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Página de 04/04/2004 Document Página de Page iii Nanomaterials Synthesis, Properties and Applications Edited by A S Edelstein Naval Research Laboratory Washington, DC and R C Cammarata Department of Materials Science and Engineering Johns Hopkins University Baltimore, MD http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_iii.html 04/04/2004 Document Página de Page iv Copyright © 1996 by IOP Publishing Ltd and individual contributors All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the written permission of the publisher, except as stated below Single photocopies of single articles may be made for private study or research Illustrations and short extracts from the text of individual contributions may be copied provided that the source is acknowledged, the permission of the authors is obtained and IOP Publishing Ltd is notified Multiple copying is permitted in accordance with the terms of the licences issued by the Copyright Licensing Agency under the terms of its agreement with the Committee of Vice-Chancellors and Principals British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 7503 0358 (hbk) ISBN 7503 0578 (pbk) Library of Congress Cataloging-in-Publication Data are available First published 1996 Paperback edition 1998 Published by Institute of Physics Publishing, wholly owned by The Institute of Physics, London Institute of Physics Publishing, Dirac House, Temple Back, Bristol BS1 6BE, UK US Office: Institute of Physics Publishing, The Public Ledger Building, Suite 1035, 150 South Independence Mall West, Philadelphia, PA 19106, USA Printed in the UK by J W Arrowsmith Ltd, Bristol http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_iv.html 04/04/2004 Document Página de Page v CONTENTS Preface xv Authors' Addresses xvii Acknowledgments xxi Part Introduction 1 Introduction Part Synthesis 11 Formation of Clusters and Nanoparticles from a Supersaturated Vapor and Selected Properties 13 2.1 Introduction 13 2.2 Clusters 14 2.2.1 Classical Nucleation Theory for Cluster Formation 14 2.2.2 Techniques for Cluster Formation 16 2.2.3 Cluster Assembled Materials 24 2.2.4 Physical and Chemical Properties of Clusters 26 2.3 Nanoparticles Produced by Sputtering and Thermal Evaporation and Laser Methods 35 2.3.1 Background 35 2.3.2 Achieving Supersaturation 38 2.3.3 Particle Nucleation and Growth 40 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_v.html 04/04/2004 Document Página de 2.3.4 Coalescence, Coagulation and Size Distributions 41 2.3.5 Particle Transport 43 2.3.6 Particle Collection 45 2.3.7 Crystal Structure and Crystal Habit 45 Particle Synthesis by Chemical Routes 3.1 Introduction 55 55 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_v.html 04/04/2004 Document Página de Page vi 3.2 Nucleation and Growth from Solutions 57 3.3 Stabilization of Fine Particles against Agglomeration 57 3.4 Materials 59 3.4.1 Metals and Intermetallics 59 3.4.2 Ceramics 62 3.4.3 Composites 63 3.4.4 Nanoparticles via Organized Membranes 65 3.4.5 Clusters 67 3.5 Conclusions Synthesis of Semiconductor Nanoclusters 68 73 4.1 Characterization Methods and Potential Pitfalls in the Synthesis 74 4.2 Colloids/Micelles/Vesicles 76 4.3 Polymers 78 4.4 Glasses 79 4.5 Crystalline and Zeolite Hosts 80 4.6 Towards Single-size Clusters 82 4.6.1 Controlled Cluster Fusion in Solution 83 4.6.2 Controlled Thermolysis in the Solid State 84 Formation of Nanostructures by Mechanical Attrition 5.1 Introduction and Background 89 89 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_vi.html 04/04/2004 Document Página de 5.2 High-energy Ball Milling and Mechanical Attrition 90 5.3 Phenomenology of Nanostructure Formation 92 5.3.1 Elements and Intermetallics 92 5.3.2 Nonequilibrium Solid Solutions 95 5.3.3 Nanocomposites by Mechano-chemistry 97 5.4 Mechanism of Grain-size Reduction 99 5.5 Property–microstructure Relationships 103 5.6 Related Topics 108 Part Artificially Multilayered Materials 111 Artificially Multilayered Materials 113 6.1 Introduction 113 6.2 Structure and Characterization 114 6.2.1 Microstructure 114 6.2.2 Dislocation Filters 117 6.2.3 Characterization 117 6.3 Processing 6.3.1 Thin-film Deposition Methods 120 120 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_vi.html 04/04/2004 Document Página de Page vii 6.3.2 Mechanical Processing Methods 6.4 Thermodynamics and Kinetics 126 126 6.4.1 Thermodynamics 126 6.4.2 Kinetics 127 6.5 Electrical and Optical Properties 128 6.5.1 Semiconductor Superlattices 128 6.5.2 Microelectronics Applications 130 6.5.3 Optoelectronics Applications 131 6.5.4 Electronic Transport in Metallic Multilayers 132 6.5.5 Bragg Reflectors 133 6.6 Superconducting Properties 134 6.6.1 Low-temperature Superconductors 134 6.6.2 High-temperature Superconductors 134 6.7 Magnetic Properties 135 6.7.1 Magnetic Superlattices 135 6.7.2 Giant Magnetoresistance 136 6.8 Mechanical Properties 137 6.8.1 Elastic Properties 137 6.8.2 Damping Capacity 138 6.8.3 Plastic Properties 138 6.8.4 Wear and Friction 140 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_vii.html 04/04/2004 Document Página de 6.8.5 Fracture 140 Part Processing of Nanomaterials 145 Processing of Nanostructured Sol–gel Materials 147 7.1 Introduction 147 7.2 Synthesis of Oxides by the Sol–gel Process 149 7.2.1 Alkoxide Solution Routes 149 7.2.2 Colloidal Sols and Suspensions 151 7.2.3 Single-component Oxides 152 7.2.4 Multicomponent Oxides 152 7.3 Powder-free Processing of Gel Shapes 152 7.3.1 Thin Films 153 7.3.2 Fibers, Sheets and Thick Layers 154 7.3.3 Microporous Monoliths 155 7.4 Unconsolidated Gels: Aging and Syneresis 155 7.5 Consolidated Gels: Sintering 156 7.6 Matrices for Access to the Nanostructure 157 7.6.1 In situ composites 159 7.6.2 Volatile Host Method 159 7.6.3 Infiltrated Composites 161 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_vii.html 04/04/2004 Document Página de Page viii 7.7 Prospects for the Sol–gel Processing of Nanostructured Materials 161 Consolidation of Nanocrystalline Materials by Compaction and Sintering 165 8.1 Introduction 165 8.2 Dry Compaction of Nanocrystalline Particles 166 8.3 Wet Compaction of Nanocrystalline Particles 169 8.4 Ideal Densification during Pressureless Sintering 170 8.5 Non-ideal Densification during Pressureless Sintering 177 8.5.1 Agglomeration Effects 177 8.5.2 Inhomogeneous Sintering/Differential Densification 179 8.6 Grain Growth during Pressureless Sintering 182 8.7 Grain Boundary Pinning by Pores during Pressureless Sintering 186 8.8 Minimizing Grain Growth and Maximizing Densification during Pressureless Sintering 187 8.9 Pressure-assisted Sintering and Sinter Forging 189 8.10 Summary 194 Part Characterization of Nanostructured Materials 199 Nanostructures of Metals and Ceramics 201 9.1 Introduction 201 9.2 Structures of Nanophase Materials 203 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_viii.html 04/04/2004 Document Página de Page 591 Van der Waals force, 30, 58 Variable range hopping, 367 Very large scale integration (VLSI), 567 W Warren–Averbach analysis, 92, 236 Weak localization, 363 Wet compaction, 169 Work function, 31 Wulff construction, 47 Wurtzite structure, 34 X X-ray diffraction, 92, 117, 376 mirror, 113 photoelectron spectroscopy (XPS), 360, 376 Y Yield strength, 138, 323 Z Zwitterionic, 58 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_591.html 11/04/2004 Document Página de Page 593 MATERIALS INDEX A A-15 compounds, 95 Ag, 96, 232, 238, 295 –Al2O3, 347 –Au, 113 –Fe, 96 –Fe0.7B0.3, 117 AgI in zeolite mordenite, 82 Ag2O, 66 Alcohol, 61 Alkoxide, 149 Al2O3, 149, 156, 310 Aluminosilicate zeolite, 80, 308 Al, 15, 25, 95, 104 –Cu, 140 –Ni, 340 –BN, 65 AlF3, 502 AlInAs–GaInAs, 132 Aluminum garnet, 152 Al(OH)3, 152 Aluminum-sec-butoxide (ASB), 152 AlRu, 92, 100, 104, Ammonium benzoate, 62 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_593.html 11/04/2004 Document Página de Anthracene-PMDA, 417 Apoferritin, 5, 466 AsS, 19 Au, 66, 232, 247, 315 B B, 59 Ba, 63 Barium ferrite, 376, 390 BaO, 390 Bacteria, 460, 468 Be0.8Fe0.2–Pd0.8Si0.2, 117 Benzene (CH6), 310 Bi, 255 BiI3, 74 Bi2Sr2CaCu2O8–Bi2Si2CuO6, 135 BN, 63, 376 Borohydride, aqueous, 59 Boric acid, 65 Bromobenzene, 61 Buckyballs (see Fullerenes), 477 Buckytubes (see Fullerenes), 478 C C, 60, 269, 309 C60 (see also Fullerenes), 82, 477 C70 (see also Fullerenes), 477 Ca, 29 Cadmium chalcogenides, 307 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_593.html 11/04/2004 Document Página de Carbides, 63, 90, 99 CaF2, 295 CdS, 66, 74, 76, 395, 400 Cd32S14SPh36DMF4, 85 CdSe, 34, 65, 395 CdSxSe1–x, 79 CdSe–ZnS, 78 CdTe, 76 CH3OH, 31 Co, 31, 33, 34, 61, 92, 104, 255, 375, 377, 379 –Ag, 369 –Cu, 59, 65, 136, 350, 367 –Cr, 135 –Pd, 135 –Pt, 135 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_593.html 11/04/2004 Document Página de Page 594 –Ru, 135 CoWC, 546 Co0.2Ag0.8, 368 CoCl2, 61 Cobalt Ferrite, 66 CoO/Co3O4, 379 Cluster (see also Fullerenes), Al, 20, 31 C, 29 Ca, 29 Co, 34 Cu, 32 Fe, 34 Hg, 30, 34 K, 28 Li, 29 Mg, 29 Na, 29 Nb, 33 Ni, 34 Pb, 29 Pl, 310 S, 30 Sb, 30 Cr, 47, 104, 231, 249, 268, 376 –Au, 136 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_594.html 11/04/2004 Document Página de CrCl3, 62 Cr2O3, 205 Cu, 32, 61, 63, 104, 209, 210, 232, 255, 327 –Co, 246 –Fe, 96 –Nb, 131, 132, 138 –Pd, 113, 137 –Ta, 96, 97 –V, 96 –W, 96 Cu(Bi), 255 Cu(Co), 255 CuBr, 395 CuCl, 80, 395 CuEr, 95, 104 CuZr, 328 Copper acetate, 61 Colloids, 76, 306 CsH, 40 D D2O, 31 Diethylene glycol, 61 Dihexadecyl phosphate, 78 Dimethyl ether, 62 Dioctadecyldimethylammonium Chloride (DODAC), 78 Dy, 136 E http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_594.html 11/04/2004 Document Página de Ethylene glycol, 61 Ethylene–methacrylic acid, 74 F Fe, 31, 33, 34, 47, 61, 96, 98, 104, 210, 251, 267, 329, 375, 376, 377, 384, 385 –Co, 375 –Co–B, 375 –Cr, 135, 136 –Cu, 59 –ErN, 97 –Li, 388 –Mg, 381, 385 –Ni–B, 375 –SiO2, 357 –Si, 360, 376 –W, 97 Fe3C, 40 FeCl3, 61, 390 FeO, 360 Fe2O3, 376, 377, 381, 571 Fe3O4, 4, 382, 466, 469, 472 Fe73.5Cu1Nb3Si13.5B9, 290 FexMg1–x, 381 FexN–BN, 65 Ferrihydrite, 460 Ferrite, barium, 376, 390 cobalt, 66 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_594.html 11/04/2004 Document Página de Fullerenes, 6, 29, 37, 82, 477 G GaAs, 19, 74, 117, 503 GaAs–AlxGa1–xAs, 124 GaAs/AlGaAs/GaAs, 518 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_594.html 11/04/2004 Document Página de Page 595 GaP, 19 Gd–Y, 136 Garnets, 390 Ge, 80, 97 Glassy matrices, 376 Glutathione peptides, 77 Glycine, 63 Goethite, 472 Graphite, 269 tubes, 6, 478 onions, 478 H Hexane, 310 Hf, 98, 104 Hg, 30, 34 Hemosiderin, 465 Hydradinium, 62 Hydrides/polysilanes, 449 Hydrocarbons, 33 Hydroorganoborates, 61 Hydroxides, 62 I In1–xGaxAs–Ga1–yAsy, 124 InGa–GaAsP, 117 InGaAs, 509 InP, 19 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_595.html 11/04/2004 Document Página de Ir, 95, 104, 310 K K, 19, 34 L La, 63 Li, 30 LiBEt3H, 61 LiF, 502 Liposomes, 65 Ludox™, 151 M Magnetite (Fe3O4), 4, 382, 466, 469, 472 Met-cars, Mg, 19, 43, 385 MgF2, 502 MgO, 43, 205, 269, 385 Micelles, 65, 76, 306 MnFe2O4, 377, 390 Mo, 47, 63, 98, 231, 259 –cubes, 29 –Ge, 127 –Si, 133 MoCl3, 62 MoCl4, 62 Molecular sorbates, 308 Methylviologen, 315 N http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_595.html 11/04/2004 Document Página de N-CaF2, 295 N-Cu, 295 Na, 34 NaCl, 502 NaH, 40 Naphthalene, 62 Nb, 31, 47, 104 Nb3Al, 95 Nb3Au, 95 Ni, 31, 61, 104, 267, 270, 329, 375, 376, 377 –Al2O3, 347 –Mo, 135 –Zr, 127 NiAl, 62 Ni3Al, 62 NiO, 360 Ni80P20, 290 NiTi, 95, 104 (NMe4)4Cd10S4SPh16, 82-84 (NMe4)2Cd17S4SPh28, 83 O Organosilane, 509 P Pb, 33 –Ge, 127 PbAs, 19 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_595.html 11/04/2004 Document Página de PbIn, 19 PbI2, 79 PbO2, 309 PbP, 19 PbS, 19, 74, 79 PbSe, 19 PbSr, 19 Pd, 34, 61, 67, 104, 203, 209, 210, 232, 233, 238, 242, 248, http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_595.html 11/04/2004 Document Página de Page 596 249, 251, 255, 258, 261, 262, 269, 297, 310, 327 –Zr, 241 PdCu, 61 Palladium acetate, 61 Polymethyl Methcrylaye (PMMA), 501 Poly(phenylenediacetylene), 318 Poly(styrene-acrylonitrile)–polycarbonate, 126 Polysilane, 449 Polystyrene–polyethylene, 126 Polystyrene–polypropylene, 126 Protein, 460 PS, 19 Pt, 31, 33, 310, 315 Pt/KL catalyst, 310 Pyridine, 307 Pyrolytic graphite, 317 R Rh, 34, 104, 243 Ru, 92, 104 S S, 310 Sb, 19 Si, 40, 80, 290, 439, 509 –Au, 264, 265 –Ge, 119 –SixGe1–x, 129 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_596.html 11/04/2004 Document Página de SiC, 40 SiHx, 449 Si3N4, 40 –SiC, 40 SiO2, 39, 376 SiRu, 104 Siloxene (Si6O3H6), 450 T Ta, 98 Tetraethyl orthosilicate, 150 Ti, 98, 310 –Pd, 266 TiAl, 328, 333 TiB2, 62 TiBO3, 62 TiCl4, 62 TiO2, 36, 38, 40, 149, 156, 168, 205, 209, 258 TiN–VNbN(100), 138 TiNi–C, 97 U Urea, 65 V V, 31, 47, 98 V3Ga, 95 W W–C, 133 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_596.html 11/04/2004 Document Página de WC–Co, 63 WCl4, 62 X Xerogels, 156 Xylenes, 61 Y Y, 152 –Fe, 239 Y2O3, 230 Z Zeolites, 82, 152, 307 aluminosilicate, 80, 308 faujasite, 312 synthetic KL, 310 Zn, 45 ZnO, 76, 205 ZnS, 66 ZnTe, 76, 80 ZnxMn1–xS, 74 Zr, 98, 103 ZrB2, 40 ZrC, 99 ZrO2, 63, 149, 258, 259, 334 –Y2O3, 172 http://www.netlibrary.com/nlreader/nlreader.dll?bookid=27445&filename=Page_596.html 11/04/2004