Principles of InorganicMaterials Design

Principles of Inorganic Materials Design

Third Edition

John N. LalenaPhysical Scientist

David A. ClearyGonzaga University

Olivier B.M. Hardouin DuparcÉcole polytechnique Institut Polytechnique Paris

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Library of Congress Cataloging-in-Publication DataNames: Lalena, John N. author. | Cleary, David A., 1957– author. | Duparc,Olivier B. M. Hardouin, author.

Title: Principles of inorganic materials design / John N. Lalena, U.S.Department of Energy, David A. Cleary, Gonzaga University, Olivier B. M.Hardouin Duparc, E’cole Polytechnique.

Description: Third edition. | Hoboken, NJ, USA : Wiley, 2020. | Includesbibliographical references and index.

Identifiers: LCCN 2019051901 (print) | LCCN 2019051902 (ebook) | ISBN9781119486831 (hardback) | ISBN 9781119486916 (adobe pdf) | ISBN9781119486763 (epub)

Subjects: LCSH: Chemistry, Inorganic–Materials. | Chemistry,Technical–Materials.

Classification: LCC QD151.3 .L35 2020 (print) | LCC QD151.3 (ebook) | DDC546–dc23

LC record available at https://lccn.loc.gov/2019051901LC ebook record available at https://lccn.loc.gov/2019051902

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10 9 8 7 6 5 4 3 2 1

Contents

Foreword to Second Edition xiiiForeword to First Edition xvPreface to Third Edition xixPreface to Second Edition xxPreface to First Edition xxiAcronyms xxiii

1 Crystallographic Considerations 11.1 Degrees of Crystallinity 11.1.1 Monocrystalline Solids 21.1.2 Quasicrystalline Solids 31.1.3 Polycrystalline Solids 41.1.4 Semicrystalline Solids 51.1.5 Amorphous Solids 81.2 Basic Crystallography 81.2.1 Crystal Geometry 81.2.1.1 Types of Crystallographic Symmetry 121.2.1.2 Space Group Symmetry 171.2.1.3 Lattice Planes and Directions 271.3 Single-Crystal Morphology and Its Relationship to Lattice Symmetry 321.4 Twinned Crystals, Grain Boundaries, and Bicrystallography 371.4.1 Twinned Crystals and Twinning 371.4.2 Crystallographic Orientation Relationships in Bicrystals 391.4.2.1 The Coincidence Site Lattice 391.4.2.2 Equivalent Axis–Angle Pairs 441.5 Amorphous Solids and Glasses 461.5.1 Oxide Glasses 491.5.2 Metallic Glasses and Metal–Organic Framework Glasses 511.5.3 Aerogels 53

Practice Problems 53References 55

2 Microstructural Considerations 572.1 Materials Length Scales 572.1.1 Experimental Resolution of Material Features 612.2 Grain Boundaries in Polycrystalline Materials 63

v

2.2.1 Grain Boundary Orientations 632.2.2 Dislocation Model of Low Angle Grain Boundaries 652.2.3 Grain Boundary Energy 662.2.4 Special Types of “Low-Energy” Boundaries 682.2.5 Grain Boundary Dynamics 692.2.6 Representing Orientation Distributions in Polycrystalline Aggregates 702.3 Materials Processing and Microstructure 722.3.1 Conventional Solidification 722.3.1.1 Grain Homogeneity 742.3.1.2 Grain Morphology 762.3.1.3 Zone Melting Techniques 782.3.2 Deformation Processing 792.3.3 Consolidation Processing 792.3.4 Thin-Film Formation 802.3.4.1 Epitaxy 812.3.4.2 Polycrystalline PVD Thin Films 812.3.4.3 Polycrystalline CVD Thin Films 832.4 Microstructure and Materials Properties 832.4.1 Mechanical Properties 832.4.2 Transport Properties 862.4.3 Magnetic and Dielectric Properties 902.4.4 Chemical Properties 922.5 Microstructure Control and Design 93

Practice Problems 96References 96

3 Crystal Structures and Binding Forces 993.1 Structure Description Methods 993.1.1 Close Packing 993.1.2 Polyhedra 1033.1.3 The (Primitive) Unit Cell 1033.1.4 Space Groups and Wyckoff Positions 1043.1.5 Strukturbericht Symbols 1043.1.6 Pearson Symbols 1053.2 Cohesive Forces in Solids 1063.2.1 Ionic Bonding 1063.2.2 Covalent Bonding 1083.2.3 Dative Bonds 1103.2.4 Metallic Bonding 1113.2.5 Atoms and Bonds as Electron Charge Density 1123.3 Chemical Potential Energy 1133.3.1 Lattice Energy for Ionic Crystals 1143.3.2 The Born–Haber Cycle 1193.3.3 Goldschmidt’s Rules and Pauling’s Rules 1203.3.4 Total Energy 1223.3.5 Electronic Origin of Coordination Polyhedra in Covalent Crystals 1243.4 Common Structure Types 127

vi Contents

3.4.1 Iono-covalent Solids 1283.4.1.1 AX Compounds 1283.4.1.2 AX2 Compounds 1303.4.1.3 AX6 Compounds 1323.4.1.4 ABX2 Compounds 1323.4.1.5 AB2X4 Compounds (Spinel and Olivine Structures) 1343.4.1.6 ABX3 Compounds (Perovskite and Related Phases) 1353.4.1.7 A2B2O5 (ABO2.5) Compounds (Oxygen-Deficient Perovskites) 1373.4.1.8 AxByOz Compounds (Bronzes) 1393.4.1.9 A2B2X7 Compounds (Pyrochlores) 1393.4.1.10 Silicate Compounds 1403.4.1.11 Porous Structures 1413.4.2 Metal Carbides, Silicides, Borides, Hydrides, and Nitrides 1443.4.3 Metallic Alloys and Intermetallic Compounds 1443.4.3.1 Zintl Phases 1473.4.3.2 Nonpolar Binary Intermetallic Phases 1493.4.3.3 Ternary Intermetallic Phases 1513.5 Structural Disturbances 1533.5.1 Intrinsic Point Defects 1543.5.2 Extrinsic Point Defects 1553.5.3 Structural Distortions 1563.5.4 Bond Valence Sum Calculations 1583.6 Structure Control and Synthetic Strategies 162

Practice Problems 165References 167

4 The Electronic Level I: An Overview of Band Theory 1714.1 The Many-Body Schrödinger Equation and Hartree–Fock 1714.2 Choice of Boundary Conditions: Born’s Conditions 1774.3 Free-Electron Model for Metals: From Drude (Classical) to Sommerfeld

(Fermi–Dirac) 1794.4 Bloch’s Theorem, Bloch Waves, Energy Bands, and Fermi Energy 1804.5 Reciprocal Space and Brillouin Zones 1824.6 Choices of Basis Sets and Band Structure with Applicative Examples 1884.6.1 From the Free-Electron Model to the Plane Wave Expansion 1894.6.2 Fermi Surface, Brillouin Zone Boundaries, and Alkali Metals versus Copper 1914.6.3 Understanding Metallic Phase Stability in Alloys 1934.6.4 The Localized Orbital Basis Set Method 1954.6.5 Understanding Band Structure Diagram with Rhenium Trioxide 1964.6.6 Probing DOS Band Structure in Metallic Alloys 1994.7 Breakdown of the Independent-Electron Approximation 2004.8 Density Functional Theory: The Successor to the Hartree–Fock Approach in Materials

Science 2024.9 The Continuous Quest for Better DFT XC Functionals 2054.10 Van der Waals Forces and DFT 208

Practice Problems 210References 210

Contents vii

5 The Electronic Level II: The Tight-Binding Electronic Structure Approximation 2135.1 The General LCAO Method 2145.2 Extension of the LCAO Treatment to Crystalline Solids 2195.3 Orbital Interactions in Monatomic Solids 2215.3.1 σ-Bonding Interactions 2215.3.2 π-Bonding Interactions 2255.4 Tight-Binding Assumptions 2295.5 Qualitative LCAO Band Structures 2325.5.1 Illustration 1: Transition Metal Oxides with Vertex-Sharing Octahedra 2365.5.2 Illustration 2: Reduced Dimensional Systems 2385.5.3 Illustration 3: Transition Metal Monoxides with Edge-Sharing Octahedra 2405.5.4 Corollary 2435.6 Total Energy Tight-Binding Calculations 244

Practice Problems 246References 246

6 Transport Properties 2496.1 An Introduction to Tensors 2496.2 Microscopic Theory of Electrical Transport in Ceramics: The Role of Point Defects 2546.2.1 Oxygen-Deficient/Metal Excess and Metal-Deficient/Oxygen Excess Oxides 2566.2.2 Substitutions by Aliovalent Cations with Valence Isoelectronicity 2616.2.3 Substitutions by Isovalent Cations That Are Not Valence Isoelectronic 2636.2.4 Nitrogen Vacancies in Nitrides 2666.3 Thermal Conductivity 2686.3.1 The Free Electron Contribution 2696.3.2 The Phonon Contribution 2716.4 Electrical Conductivity 2746.4.1 Band Structure Considerations 2786.4.1.1 Conductors 2786.4.1.2 Insulators 2796.4.1.3 Semiconductors 2816.4.1.4 Semimetals 2906.4.2 Thermoelectric, Photovoltaic, and Magnetotransport Properties 2926.4.2.1 Thermoelectrics 2926.4.2.2 Photovoltaics 2986.4.2.3 Galvanomagnetic Effects and Magnetotransport Properties 3016.4.3 Superconductors 3036.4.4 Improving Bulk Electrical Conduction in Polycrystalline, Multiphasic, and

Composite Materials 3076.5 Mass Transport 3086.5.1 Atomic Diffusion 3096.5.2 Ionic Conduction 316

Practice Problems 321References 322

7 Hopping Conduction and Metal–Insulator Transitions 3257.1 Correlated Systems 3277.1.1 The Mott–Hubbard Insulating State 329

viii Contents

7.1.2 Charge-Transfer Insulators 3347.1.3 Marginal Metals 3347.2 Anderson Localization 3367.3 Experimentally Distinguishing Disorder from Electron Correlation 3407.4 Tuning the M–I Transition 3437.5 Other Types of Electronic Transitions 345

Practice Problems 347References 347

8 Magnetic and Dielectric Properties 3498.1 Phenomenological Description of Magnetic Behavior 3518.1.1 Magnetization Curves 3548.1.2 Susceptibility Curves 3558.2 Atomic States and Term Symbols of Free Ions 3598.3 Atomic Origin of Paramagnetism 3658.3.1 Orbital Angular Momentum Contribution: The Free Ion Case 3668.3.2 Spin Angular Momentum Contribution: The Free Ion Case 3678.3.3 Total Magnetic Moment: The Free Ion Case 3688.3.4 Spin–Orbit Coupling: The Free Ion Case 3688.3.5 Single Ions in Crystals 3718.3.5.1 Orbital Momentum Quenching 3718.3.5.2 Spin Momentum Quenching 3738.3.5.3 The Effect of JT Distortions 3738.3.6 Solids 3748.4 Diamagnetism 3768.5 Spontaneous Magnetic Ordering 3778.5.1 Exchange Interactions 3798.5.1.1 Direct Exchange and Superexchange Interactions in Magnetic Insulators 3828.5.1.2 Indirect Exchange Interactions 3878.5.2 Itinerant Ferromagnetism 3908.5.3 Noncollinear Spin Configurations and Magnetocrystalline Anisotropy 3948.5.3.1 Geometric Frustration 3948.5.3.2 Magnetic Anisotropy 3978.5.3.3 Magnetic Domains 3988.5.4 Ferromagnetic Properties of Amorphous Metals 4018.6 Magnetotransport Properties 4018.6.1 The Double Exchange Mechanism 4028.6.2 The Half-Metallic Ferromagnet Model 4038.7 Magnetostriction 4048.8 Dielectric Properties 4058.8.1 The Microscopic Equations 4078.8.2 Piezoelectricity 4088.8.3 Pyroelectricity 4148.8.4 Ferroelectricity 416

Practice Problems 421References 422

Contents ix

9 Optical Properties of Materials 4259.1 Maxwell’s Equations 4259.2 Refractive Index 4289.3 Absorption 4369.4 Nonlinear Effects 4419.5 Summary 446

Practice Problems 446References 447

10 Mechanical Properties 44910.1 Stress and Strain 44910.2 Elasticity 45210.2.1 The Elasticity Tensors 45510.2.2 Elastically Isotropic and Anisotropic Solids 45910.2.3 The Relation Between Elasticity and the Cohesive Forces in a Solid 46510.2.3.1 Bulk Modulus 46610.2.3.2 Rigidity (Shear) Modulus 46710.2.3.3 Young’s Modulus 47010.2.4 Superelasticity, Pseudoelasticity, and the Shape Memory Effect 47310.3 Plasticity 47510.3.1 The Dislocation-Based Mechanism to Plastic Deformation 48110.3.2 Polycrystalline Metals 48710.3.3 Brittle and Semi-brittle Solids 48910.3.4 The Correlation Between the Electronic Structure and the Plasticity

of Materials 49010.4 Fracture 491

Practice Problems 494References 495

11 Phase Equilibria, Phase Diagrams, and Phase Modeling 49911.1 Thermodynamic Systems and Equilibrium 50011.1.1 Equilibrium Thermodynamics 50411.2 Thermodynamic Potentials and the Laws 50711.3 Understanding Phase Diagrams 51011.3.1 Unary Systems 51011.3.2 Binary Systems 51111.3.3 Ternary Systems 51811.3.4 Metastable Equilibria 52211.4 Experimental Phase Diagram Determinations 52211.5 Phase Diagram Modeling 52311.5.1 Gibbs Energy Expressions for Mixtures and Solid Solutions 52411.5.2 Gibbs Energy Expressions for Phases with Long-Range Order 52711.5.3 Other Contributions to the Gibbs Energy 53011.5.4 Phase Diagram Extrapolations: The CALPHAD Method 531

Practice Problems 534References 535

12 Synthetic Strategies 53712.1 Synthetic Strategies 53812.1.1 Direct Combination 538

x Contents

12.1.2 Low Temperature 54012.1.2.1 Sol–Gel 54012.1.2.2 Solvothermal 54312.1.2.3 Intercalation 54412.1.3 Defects 54612.1.4 Combinatorial Synthesis 54812.1.5 Spinodal Decomposition 54812.1.6 Thin Films 55012.1.7 Photonic Materials 55212.1.8 Nanosynthesis 55312.1.8.1 Liquid Phase Techniques 55412.1.8.2 Vapor/Aerosol Methods 55612.1.8.3 Combined Strategies 55612.2 Summary 558

Practice Problems 559References 559

13 An Introduction to Nanomaterials 56313.1 History of Nanotechnology 56413.2 Nanomaterials Properties 56513.2.1 Electrical Properties 56613.2.2 Magnetic Properties 56713.2.3 Optical Properties 56713.2.4 Thermal Properties 56813.2.5 Mechanical Properties 56913.2.6 Chemical Reactivity 57013.3 More on Nanomaterials Preparative Techniques 57213.3.1 Top-Down Methods for the Fabrication of Nanocrystalline Materials 57213.3.1.1 Nanostructured Thin Films 57213.3.1.2 Nanocrystalline Bulk Phases 57313.3.2 Bottom-Up Methods for the Synthesis of Nanostructured Solids 57413.3.2.1 Precipitation 57513.3.2.2 Hydrothermal Techniques 57613.3.2.3 Micelle-Assisted Routes 57713.3.2.4 Thermolysis, Photolysis, and Sonolysis 58013.3.2.5 Sol–Gel Methods 58113.3.2.6 Polyol Method 58213.3.2.7 High-Temperature Organic Polyol Reactions (IBM Nanoparticle Synthesis) 58413.3.2.8 Additive Manufacturing (3D Printing) 584

References 586

14 Introduction to Computational Materials Science 58914.1 A Short History of Computational Materials Science 59014.1.1 1945–1965: The Dawn of Computational Materials Science 59114.1.2 1965–2000: Steady Progress Through Continued Advances in Hardware and

Software 59514.1.3 2000–Present: High-Performance and Cloud Computing 59814.2 Spatial and Temporal Scales, Computational Expense, and Reliability of Solid-State

Calculations 600

Contents xi

14.3 Illustrative Examples 60414.3.1 Exploration of the Local Atomic Structure in Multi-principal Element Alloys by

Quantum Molecular Dynamics 60414.3.2 Magnetic Properties of a Series of Double Perovskite Oxides A2BCO6 (A = Sr, Ca;

B =Cr; C = Mo, Re, W) by Monte Carlo Simulations in the Framework of theIsing Model 606

14.3.3 Crystal Plasticity Finite Element Method (CPFEM) Analysis for Modeling Plasticity inPolycrystalline Alloys 613References 617

15 Case Study I: TiO2 61915.1 Crystallography 61915.2 Microstructure 62315.3 Bonding 62615.4 Electronic Structure 62715.5 Transport 62815.6 Metal–Insulator Transitions 63215.7 Magnetic and Dielectric Properties 63215.8 Optical Properties 63415.9 Mechanical Properties 63515.10 Phase Equilibria 63615.11 Synthesis 63815.12 Nanomaterial 639

Practice Questions 639References 640

16 Case Study II: GaN 64316.1 Crystallography 64316.2 Microstructure 64616.3 Bonding 64716.4 Electronic Structure 64716.5 Transport 64816.6 Metal–Insulator Transitions 65016.7 Magnetic and Dielectric Properties 65216.8 Optical Properties 65216.9 Mechanical Properties 65316.10 Phase Equilibria 65416.11 Synthesis 65416.12 Nanomaterial 656

Practice Questions 657References 658

Appendix A: List of the 230 Space Groups 659Appendix B: The 32 Crystal Systems and the 47 Possible Forms 665Appendix C: Principles of Tensors 667Appendix D: Solutions to Practice Problems 679

Index 683

xii Contents

Foreword to Second Edition

Materials science is one of the broadest of the applied science and engineering fields since it usesconcepts from so many different subject areas. Chemistry is one of the key fields of study, and inmanymaterials science programs, students must take general chemistry as a prerequisite for all butthe most basic of survey courses. However, that is typically the last true chemistry course that theytake. The remainder of their chemistry training is accomplished in their materials classes. This hasserved the field well for many years, but over the past couple of decades, new materials develop-ment has become more heavily dependent upon synthetic chemistry. This second edition ofPrinciples of Inorganic Materials Design serves as a fine text to introduce the materials studentto the fundamentals of designing materials through synthetic chemistry and the chemist to someof the issues involved in materials design.When I obtained my BS in ceramic engineering in 1981, the primary fields of materials science –

ceramics, metals, polymers, and semiconductors – were generally taught in separate departments,although there was frequently some overlap. This was particularly true at the undergraduate level,although graduate programs frequently had more subject overlap. During the 1980s, many of thesedepartments merged to form materials science and engineering departments that began to take amore integrated approach to the field, although chemical and electrical engineering programstended to cover polymers and semiconductors in more depth. This trend continued in the 1990sand included the writing of texts such as The Production of Inorganic Materials by Evans andDe Jonghe (Prentice Hall College Division, 1991), which focused on traditional production meth-ods. Synthetic chemical approaches became more important as the decade progressed and acade-mia began to address this in the classroom, particularly at the graduate level. The first edition ofPrinciples of Inorganic Materials Design strove to make this material available to the upper divisionundergraduate student.The second edition of Principles of Inorganic Materials Design corrects several gaps in the first

edition to convert it from a very good compilation of the field into a text that is very usable inthe undergraduate classroom. Perhaps the biggest of these is the addition of practice problemsat the end of every chapter since the second best way to learn a subject is to apply it to problems(the best is to teach it), and this removes the burden of creating the problems from the instructor.Chapter 1, Crystallographic Considerations, is new and both reviews the basic information in mostintroductory materials courses and clearly presents the more advanced concepts such as the math-ematical description of crystal symmetry that are typically covered in courses on crystallography ofphysical chemistry. Chapter 10, Mechanical Properties, has also been expanded significantly toprovide both the basic concepts needed by those approaching the topic for the first time and thesolid mathematical treatment needed to relate the mechanical properties to atomic bonding,

xiii

crystallography, and other material properties treated in previous chapters. This is particularlyimportant as devices use smaller active volumes of material, since this seldom results in the materi-als being in a stress-free state.In summary, the second edition of Principles of Inorganic Materials Design is a very good text for

several applications: a first materials course for chemistry and physics students, a consolidatedmaterials chemistry course for materials science students, and a second materials course for otherengineering and applied science students. It also serves as the background material to pursue thechemical routes to make these new materials described in texts such as Inorganic Materials Syn-thesis and Fabrication by Lalena and Cleary (Wiley, 2008). Such courses are critical to insure thatstudents from different disciplines can communicate as they move into industry and face the needto design new materials or reduce costs through synthetic chemical routes.

Martin W. Weiser

Martin earned his BS in ceramic engineering from Ohio State University and MS and PhD inMaterials Science andMineral Engineering from theUniversity of California, Berkeley. At Berkeleyhe conducted fundamental research on sintering of powder compacts and ceramic matrix compo-sites. After graduation he joined the University of NewMexico (UNM)where he was a visiting assis-tant professor in chemical engineering and then assistant professor in mechanical engineering. AtUNM he taught introductory and advanced materials science classes to students from all branchesof engineering. He continued his research in ceramic fabrication as part of the Center for Micro-Engineered Ceramics and also branched out into solder metallurgy and biomechanics in collabo-ration with colleagues from Sandia National Laboratories and the UNM School of Medicine,respectively.Martin joined Johnson Matthey Electronics in a technical service role supporting the Discrete

Power Products Group (DPPG). In this role he also initiated JME’s efforts to develop Pb-free soldersfor power die attach that came to fruition in collaboration with John N. Lalena several years laterafter JME was acquired by Honeywell. Martin spent several years as the product manager for theDPPG and then joined the Six Sigma Plus organization after earning his Six Sigma Black Belt work-ing on polymer/metal composite thermal interface materials (TIMs). He spent the last several yearsin the R&D group as both a groupmanager and principle scientist where he lead the development ofimproved Pb-free solders and new TIMs.

xiv Foreword to Second Edition

Foreword to First Edition

Whereas solid-state physics is concerned with the mathematical description of the varied physicalphenomena that solids exhibit and the solid-state chemist is interested in probing the relationshipsbetween structural chemistry and physical phenomena, the materials scientist has the task of usingthese descriptions and relationships to design materials that will perform specified engineeringfunctions. However, the physicist and the chemist are often called upon to act as material designers,and the practice of materials design commonly requires the exploration of novel chemistry that maylead to the discovery of physical phenomena of fundamental importance for the body of solid-statephysics. I cite three illustrations where an engineering need has led to new physics and chemistry inthe course of materials design.In 1952, I joined a group at the MIT Lincoln Laboratory that had been charged with the task of

developing a square B–H hysteresis loop in a ceramic ferrospinel that could have its magnetizationreversed in less than 1 μs by an applied magnetic field strength less than twice the coercive fieldstrength. At that time, the phenomenon of a square B–H loop had been obtained in a few iron alloysby rolling them into tapes so as to align the grains, and hence the easy magnetization directions,along the axis of the tape. The observation of a square B–H loop led Jay Forrester, an electricalengineer, to invent the coincident-current, random-access magnetic memory for the digital com-puter since, at that time, the only memory available was a 16 × 16 byte electrostatic storage tube.Unfortunately, the alloy tapes gave too slow a switching speed. As an electrical engineer, Jay For-rester assumed the problem was eddy-current losses in the tapes, so he had turned to the ferrimag-netic ferrospinels that were known to be magnetic insulators. However, the polycrystallineferrospinels are ceramics that cannot be rolled! Nevertheless, the Air Force had financed theMIT Lincoln Laboratory to develop an air defense system of which the digital computer was tobe a key component. Therefore, Jay Forrester was able to put together an interdisciplinary teamof electrical engineers, ceramists, and physicists to realize his random-access magnetic memorywith ceramic ferrospinels.The magnetic memory was achieved by a combination of systematic empiricism, careful materi-

als characterization, theoretical analysis, and the emergence of an unanticipated phenomenon thatproved to be a stroke of good fortune. A systematic mapping of the structural, magnetic, and switch-ing properties of the Mg–Mn–Fe ferrospinels as a function of their heat treatments revealed that thespinels, in one part of the phase diagram, were tetragonal rather than cubic and that compositions,just on the cubic side of the cubic–tetragonal phase boundary, yield sufficiently square B–H loops ifgiven a carefully controlled heat treatment. This observation led me to propose that the tetragonaldistortion was due to a cooperative orbital ordering on the Mn3+ ions that would lift the cubic-fieldorbital degeneracy; cooperativity of the site distortions minimizes the cost in elastic energy andleads to a distortion of the entire structure. This phenomenon is now known as a cooperative

xv

Jahn–Teller distortion since Jahn and Teller had earlier pointed out that a molecule or molecularcomplex, having an orbital degeneracy, would lower its energy by deforming its configuration to alower symmetry that removed the degeneracy. Armed with this concept, I was able almost imme-diately to apply it to interpret the structure and the anisotropic magnetic interactions that had beenfound in the manganese–oxide perovskites since the orbital order revealed the basis for specifyingthe rules for the sign of a magnetic interaction in terms of the occupancies of the overlapping orbi-tals responsible for the interatomic interactions. These rules are now known as the Goodenough–Kanamori rules for the sign of a superexchange interaction. Thus an engineering problemprompted the discovery and description of two fundamental phenomena in solids that ever sincehave been used by chemists and physicists to interpret structural andmagnetic phenomena in tran-sition metal compounds and to design new magnetic materials. Moreover, the discovery of coop-erative orbital ordering fed back to an understanding of our empirical solution to the engineeringproblem. By annealing at the optimum temperature for a specified time, the Mn3+ ions of a cubicspinel would migrate to form Mn-rich regions where their energy is lowered through cooperative,dynamic orbital ordering. The resulting chemical inhomogeneities acted as nucleating centers fordomains of reverse magnetization that, once nucleated, grew away from the nucleating center. Wealso showed that eddy currents were not responsible for the slow switching of the tapes, but a smallcoercive field strength and an intrinsic damping factor for spin rotation.In the early 1970s, an oil shortage focused worldwide attention on the need to develop alternative

energy sources, and it soon became apparent that these sources would benefit from energy storage.Moreover, replacing the internal combustion engine with electric-powered vehicles, or at least theintroduction of hybrid vehicles, would improve the air quality, particularly in big cities. Therefore, aproposal by the Ford Motor Company to develop a sodium–sulfur battery operating at 3008 C withmolten electrodes and a ceramic Na+-ion electrolyte stimulated interest in the design of fast alkaliion conductors. More significant was interest in a battery in which Li+ rather than H+ is the work-ing ion, since the energy density that can be achieved with an aqueous electrolyte is lower thanwhat, in principle, can be obtained with a nonaqueous Li+-ion electrolyte. However, realizationof a Li+-ion rechargeable battery would require identification of a cathode material into/fromwhich Li+ ions can be inserted/extracted reversibly. Brian Steele of Imperial College, London, firstsuggested the use of TiS2, which contains TiS2 layers held together only by van der Waals S2––S2–

bonding; lithium can be inserted reversibly between the TiS2 layers. M. Stanley Whittingham’sdemonstration was the first to reduce this suggestion to practice while he was at the Exxon Cor-poration. Whittingham’s demonstration of a rechargeable Li–TiS2 battery was commercially non-viable because the lithium anode proved unsafe. Nevertheless, his demonstration focused attentionon the work of the chemists Jean Rouxel of Nantes and R. Schöllhorn of Berlin on insertion com-pounds that provide a convenient means of continuously changing the mixed valency of a fixedtransition metal array across a redox couple. Although work at Exxon was halted, their demonstra-tion had shown that if an insertion compound, such as graphite, was used as the anode, a viablelithium battery could be achieved, but the use of a less electropositive anode would require an alter-native insertion-compound cathode material that provided a higher voltage versus a lithium anodethan TiS2. I was able to deduce that no sulfide would give a significantly higher voltage than thatobtained with TiS2 and therefore that it would be necessary to go to a transition metal oxide.Although oxides other than V2O5 and MoO3, which contain vandyl or molybdyl ions, do not formlayered structures analogous to TiS2, I knew that LiMO2 compounds exist that have a layered struc-ture similar to that of LiTiS2. It was only necessary to choose the correct M3+ cation and to deter-mine how much Li could be extracted before the structure collapsed. That was how the Li1−xCoO2

cathode material was developed, which now powers the cell telephones and laptop computers. The

xvi Foreword to First Edition

choice of M = Co, Ni, or Ni0.5+δMn0.5−δ was dictated by the position of the redox energies and anoctahedral site preference energy strong enough to inhibit migration of the M atom to the Li layerson the removal of Li. Electrochemical studies of these cathode materials, and particularly of Li1−xNi0.5+δMn0.5−δO2, have provided a demonstration of the pinning of a redox couple at the top of thevalence band. This is a concept of singular importance for interpretation of metallic oxides havingonly M–O–M interactions, of the reason for oxygen evolution at critical Co(IV)/Co(III) or Ni(IV)/Ni(III) ratios in Li1−xMO2 studies, and of why Cu(III) in an oxide has a low-spin configuration. More-over, exploration of other oxide structures that can act as hosts for insertion of Li as a guest specieshas provided a means of quantitatively determining the influence of a counter cation on the energyof a transitionmetal redox couple. This determination allows tuning of the energy of a redox couple,which may prove important for the design of heterogenous catalysts.As a third example, I turn to the discovery of high-temperature superconductivity in the copper

oxides, first announced by Bednorz and Müller of IBM Zürich in the summer of 1986. Karl A.Müller, the physicist of the pair, had been thinking that a dynamic Jahn–Teller ordering might pro-vide an enhanced electron–phonon coupling that would raise the superconductive critical temper-ature TC. He turned to his chemist colleague Bednorz to make a mixed-valence Cu3+/Cu2+

compound since Cu2+ has an orbital degeneracy in an octahedral site. This speculation led tothe discovery of the family of high-TC copper oxides; however, the enhanced electron–phonon cou-pling is not due to a conventional dynamic Jahn–Teller orbital ordering, but rather to the first-ordercharacter of the transition from localized to itinerant electronic behavior of σ-bonding Cu: 3d elec-trons of (x2− y2) symmetry in CuO2 planes. In this case, the search for an improved engineeringmaterial has led to a demonstration that the celebrated Mott–Hubbard transition is generallynot as smooth as originally assumed, and it has introduced an unanticipated new physics associatedwith bond length fluctuations and vibronic electronic properties. It has challenged the theorist todevelop new theories of the crossover regime that can describe the mechanism of superconductivepair formation in the copper oxides, quantum critical-point behavior at low temperatures, and ananomalous temperature dependence of the resistivity at higher temperatures as a result of strongelectron–phonon interactions.These examples show how the challenge of materials design from the engineer may lead to new

physics as well as to new chemistry. Sorting out of the physical and chemical origins of the newphenomena fed back to the range of concepts available to the designer of new engineering materi-als. In recognition of the critical role in materials design of interdisciplinary cooperation betweenphysicists, chemists, ceramists, metallurgists, and engineers that is practiced in industry and gov-ernment research laboratories, John N. Lalena and David A. Cleary have initiated, with their book,what should prove to be a growing trend toward greater interdisciplinarity in the education of thosewho will be engaged in the design and characterization of tomorrow’s engineering materials.

John B. Goodenough

John received the Nobel Prize in Chemistry in 2019. See his biography page 386.

Foreword to First Edition xvii

Preface to Third Edition

I contacted John Nick Lalena almost ten years ago, electronically by e-mail to inform him of myenthusiasm for a review paper he had written on crystallography and share some comments. Nickresponded immediately, and we started an intense e-mail correspondence. I then discovered thesecond edition of this book, and I loved it very much, as a kind of multifacetted diamond. Of course,diamonds always have some defects, and I commented on them with Nick again, besides my admi-ration for the broad scope of the book and its most pleasant style to my taste. Somewhat later, inAugust 2018, Nick let me know about the preparation of a third edition and asked me if I wouldaccept to review some of the new and rewritten chapters. As I started the job, I naturally madecomments and even suggested new lines that could be added here and there – so much so that Nickand Dave proposed me to become a third co-author for the third edition. Principles of InorganicMaterials Design now has an added French touch in some places, even if science is naturallyuniversal.The third edition is thicker than the second, which was thicker than the first. Quite a few sections

in existing chapters have been rewritten and/or expanded. Three chapters have been added, two ofthem being case study chapters. Thanks to the skills of its three authors, PIMD3, as we like to call it,is very versatile. It has fundamental aspects presented pedagogically as appropriate for a textbook,with additional historical focus and biographical presentations of some of our heroes in crystallog-raphy, solid-state physics, and materials science. It has some sections on rather recent develop-ments in electron density functional theory as well as a new appendix presenting tensors fromdifferent physical points of view. It also touches on a plethora of topics of relevance to the practi-tioners of materials science such as mechanical engineers, including a new section about additivemanufacturing,Diamonds must be sculpted so that they can shine from whatever angle they are looked at, just as

with the French Blue Diamond of the Crown now visible at the Smithsonian Institution. At thesame time the best natural diamonds contain defects, and, to quote a phrase attributed to SirCharles Frank, “crystals are like people: it is the defects in them that make them interesting.”I thus believe that readers, either students, teachers, researchers or practitioners, will learn a lotfrom this book and enjoy it even more than I enjoyed PIMD2, while, at the same time, they shouldhopefully find it not absolutely perfect in places from their own point of view. Science is not a closedbook, and no science book should be a closed book either: a good science book should stay open andbe read and annotated.

Olivier B. M. Hardouin Duparc

xix

Preface to Second Edition

In our first attempt at writing a textbook on the highly interdisciplinary subject of inorganic mate-rials design, we recognized the requirement that the book needed to appeal to a very broad-basedaudience. Indeed, practitioners of materials science and engineering come from many differenteducational backgrounds, each emphasizing different aspects. These include solid-state chemistry,condensed-matter physics, metallurgy, ceramics, mechanical engineering, and materials scienceand engineering (MS&E). Unfortunately, we did not adequately anticipate the level of difficultythat would be associated with successfully implementing the task of attracting readers from somany disciplines that, though distinct, possess the common threads of elucidating and utilizingstructure/property correlation in the design of new materials.As a result, the first edition had a number of shortfalls. First and foremost, owing to a variety of

circumstances, there were many errors that, regrettably, made it into the printed book. Great carehas been taken to correct each of these. In addition to simply revising the first edition, however, thecontent has been updated and expanded as well. As was true with the first edition, this book is con-cerned, by and large, with theoretical structure/property correlation as it applies to materialsdesign. Nevertheless, a small amount of space is dedicated to the empirical practice of synthesisand fabrication. Much more discussion is devoted to these specialized topics concerned with thepreparation of materials, as opposed to their design, in numerous other books, one of which isour companion textbook, Inorganic Materials Synthesis and Fabrication.Some features added to this second edition include an expanded number of worked examples and

an appendix containing solutions to selected end-of-chapter problems. The overall goal of our sec-ond edition is, quite simply, to rectify the problems we encountered earlier, thereby producing awork that is much better suited as a tool to the working professionals, educators, and studentsof this fascinating field.

John N. Lalena and David A. Cleary

xx

Preface to First Edition

Inorganic solid-state chemistry has matured into its own distinct subdiscipline. The reader maywonder why we have decided to add another textbook to the plethora of books already published.Our response is that we see a need for a single source presentation that recognizes the interdisci-plinary nature of the field. Solid-state chemists typically receive a small amount of training in con-densed-matter physics, and none inmaterials science or engineering, and yet all of these traditionalfields are inextricably part of inorganic solid-state chemistry.Materials scientists and engineers have traditionally been primarily concerned with the fabrica-

tion and utilization of materials already synthesized by the chemist and identified by the physicistas having the appropriate intrinsic properties for a particular engineering function. Although thedemarcation between the three disciplines remains in an academic sense, the separate job distinc-tions for those working in the field is fading. This is especially obvious in the private sector whereone must ensure that materials used in real commercial devices not only perform their primaryfunction but also meet a variety of secondary requirements.Individuals involved with these multidisciplinary and multitask projects must be prepared to

work independently or to collaborate with other specialists in facing design challenges. In the lattercase, communication is enhanced if each individual is able to speak the “language” of the other.Therefore, in this book we introduce a number of concepts that are not usually covered in standardsolid-state chemistry textbooks. When this occurs, we try to follow the introduction of the conceptwith an appropriate worked example to demonstrate its use. Two areas that have lacked thoroughcoverage in most solid-state chemistry texts in the past, namely, microstructure and mechanicalproperties, are treated extensively in this book.We have kept the mathematics to a minimum – but adequate – level, suitable for a descriptive

treatment. Appropriate citations are included for those needing the quantitative details. It isassumed that the reader has sufficient knowledge of calculus and elementary linear algebra, par-ticularly matrix manipulations, and some prior exposure to thermodynamics, quantum theory, andgroup theory. The book should be satisfactory for senior level undergraduate or beginning graduatestudents in chemistry. One will recognize from the Table of Contents that the entire textbooks havebeen devoted to each of the chapters in this book, and this limits the depth of coverage out of neces-sity. Along with their chemistry colleagues, physics and engineering students should also find thebook to be informative and useful.Every attempt has been made to extensively cite all the original and pertinent research in a fash-

ion similar to that found in a review article. Students are encouraged to seek out this work. We havealso included biographies of several individuals who have made significant fundamental contribu-tions to inorganic materials science in the twentieth century. Limiting these to the small number wehave room for was, of course, difficult. The reader should be warned that some topics have been left

xxi

out. In this book, we only cover nonmolecular inorganic materials. Polymers and macromoleculesare not discussed. Nor are the other extreme, for example, molecular electronics. Also omitted arecoverages of surface science, self-assembly, and composite materials.We are grateful to Professor John B. Wiley, Dr. Nancy F. Dean, Dr. Martin W. Weiser, Professor

Everett E. Carpenter, and Dr. Thomas K. Kodenkandath for reviewing various chapters in this book.We are grateful to Professor John F. Nye, Professor John B. Goodenough, Dr. Frans Spaepen,Dr. Larry Kaufman, and Dr. Bert Chamberland for providing biographical information. We wouldalso like to thank Professor Philip Anderson, Professor Mats H. Hillert, Professor Nye, Dr. Kaufman,Dr. Terrell Vanderah, Dr. Barbara Sewall, and Mrs Jennifer Moss for allowing us to use photographsfrom their personal collections. Finally, we acknowledge the inevitable neglect our families musthave felt during the period taken to write this book. We are grateful for their understanding andtolerance.

John N. Lalena and David A. Cleary

xxii Preface to First Edition

Acronyms

AC alternating currentAFMs antiferromagnetsAIMD Ab initio molecular dynamicsAOT aerosol OT (sodium dioctylsulfosuccinate)APW augmented plane waveBCC body-centered cubicBM Bohr magnetonBMGs bulk metallic glassesBOs Bloch orbitals - also referred as Bloch sumsBVS bond valence sumsBZ Brillouin zoneCA cellular automationCALPHAD CALculation of PHAse DiagramsCB carbazole-9-carbonyl chlorideCCP cubic-close packageCCSL constrained coincidence site latticeCDW charge density waveCFSE crystal field stabilization energyCI configuration interactionCMR colossal magnetoresistanceCOs crystal orbitalsCRSS critical resolved shear stressCSL coincidence site latticeCTAB cetyltrimethylammonium bromideCTE coefficient of thermal expansionCVD chemical vapor depositionCVM cluster variation methodDE double exchangeDFT density functional theoryDMFT dynamical mean field theoryDOS density-of-statesDR1 disperse red 1DSC (lattice) displacement shift complete (lattice)DSC differential scanning calorimetryDTA differential thermal analysis

xxiii

EAM embedded atom methodEBS electrostatic bond strengthEBSD electron backscatter diffractionECAE equal-channel angular extrusionECAP equal-channel angular pressingEDTA ethylenediamine tetraacetateEMF electromagnetic fieldEOS equation of stateEPMA electron probe microanalysisFC field cooledFCC face-centered cubicFDM finite difference methodFEM finite element methodFVM finite volume methodGB grain boundaryGGA generalized gradient approximationGLAD glancing angle depositionGMR giant magnetoresistanceGTOs Gaussian-type orbitalsHCP hexagonal close packedHeIM helium ion microscopeHF Hartree FockHOMO highest occupied molecular orbitalHRTEM high-resolution transmission electron microscopyIC integrated circuitsIR infrared radiationJT Jahn–TellerLCAO linear combination of atomic orbitalsLCAO-MO linear combination of atomic orbitals - molecular orbitalsLCOAO linear combination of orthogonalized atomic orbitalsLDA local density approximationLHB lower Hubbard bandLRO long-range (translational) orderLSDA local spin-density approximationLUMO lowest unoccupied molecular orbitalMC Monte CarloMCE magnetocaloric effectMD molecular dynamicsM-I metal-insulatorMMC metal matrix compositeM–NM metallic–nonmetallicMO molecular orbitalMOCVD metal–organic chemical vapor depositionMP Møller–PlessetMPB morphotropic phase boundaryMRO medium-range order

xxiv Acronyms

MS&E materials science and engineeringMSD microstructure sensitive designMWNT multiwalled carbon nanotubesNA numerical apertureND normal directionsNFE nearly free electronNMR nuclear magnetic resonanceODF orientation distribution functionPFCM phase field crystal modelingPFM phase field modelingPIMD principles of inorganic materials designPIMD path integral molecular dynamicsPCF (single-mode) photonic crystal fiberPLD pulsed laser depositionPV photovoltaicPVD physical vapor depositionPVP poly(vinylpyrrolidone)PZT Pb(Zr,Ti)O3

QMC quantum Monte CarloQMD quantum molecular dynamicsRD radial directionsRKKY Rudderman–Kittel–Kasuya–YoshidaRP Ruddlesden–PopperRPA random-phase approximationSALC symmetry-adapted linear combinationSANS small-angle Newton scatteringSAXS small-angle X-ray scatteringSC simple cubicSCF self-consistent fieldSDS sodium dodecylsulfateSDW spin-density waveSEM scanning electron microscopeSHS self-propagating high-temperature synthesisSK Slater-KosterSMA shape memory alloysSP spin-polarizedSPD severe plastic deformationSRO short-range orderSTM scanning tunneling microscopeSTOs Slater-type orbitalsSWNT single-walled carbon nanotubesTB tight bindingTD transverse directionsTE thermoelectricTEM transmission electron microscopeTEOS tetraethyl orthosilicate

Acronyms xxv

TGG templated grain growthTIM thermal interface materialTOPO trioctylphosphine oxideTSSG top-seeded solution growthUFG ultrafine-grainedUHB upper Hubbard bandUTS ultimate tensile strengthVEC valence electron concentrationVRH variable range hoppingVSEPR valence shell electron pair repulsionXC exchange and correlationXRD X-ray diffractionZFC zero-field cooled

xxvi Acronyms

1

Crystallographic Considerations

There are many possible classification schemes for solids that can be envisioned. We can categorizea material based solely on its chemical composition (inorganic, organic, or hybrid), the primarybonding type (ionic, covalent, metallic), its structure type (catenation polymer, extended three-dimensional network), or its crystallinity (crystalline or noncrystalline). It is the latter scheme thatis the focus of this chapter. A crystalline material exhibits a large degree of structural order in thearrangement of its constituent particles, be they atoms, ions, or molecules, over a large length scalewhereas a noncrystalline material exhibits structural order only over the very short-range lengthscale corresponding to the first coordination sphere. It is structural order – the existence of amethodical arrangement among the component particles – that makes the systematic study anddesign of materials with prescribed properties possible.A crystal may be explicitly defined as a homogeneous solid consisting of a periodically repeating

three-dimensional pattern of particles. There are three key structural features to crystals, betweenphysics and mathematics:

1) The motif, which is the group of atoms or molecules repeated at each lattice point.2) Symmetry, the geometric arrangement of the lattice points, defined by a repeating unit cell.3) Long-range (translational) order (LRO), referring to the periodicity, or regularity in the arrange-

ment of the material’s atomic or molecular constituents on a length scale at least a few timeslarger than the size of the unit cell.

The presence of a long-range order allows crystals to scatter incoming waves, of appropriate wave-lengths, so as to produce discrete diffraction patterns, which, in turn, ultimately enables ascertain-ment of the actual atomic positions and, hence, crystalline structure. The periodic LRO can beextended to quasiperiodic LRO to encompass quasicrystals; see Section 1.1.2.

1.1 Degrees of Crystallinity

Crystallinity, like most things, can vary in degree. Even single crystals (a.k.a. monocrystals) haveintrinsic point defects (e.g. lattice site vacancies) and extrinsic point defects (e.g. impurities), as wellas extended defects such as dislocations. Defects are critical to the physical properties of crystalsand will be extensively covered in later chapters. What we are referring to here with the degreeof crystallinity is not the simple proportion of defects present in the solid, but rather the spectrum

1

Principles of Inorganic Materials Design, Third Edition. John N. Lalena, David A. Cleary,and Olivier B. M. Hardouin Duparc.© 2020 John Wiley & Sons, Inc. Published 2020 by John Wiley & Sons, Inc.

of crystallinity that encompasses the entire range from really crystalline to fully disordered amor-phous solids. Table 1.1 lists the various classes. Let us take each of them in the order shown.

1.1.1 Monocrystalline Solids

At the top of the list is the single crystal, or monocrystal, which has the highest degree of order.Several crystalline materials of enormous technological or commercial importance are used inmonocrystalline form. Figure 1.1a shows a drawing of a highly symmetrical quartz crystal, suchas might be grown freely suspended in a fluid. For a crystal, the entire macroscopic body can beregarded as a monolithic three-dimensional space-filling repetition of the fundamental crystallo-graphic unit cell. Typically, the external morphology of a single crystal is faceted (consisting offaces), as in Figure 1.1a, although this need not be the case. The word habit is used to describethe overall external shape of a crystal specimen. Habits, which can be polyhedral or non-polyhedral,may be described as cubic, octahedral, fibrous, acicular, prismatic, dendritic (treelike), platy,

Table 1.1 Degrees of crystallinity.

Type Defining features

Monocrystalline LRO

Quasicrystalline Noncrystallographic rotational symmetry, no LRO

Polycrystalline Crystallites separated by grain boundaries

Semicrystalline Crystalline regions separated by amorphous regions

Amorphous and glassy state No LRO, no rotational symmetry, does possess short-range order

(a) (b) (c)

Figure 1.1 (a) A drawing of a quartz monocrystal. The morphology exhibits the true point symmetry ofthe lattice. (b) A portion of a Penrose tiling with fivefold rotational symmetry based on two rhombuses.A Penrose tiling is a nonperiodic tiling of the plane and is a two-dimensional analog of a quasicrystal.(c) A micrograph of a polycrystalline sample of aluminum plastically deformed under uniaxial tension.

2 1 Crystallographic Considerations