Nanocrystalline Metals and Oxides

Contents......Page 6
Preface......Page 8
1. Introduction......Page 12
2. Remarks on the Structure of Grain Boundaries in Nanocrystalline Solids......Page 13
3.1 Specific Excess......Page 14
3.2 Specific Layer Content......Page 17
4.1 Intrinsic instability; grain growth......Page 19
4.2 Size- or curvature-dependent interface free energy......Page 20
4.4 Size-Dependent Chemical Potential: Isolated Small Particle versus Nanocrystalline Solid......Page 22
5.1 Metastable nanocrystalline alloys with finite grain size and vanishing γ......Page 24
5.2 Destabilization of compounds by grain boundary segregation......Page 27
6.1 Deformation of grain boundaries......Page 28
6.2 Interface stress; capillary equation for solids......Page 30
6.3 Failure of the Young-Laplace equation in solids......Page 32
6.4 Size-dependent interface free energy due to interface-induced strain......Page 33
6.6 Defining Equation for the Interface Stress......Page 35
7.1 Effect of the interface stress on the lattice constant in a solid solution......Page 36
7.2 Variation of the interface stress and stretch due to solute segregation......Page 39
7.3 Layer thickness and layer properties......Page 40
7.4 Size-dependent miscibility gap......Page 41
8.1 Intrinsic nature of the microstrain......Page 43
8.2 Experimental microstrain......Page 45
8.3 Size-dependent interface free energy due to microstrain......Page 46
9. Concluding Remarks......Page 47
References......Page 48
1.Introduction......Page 52
2.1. Fisher’s model......Page 54
2.2. Kinetics regime of diffusion in static and mobile GBs......Page 56
2.3. GB segregation and shape of the penetration profiles......Page 60
2.5. Experimental methods allowing the determination of GB diffusion data......Page 62
2.6. GB diffusion measurements in nanocrystals and structure of GBs......Page 64
3.1. Diffusion on a discrete lattice......Page 67
3.2. Diffusion in amorphous materials......Page 74
3.3. Stress effects......Page 75
3.4. Segregation kinetics......Page 81
3.5. Reaction or diffusion control and nucleation problems......Page 83
References......Page 87
1. Introduction......Page 92
2. Point Defects and Conductivity in the Bulk......Page 93
3. Interfaces: Core and Space Charge Effects......Page 97
4.1 General Considerations......Page 104
4.2 Trivial and Proper Size Effects on Defect Chemistry......Page 106
5.1 Nano-Sized Li Conductors......Page 110
5.2 Nanocrystalline CeO[sub(2)]......Page 111
5.3 Nanocrystalline CaF[sub(2)]......Page 112
5.4 Nano-Sized CaF[sub(2)]-BaF[sub(2)] Heterolayers......Page 113
5.5 AgI-Al[sub(2)]O[sub(3)] Composites: Interfacial Phase Transformation and High Conductivities in Stacking Faults Arrangements......Page 114
6. Perspectives of Nano-Ionics and Soft Materials Science......Page 115
References......Page 118
Glossary of Terms......Page 122
Introduction......Page 123
Experimental Issues......Page 125
Methodology......Page 127
Analysis and Discussion......Page 131
Conclusions......Page 138
Appendix......Page 139
References......Page 141
I. Introduction......Page 144
II.1. Basic Theory......Page 146
II.2. Experimental Procedures......Page 148
III.1. General considerations......Page 151
III.2. Tin Oxide......Page 152
III.3. Zinc Oxide......Page 156
III.4. Zirconium Oxide......Page 158
III.5. Cerium Oxide......Page 165
IV. Conclusions and Overview......Page 169
References......Page 172
1. Introduction......Page 176
2. Fundamentals of the Characterization Technique......Page 178
2.1. FTIR Surface Characterization......Page 179
2.2. FTIR Analysis of Semiconducting Nanoparticles......Page 181
3.1. Titanium Oxide......Page 183
3.2. Tin Oxide......Page 184
4.1. Tin Oxide......Page 186
4.2. Titanium Oxide......Page 188
5.1. Surface Chemical Modifications......Page 192
5.2. Humidity Effects on Modified Surfaces......Page 194
6. Concolusion......Page 196
7. References......Page 197
1. Introduction......Page 200
2. Equilibrium and Mixed Potential Gas Sensors......Page 202
3.1. Bulk conductivity sensors......Page 204
3.2. Boundary conductivity sensors......Page 207
4. Conclusions......Page 214
References......Page 216
2. Introduction......Page 220
3. Dye Sensitized Solar Cell Operation......Page 222
3.1. The Injection Process (Figure 1a)......Page 223
3.3. The Charge Transport (Figure 1c-d)......Page 224
4. Materials......Page 225
4.1. Thermodynamic and Kinetic Consideration......Page 226
4.2. The Nanoporous Electrode......Page 227
4.3. The Dye......Page 228
4.4. The Electrolyte......Page 229
5.1. General Considerations......Page 230
5.2. Electric Potential Distribution and Charge Screening......Page 231
5.4. Band Bending......Page 234
5.5. Core Shell Electrodes......Page 235
5.6. Electron Motion in the Nanoporous Electrode......Page 237
5.7. Relative Energetics in the Nanoporous System......Page 238
5.8. The Open Circuit Potential in Dye Sensitized Solar Cells......Page 239
6. References......Page 242
D......Page 246
E......Page 247
G......Page 248
L......Page 249
N......Page 250
S......Page 251
T......Page 252
Z......Page 253