Solid State Chemistry

Third Edition SOLID STATE CHEMISTRY An Introduction Third Edition SOLID STATE CHEMISTRY An Introduction Lesley E.Smart Elaine A.Moore Taylor & Francis Taylor & Francis Group Boca Raton London New York Singapore A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc. Published in 2005 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487–2742 © 2005 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group This edition published in the Taylor & Francis e-Library, 2005. To purchase your own copy of this or any of Taylor & Francis or Routledge’s collection of thousands of eBooks please go to http://www.ebookstore.tandf.co.uk/. No claim to original U.S. Government works 10 9 8 7 6 5 4 3 2 1 ISBN 0-203-49635-3 Master e-book ISBN ISBN 0-203-61063-6 (OEB Format) International Standard Book Number-10:0-7487-7516-1 (Print Edition) (Hardcover) International Standard Book Number-13:9780-7487-7516-3 (Print Edition) (Hardcover) Library of Congress Card Number 2004058533 This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access http://www.copyright.com/ (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, Danvers, MA 01923, 978–750–8400. CCC is a not-for- profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Smart, Lesley. Solid state chemistry: an introduction/Lesley Smart and Elaine Moore.–3rd ed. p. cm. Includes bibliographical references and index. ISBN 0-7487-7516-1 (alk. paper) 1. Solid state chemistry. I. Moore, Elaine (Elaine A.) II. Title. QD478.S53 2005 541′.0421–dc22 2004058533 Taylor & Francis Group is the Academic Division of T&F Informa plc. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Dedicated to Graham, Sam, Rosemary, and Laura Preface to the Third Edition Solid state and materials chemistry is a rapidly moving field, and the aim of this edition has been to bring the text as up to date as possible with new developments. A few changes of emphasis have been made along the way. Single crystal X-ray diffraction has now been reduced in Chapter 2 to make way for a wider range of the physical techniques used to characterize solids, and the number of synthetic techniques has been expanded in Chapter 3. Chapter 5 now contains a section on fuel cells and electrochromic materials. In Chapter 6, the section on low-dimensional solids has been replaced with sections on conducting organic polymers, organic superconductors, and fullerenes. Chapter 7 now covers mesoporous solids and ALPOs, and Chapter 8 includes a section on photonics. Giant magnetoresistance (GMR) and colossal magnetoresistance (CMR) have been added to Chapter 9, and p-wave (triplet) superconductors to Chapter 10. Chapter 11 is new, and looks at the solid state chemical aspects of nanoscience. We thank our readers for the positive feedback on first two editions and for the helpful advice which has led to this latest version. As ever, we thank our friends in the Chemistry Department at the OU, who have been such a pleasure to work with over the years, and have made enterprises such as this possible. Preface to the Second Edition We were very pleased to be asked to prepare a second edition of this book. When we tried to decide on the changes (apart from updating) to be made, the advice from our editor was “if it ain’t broke, don’t fix it.” However, the results of a survey of our users requested about five new subjects but with the provisos that nothing was taken out, that the book didn’t get much longer, and, above all, that it didn’t increase in price! Therefore, what you see here is an attempt to do the impossible, and we hope that we have satisfied some, if not all, of the requests. The main changes from the first edition are two new chapters: Chapter 2 on X-ray diffraction and Chapter 3 on preparative methods. A short discussion of symmetry elements has been included in Chapter 1. Other additions include an introduction to ALPOs and to clay minerals in Chapter 7 and to ferroelectrics in Chapter 9. We decided that there simply was not enough room to cover the Phase Rule properly and for that we refer you to the excellent standard physical chemistry texts, such as Atkins. We hope that the book now covers most of the basic undergraduate teaching material on solid state chemistry. We are indebted to Professor Tony Cheetham for kindling our interest in this subject with his lectures at Oxford University and the beautifully illustrated articles that he and his collaborators have published over the years. Our thanks are also due to Dr. Paul Raithby for commenting on part of the manuscript. As always, we thank our colleagues at the Open University for all their support and especially the members of the lunch club, who not only keep us sane, but also keep us laughing. Finally, thanks go to our families for putting up with us and particularly to our children for coping admirably with two increasingly distracted academic mothers—our book is dedicated to them. Lesley E.Smart and Elaine A.Moore Open University, Walton Hall, Milton Keynes Preface to the First Edition The idea for this book originated with our involvement in an Open University inorganic chemistry course (S343: Inorganic Chemistry). When the Course Team met to decide the contents of this course, we felt that solid state chemistry had become an interesting and important area that must be included. It was also apparent that this area was playing a larger role in the undergraduate syllabus at many universities, due to the exciting new developments in the field. Despite the growing importance of solid state chemistry, however, we found that there were few textbooks that tackled solid state theory from a chemist’s rather than a physicist’s viewpoint. Of those that did most, if not all, were aimed at final year undergraduates and postgraduates. We felt there was a need for a book written from a chemist’s viewpoint that was accessible to undergraduates earlier in their degree programme. This book is an attempt to provide such a text. Because a book of this size could not cover all topics in solid state chemistry, we have chosen to concentrate on structures and bonding in solids, and on the interplay between crystal and electronic structure in determining their properties. Examples of solid state devices are used throughout the book to show how the choice of a particular solid for a particular device is determined by the properties of that solid. Chapter 1 is an introduction to crystal structures and the ionic model. It introduces many of the crystal structures that appear in later chapters and discusses the concepts of ionic radii and lattice energies. Ideas such as close-packed structures and tetrahedral and octahedral holes are covered here; these are used later to explain a number of solid state properties. Chapter 2 introduces the band theory of solids. The main approach is via the tight binding model, seen as an extension of the molecular orbital theory familiar to chemists. Physicists more often develop the band model via the free electron theory, which is included here for completeness. This chapter also discusses electronic conductivity in solids and in particular properties and applications of semiconductors. Chapter 3 discusses solids that are not perfect. The types of defect that occur and the way they are organized in solids forms the main subject matter. Defects lead to interesting and exploitable properties and several examples of this appear in this chapter, including photography and solid state batteries. The remaining chapters each deal with a property or a special class of solid. Chapter 4 covers low-dimensional solids, the properties of which are not isotropic. Chapter 5 deals with zeolites, an interesting class of compounds used extensively in industry (as catalysts, for example), the properties of which strongly reflect their structure. Chapter 6 deals with optical properties and Chapter 7 with magnetic properties of solids. Finally, Chapter 8 explores the exciting field of superconductors, particularly the relatively recently discovered high temperature superconductors. The approach adopted is deliberately nonmathematical, and assumes only the chemical ideas that a first-year undergraduate would have. For example, differential calculus is used on only one or two pages and non-familiarity with this would not hamper an understanding of the rest of the book; topics such as ligand field theory are not assumed.

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