Physico-Chemical Phenomena in Thin Films and at Solid Surfaces

Physico-Chemical Phenomena in Thin Films and at Solid Surfaces, Volume 34
......Page 1
Contents......Page 2
1 
Introduction......Page 13
Introduction......Page 19
Born-Oppenheimer’s Adiabatic Approach......Page 21
General Expression for Transition Probability in Unit of Time......Page 23
Influence of Changes of Equilibrium Positions and Frequencies......Page 25
Calculation of Multi-Phonon Transition Probability in Unit of Time......Page 28
Local Vibrations. Method of Density Matrix......Page 34
Electron Transfer in Polar Medium......Page 38
Adiabatic Transitions......Page 40
Conclusions......Page 43
References......Page 44
Introduction......Page 46
Amplitude of Electron Tunneling Transfer......Page 47
Influence of Crystal Medium on Electron Tunneling......Page 53
Multiple Tunneling Scattering and Bridge Effect......Page 57
Violation of Born-Oppenheimer’s Approach in Electron Tunneling Transfer......Page 63
Conclusions......Page 72
References......Page 73
4 
Ab Initio Calculations of Electronic Transitions and Photoabsorption and Photoluminescence Spectra of Silica and Germania Nanoparticles......Page 75
Introduction......Page 76
Model Clusters and Geometry Optimization......Page 80
Calculations of Excitation Energies......Page 83
Calculations of Vibronic Spectra......Page 89
Red and Near Infrared Photoluminescence Bands in Silica Nanostructures......Page 91
PL Properties of the Silanone and Dioxasilyrane Point Defects......Page 97
Photoabsorption and Photoluminescence of the [AlO4]0 Defect in SiO2......Page 103
NBO or -O-Geequiv Defect......Page 107
Peroxy Radical or -O-O-Geequiv Defect......Page 111
O2Geequal Defect......Page 112
OequalGeequal Defect......Page 115
Photoluminescence of Oxygen-Deficient Defects in Germanium Oxides......Page 116
Surface Eprime-Center, or -Geequiv Defect......Page 117
Combination of the -Geequiv Defect with an Oxygen Vacancy, Eprime-OV......Page 120
Summary and Outlook......Page 121
Discussion Topics and Questions on Concepts......Page 123
References......Page 124
5 
Density Matrix Treatments of Ultrafast Radiationless Transitions......Page 129
Introduction......Page 130
Definition of Density Matrix......Page 131
Dynamics of Isolated Systems......Page 134
Dynamics of a System Embedded in Heat Bath......Page 140
Reduced Density Matrix and its Equation of Motion......Page 142
Generalized Master Equations......Page 144
Ultrafast Non-Adiabatic Dynamics of Molecular Systems......Page 146
Single-Vibronic-Level and Thermal Average Rate Constant......Page 150
Steady State Spectroscopy......Page 155
Pump-Probe Experiments......Page 159
An Example - Interfacial Electron Transfer in Organic Solar Cells......Page 164
Experimental Results and Theoretical Analysis......Page 165
Summary......Page 180
Appendix A. Gvj(t) for Displaced-Distorted Oscillator......Page 181
Appendix B. Derivation of the TCF for the Band-Shape Function......Page 185
References......Page 188
6 
Ultrafast Radiationless Transitions......Page 191
Introduction......Page 192
Theoretical Approach and Methods......Page 193
Non-Adiabatic Processes......Page 194
Rate Constants......Page 198
Radiationless Transitions......Page 201
Internal Conversion (IC)......Page 202
Intersystem Crossing (ISC)......Page 203
General Consideration......Page 207
Photo-Induced Electron Transfer......Page 208
Photo-Induced Energy Transfer......Page 209
Pump-Probe Time-Resolved Stimulated Emission Spectra......Page 212
Relaxation and Coherence Dynamics......Page 213
A Model of Vibrational Relaxation and Dephasing......Page 214
A Single Harmonic Displaced Oscillator Mode System......Page 216
Bacterial Photosynthetic RCs......Page 219
Vibrational Coherence and Relaxation in Photosynthetic Reaction Centers......Page 220
Rapid Electron Transfer in Photosynthetic Reaction Centers......Page 222
Vibronic Coherence in Photosynthetic Reaction Center......Page 223
Summary......Page 227
References......Page 230
7 
Point Defects on the Silica Surface: Structure and Reactivity......Page 236
Introduction......Page 238
Preparation of the Thermo-Activated Silica (TSi) Samples......Page 241
Preparation of the Mechano-Activated Silica Samples (MSi)......Page 242
Preparation of the ‘‘Reactive Silica’’ (RSi) Samples......Page 243
Structure and Concentration of Paramagnetic and Diamagnetic Point Defects on Activated Silica Surface......Page 244
Quantum-Chemical Calculations......Page 245
Chemical Modification of the Surface Defects......Page 248
Preparation of equivSi-O* Radicals: The System (equivSi*+N2O)......Page 249
SiequalO Bond Strength in the (equivSi-O)2SiequalO Group......Page 253
Microcalorimetry of the Processes at the SiO2 and GeO2 Surfaces......Page 257
Interrelation Between the EPR Parameters of the Silicon-Centered Paramagnetic Centers and Their Spatial Structure: Results of Quantum-Chemical Calculations......Page 258
PC (equivSibeta -O)3Sialpha bull on the Surface and in the Bulk of Silica......Page 265
PC (equivSibeta -O)2Sialpha bull-r, Where requalH(D), OH(OD), NH2, and CH3(CD3)......Page 269
Stretching Vibration Frequencies of the Si-H Bonds in the Hydrogenation Products of Silicon-Centered PCs......Page 274
Optical Characteristics of the Silicon-Centered PCs......Page 275
Paramagnetic Centers equivSi-Obull on the Silica Surface (Non-Bridging Oxygen Center)......Page 280
The (equivSi-O)3Si-O-O* Radicals: Structure and Reactivity......Page 284
Diamagnetic Point Defects on Silica Surface......Page 286
(equivSi-O-)2SiltO2gtSi(-O-Siequiv)2 Groups (Strained Rings, SRs) on the Silica Surface......Page 287
Method of paramagnetic spin labeling......Page 290
Products of SC hydrogenation......Page 291
Products of High-Temperature Hydration of RSi Samples......Page 293
Optical Parameters of SC......Page 295
The Mechanism of Singlet-Triplet Conversion of SC......Page 296
Silanone Groups (equivSi-O)2SiequalO on Silica Surface......Page 297
Dioxasilyrane Groups ((equivSi-O)2SiltO2)......Page 301
Reactivity of the gtSiltO2 Groups Toward the Polar X-H (XequalOH, NH2, OCH3) Molecules......Page 310
Inhomogenity of Physico-Chemical Properties of Surface Defects......Page 314
equivSi-bullCH2, (equivSi-)2bullCH, and (equivSi-)3Cbull Radicals......Page 319
Increase in the Concentration of Paramagnetic Centers Upon the Thermo Oxidizing Treatment of the RSi Samples......Page 322
Nitrogen in Silica......Page 324
PCs (equivSi-O)2Si*(NH2), (equivSi-O)2Si*-N(Siequiv)2, (equivSi-O)2(HO)Si-N*H, and equivSi-N*-Siequiv......Page 325
Reactions of equivSi-N*-H and equivSi-N*-Siequiv PC With H2(D2)......Page 329
On the Strengths of Si-O and Si-N Bonds in Vitreous Silica......Page 333
Surface and Near-Surface Defects in Silica......Page 334
Design of Intermediates With Desired Structure on Silica Surface......Page 335
Conclusions......Page 340
Questionnaire......Page 344
References......Page 345
8 
Atomic-Molecular Kinetic Theory of Physico-Chemical Processes in Condensed Phase and Interfaces......Page 351
Introduction......Page 353
Gas Phase......Page 356
Solid......Page 357
Adsorption......Page 358
Absorption......Page 360
Lattice-Gas Model and Elementary Processes......Page 361
Elementary Processes and their Models......Page 363
Surface Mobility......Page 366
Lateral Interactions......Page 367
Quasi-Particle Description of Elementary Rates......Page 368
One-Site Reactions......Page 369
Two-Site Reactions......Page 372
Kinetic Equations for Multistage Processes in Condensed Phase......Page 374
Hamiltonian......Page 375
Master Equation......Page 376
Probabilities of Elementary Reactions......Page 379
Kinetic Equations......Page 382
Reaction Rates......Page 384
Hierarchy of the Kinetic Equations......Page 386
Two-Dimensional Model......Page 388
Point-Like Models of a Reaction......Page 391
Restricted Mobility of the Reactants......Page 392
Different Mobilities of Reactants......Page 394
Surface Processes......Page 395
Physical Adsorption and Chemisorption......Page 396
Adsorption and Thermodesorption Spectra......Page 399
Multistage Processes......Page 403
Islands and Two-Dimensional Phases......Page 406
Self-Consistency of the Lattice-Gas Model......Page 408
Surface Diffusion......Page 413
Interface States......Page 416
Diffusion Through Solids......Page 418
Phase Transitions and Topochemical Processes......Page 422
Rates of Elementary Stages at Solid Deformations......Page 423
Hydrogen-Palladium System......Page 425
Effective Potential......Page 426
Mechanical and Transport Properties of the Pd-H2 System......Page 427
Effect of Lattice Deformation on the Properties of Membranes......Page 430
Cellular Automata Technique......Page 431
Adsorption Processes and Surface Reactions......Page 433
Surface Diffusion and Phase Formation......Page 435
Crystal Growth......Page 437
Complex Processes......Page 438
Correlation Between Monte-Carlo Simulations and Kinetic Theory......Page 439
Summary and Perspectives......Page 442
Appendix A. Equilibrium Distributions of Particles on Heterogeneous Lattices in Condensed Phases......Page 445
Cluster Methods......Page 446
Isotherms of Adsorption......Page 447
Multiparticles Configurations......Page 449
Matrix Method......Page 450
Method of Fragments......Page 451
Appendix B. Lowering the Dimension of a System of Equations in the Quasi-Chemical Approximation......Page 452
Problems......Page 455
References......Page 456
9 
Integrated Approach to Dielectric Film Growth Modeling: Growth Mechanisms and Kinetics......Page 469
Introduction......Page 470
Quantum-Chemical Modeling......Page 472
Description of the Model......Page 473
Master Equation and Macroscopic Rate Constants......Page 474
Macroscopic Rate Constant of a Barrierless Adsorption-Desorption Reaction......Page 479
Molecular Dynamics......Page 481
Equation of Motion......Page 482
Energy Functional for MD......Page 483
Kinetic Monte Carlo Method......Page 485
Lattice and Dynamic Versions of Kinetic Monte Carlo......Page 487
Kinetic Monte Carlo Method with Dynamic Relaxation (KMC-DR)......Page 488
Reactor Modeling of Thin-Film Deposition......Page 490
Molecular Dynamics Modeling of Precursor Interaction With Surface......Page 495
Kinetic Mechanism of Zirconium and Hafnium Oxide Film Deposition......Page 496
Reduction of the Kinetic Mechanism of Zr(Hf)O2 Film Growth......Page 504
Kinetic Monte Carlo and Molecular Dynamics Modeling of ZrO2 Film Roughness in an ALD Process......Page 505
Modeling of the ZrO2 Film Composition Using the Monte Carlo Method......Page 510
Modeling of the Si/ZrO2 Interface Structure Using the KMC-DR Method......Page 514
Questions and Problems......Page 518
References......Page 519
10 
Vapor Deposited Composite Films Consisting of Dielectric Matrix with Metal/Semiconductor Nanoparticles......Page 525
Introduction......Page 526
Metal Nanocrystals......Page 528
Semiconductor Nanocrystals......Page 533
Methods of Preparation and Structure of Nanocomposite Films......Page 538
M/SC Nanoparticle Deposition on a Surface of Dielectric Substrate......Page 539
Co-Deposition of M/SC and a Dielectric Material......Page 546
Conductivity and Photoconductivity......Page 556
Sensor Properties......Page 559
Dielectric Properties......Page 564
Catalytic Activity......Page 568
Conclusions......Page 573
References......Page 576
11 
Transport and Magnetic Properties of Nanogranular Metals......Page 582
Introduction......Page 583
Production of Nanocomposite Films......Page 586
Structure of Granular Metals (Nanocomposites)......Page 590
Magnetic Properties of Granular Magnetic Metals......Page 596
General Statements and Magnetization at Low Temperatures......Page 598
Magnetization at High Temperatures (Paramagnetic Region)......Page 600
Magnetization of Granular Ferromagnetic Metals with Non-Spherical Granules......Page 602
A Relaxation of Magnetization and Nanocomposite as Cluster Spin Glass......Page 605
Magnetotransport Properties of the Granular Metals......Page 608
Conductivity Dependence on a Metal Granules Fraction: The Percolation Threshold......Page 609
Temperature Dependence of Conductivity......Page 613
Magnetoresistance: Field Dependence of Conductivity......Page 615
Hall Effect......Page 622
Quantum-Size Effects in Granular Metals Near the Percolation Threshold......Page 628
Conclusions......Page 632
Questions for Readers......Page 633
References......Page 634
12 Organized Organic Thin Films: Structure, Phase Transitions and Chemical Re
actions......Page 639
Introduction......Page 640
Preparation and Structure of Langmuir-Blodgett Films......Page 645
Langmuir Monolayers......Page 646
Film Transfer......Page 648
Structure of Langmuir-Blodgett Films......Page 649
Temperature-Induced Phase Transitions in Langmuir-Blodgett Films......Page 650
Order-Disorder Transitions......Page 651
Effect of Phase Transitions on the Reactivity of Langmuir-Blodgett Films......Page 652
Self-Assembled Films......Page 654
Covalently Bonded Silane Monolayers......Page 655
Stability of Self-Assembled Silane Films......Page 656
Self-Assembled Silane Multilayers......Page 657
Conclusions......Page 659
References......Page 661
13 
Non-Catalytic Photo-Induced Immobilization Processes in Polymer Films......Page 665
Introduction......Page 666
Photo-Induced Processes in Natural Polymers - DNA......Page 671
Photopolymers and Photoresists Containing DNA Bases......Page 676
Light-Induced Immobilization of Crosslinkable Photoresists......Page 679
Reverse Processes......Page 687
Conclusions......Page 690
References......Page 691
Introduction: Reactions in the Films Obtained by Co-Condensation of Metal Vapor with Organic Compounds......Page 696
Synthesis of Magnesium-Containing Films by Co-Condensation of Reagents......Page 700
Synthesis of RMg4X Compounds in Thin Films of Co-Condensates......Page 702
Mechanism of the Processes in Organic Magnesium-Containing Films and the Nature of the Magic Number Four......Page 704
Competition between the Aggregation of Magnesium Atoms and the Generation of Radicals in Mg-RX Films......Page 709
Structure and Reactivity of Unconventional Organomagnesium Compounds Obtained in Co-Condensate Films......Page 711
Catalytic Reactions in Mg-RH Films......Page 713
Synthesis of Catalysts in Multicomponent Films Containing Magnesium and a Transition Metal......Page 716
Conclusions......Page 718
References......Page 719
15 
Charge Effects in Catalysis by Nanostructured Metals......Page 723
Introduction......Page 724
Catalyst Fabrication by Laser Electrodispersion of Metals......Page 727
Structural Properties of the Catalyst Coatings......Page 730
Charge State of Metallic Nanostructures......Page 733
Effect of Nanoparticle Charging on the Catalytic Properties......Page 739
Analytical Estimates......Page 740
Experimental Results and Discussion......Page 742
Summary......Page 748
References......Page 750
16 
Synthesis of Crystalline C-N Thin Films......Page 753
Introduction......Page 754
Synthesis......Page 756
Thermodynamic Models......Page 759
Molecular Dynamics Simulation......Page 763
Thermal Spike Model......Page 764
Microstructure: XRD and TEM......Page 768
Chemical State: EELS and XPS......Page 769
Composition: AES and RBS......Page 771
Closure......Page 772
References......Page 773
Subject Index
......Page 777
Recent Volumes In This Series......Page 781