Fundamentals of Electroceramics

R. K. Pandey, PhD, is Ingram Professor Emeritus of Texas State University, San Marcos, TX, Cudworth Professor Emeritus of the University of Alabama, Tuscaloosa, AL, and Professor Emeritus of Texas A&M University, College Station, TX. He is also a Fellow of the American Ceramic Society, a Life Senior Member of the IEEE, and a Senior Member of the American Physical Society.

• Preface xiiiAbout the CompanionWebsite xvii1 Nature and Types of Solid Materials 11.1 Introduction 11.2 Defining Properties of Solids 11.2.1 Electrical Conductance (G) 11.2.2 Bandgap, Eg 21.2.3 Permeability, 𝜀 31.3 Fundamental Nature of Electrical Conductivity 41.4 Temperature Dependence of Electrical Conductivity 41.4.1 Case of Metals 51.4.2 Case of Semiconductors 51.4.3 Frequency Spectrum of Permittivity (or Dielectric Constant) 61.5 Essential Elements of Quantum Mechanics 71.5.1 Planck’ Radiation Law 71.5.2 Photoelectric Effect 81.5.3 Bohr’sTheory of Hydrogen Atom 101.5.4 Matter–Wave Duality: de Broglie Hypothesis 111.5.5 Schrödinger’sWave Equation 121.5.6 Heisneberg’s Uncertainty Principle 131.6 Quantum Numbers 131.7 Pauli Exclusion Principle 141.8 Periodic Table of Elements 151.9 Some Important Concepts of Solid-State Physics 181.9.1 Ceramic Superconductivity 181.9.2 Superconductivity and Technology 191.10 Signature Properties of Superconductors 191.10.1 Thermal Behavior of Resistivity of a Superconductor 201.10.2 Magnetic Nature of Superconductivity: Meissner–Ochsenfeld Effect 201.10.3 Josephson Effect 221.11 Fermi–Dirac Distribution Function 241.12 Band Structure of Solids 27Glossary 29Problems 30References 31Further Reading 312 Processing of Electroceramics 332.1 Introduction 332.2 Basic Concepts of Equilibrium Phase Diagram 332.2.1 Gibbs’ Phase Rule 342.2.2 Triple Point and Interfaces 342.2.3 Binary Phase Diagrams 352.2.3.1 Totally Miscible Systems 352.2.3.2 Systems with Limited Solubility in Solid Phase 372.3 Methods of Ceramic Processing 382.3.1 Room Temperature Uniaxial Pressing (RTUP) 382.3.2 Other Methods for Powder Compaction and Densification 412.3.2.1 Hot Isostatic Pressing (HIP) 412.3.2.2 Cold Isostatic Pressing (CIP) 412.3.2.3 Low Temperature Sintering (LTP) 422.3.3 Nanoceramics 422.3.4 Thin Film Ceramics 422.3.5 Methods for Film Growth 432.3.5.1 Solgel Method 432.3.5.2 Pulsed Laser Deposition (PLD) Method 442.3.5.3 Molecular Beam Epitaxy (MBE) Method 462.3.5.4 RF Magnetron Sputtering Method 472.3.5.5 Liquid Phase Epitaxy (LPE) Method 492.3.6 Single Crystal Growth Methods for Ceramics 492.3.6.1 High Temperature Solution Growth (HTSG) Method or Flux Growth Method 502.3.6.2 Czochralski Growth Method 512.3.6.3 Top Seeded Solution Growth (TSSG) Method 522.3.6.4 Hydrothermal Growth 532.3.6.5 Some Other Methods of Crystal Growth 53Glossary 54Problems 55References 553 Methods for Materials Characterization 573.1 Introduction 573.2 Methods for Surface and Structural Characterization 573.2.1 Optical Microscopes 583.2.2 X-ray Diffraction Analysis (XRD) 603.2.2.1 XRD Diffractometer: Intensity vs. 2𝜃 Plot 603.2.2.2 Laue X-ray Diffraction Method 613.2.3 Electron Microscopes 633.2.3.1 Transmission Electron Microscope (TEM) 643.2.3.2 Scanning Electron Microscope (SEM) 653.2.3.3 Scanning Transmission Electron Microscope (STEM) 653.2.3.4 X-ray Photoelectron Spectroscopy (XPS) 663.2.4 Force Microscopy 683.2.4.1 Atomic Force Microscope (AFM) 683.2.4.2 Magnetic Force Microscope (MFM) 693.2.4.3 Piezoelectric Force Microscope (PFM) 69Glossary 70Problems 71References 714 Binding Forces in Solids and Essential Elements of Crystallography 734.1 Introduction 734.2 Binding Forces in Solids 734.2.1 Ionic Bonding 744.2.2 Covalent Bonding 744.2.3 Metallic Bonding 744.2.4 Van der Waals Bonding 754.2.5 Polar-molecule-induced Dipole Bonds 754.2.6 Permanent Dipole Bonding 754.3 Structure–Property Relationship 754.4 Basic Crystal Structures 774.4.1 Bravais Lattice 784.4.2 Miller Indices for Planes and Directions 794.4.2.1 Rule for Indexing a Crystal Direction 804.5 Reciprocal Lattice 814.6 Relationship between d* and Miller Indices for Selected Crystal Systems 814.7 Typical Examples of Crystal Structures 824.7.1 Sodium Chloride, NaCl 824.7.2 Perovskite Calcium Titanate 824.7.3 Diamond Structure 834.7.4 Zinc Blende (Also Wurtzite) 844.8 Origin of Voids and Atomic Packing Factor (apf) 844.8.1 apf for a Primitive Cubic Structure (P) 854.9 Hexagonal and Cubic Close-packed Structures 854.10 Predictive Nature of Crystal Structure 864.11 Hypothetical Models of Centrosymmetric and Noncentrosymmetric Crystals 874.12 Symmetry Elements 884.13 Classification of Dielectric Materials: Polar and Nonpolar Groups 894.14 Space Groups 90Glossary 91Problems 92References 93Further Reading 935 Dominant Forces and Effects in Electroceramics 955.1 Introduction 955.2 Agent–Property Relationship 955.3 Electric Field (E), Mechanical Stress (X), and Temperature (T) Diagram: Heckmann Diagram 965.3.1 Piezoelectric Zone 975.3.2 Pyroelectric Zone 975.3.3 Thermoelastic Zone 985.4 Electric Field, Mechanical Stress, and Magnetic Field Diagram 995.5 Multiferroics Phenomena and Materials 1015.6 Magnetoelectric (ME) Effect and Associated Issues 1035.6.1 Basic Formulations Governing the ME Effect 1035.6.2 Composite ME Materials 1045.6.3 ME Integrated Structures 1045.6.4 Experimental Determination 1045.7 Applications of Multiferroics 1055.7.1 Ferroelectric and Ferromagnetic Coupled Memory 1055.7.2 Multiferroic Tunnel Junctions (MTJ) 1065.8 Magnetostriction and Electrostriction 1065.8.1 Magnetostriction 1065.8.2 Electrostriction 1075.9 Piezoelectricity 1085.9.1 Crystallographic Considerations for Piezoelectricity 1085.9.2 Mathematical Representation of Piezoelectric Effects 1095.9.3 Constitutive Equations for Piezoelectricity 1105.10 Experimental Determination of Piezoelectric Coefficients 1115.10.1 Charge Coefficient, d 1115.10.2 Stress Coefficient, e 1125.10.3 Piezoelectric Devices and Applications 1135.10.3.1 Piezoelectric Transducers 1145.10.3.2 Generation of Sound and an AC Signal 1145.10.3.3 Surface AcousticWave (SAW) Device 1155.10.3.4 Piezoelectric Acoustic Amplifier 1165.10.3.5 Piezoelectric Frequency Oscillator 1165.10.4 MEMS Actuator 116Glossary 118Problems 119References 1206 Coupled Nonlinear Effects in Electroceramics 1216.1 Introduction 1216.2 Historical Perspective 1236.3 Signature Properties of Ferroelectric Materials 1236.3.1 Hysteresis Loop: Its Nature and Technical Importance 1246.3.2 Temperature Dependence of Ferroelectric Parameters 1256.3.3 Temperature Dependence of Dielectric Constant 1256.3.4 Ferroelectric Domains 1266.3.5 Electrets 1266.3.6 Relaxor Ferroelectrics 1266.4 Perovskite and Tungsten Bronze Structures 1276.4.1 Perovskite Structure 1276.4.2 Tungsten Bronze Structure 1306.5 Landau–Ginsberg–Devonshire Mean Field Theory of Ferroelectricity 1306.6 Experimental Determination of Ferroelectric Parameters 1346.6.1 Poling of Samples for Experiments 1346.6.2 Polarization vs. Electric Field 1356.6.3 CapacitanceMeasurement and C–V Plot 1366.6.4 Ferroelectric Domains (Experimental Determination) 1376.7 Recent Applications of Ferroelectric Materials 1386.8 Antiferroelectricity 1396.9 Pyroelectricity 1436.9.1 Historical Perspective 1436.9.2 Pyroelectric Effect 1436.9.3 Experimental Determination of Pyroelectric Coefficient 1456.9.4 Applications of Pyroelectricity 1466.10 Pyro-optic Effect 147Glossary 148Problems 150References 150Further Reading 1517 Elements of a Semiconductor 1537.1 Introduction 1537.2 Nature of Electrical Conduction in Semiconductors 1537.3 Energy Bands in Semiconductors 1557.4 Origin of Holes and n- and p-Type Conduction 1567.5 Important Concepts of Semiconductor Materials 1587.5.1 Mobility, 𝜇 1587.5.2 Direct and Indirect Bandgap, Eg 1597.5.3 Effective Mass, m* 1607.5.4 Density of States and Fermi Energy 1617.6 Experimental Determination of Semiconductor Properties 1627.6.1 Determination of Resistivity, 𝜌 1627.6.2 Four-Point Probe (van der Pauw) Method 1637.6.3 Two-Point Probe Method 1637.6.4 Determination of Bandgap, Eg 1647.6.5 Determination of N- and P-Type Nature: Seebeck Effect 1647.6.6 Determination of Direct and Indirect Bandgap, Eg 1667.6.7 Determination of Mobility, 𝜇 1667.6.7.1 Haynes–Shockley Method 1677.6.7.2 Hall Effect 168Glossary 170Problems 170References 171Further Reading 1718 Electroceramic Semiconductor Devices 1738.1 Introduction 1738.2 Metal–Semiconductor Contacts and the Schottky Diode 1748.2.1 Metal–Metal Contact 1748.2.2 Metal Semiconductor Contact 1758.2.3 Schottky Diode 1768.2.4 Determination of Contact Potential and DepletionWidth 1788.2.5 Oxide Semiconductor Materials andTheir Properties 1798.2.6 In Search of UV-blue LED 1818.2.7 Determination of I–V Characteristics of a LED 1828.2.8 Thin-film Transistor (TFT) 1838.3 Varistor Diodes 1848.3.1 Metal Oxide Varistors 1858.4 Theoretical Considerations for Varistors 1868.4.1 Equivalent Circuit of a Varistor 1868.4.2 Idealized Model of Varistor Microstructure 1868.4.3 Energy Band Diagram: Grain–Grain Boundary–Grain (G–GB–G) Structure 1888.5 Varistor-Embedded Devices 1908.5.1 Voltage Biased Varistor and Embedded Voltage Biased Transistor (VBT) 1908.5.1.1 Frequency Dependence of IHC 45 VBT Device 1948.5.1.2 Comparison between a VBT, BJT, and Schottky Transistor 1958.5.2 Electric Field Tuned Varistor and Its Embedded Electric Field Effect Transistor (E-FET) 1968.5.2.1 Frequency Dependence of IHC 45 E-FET Device 1988.5.3 Magnetically Tuned Varistor and Embedded Magnetic Field Effect Transistor (H-FET) 1988.6 Magnetic Field Sensor 2028.7 Thermistors 2068.7.1 Heating Effects in Thermistors 207Glossary 210Problems 212References 213Further Reading 2149 Electroceramics and Green Energy 2159.1 Introduction 2159.2 What is Green Energy? 2159.3 Energy Storage and Its Defining Parameters 2179.3.1 Capacitor as an Energy Storage Device 2189.3.2 Battery-Supercapacitor Hybrid (BSH) Devices 2209.3.3 Piezoelectric Energy Harvester 2209.3.4 MEMS Power Generator 2229.3.5 Ferroelectric Photovoltaic Devices 2229.3.6 Solid Oxide Fuel Cells (SOFC) 2249.3.7 Antiferroelectric Energy Storage 225Glossary 227Problems 227References 22810 Electroceramic Magnetics 22910.1 Introduction 22910.2 Magnetic Parameters 22910.3 Relationship between Magnetic Flux, Susceptibility, and Permeability 23010.4 Signature Properties of Ferrites 23110.4.1 Temperature Dependence of Magnetic Parameters 23410.5 Typical Structures Associated with Ferrites 23410.6 Essential Theoretical Concepts 23510.7 Magnetic Nature of Electron 23510.7.1 Molecular FieldTheory 23610.7.2 Antiferromagnetism and Ferrimagnetism 23710.7.3 Quantum Mechanics and Magnetism 23810.8 Classical Applications of Ferrites 23910.9 Novel Magnetic Technologies 23910.9.1 GMR Effect 24010.9.2 CMR Effect 24110.9.3 Spintronics 241Glossary 242Problems 243References 245Further Reading 24511 Electro-optics and Acousto-optics 24711.1 Introduction 24711.2 Nature of Light 24711.2.1 Fundamental Optical Properties of a Crystal 24811.2.2 Electro-optic Effects 24911.2.3 Selected Electro-optic Applications 25111.2.3.1 OpticalWaveguides 25111.2.3.2 Phase Shifters 25211.2.3.3 Electro-optic Modulators 25211.2.3.4 Night Vision Devices (NVD) 25211.2.4 Acousto-optic Effect and Applications 253Glossary 254Problems 255References 255Further Reading 255AppendixA Periodic Table of the Elements 257AppendixB Fundamental Physical Constants and Frequently Used Symbols and Units (Rounded to Three Decimal Points) 259AppendixC List of Prefixes Commonly Used 261AppendixD Frequently Used Symbols and Units 263Index 265