Physics of Nonmetallic Thin Films N ATO ADVANCED STUDY INSTITUTES SERIES A series of edited volumes comprising multifaceted studies of contemporary scientific issues by some of the best scientific minds in the world, as- sembled in cooperation with NATO Scientific Affairs Division. Series B: Physics RECENT VOLUMES IN THIS SERIES Volume 7 - Low·Dimensional Cooperative Phenomena edited by H. J. Keller Volume 8 Optical Properties of Ions in Solids edited by Baldassare Di Bartolo Volume 9 - Electronic Structure of Polymers and Molecular Crystals edited by Jean-Marie Andre and Hnos Ladik Volume 10 - Progress in Electro-Optics edited by Ezio Camatini Volume 11 - Fluctuations, Instabilities, and Phase Transitions edited by Tormod Riste Volume 12 - Spectroscopy of the Excited State edited by Baldassare Di Bartolo Volume 13 - Weak and Electromagnetic Interactions at High Energies (parts A and B) edited by Maurice Levy, Jean-Louis Basdevant, David Speiser, and Raymond Gastmans Volume 14 - Physics of Nonmetallic Thin Films edited by C.H.S. Dupuy and A. Cachard Volume 15 - Nuclear and Particle Physics at Intermediate Energies edited by J. B. Warren Volume 16 - Electronic Structure and Reactivity of Metal Surfaces edited by E. G. Derouane and A. A. Lucas Volume 17 - Linear and Nonlinear Electron Transport in Solids edited by J.T. Devreese and V. van Doren The series is published by an international board of publishers in con- junction with NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics New York and London C Mathematical and D. Reidel Publishing Company Physical Sciences Dordrecht and Boston D Behavioral and Sijthoff International Publishing Company Social Sciences Leiden E Applied Sciences Noordhoff International Publishing Leiden Physics of Nonmetallic Thin Films Edited by C. H. S. Dupuy and A. Cachard Universite Claude Bernard Lyon 1 Villeurbanne,Jlrance PLENUM PRESS. NEW YORK AND LONDON Published in cooperation with NATO Scientific Affairs Division Library of Congress Cataloging in Publication Data Nato Summer School on Metallic and Nonmetallic Thin Films, 2d, Corsica, 1974. Physics of nonmetallic thin films. (NATO advanced study institutes series: Series B. Physics; v. 14) Includes index. 1. Nonmetallic materials- Addresses, essays. lectures. 2. Thin fIlms- Addresses, es- says. lectures. I. Dupuy. Claude H. S. II. Cachard, A. III. Title. IV. Series. QC176.N38 1974 530.4'1 76-8385 ISBN-13: 978-1-4684-0849-2 e-ISBN-13: 978-1-4684-0847-8 DOl: 10.1007/978-1-4684-0847-8 Lectures presented at the Second NATO Summer School on Metallic and Nonmetallic Thin Films held in Corsica. Serra di Ferro. September 1-5. 1974 © 1976 Plenum Press, New York Softcover reprint of the hardcover 1st edition 1976 A Division of Plenum Publishing Corporation 227 West 17th Street, New York. N. Y. 10011 United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Company. Ltd. Davis House (4th Floor), 8 Scrubs Lane, Harlesden, London, NW10 6SE, England All rights reserved No part of this book may be reproduced. stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying. microirlming. recording, or otherwise, without written permission from the Publisher Preface For several years now the intense development in the field of microelectronics, the interest in coating materials, and activity in integrated optics have produced many advances in the field of thin solid filmg~ The research activity has become so intensive and so broad that it is necessary to divide the field into metallic and non metallic thin films. A summer school in the area of non metallic thin films appeared to be a very fruitful concept and, hence, in October, 1973, A.S.l.M.S. made a proposal to N.A.T.O to hold this second summer school in Corsica in September 1974. The basic idea behind this summer school was essentially to stress and synthesize physical properties and structure of non metallic thin films. The main reason for this was the feeling that many laboratories are very specialized and that few engage in both physical and structural analysis of these films. The program included a large section on' physical studies: electrical (transport, interface effects, switching), mechanical and optical. There was also a large section o~characterization, crystal structure, chemical composition (stoichiometry is always a difficult problem), bonding and electronic structure. Certainly it is different for every laboratory to pursue all these avenues of research. However, perhaps a good result of this summer school will be a deeper realization among scientists of the connection between physical properties and structure. Collaboration is probably necessary in many of these areas and in this respect I am sure that the summer school was profitable. I want to acknowledge the many people who helped me organize this summer school. I want to especially acknowledge the members of the scientific committee and the lecturers. I wish to give special mention to the scientific codirectors, Dr. A. Cachard, Universite Claude Bernard (Lyon), and Dr. S. Fonash, Penn State University, and Ms. pivot and Chassagne, treasurer and secretary, respectively. v PREFACt My special thanks to the staff of the Village de Detente et de Loisirs in Serra di Ferro. I want to mention especially Mr. A. Paolini, Director and Mrs Pelamourgue, Assistant. To all the people of Corsica I give my thanks. I am sure that no one will forget the friendly reception of Serra di Ferro and its mayor Mr. J.R. Tomi. As was the case for the first A.S.I.M.S. summer school in Porto Vecchio, Mr. J. de Rocca Serra, Chef de la Mission Regionale, helped us and I thank him. During this summer school Dr. J. A. Roger presented and defend- ed his Ph. D. Thesis. It is very pleasant for me to thank him for presenting this first Ph. D. in Corsica. The help from N.A.T.O allowed the school to be organized and permitted it to take place. The D.G.R.S.T. helped us too, and I thank them. C.H.S. DUPUY Contents General Introduction 1 A.K. Jonscher Part I BASIC NOTIONS Preparation Methods for Thin Films 9 D.S. Campbell Growth Processes 49 R. Niedermayer Electronic States in Semiconductors 93 D.A. Greenwood Part II CHARACTERIZATION Structure Determination of Thin Films • . 123 H. Raether Physico-Chemical Analysis of Thin Films . • . • . . • .. 141 A. Cachard Thickness Measurements 163 D.S. Campbell Part III PHYSICAL PROPERTIES Electronic Transport Properties • . . . • 189 R.M. Hill vii viii CONTENTS Ionic Transport in Thin Films . • • • • • . . • . • • •• 219 S.J. Fonash Dielectric Properties of Thin Films: Polarization and Effective Polarization . . • . . . . • . 225 S.J. Fonash Threshold Switching: A Discussion of Thermal and Electronic Issues • • • . . • . . 253 H.K. Henisch and C. Popescu Mechanical Properties of Non-Metallic Thin Films 273 R. W. Hoffman Thin Films in Optics 355 G. Baldini and L. Rigaldi Radiation Effects in Thin Films 383 A. Holmes-Siedle Part IV APPLICATIONS Thin Film Applications in Microelectronics 417 V. Le Goascoz Application of Thin Non-Metallic Films in Optics 445 E. Pelletier Some Applications of Non-Metallic Thin Films 459 M.H. Francombe List of Participants 495 Index 501 GENERAL INTRODUCTION A.K. Jonscher Chelsea College, University of London Pulton Place, London SW6 5PR. U.K. The purpose of this Introduction is to attempt to place the subject of Non-Metallic Thin Films into proper perspective against the more general background of modern physics and technology and also to discuss some problems relevant to research policiy in this field. The fist question that may be asked is : "What is so signifi- cant in this subject that it should have been chosen as the theme of a specialist Summer School? ". The answer to this, in my opi- nion, is that thin non-metallic films are commonly found in natu- re, that they have many useful applications and that their physi- cal properties present certain unique feature which are not normal- ly associated with bulk materials. From the standpoint of a Summer School, with its definite di- dactic purpose, the subject of Thin Films is uniquely suited as a vehicle for conveying to the student a wide range of specialist topics - it is a multidisciplinary field which is both challenging and rewarding asa subject of study, provided care is taken to ap- proach it in the correct manner- I shall have something more to say about this later. It is desirable at the outset to define what is meant by the term "Thin Films". The commonly accepted limitation at the upper end of thickness is the concept of Ii Thick Films", typically some tens of micrometers in thickness. Thus it would appear that we would be justified to describe films up to one micrometer in thickness as "thin", without placing too much significance on the precise fi- gure. However, even 1 ~m contains some four thousand atomic layers and it may have many properties of "bulk" material. Figure 1 shows schematically some relevant orders of magnitude. 2 A.K. JONSCHER Thin Thick Mono- ShAric Ia.yer Acid 1A II I 1mm 0.1 1 10 nm 5 I. ..... .1 cree rlln g lunnel'''f distanc.e in meta.1s Fig. 1 Typical order of magnitude relating to thin non-metallic films. Whether the behaviour of a thin film is distinct from that of the corresponding bulk material depends upon the precise context. Thus the structure may be influenced by interfacial processes, e.g. epitaxy or strain due to lattice mismatch and this may carryon for hundreds of atomic layers from the interface. The elec-trical properties will be determined by the relation between the mean free path and the film thickness - in very disordered non-metallic films the mean free path is effectively the tunnelling distance, of the order of 5 nm and thus most films are bulk-like from this point of view. However, this is not so in metallic or highly crystalline films in which the mean free path may be significantly large than,. say, 10 nm and thus film thickness may become a limitation. The electrical effect of the interface may extend to several Debye lengths into the material and this, as we shall see in Dr. Fonash's lectures, may be a serious consideration. in non-metallic films, but it is not important in metallic ones where the screening length is of the order of 0.1 nm, or less than one atomic layer. Not much will be said in the context of the present Summer School of very thin films - of tunnelling thickness - nor of the problem of quantisat.ion of energy levels in the direction normal to the plane of the film. Some of these questions are however im- plicit, for example, in the operation of MNOS transistors, as dis- cussed by Dr. Le Goascoz. The presence on metallic surfaces of naturally occuring oxide and other films was known for a long time to influence their opti- cal and electrical properties. Where the films are mechanically ro- bust and chemically inert, as in the case of aluminium, tantalum and silicon, they may act as protective coatings and they have been