Physico-Chemical Phenomena in Thin Films and at Solid Surfaces (eBook)

Cover 1
Copyright page 5
Contents 6
Chapter 1. Introduction 18
Part 1: Theoretical Approaches to the Study of the Processes in Films and on Surfaces 24
Chapter 2. Conventional Theory of Multi-Phonon Electron Transitions 26
1. Introduction 26
2. Born–Oppenheimer’s Adiabatic Approach 28
3. General Expression for Transition Probability in Unit of Time 30
4. Influence of Changes of Equilibrium Positions and Frequencies 32
5. Calculation of Multi-Phonon Transition Probability in Unit of Time 35
6. Local Vibrations. Method of Density Matrix 41
7. Electron Transfer in Polar Medium 45
8. Adiabatic Transitions 47
9. Conclusions 50
References 51
Chapter 3. Contemporary Theory of Electrons Tunneling in Condensed Matter 54
1. Introduction 54
2. Amplitude of Electron Tunneling Transfer 55
3. Influence of Crystal Medium on Electron Tunneling 61
4. Multiple Tunneling Scattering and Bridge Effect 65
5. Violation of Born–Oppenheimer’s Approach in Electron Tunneling Transfer 71
6. Conclusions 80
References 81
Chapter 4. Ab Initio Calculations of Electronic Transitions and Photoabsorption and Photoluminescence Spectra of Silica and Germania Nanoparticles 84
1. Introduction 85
2. Theoretical Approach and Methods 89
3. Photoluminescence Properties of Point Defects in SiO2 100
4. Optical Properties of Point Defects in GeO2 116
5. Summary and Outlook 130
6. Discussion Topics and Questions on Concepts 132
References 133
Chapter 5. Density Matrix Treatments of Ultrafast Radiationless Transitions 138
1. Introduction 139
2. Density Matrix and Liouville Equation 140
3. Dynamics of a System Embedded in Heat Bath 149
4. Density Matrix Method and Spectroscopies 164
5. An Example „ Interfacial Electron Transfer in Organic Solar Cells 173
6. Summary 189
Appendix A. Gvj(t) for Displaced–Distorted Oscillator 190
Appendix B. Derivation of the TCF for the Band-Shape Function 194
References 197
Chapter 6. Ultrafast Radiationless Transitions 200
1. Introduction 201
2. Theoretical Approach and Methods 202
3. Photo-Induced Electronic Transfer and Photo-Induced Energy Transfer 216
4. Applications 221
5. Summary 236
References 239
Part 2: Physico-Chemical Processes at the Surface of Solids 246
Chapter 7. Point Defects on the Silica Surface: Structure and Reactivity 248
1. Introduction 250
2. Methods for Creation of Defects on Silica Surface 253
3. Quantum-Chemical Calculations 257
4. Chemical Modification of the Surface Defects 260
5. Interrelation Between the EPR Parameters of the Silicon-Centered Paramagnetic Centers and Their Spatial Structure: Results of Quantum-Chemical Calculations 270
6. Silicon-Centered Paramagnetic Centers (PCs) in SiO2 277
7. Paramagnetic Centers =Si-O• on the Silica Surface (Non-Bridging Oxygen Center) 292
8. The (=Si-O)3Si-O-O* Radicals: Structure and Reactivity 296
9. Diamagnetic Point Defects on Silica Surface 298
10. Inhomogenity of Physico-Chemical Properties of Surface Defects 326
11. Impurity Centers in Quartz Glass: Carbon in the Silica Structure 331
12. Nitrogen in Silica 336
13. Surface and Near-Surface Defects in Silica 346
14. Design of Intermediates With Desired Structure on Silica Surface 347
15. Conclusions 352
16. Questionnaire 356
References 357
Chapter 8. Atomic-Molecular Kinetic Theory of Physico-Chemical Processes in Condensed Phase and Interfaces 364
1. Introduction 366
2. Gas–Solid Processes 369
3. Kinetic Equations for Multistage Processes in Condensed Phase 387
4. Surface Processes 408
5. Solid Phase Processes in Solid–Gas Systems 429
6. Physico-Chemical Mechanics Problems 436
7. Numerical Dynamics Investigations 444
8. Summary and Perspectives 455
Appendix A. Equilibrium Distributions of Particles on Heterogeneous Lattices in Condensed Phases 458
Appendix B. Lowering the Dimension of a System of Equations in the Quasi-Chemical Approximation 465
Problems 468
References 469
Part 3: Formation and Physico-Chemical Properties of the Films 482
Chapter 9. Integrated Approach to Dielectric Film Growth Modeling: Growth Mechanisms and Kinetics 484
1. Introduction 485
2. Quantum-Chemical Modeling 487
3. Gas–Surface Reactions Proceeding via a Strongly Adsorbed Precursor 488
4. Simulation Methods 496
5. Modeling of the Deposition of Thin Dielectric Films 510
6. Conclusions and Outlook 533
Questions and Problems 533
References 534
Chapter 10. Vapor Deposited Composite Films Consisting of Dielectric Matrix with Metal/Semiconductor Nanoparticles 540
1. Introduction 541
2. Features of Metal and Semiconductor Nanoparticles 543
3. Methods of Preparation and Structure of Nanocomposite Films 553
4. Physico-Chemical Properties of Nanocomposite Films 571
5. Conclusions 588
Acknowledgments 591
References 591
Chapter 11. Transport and Magnetic Properties of Nanogranular Metals 598
1. Introduction 599
2. Production of Nanocomposite Films 602
3. Structure of Granular Metals (Nanocomposites) 606
4. Magnetic Properties of Granular Magnetic Metals 612
5. Magnetotransport Properties of the Granular Metals 624
6. Quantum-Size Effects in Granular Metals Near the Percolation Threshold 644
7. Conclusions 648
8. Questions for Readers 649
References 650
Chapter 12. Organized Organic Thin Films: Structure, Phase Transitions and Chemical Reactions 656
1. Introduction 657
2. Preparation and Structure of Langmuir–Blodgett Films 662
3. Temperature-Induced Phase Transitions in Langmuir–Blodgett Films 667
4. Self-Assembled Films 671
5. Conclusions 676
Acknowledgments 678
References 678
Chapter 13. Non-Catalytic Photo-Induced Immobilization Processes in Polymer Films 682
1. Introduction 683
2. Photo-Induced Processes in Natural Polymers – DNA 688
3. Photopolymers and Photoresists Containing DNA Bases 693
4. Light-Induced Immobilization of Crosslinkable Photoresists 696
5. Reverse Processes 704
6. Conclusions 707
Acknowledgments 708
References 708
Chapter 14. Formation of Unconventional Compounds and Catalysts in Magnesium-Containing Organic Films 714
1. Introduction: Reactions in the Films Obtained by Co-Condensation of Metal Vapor with Organic Compounds 714
2. Synthesis of Magnesium-Containing Films by Co-Condensation of Reagents 718
3. Synthesis of RMg4X Compounds in Thin Films of Co-Condensates 720
4. Mechanism of the Processes in Organic Magnesium-Containing Films and the Nature of the Magic Number Four 722
5. Competition between the Aggregation of Magnesium Atoms and the Generation of Radicals in Mg–RX Films 727
6. Structure and Reactivity of Unconventional Organomagnesium Compounds Obtained in Co-Condensate Films 729
7. Catalytic Reactions in Mg–RH Films 731
8. Synthesis of Catalysts in Multicomponent Films Containing Magnesium and a Transition Metal 734
9. Conclusions 736
References 737
Chapter 15. Charge Effects in Catalysis by Nanostructured Metals 742
1. Introduction 743
2. Catalyst Fabrication and Structural Properties 746
3. Charge State of Metallic Nanostructures 752
4. Effect of Nanoparticle Charging on the Catalytic Properties 758
5. Summary 767
References 769
Chapter 16. Synthesis of Crystalline C-N Thin Films 772
1. Introduction 773
2. Synthesis 775
3. Theoretical Models 778
4. Characterization 787
5. Potential Applications of CN Films 791
6. Closure 791
Acknowledgement 792
Questions 792
References 792
Subject Index 796
Recent Volumes In This Series 800