM 115 STO 643 strain 5, 15, 77, 221, 325 strain analysis 13 strain contrast 397 strain engineering 669 stress 547, 615 stress-strain response 649 structural 683 structural change 283 structural properties 363 structure 161, 217, 237 structure determination 541 structured surfaces 743 STXM 753 SU-8 693 sub-nano analysis 511 sulfated zirconia 237 superalloy 411 superaustenitic stainless steel 451 superferritic stainless steel 449 superlattice reflections 539 superlattices 101 surface 725 surface composition 183 surface layers 497 surface Ostwald ripening 253 surface oxidation 225 surface plasmon mapping 243

Subject Index

surface precipitates 659 surface restructuring 193 surface structure 183 swift ions irradiation 87

T TEM (transmission electron microscopy) 27, 45, 53, 61, 65, 67, 75, 79, 81, 87, 89, 113, 123, 131, 137, 153, 175, 179, 185, 189, 209, 215, 227, 229, 253, 259, 263, 273, 275, 295, 317, 329, 363, 367, 371, 399, 403, 415, 427, 439, 453, 455, 463, 489, 497, 499, 509, 513, 515, 523, 527, 531, 533, 539, 545, 571, 585, 603, 607, 621, 625, 643, 649, 661, 691, 699, 733, 741, 745, 759, 761, 777, 785, 801, 819, 823 TEM analysis 149 TEM and X-ray EDS analysis 31 TEM study 407 TEM tomography 795 TEM/SAED 157 tempering 431 TEM-STEM imaging 51 tensile tests 771 texture 365 TG Measurements 703 thermal analysis 401 thermal reaction 105 thermal spray 705 thermal treatments 421 thermoelectric film 337 thermogavimetric measurements 705 thin film 73, 335, 351, 353, 355, 357, 367, 373, 509, 559, 603, 623 thin film characterization 515 thin film diffusion 817 thin films solar cells 363 threshold photoemission 151 Ti6Al4V 499 TiAlSiN 709 TiAlYN/CrN 711

869

TiC 697 tin oxide 127 Ti-Ni-P 681 Ti-Ni-Pd 515 TiO2 765 titanate nanotubes 765 titania 219 titania surfaces 741 titanium 725 titanium alloy 675, 699 titanium dioxide 267 titanoniobates 785 tomography 29, 159, 367, 753 tool steels 703 toxicity 723 transition elements in silicon 671 transition insulator-metal 167 transmission electron microtomography 773 transmission electron tomography 751 transport measurements 289 transport of intensity equation 611 TRIP 485 tungsten 503, 707 twin 203, 385, 803 twinning 413, 479 twinning mechanism 649 TWIP 485 TWIP steels 649

U UHP metamorphism 801 ultrahigh molecular weight polyethylene 767 ultra-low-k 51 UNCD 167 uncompensated spins 99

V vacancies 231 vacancy clusters 399 valence states 811

870

Van Gogh 819 vanadium oxide 317 vapour-liquid-solid growth 133 varistor 361 VEELS 51

W wax crystallisation 743 WDXS 617 wetting layer 377 wires 93 wollastonite 537

X XANES 821 XEDS 515 xidation 705 XPEEM 151 X-ray 375 X-ray absorption 753 X-ray grazing incidence diffraction 11 X-ray micro-CT 837

Subject Index

X-ray optics 691 XRD (X-ray diffraction) 571, 653, 707 XRPD 201

Y Yb2O3 555 YBa2Cu3O7-δ 357 YBaCo4O7+δ 535 YBCO 291, 371 Y-junction 179 yttria 475

Z Z-contrast 665 zeolite 201 zeolite beta 679 zinc 707 zirconium 483 zirconolite 811 (Zn,Mn)Te 301 ZnO 139, 361, 667 Zr3Al 647