Handbook of Inorganic Electrochromic Materials

Handbook of Inorganic Electrochromic Materials......Page 4
Copyright Page......Page 5
PREFACE......Page 8
Contents......Page 10
1.1 Prototype Device Design and Some Key Concepts......Page 18
1.2 Survey of Electrochromic Oxide Films......Page 22
1.3 Applications Areas for Electrochromic Devices......Page 26
1.4 Some Notes on the History of Electrochromism......Page 30
PART ONE: CASE STUDY ON TUNGSTEN OXIDE......Page 34
2.1 Crystal Structures of Tungsten Oxide......Page 36
2.2 Crystal Structures of Tungsten Bronzes and Ion Intercalated Tungsten Oxide......Page 38
2.3 Optical Properties......Page 40
2.4 Electrical Properties......Page 43
3.1 Deposition Aspects......Page 46
3.2 Density......Page 48
3.3 Elemental Composition: Oxygen Deficiency and Hydrogen Content......Page 50
3.5 Microstructure Studied by X-ray Extinction......Page 54
3.6 Molecular Bonding Studied by Raman Spectroscopy......Page 56
3.7 Molecular Bonding Studied by Infrared Absorption Spectroscopy......Page 58
3.8 Cluster-type Microstructures......Page 62
3.9 Columnar Microstructures......Page 66
3.10 Crystallization of As-deposited Films......Page 68
4.1 Deposition Aspects......Page 72
4.2 Characterization of As-deposited Films by Several Techniques......Page 74
4.3 Cluster-type Microstructures......Page 76
4.5 Crystallization of As-deposited Films......Page 78
5.1 Electrodeposition......Page 82
5.2 Anodization......Page 84
5.3 Chemical Vapor Deposition and Spray Deposition......Page 85
5.4 Sol-gel-based Techniques......Page 88
5.5 Miscellaneous Techniques......Page 94
6.1 Ion Intercalation Reactions and Electrochemical Analysis: Some Introductory Remarks......Page 96
6.2 Diffusion Constants......Page 98
6.3 Electromotive Force......Page 104
6.4 Chronoamperometry: Kinetics for Ion Intercalation and Deintercalation......Page 108
6.5 Cyclic Voltammetry......Page 112
6.6 Impedance Spectrometry......Page 120
6.7 Beam Deflectometry......Page 124
6.8 Microbalance Measurements......Page 126
7.1 Depth Profiling of Intercalated Species......Page 128
7.2 Structure Determination by X-ray Extinction and Electron Diffraction......Page 130
7.3 Raman Spectroscopy......Page 134
7.4 Infrared Absorption Spectroscopy......Page 140
7.5 Electron Paramagnetic Resonance......Page 146
7.7 Electron Spectroscopies Applied to Core Levels......Page 148
7.8 Electron Spectroscopies Applied to Valence and Conduction Bands......Page 150
8.1 Semiconductor Bandgap in As-prepared Films......Page 156
8.2 Bandgap Widening in Disordered Films: Possible Explanations......Page 160
8.4 Bandgap Widening upon Ion Intercalation......Page 162
9.1 Spectral Absorptance of As-prepared Films......Page 164
9.2 Refractive Index of As-prepared Films......Page 166
9.3 Coloration Techniques for Disordered Films: The Eightfold Way......Page 170
9.5 Transmittance and Reflectance of Ion Intercalated Films......Page 176
9.7 Coloration Efficiency......Page 182
10.1 Absorption in Disordered Films: Color Centers......Page 192
10.2 Absorption in Disordered Films: Small Polarons......Page 193
10.4 Transmittance and Reflectance of Crystalline Films: Drude Theory......Page 198
10.5 Transmittance and Reflectance of Crystalline Films: Theory for Heavily Doped Semiconductors with Ionized Impurity Scattering......Page 200
10.6 Optical Properties of Granular Films: Effective Medium Theories......Page 204
11.1 Electrical dc Conductivity......Page 210
11.2 Electrical ac Conductivity......Page 214
11.3 Thermoelectric Effect......Page 216
11.4 Photoelectric Effects......Page 218
PART TWO: ELECTROCHROMISM AMONG THE OXIDES (EXCEPT TUNGSTEN OXIDE)......Page 224
12.1 Crystal Structure of Bulk-like Molybdenum Oxide......Page 226
12.2 Films Made by Evaporation: Preparation and Characterization......Page 228
12.4 Films Made by Electrochemical and Chemical Techniques: Preparation and Characterization......Page 230
12.5 Ion Intercalation/deintercalation Reactions and Diffusion Constants......Page 232
12.7 Ion Intercalation/deintercalation Studied by Physical Techniques......Page 234
12.8 Ultraviolet Absorption and Semiconductor Bandgap......Page 236
12.9 Optical Properties in the Luminous and Near-infrared Range......Page 238
12.10 Coloration Efficiency......Page 240
13.1 Binary Oxides, Especially Tungsten-Molybdenum oxide......Page 242
13.2 Ternary Oxides, Especially Tungsten-Molybdenum-Vanadium Oxide......Page 246
13.3 Tungsten Oxyfluoride......Page 248
13.4 Composites of Tungsten oxide and Metal......Page 252
14.1 Crystal Structure of Bulk-like Iridium Oxide......Page 254
14.2 Films Made by Evaporation and Sputter-deposition: Preparation and Characterization......Page 255
14.3 Films Made by Electrochemical and Chemical Techniques: Preparation and Characterization......Page 259
14.4 Ion Intercalation/deintercalation Reactions and Diffusion Constants......Page 261
14.5 Ion Intercalation/deintercalation Studied by Electrochemical Techniques......Page 262
14.6 Ion Intercalation/deintercalation Studied by Physical Techniques......Page 268
14.7 Optical Properties......Page 274
14.8 Coloration Efficiency......Page 280
15.1 Crystal Structure of Bulk-like Titanium Oxide......Page 282
15.3 Films Made by Electrochemical and Chemical Techniques: Preparation and Characterization......Page 283
15.4 Ion Intercalation/deintercalation Reactions and Diffusion Constants......Page 284
15.6 Ion Intercalation/deintercalation Studied by Physical Techniques......Page 286
15.7 Optical Properties......Page 288
15.8 Coloration Efficiency......Page 292
16.1 Crystal Structure of Bulk-like Manganese Oxide......Page 294
16.3 Ion Intercalation/deintercalation Reactions and Diffusion Constants......Page 296
16.5 Optical Properties......Page 298
17.1 Crystal Structure and Electrical Properties of Bulk-like Vanadium Dioxide......Page 302
17.2 Preparation and Characterzation of Thin Films......Page 304
17.3 Ion Intercalation/deintercalation Reactions and Changes in Electrical Conductivity......Page 306
17.4 Optical Properties......Page 308
18.1 Crystal Structure of Bulk-like Vanadium Pentoxide......Page 312
18.2 Films Made by Evaporation: Preparation and Characterization......Page 315
18.3 Films Made by Sputter-deposition: Preparation and Characterization......Page 318
18.4 Films Made by Electrochemical and Chemical Techniques (Especially Sol-gel Deposition): Preparation and Characterization......Page 320
18.5 Ion Intercalation/deintercalation Reactions, Ion Exchange, and Diffusion Constants......Page 326
18.6 Ion Intercalation/deintercalation Studied by Electrochemical Techniques......Page 328
18.7 Ion Intercalation/deintercalation Studied by Physical Techniques......Page 334
18.8 Optical Properties of As-prepared Films......Page 340
18.9 Optical Properties of Ion Intercalated Films, and Coloration Efficiency......Page 346
18.10 Theoretical Models for The Optical Properties......Page 348
18.11 CF-doped Vanadium Pentoxide Films......Page 350
19.1 Crystal Structure of Bulk-like Nickel Oxide, Especially Materials Used as Battery Electrodes......Page 356
19.2 Films Made by Evaporation: Preparation and Characterization......Page 357
19.3 Films Made by Sputter-deposition: Preparation and Characterization......Page 359
19.4 Films Made by Electrochemical and Chemical Techniques: Preparation and Characterization......Page 362
19.5 Ion Intercalation/deintercalation Reactions and Diffusion Constants......Page 364
19.6 Ion Intercalation/deintercalation Studied by Electrochemical Techniques......Page 366
19.7 Ion Intercalation/deintercalation Studied by Physical Techniques......Page 376
19.8 Ultraviolet Absorption and Semiconductor Bandgap......Page 382
19.10 Optical Properties in the Luminous and Near-infrared Range: Sputter-deposited Films......Page 384
19.11 Optical Properties in the Luminous and Near-infrared Range: Films Made by Electrochemical and Chemical Techniques......Page 388
19.13 Towards a Theoretical Model for the Optical Properties......Page 392
20.1 Crystal Structure of Bulk-like Cobalt Oxide......Page 396
20.3 Films Made by Electrochemical and Chemical Techniques: Preparation and Characterization......Page 397
20.5 Ion Intercalation/deintercalation Studied by Electrochemical Techniques......Page 402
20.7 Optical Properties......Page 404
20.8 Towards a Theoretical Model for the Optical Properties......Page 406
21.1 Crystal Structure of Bulk-like Niobium Oxide......Page 408
21.3 Films Made by Electrochemical and Chemical Techniques: Preparation and Characterization......Page 409
21.4 Ion Intercalation/deintercalation Reactions and Diffusion Constants......Page 410
21.6 Ion Intercalation/deintercalation Studied by Physical Techniques......Page 412
21.7 Optical Properties......Page 414
21.8 Coloration Efficiency......Page 416
22.2 Rhodium Oxide......Page 418
22.3 Ruthenium Oxide......Page 420
22.4 Iron Oxide......Page 421
22.5 Chromium Oxide......Page 422
22.6 Tantalum Oxide......Page 425
22.7 Copper Oxide......Page 426
22.9 Doped Strontium Titanate......Page 428
23.1 The Ubiquitous MeO6 Octahedron......Page 430
23.2 Canonical Bandstructure......Page 432
23.3 A Conceptual Framework for Electrochromism Among the Transition Metal Oxides......Page 434
24.2 Heteropolyacids, Especially Phosphotungstic Acid......Page 438
24.5 β-zirconium Nitride Chloride......Page 440
24.7 Prussian Blue: Preparation and Characterization of Thin Films......Page 441
24.8 Prussian Blue: Optical Properties......Page 442
24.9 Altenative Hexacyanometallates......Page 444
PART THREE: ELECTROCHROMIC DEVICES......Page 448
25.1 Doped Oxide Semiconductor Films......Page 450
25.2 Coinage Metal Films......Page 452
26.1 Liquid Electrolytes......Page 458
26.2 Inorganic Solid Electrolytes and Ion Conductors: Introductory Remarks......Page 461
26.3 Inorganic Solid Electrolytes and Ion Conductors: Mainly Alkali Ion Conductors......Page 462
26.4 Polymer Electrolytes: Introductory Remarks and Data for Proton Conductors......Page 463
26.5 Polymer Electrolytes: Mainly Lithium Ion Conductors......Page 466
27.1 Materials for Reflecting Display-type Devices......Page 470
27.2 Materials for Transparent Devices......Page 472
27.3 Comments on Ion Storage in Transparent Electrical Conductors......Page 474
28.1 Display-type Devices with Proton Conducting Electrolytes......Page 476
28.2 Display-type Devices with Lithium Ion Conducting Electrolytes......Page 478
28.3 Transparent Devices with Dispersed Redox Agents, Including Area-related Effects and Durability Issues......Page 480
28.4 Transparent Charge-balanced Devices......Page 482
28.5 Comment on Devices for Variable Thermal Emittance......Page 486
29.1 Reflecting Devices with Bulk-type Proton Conductors......Page 490
29.3 Devices with Thin Film Proton Conductors Relying on Incorporated Water (Deb Devices)......Page 493
29.4 Charge-balanced Devices with Thin Film Proton Conductors......Page 496
29.5 Devices with Thin Film Alkali Ion Conductors and Silver Ion Conductors......Page 502
29.6 A Photo-electrochromic Thin Film Device......Page 504
30.1 Proton Conducting Polymers......Page 506
30.2 Lithium Ion Conducting Polymers......Page 511
30.3 Sodium and Potassium Conducting Polymers......Page 514
31.1 Color/bleach Response Time: Effects of Film Porosity......Page 516
31.2 Color/bleach Response Time: Effects of Applied Voltage and Electrolyte Hydration......Page 518
31.3 Color/bleach Response Time: Effects of Temperature......Page 520
31.5 Non-volatility of the Optical Memory: Open Circuit Performance......Page 524
31.7 Durability: Etching of Tungsten Oxide in Acid Electrolytes......Page 526
31.8 Durability: Non-reversible Ion Incorporation from the Electrolyte, and Cycling-induced Crystallization of Tungsten Oxide Films......Page 530
31.10 Durability: Comments on Iridium Oxide Films......Page 532
Appendix: Abbreviations, Acronyms, and Symbols......Page 536
References......Page 544
Index......Page 634