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Third EditionSOLID STATE CHEMISTRYAn Introduction

Third Edition

SOLID STATE CHEMISTRYAn IntroductionLesley E.SmartElaine A.MooreTaylor & FrancisTaylor & Francis GroupBoca Raton London New York Singapore

A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & FrancisGroup, 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, LLCCRC Press is an imprint of Taylor & Francis GroupThis 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 ofthousands of eBooks please go to http://www.ebookstore.tandf.co.uk/.No claim to original U.S. Government works10 9 8 7 6 5 4 3 2 1ISBN 0-203-49635-3 Master e-book ISBNISBN 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 2004058533This book contains information obtained from authentic and highly regarded sources. Reprintedmaterial is quoted with permission, and sources are indicated. A wide variety of references arelisted. Reasonable efforts have been made to publish reliable data and information, but the authorand the publisher cannot assume responsibility for the validity of all materials or for theconsequences of their use.No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by anyelectronic, mechanical, or other means, now known or hereafter invented, including photocopying,microfilming, and recording, or in any information storage or retrieval system, without writtenpermission from the publishers.For permission to photocopy or use material electronically from this work, please accesshttp://www.copyright.com/ (http://www.copyright.com/) or contact the Copyright ClearanceCenter, Inc. (CCC) 222 Rosewood Drive, Danvers, MA 01923, 978–750–8400. CCC is a not-forprofit organization that provides licenses and registration for a variety of users. For organizationsthat have been granted a photocopy license by the CCC, a separate system of payment has beenarranged.Trademark Notice: Product or corporate names may be trademarks or registered trademarks, andare used only for identification and explanation without intent to infringe.

Library of Congress Cataloging-in-Publication DataSmart, 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. Solidstate chemistry. I. Moore, Elaine (Elaine A.) II. Title. QD478.S53 2005 541′.0421–dc222004058533Taylor & Francis Group is the Academic Division of T&F Informa plc.Visit the Taylor & Francis Web site at http://www.taylorandfrancis.comand the CRC Press Web site at http://www.crcpress.com

Dedicated toGraham, Sam, Rosemary, and Laura

Preface to the Third EditionSolid state and materials chemistry is a rapidly moving field, and the aim of this editionhas been to bring the text as up to date as possible with new developments. A fewchanges of emphasis have been made along the way.Single crystal X-ray diffraction has now been reduced in Chapter 2 to make way for awider range of the physical techniques used to characterize solids, and the number ofsynthetic techniques has been expanded in Chapter 3. Chapter 5 now contains a sectionon fuel cells and electrochromic materials. In Chapter 6, the section on low-dimensionalsolids has been replaced with sections on conducting organic polymers, organicsuperconductors, and fullerenes. Chapter 7 now covers mesoporous solids and ALPOs,and Chapter 8 includes a section on photonics. Giant magnetoresistance (GMR) andcolossal 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 chemicalaspects of nanoscience.We thank our readers for the positive feedback on first two editions and for the helpfuladvice which has led to this latest version.As ever, we thank our friends in the Chemistry Department at the OU, who have beensuch a pleasure to work with over the years, and have made enterprises such as thispossible.

Preface to the Second EditionWe were very pleased to be asked to prepare a second edition of this book. When wetried to decide on the changes (apart from updating) to be made, the advice from oureditor was “if it ain’t broke, don’t fix it.” However, the results of a survey of our usersrequested about five new subjects but with the provisos that nothing was taken out, thatthe 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 satisfiedsome, if not all, of the requests.The main changes from the first edition are two new chapters: Chapter 2 on X-raydiffraction and Chapter 3 on preparative methods. A short discussion of symmetryelements has been included in Chapter 1. Other additions include an introduction toALPOs and to clay minerals in Chapter 7 and to ferroelectrics in Chapter 9. We decidedthat there simply was not enough room to cover the Phase Rule properly and for that werefer you to the excellent standard physical chemistry texts, such as Atkins. We hope thatthe book now covers most of the basic undergraduate teaching material on solid statechemistry.We are indebted to Professor Tony Cheetham for kindling our interest in this subjectwith his lectures at Oxford University and the beautifully illustrated articles that he andhis collaborators have published over the years. Our thanks are also due to Dr. PaulRaithby for commenting on part of the manuscript.As always, we thank our colleagues at the Open University for all their support andespecially the members of the lunch club, who not only keep us sane, but also keep uslaughing. Finally, thanks go to our families for putting up with us and particularly to ourchildren for coping admirably with two increasingly distracted academic mothers—ourbook is dedicated to them.Lesley E.Smart and Elaine A.MooreOpen University, Walton Hall, Milton Keynes

Preface to the First EditionThe idea for this book originated with our involvement in an Open University inorganicchemistry course (S343: Inorganic Chemistry). When the Course Team met to decide thecontents of this course, we felt that solid state chemistry had become an interesting andimportant area that must be included. It was also apparent that this area was playing alarger role in the undergraduate syllabus at many universities, due to the exciting newdevelopments in the field.Despite the growing importance of solid state chemistry, however, we found that therewere few textbooks that tackled solid state theory from a chemist’s rather than aphysicist’s viewpoint. Of those that did most, if not all, were aimed at final yearundergraduates and postgraduates. We felt there was a need for a book written from achemist’s viewpoint that was accessible to undergraduates earlier in their degreeprogramme. 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 havechosen to concentrate on structures and bonding in solids, and on the interplay betweencrystal and electronic structure in determining their properties. Examples of solid statedevices are used throughout the book to show how the choice of a particular solid for aparticular device is determined by the properties of that solid.Chapter 1 is an introduction to crystal structures and the ionic model. It introducesmany of the crystal structures that appear in later chapters and discusses the concepts ofionic radii and lattice energies. Ideas such as close-packed structures and tetrahedral andoctahedral holes are covered here; these are used later to explain a number of solid stateproperties.Chapter 2 introduces the band theory of solids. The main approach is via the tightbinding 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 isincluded here for completeness. This chapter also discusses electronic conductivity insolids and in particular properties and applications of semiconductors.Chapter 3 discusses solids that are not perfect. The types of defect that occur and theway they are organized in solids forms the main subject matter. Defects lead tointeresting 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 4covers low-dimensional solids, the properties of which are not isotropic. Chapter 5 dealswith 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 withoptical properties and Chapter 7 with magnetic properties of solids. Finally, Chapter 8explores the exciting field of superconductors, particularly the relatively recentlydiscovered high temperature superconductors.The approach adopted is deliberately nonmathematical, and assumes only the chemicalideas 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 anunderstanding of the rest of the book; topics such as ligand field theory are not assumed.As this book originated with an Open University text, it is only right that we shouldacknowledge the help and support of our colleagues on the Course Team, in particularDr. David Johnson and Dr. Kiki Warr. We are also grateful to Dr. Joan Mason who readand commented on much of the script, and to the anonymous reviewer to whomChapman & Hall sent the original manuscript and who provided very thorough and usefulcomments.The authors have been sustained through the inevitable drudgery of writing by anenthusiasm for this fascinating subject. We hope that some of this transmits itself to thestudent.Lesley E.Smart and Elaine A.MooreOU, Walton Hall, Milton Keynes

About the AuthorsLesley E.Smart studied chemistry at Southampton University. After completing a Ph.D.in Raman spectroscopy, also at Southampton, she moved to a lectureship at the RoyalUniversity of Malta. After returning to the United Kingdom, she took an SRC Fellowshipto Bristol University to work on X-ray crystallography for 3 years. Since 1977, she hasworked at the Open University as a lecturer, and then senior lecturer (2000), in inorganicchemistry. At the Open University, she has been involved in the production ofundergraduate courses in inorganic and physical chemistry. Most recently, she was thecoordinating editor of The Molecular World course, which has been copublished with theRSC as a series of eight books. She was also an author on two of these, The ThirdDimension and Separation, Purification and Identification.Her research interests are in the characterization of the solid state, and she has over 40publications in single-crystal Raman studies, X-ray crystallography, zintl phases,pigments, and heterogeneous catalysis.Solid State Chemistry was first produced in 1992. Since then, it has been translatedinto French, German, Spanish, and Japanese.Elaine A.Moore studied chemistry as an undergraduate at Oxford University and thenstayed on to complete a D.Phil, in theoretical chemistry with Peter Atkins. After a 2-year,postdoctoral position at Southampton, she joined the Open University in 1975 as courseassistant, becoming a lecturer in Chemistry in 1977 and Senior lecturer in 1998. She hasproduced OU teaching texts in chemistry for courses at levels 1, 2, and 3 and has writtentexts in astronomy at level 2. The text Molecular Modelling and Bonding, which formspart of the OU Level 2 Chemistry Course, was copublished by the Royal Society ofChemistry as part of The Molecular World series. She oversaw the introduction ofmultimedia into chemistry courses and designed multimedia material for levels 1 and 2.She is coauthor, with Dr. Rob Janes of the Open University, of Metal-Ligand Bonding,which is part of a level 3 Course in Inorganic Chemistry and copublished with the RoyalSociety of Chemistry.Her research interests are in theoretical chemistry applied to solid state systems and toNMR spectroscopy. She is author or coauthor on over 40 papers in scientific journals.She was coauthor of an article in Chemical Reviews on nitrogen NMR spectroscopy ofmetal nitrosyl complexes.

BASIC SI UNITSPhysical quantity (and symbol)Name of SI unitLength (l)MetremMass (m)KilogramkgTime (t)SecondsElectric current (I)AmpereAThermodynamic temperature (T)KelvinKAmount of substance (n)MoleLuminous intensity (Iv)CandelaSymbol for unitmolcdDERIVED SI UNITSPhysical quantity (andsymbol)Name of SIunitSymbol for SI derived unit anddefinition of unitFrequency (v)HertzHz ( s 1)Energy (U), enthalpy (H)JouleJ ( kg m2 s 2)ForceNewtonN ( kg m s 2 J m 1)PowerWattW ( kg m2 s 3 J s 1)Pressure (p)PascalPa ( kg m 1 s 2 N m 2 J m 3)Electric charge (Q)CoulombC ( A s)Electric potential difference (V) VoltV( kg m2 s 3 A 1 J A 1 s 1)Capacitance (c)FaradF ( A2 s4 kg 1 m 2 A s V 1 A2 s2 J 1)Resistance (R)OhmΩ ( V A 1)Conductance (G)SiemenS ( A V 1)Magnetic flux density (B)TeslaT ( V s m 2 J C 1 s m 2)SI ��210–1altofemtopiconanomicromillicentideci kiloafpnµmcd103k1061091012 1015 1018megagigaterapetaexaMGTPEFUNDAMENTAL CONSTANTSConstantSymbolValueSpeed of light in a vacuumc2.997925 108 m s 1

1.602189 10–19 CCharge of a protoneCharge of an electron eAvogadro constantNA6.022045 1023 mol 1Boltzmann constantk1.380662 10–23 J K 1Gas constantR NAk8.31441 J K 1 mol 1Faraday constantF NAe9.648456 104 mol 1Planck constanth6.626176 10–34 J s1.05457 10–34 J sVacuum permittivityε08.854 10–12 F m 1Vacuum permeabilityµ04π 10–7 J s2 C 2 m 1Bohr magnetonµB9.27402 10–24 J T 1Electron g valuege2.00232MISCELLANEOUS PHYSICAL QUANTITIESName of physical quantitySymbolSI unitEnthalpyHJEntropySJ K 1Gibbs functionGJStandard change of molar enthalpyJ mol 1Standard of molar entropyJ K 1 mol 1Standard change of molar Gibbs functionzJ mol 1Wave numbercm 1Atomic numberZDimensionlessConductivityσS m 1Molar bond dissociation energyDmJ mol 1kg mol 1Molar massTHE GREEK ALPHABETalphaAαnuNvbetaBβxiΞξ

gammaΓγomicronOodelta δpiΠπepsilonEεrhoPρzetaZζsigma C CLASSIFICATION OF THE ELEMENTS

Table of ContentsChapter 1 An Introduction to Crystal StructuresChapter 2 Physical Methods for Characterizing Solids191Chapter 3 Preparative Methods148Chapter 4 Bonding in Solids and Electronic Properties179Chapters 5 Defects and Non-Stoichiometry201Chapter 6 Carbon-Based Electronics282Chapter 7 Zeolites and Related Structures301Chapter 8 Optical Properties of Solids342Chapter 9 Magnetic and Dielectric Properties365Chapter 10 Superconductivity394Chapter 11 Nanoscience412Further Reading442Answers Odd Number Questions446Index463

Third EditionSOLID STATE CHEMISTRYAn Introduction

1An Introduction to Crystal StructuresIn the last decade of the twentieth century, research into solid state chemistry expandedvery rapidly, fuelled partly by the dramatic discovery of ‘high temperature’ ceramicoxide superconductors in 1986, and by the search for new and better materials. We haveseen immense strides in the development and understanding of nano-technology, microand meso-porous solids, fuel cells, and the giant magnetoresistance effect, to mention buta few areas. It would be impossible to cover all of the recent developments in detail in atext such as this, but we will endeavour to give you a flavour of the excitement that someof the research has engendered, and perhaps more importantly the background withwhich to understand these developments and those which are yet to come.All substances, except helium, if cooled sufficiently form a solid phase; the vastmajority form one or more crystalline phases, where the atoms, molecules, or ions packtogether to form a regular repeating array. This book is concerned mostly with thestructures of metals, ionic solids, and extended covalent structures; structures which donot contain discrete molecules as such, but which comprise extended arrays of atoms orions. We look at the structure and bonding in these solids, how the properties of a soliddepend on its structure, and how the properties can be modified by changes to thestructure.1.1 INTRODUCTIONTo understand the solid state, we need to have some insight into the structure of simplecrystals and the forces that hold them together, so it is here that we start this book.Crystal structures are usually determined by the technique of X-ray crystallography.This technique relies on the fact that the distances between atoms in crystals are of thesame order of magnitude as the wavelength of X-rays (of the order of 1 Å or 100 pm): acrystal thus acts as a three-dimensional diffraction grating to a beam of X-rays. Theresulting diffraction pattern can be interpreted to give the internal positions of the atomsin the crystal very precisely, thus defining interatomic distances and angles. (Some of theprinciples underlying this technique are discussed in Chapter 2, where we review thephysical methods available for characterizing solids.) Most of the structures discussed inthis book will have been determined in this way.The structures of many inorganic crystal structures can be discussed in terms of thesimple packing of spheres, so we will consider this first, before moving on to the moreformal classification of crystals.

Solid state chemistry21.2 CLOSE-PACKINGThink for the moment of an atom as a small hard sphere. Figure 1.1 shows two possiblearrangements for a layer of such identical atoms. On squeezing the square layer in Figure1.1 (a), the spheres would move to the positions in Figure 1.1 (b) so that the layer takesup less space. The layer in Figure 1.1 (b) (layer A) is called close-packed. To build up aclose-packed structure in three-dimensions we must now add a second layer (layer B).The spheres of the second layer sit in half of the hollows of the first layer: these havebeen marked with dots and crosses. The layer B in Figure 1.2 sits over the hollowsmarked with a cross (although it makes no difference which type we chose). When weadd a third layer, there are two possible positions where it can go. First, it could godirectly over layer A, in the unmarked hollows: if we then repeated this stackingsequence we would build up the layers ABABABA and so on. This is known ashexagonal close-packing (hcp) (Figure 1.3(a)). In this structure, the hollows markedwith a dot are never occupied by spheres, leaving very small channels through the layers(Figure 1.3(b)).Second, the third layer could be positioned over those hollows marked with a dot. Thisthird layer, which we could label C, would not be directly over either A or B, and thestacking sequence when repeated would be ABC ABC AB and so on. This is known ascubic close-packing (ccp) (Figure 1.4). (The names hexagonal and cubic for thesestructures arise from the resulting symmetry of the structure—this will be discussed morefully later on.)Close-packing represents the most efficient use of space when packing identicalspheres—the spheres occupy 74% of the volume: the packing efficiency is said to be74%. Each sphere in the structure is surrounded by twelve equidistant neighbours—six inthe same layer, three in the layer above and three in the layer below: the coordinationnumber of an atom in a close-packed structure is thus 12.Another important feature of close-packed structures is the shape and nu

Solid State Chemistry was first produced in 1992. Since then, it has been translated into French, German, Spanish, and Japanese. Elaine A.Moore studied chemistry as an undergraduate at Oxford University and then stayed on to complete a D.Phil, in theoretical chemistry with Peter Atkins. After a 2-year,

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