Physico-Chemical Phenomena in Thin Films and at Solid Surfaces, Volume 34 (Thin Films and Nanostructures) (Thin Films and Nanostructures)

The book is devoted to the consideration of the different processes taking place in thin films and at surfaces. Since the most important physico-chemical phenomena in such media are accompanied by the rearrangement of an intra- and intermolecular coordinates and consequently a surrounding molecular ensemble, the theory of radiationless multi-vibrational transitions is used for its description. The second part of the book considers the numerous surface phenomena. And in the third part is described the preparation methods and characteristics of different types of thin films. Both experimental and theoretical descriptions are represented. Media rearrangement coupled with the reagent transformation largely determines the absolute value and temperature dependence of the rate constants and other characteristics of the considered processes. These effects are described at the atomic or molecular level based on the multi-phonon theory, starting from the first pioneering studies through to contemporary studies. A number of questions are included at the end of many chapters to further reinforce the material presented. · Unified approach to the description of numerous physico-chemical phenomena in different materials · Based on the pioneering research work of the authors · Explantion of a variety of experimental observations · Material is presented at two levels of complexity for specialists and non-specialists · Identifies existing and potential applications of the processes and phenomena · Includes questions at the end of some chapters to further reinforce the material discussed 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 Ch. 1. Introduction / L. I. Trakhtenberg, S. H. Lin And O. J. Ilegbusi -- Ch. 2. Conventional Theory Of Multi-phonon Electron Transitions / M. A. Kozhushner -- Ch. 3. Contemporary Theory Of Electrons Tunneling In Condensed Matter / M. A. Kozhushner -- Ch. 4. Ab Initio Calculations Of Electronic Transitions And Photoabsorption And Photoluminescence Spectra Of Silica And Germania Nanoparticles / A. M. Mebel, A. S. Zyubin, M. Hayashi And S. H. Lin -- Ch. 5. Density Matrix Treatments Of Ultrafast Radiationless Transitions / S. H. Lin, K. K. Liang, M. Hayashi And A. M. Mebel -- Ch. 6. Ultrafast Radiationless Transitions / M. Hayashi, A. M. Mebel And S. H. Lin -- Ch. 7. Point Defects On The Silica Surface : Structure And Reactivity / V. A. Radzig -- Ch. 8. Atomic-molecular Kinetic Theory Of Physico-chemical Processes In Condensed Phase And Interfaces / Y. K. Tovbin -- Ch. 9. Integrated Approach To Dielectric Film Growth Modeling : Growth Mechanisms And Kinetics / A. A. Bagatur'yants, M. A. Deminskii, A. A. Knizhnik, B. V. Potapkin And S. Y. Umanskii -- Ch. 10. Vapor Deposited Composite Films Consisting Of Dielectric Matrix With Metal/semiconductor Nanoparticles / G. N. Gerasimov And L. I. Trakhtenberg -- Ch. 11. Transport And Magnetic Properties Of Nanogranular Metals / B. A. Aronzon, S. V. Kapelnitsky And A. S. Lagutin -- Ch. 12. Organized Organic Thin Films : Structure, Phase Transitions And Chemical Reactions / S. Trakhtenberg -- Ch. 13. Non-catalytic Photo-induced Immobilization Processes In Polymer Films / S. Trakhtenberg, A. S. Cannon And J. C. Warner -- Ch. 14. Formation Of Unconventional Compounds And Catalysts In Magnesium-containing Organic Films / V. V. Smirnov, L. A. Tyurina And I. P. Beletskaya -- Ch. 15. Charge Effects In Catalysis By Nanostructured Metals / S. A. Gurevich, V. M. Kozhevin, I. N. Yassievich, D. A. Yavsin, T. N. Rostovshchikova And V. V. Smirnov -- Ch. 16. Synthesis Of Crystalline C-n Thin Films / H. Song And O. J. Ilegbusi. Leonid I. Trakhtenberg, Sheng H. Lin, Olusegun J. Ilegbusi. Includes Bibliographical References And Index.