Electrochemical Phase Formation and Growth: An Introduction to the Initial Stages of Metal Deposition PDF
Preview Electrochemical Phase Formation and Growth: An Introduction to the Initial Stages of Metal Deposition
E. Budevski, G. Staikov W. J. Lorenz Electrochemical Phase Fomation and Growth Keep up to date with VCH's book series .. . Advances in Electrochemical Science and Engineering Edited by R. C. Alkire, H. Gerischer -t, D. M. Kolb, C. W. Tobias t ISSN 0938-5193 Volume 1 with contributions from V Brusic, J. Horkans, D. J. Barclay, D.-T. Chin, G. P. Evans, T. Iwasita-Vielstich, R. Kotz, J. Winnick 1990. Hardcover. Sold Volume 2 with contributions from C. Deslouis, B. Tribollet, A. Hammou, G. L. Richmond, S. Trasatti 1992. Hardcover. ISBN 3-527-28273-4 Volume 3 with contributions from W P. Gomes, H. H. Goossens, Y. Okinaka, T. Osaka, J. 0. Dukovic, H. Lehmkuhl, K. Mehler, U. Landau, P. C. Andricacos, L. T. Romankiw 1994. Hardcover. ISBN 3-527-29002-8 Volume 4 with contributions from P. Allongue, P. C. Searson, T. Iwasita, E C. Nart, Z. Galus, Z. Samec, K. Kakiuchi, P. Tatapudi, J. M. Fenton 1995. Hardcover. ISBN 3-527-29205-5 Volume 5 with contributions from 0. A. Petrii, G. A. Tsirlina, F. Beck, D. D. McDonald, A. Kapturkiewicz, S. Gottesfeld 1997. Hardcover. ISBN 3-527-29385-X 0 VCH Verlagsgesellschaft mbH, D-69451 Weinheim (Federal Republic of Germany), 1996 Distrihution: VC'H, P.O. Box 101161, D-69451 Wcinheim, Federal Republic of Germany Switzerland: VCH, P. 0. Box, CH-4020 Basel, Switzerland United Kingdom and Ireland: VCH, 8 Wellington Court, Cambridge CBl lHZ, United Kingdom USAand Canada: VCH, 333 7th Avcnue, New York, NY 10001, USA Japan: VCH, Eikow Building, 10-9 Hongo 1-chome, Bunkyo-ku, Tokyo 113, Japan ISBN 3-527-29422-8 E. Budevski, G. Staikov, W J. Lorenz Electrochemical Phase Formation and Growth An Introduction to the Initial Stages of Metal Deposition Weinheim New York VCH - a - Base1 Cambridge Tokyo Prof. Dr. E. Budevski Prof. Dr. E. Staikov Central Laboratory for Electrochemical Prof. Dr. W. J. Lorenz Power Sources Institute for Physical Chemistry Bulgarian Academy of Sciences and Electrochemistry Sofia 1113 University of Karlsruhe Bulgaria KaiserstralJe 12 D-76131 Karlsruhc Germany This book was carefully produced. Nevertheless, authors and publisher do not warrant thc information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustra- tions, procedural details or othcr items may inadvertently be inaccurate. Published jointly by VCH Vcrlagsgcscllscliaft mbH, Weinheim (Federal Republic of Germany) VCH Pitblislicrs, New York, NY (USA) Editorial Director: Dr. Michael Bar Production Manager: Claudia Gross1 Library of Coiigrcss Card No. applied for A cataloguc record for this book is available from the British Library Die Deutsche Bibliothck - CIP-Einheitsaufiialime Budevski, Evgeni B.: Electrochemical phasc formation and growth : an introduction to the initial stagcs of mctal deposition I E. Budevski ; G. Staikov ; W. J. Imrenz. - Wcinhcini ; New York : Basel ; Camhridge ;Tokyo : VCH, 1996 ISBN 3-527-29422-8 NE: Stajkov, Georgi T.:: Lorenz, Wolfgang J.: 0V CH Verlagsgesellachaft mbH, D-69451 Wcinheim (Federal Republic of Germany), 1YY6 Printed on acid-free and low-chlorine paper All rights reserved (including thow of translation into other languages). No part of this hook may be rcpro- duced in any form - by photoprinting, microfilm, or auy other means - nor transmitted or lranslated into a machine language without written permission from the publishers. Registered name5, trademarks, etc. used in this book, even when not spccifically marked as such, are not to be considered unprotected by law. Composition: Dipl.-Ing. A. Frocse, Univcrsity of Karlsruhe Printing: betz-druck GmhH, D-64291 Darmstadt Binding: GroBbuchhinderei J. Schlffer, D-67269 Grunstadt Printed in the Federal Republic of Germany Preface This book is a result of a collaboration by the authors over a long period of time. It is devoted to fundamental problems of electrochemical metal deposition. The first part gives an introduction to electrocrystallization. The second part describes structure, morphology, and reconstruction of solid metal surfaces treated as crystalline sub strates including the dynamic behavior of surface atoms. The third part treats surface modification by underpotential deposition (UPD) of metals. Physical nature, thermodynamics, structural aspects, kinetics, as well as sur- face alloy formation are discussed. Experimental support is given based on classical electrochemical investigations as well as on some recent results from modern in situ surface analytical studies including atomic imaging by in situ STM and AFM. In the fourth part of the book the problem of three-dimensional phase formation and growth by overpotential deposition (OPD) is presented. Thermodynamic and ki- netic aspects are considered. The atomistic approach is discussed and illustrated on bare and UPD modified substrates. The f&h part deals with growth mechanisms of single crystal faces. The growth by 2D nucleation of quasi-perfect faces as well as the spiral growth mechanism of real crystal faces are discussed. Experimental verification is presented for the case of silver electrocrystallization. The transition from the initial nucleation stages of metal deposition to 3D compact bulk deposits is described in the sixth part. Nanoscale structuring and modification of solid state surfaces by in situ STM and AFM are also considered. At the end of the book, an outlook is given in which future research and some practical aspects of metal thin films and bulk deposits are discussed. The book is directed to advanced students and scientists working in the fields of electrochemistry, phase formation and crystal growth, surface chemistry and physics, ultrathin film formation, and structuring and modification of solid state surfaces. The authors gratefully acknowledge scientific cooperation with the following col- leagues: R Kaischew and the coworkers V. Bostanov, D. Kashchiev, I. Markov, A. Milchev, W. Obretenov, A. Popov, S. Stoyanov, T. Vitanov, all working at the Bulgarian Academy of Sciences, Sofia, Bulgaria, as well as H. Fischer and the coworkers H. Bort, v7 Preface K. Engelsmann, A. Froese, H.-D. Herrmann, R Hopfner, K. Juttner, R Potzschke, U. Schmidt, S. Vinzelberg, N. Wiithrich, all working at the Institute of Physical Chemistry and Electrochemistry of the University of Karlsruhe, Germany. The authors also gratefully acknowledge international cooperation with the follow- ing colleagues: H. Rohrer (IBM Rlischlikon, Switzerland), E. Schmidt and H. Siegenthaler (University of Bern, Switzerland), B. Mutaftschiev (CNRS, Paris, France), D. Kolb (University of Ulm, Germany), J. van der Eerden (University of Ni- jmegen, The Netherlands), R Barradas (University of Ottawa, Canada), M. Fleisch- mann (University of Southampton, England), D. Roe (University of Portland, USA), J. Harrison (University of Newcastle upon Tyne, England), C. Mayer, S. Garcia and D. Salinas (Universidad Nacional del Sur, Bahia Blanca, Argentina), M. Froment (CNRS, Paris, France), R Wiart (CNRS, Paris, France), P. Allongue (CNRS,P aris, France) and W. Paatsch (Bundesanstalt fiir Materialforschung und -priifung, Berlin, Germany). For helpful and critical discussions during preparation of this book the authors are indebted to E. Schmidt, D. Kolb, and W. Schmickler (University of Ulm, Germany) and V. Bostanov (Bulgarian Academy of Sciences, Sofia). The authors would also like to thank I. Mackiw, K. Richter, A. Froese and R T. Potzschke for technical assistance preparing this book. Special gratitude should be expressed to the following associations for making possible long-time projects by financial support: Bulgarian Academy of Sciences (BAS), Deutsche Forschungs- gemeinschaft (DFG), Arbeitsgemeinschaft Industrieller Forschungsgemeinschaften (AIF), Bundesministerium fir Bildung und Forschung (BMBF), Deutsche Gesellschaft fur Chemisches Apparatewesen und Biotechnologie e.V. (DECHEMA), Fonds der Chemischen Industrie, and Volkswagen-Stiftung, The STM images obtained by the Karlsruhe electrochemistry group and presented in this book were taken with commercial NanoScope I1 and I11 instruments produced by Digital Instruments, Santa Barbara, USA. The authors gratefully acknowledge suc- cessful cooperation with this company in respect to R&D. Extended exchange of scientists between Sofia and Karlsruhe over a period of more than two decades was supported by BAS and DFG, Alexander von Humboldt Stiftung, Deutscher Akademischer Austauschdienst (DAAD), and International Semi- nar for Science and Teaching in Chemical Engineering, Technical and Physical Chem- istry at the University of Karlsruhe, to all of whom we express our thanks. Finally, the authors gratefully acknowledge the cooperation with the publisher VCH, Weinheim. Evgeni Budevski Georgi Staikov Wolfgang J. Lorenz Contents ..................... 1 Fundamentals of Electrocrystallization of Metals 1 ............................................................................... 1.1 Thermodynamic and Kinetic Aspects 1 ......................................................................................... 1.2 Metal Deposition Mechanisms 4 1.3 Topics of this Book ........................................................................................................... -7 ........................................................... 2 Crystalline Metal Surfaces 9 .............................................................................................................. 2.1 Structural Aspects 9 .................................................................... Close-packed 2D and 3D crystal structures 9 ...................................................... Crystal imperfections and surface inhomogeneities 12 .................................................................................................... Surface reconstruction 13 ........................................................................ Surface roughness and the kink position 16 ................................................................................................................ Step roughness 19 ............................................................................................................. 2.2 Atomic Dynamics 20 ............................................................................................ Atom exchange frequencies 20 .................................................................... Local. partial. and overall current densities 23 .......................................................... Kink atoms and the Nernst equilibrium potential 24 ....................................................................... Exchange current density of kink atoms 25 ................................................................................................ Concentration of adatoms 26 Exchange current density of adatoms .......................................................................... -28 Mean residence time and surface displacement of adatoms ........................................ 29 ................................................................................................... 2.3 Surface Profile Mobility 29 .................................................... Surface diffusion and mean displacement of adatoms 30 . .............................................................................. Surface diffusion The exact solution 30 .................................................................................................................. Direct transfer 36 ....................................................................... Current density on a stepped crystal face 37 ...................................................................................................................... 2.4 Conclusions 39 WZI Contents ............... 3 Underpotential Deposition of Metals .2D Phases 41 ..................................................................................................... 3.1 Historical Background 41 ............................................................................................................... 3.2 Phenomenology 43 ............................................................................................................. 3.3 Thermodynamics 52 ............................................................................................. Thermodynamic formalism 52 ........................................................................................... Adsorption isotherm models 55 ........................................................................................................ Experimental results 58 ...................................................................................... 3.4 Structures of 2D Meads Phases 63 ............................................................................................................ Degree of registry 63 ................................................................................................................... Internal strain 68 ................................................................................................... Electrochemical results 71 ............................................................................. Comparative and ex situ UHV results 74 ...................................................................................... In situ surface analytical results 75 .......................................................................................................................... 3.5 Kinetics 101 ........................................................ Quasi-homogeneous substrate surface approach 102 ................................................................ Inhomogeneous substrate surface approach 107 ............................................................................................................ Phase transitions 111 ................................................................................ 3.6 2D and 3D Me-S Alloy Formation 128 ............................................................................................................. Phenomenology 128 ........................................................................................................... Thermodynamics 129 ............................................................................... Structures of 2D and 3D Me alloys 134 .......................................................................................................................... Kinetics 140 ..................................................................................................................... 3.7 Conclusion 146 ................................ 4 Initial Stages of Bulk Phase Formation 149 ................................................... 4.1 Equilibrium Form of Crystals and Forms of Growth 149 .. ............................................................................................................ Equilibrium form 149 ....................................................................................... Crystal-substrate interaction 150 .................................................................................... Gibbs-Wulff-Kaishew theorem 152 ............................................................................................... "kdimensional crystal 154 ............................................................................................................ Forms of growth 156 Contents Lx ........................................................................................... Energy of cluster formation 157 ................................................................................................................. 3D nucleation 157 ................................................................................................................. 2D nucleation 160 ............................................................................................. Gibbs-Thomson equation 161 .............................................................................................................. 4.2 Nucleation Rate 163 ...................................................................... Classical approach (Volmer and Weber) 163 ....................................................................... Kinetic approach (Becker and Doering) 165 .................................................................. Binding energies and energy of nucleation 166 ............................................................................................................. Atomistic model 168 ................................................................................................ Nucleation rate equation 171 ....................................................................................................... Small cluster model 173 ...................................................................................................... Experimental results 174 .......................... 4.3 3D Phase Formation on UPD Modified Foreign Substrate Surfaces 180 ................................................................................................... UPD-OPD transitions 181 .................................................................................................. Nucleation and growth 182 ............................................................................................................................ Epitaxy 184 ...................................................................................................... Experimental results 185 .................................................................................................................... 4.4 Conclusions 199 ..................................................... 5 Growth of Crystalline Faces 201 5.1 Dislocation-Free Crystal Faces .................................................................................... 201 .............................................. Preparation of single crystal faces by electrodeposition 203 ................................................................................................. Double pulse technique 207 ..................................................................... Nucleation rate-overvoltage dependence 210 ................................................................... Time distribution of the nucleation events 213 ............................................................................ Form of growth of monatomic layers 214 Propagation rate of monatomic steps ............................................................................ 216 Space distribution of nucleation events. ........................................................................ 221 ............................................................................ Propagation rate of polyatomic steps 223 ........................................ Mechanism of metal deposition and adatom concentration 225 X Contents ................................................................................. 5.2 Growth Kinetics of Perfect Faces 226 ............................................................................ Mononuclear layer-by-layer growth 227 ............................................................................... Multinuclear monolayer formation 227 ....................................................... Deposition kinetics on quasi-perfect crystal faces 231 ......................................................................................................... 5.3 Real Crystal Faces 235 .................................................................................................................... Dislocations 235 .............................................................................................. Spiral growth mechanism 237 ................................................................................................. Theory of spiral growth 239 ...................................................................................................... Growth morphology 245 ................................................................. Steady state and transient current densities 252 Impedance behavior ...................................................................................................... 257 .................................................................................................................... 5.4 Conclusions 260 . 6 Metal Deposits and Surface Structuring and Modification 263 ............................................................................. 6.1 Formation of Compact Me Deposits 263 .................................................... Phenomenological classification of 3D Me deposits 263 Texture. epitaxy and morphology of 3D Me deposits .................................................. 264 ...................................................................... Impedance studies of 3D Me deposition 270 ........................................................................... Metal deposition by pulse techniques 271 Laser-induced metal deposition. ................................................................................... 275 ................................................................................ Electrodeposition of 3D Me alloys 280 ........................................................................................... 6.2 Theoretical Considerations 280 ................................................................ 6.3 Ultrathin Metal Films and Heterostructures 283 Ultrathin metal films on foreign metal substrates ........................................................ 286 Heterostructures on foreign metal substrates .............................................................. 288 ..................................................... Ultrathin metal films on semiconductor substrates 294 ........................................................................... 6.4 Surface Structuring and Modification 299 Metal single crystal surfaces ......................................................................................... 300 HOPG surfaces .............................................................................................................. 304 ................................................................................................ HTSC thin film surfaces 308 Semiconductor single crystal surfaces. ......................................................................... 311 .................................................................................................................... 6.5 Conclusions 312
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