Chemical Vapor Transport Reactions (eBook)

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Michael Binnewies, Leibniz University, Hannover; Robert Glaum, University ofBonn; Marcus Schmidt, Max-Planck Institute for Chemical Physics of Solids, Dresden; Peer Schmidt,University ofApplied Sciences, Lausitz, Germany.

1 Chemical Vapor Transport Reactions – an Introduction 15
1.1 Historical Development and Principles 15
1.2 Experimental 17
1.3 Thermodynamic Considerations 18
1.4 Equilibrium Solids in Source and Sink 23
1.5 Transport Agent 24
1.6 Overview of Vapor Deposition Methods 27
Bibliography 30
2 Chemical Vapor Transport – Models 31
2.1 Thermodynamic Basis for Understanding Chemical Vapor Transport Reactions 33
2.2 Condensed Phases in a Transport Experiment – the Most Simple Case 42
2.3 Complex, Congruent Transports 45
2.4 Incongruent Dissolution and Quasi-stationary Transport Behavior 50
2.4.1 Phase Relations Accompanying Incongruent Dissolution of a Solid 50
2.4.2 The Extended Transport Model 53
2.5 Non-stationary Transport Behavior 74
2.5.1 Chemical Reasons for the Occurrence of Multi-phase Solids 74
2.5.2 The Time Dependence of Chemical Vapor Transport Experiments with Multi-Phase Solids 82
2.5.3 The Model of Co-operative Chemical Vapor Transport 89
2.6 Diffusion, Stoichiometric Flow, and Transport Rate 92
2.6.1 Steady-state Diffusion 92
2.6.2 One-dimensional Steady-state Diffusion as Rate-determining Step 92
2.6.3 The Use of X for the Calculation of Transport Rates of Complex Transport Systems in Closed Ampoules 95
2.6.4 The Use of Solubility X in Open Transport Systems 97
2.6.5 An Example – Calculation of the Transport Rate for the Nickel/Carbon Monoxide System 98
2.7 Diffusion Coefficients 101
2.7.1 The Binary Diffusion Coefficient D0 101
2.7.2 D0 in Multi-compound Systems 105
2.8 Survey of Gas Motion in Ampoules 107
2.8.1 General Remarks 107
2.8.2 Experiments on Gas Motion – Diffusion and Convection in Closed Ampoules 109
2.8.3 Experiments Concerning Thermal Convection 113
2.9 Chemical Kinetics of Heterogeneous Reactions 117
2.9.1 Reaction Behavior at an Atomic Level 117
2.9.2 Kinetic Influences Observed by Transport Experiments 119
2.9.3 Some Observations on Catalytic Effects 120
2.9.4 Indirect Transport 121
Bibliography 122
3 Chemical Vapor Transport of Elements 127
3.1 Transport with Halogens 128
3.2 Conproportionation Reactions 132
3.3 Reversal of the Transport Direction 134
3.4 Transport via Gas Complexes 136
3.5 Transport with the Addition of Hydrogen Halides and Water 137
3.6 Oxygen as a Transport Agent 138
3.7 Technical Applications 139
Bibliography 147
4 Chemical Vapor Transport of Metal Halides 153
4.1 Formation of Higher Halides 154
4.2 Conproportionating Reactions 155
4.3 Formation of Gas Complexes 155
4.4 Halogen Transfer Reactions 158
4.5 Formation of Interhalogen Compounds 159
Bibliography 164
5 Chemical Vapor Transport of Binary and Multinary Oxides 167
5.1 Transport Agents 172
5.2 Solids 179
5.2.1 Group 1 179
5.2.2 Group 2 180
5.2.3 Group 3, Lanthanoids and Actinoids 182
5.2.4 Group 4 198
5.2.5 Group 5 204
5.2.6 Group 6 214
5.2.7 Group 7 220
5.2.8 Group 8 226
5.2.9 Group 9 229
5.2.10 Group 10 231
5.2.11 Group 11 236
5.2.12 Group 12 239
5.2.13 Group 13 241
5.2.14 Group 14 246
5.2.15 Group 15 254
5.2.16 Group 16 256
5.3 Overview of the Trasport of Oxides 259
Bibliography 289
6 Chemical Vapor Transport of Oxido Compounds with Complex Anions 305
6.1 Transport of Sulfates 306
6.2 Transport of Phosphates, Arsenates, Antimonates, and Vanadates 309
6.2.1 Chlorine as Transport Agent for Anhydrous Phosphates 310
6.2.2 Halogens Combined with Reducing Additives as Transport Agents for Phosphates 311
6.2.3 Transport of Multinary Phosphates 317
6.2.4 Deposition of Thermodynamically Metastable Phosphates from the Gas Phase 318
6.2.5 Formation of Silicophosphates during the Transport of Phosphates 320
6.2.6 Transport of Arsenates(V), Antimonates(V), and Vanadates(V) 321
6.3 Transport of Carbonates, Silicates, and Borates 322
Bibliography 331
7 Chemical Vapor Transport of Sulfides, Selenides, and Tellurides 335
7.1 Transport of Sulfides 336
Bibliography of Section 7.1 363
7.2 Transport of Selenides 374
Bibliography of Section 7.2 392
7.3 Transport of Tellurides 399
Bibliography of Section 7.3 412
8 Chemical Vapor Transport of Chalcogenide Halides 417
8.1 Transport of Oxide Halides 424
8.2 Transport of Sulfide Halides, Selenide Halides, and Telluride Halides 435
8.3 Transport of Compounds with Chalcogen Poly-cations and Chalcogenate(IV)-halides 445
Bibliography 459
9 Chemical Vapor Transport of Pnictides 465
9.1 Transport of Phosphides 466
Bibliography of Section 9.1 475
9.2 Transport of Arsenides 478
Bibliography of Section 9.2 496
10 Chemical Vapor Transport of Intermetallic Phases 501
10.1 Selected Examples 506
Bibliography 525
11 Gas Species and their Stability 529
11.1 Halogen Compounds 529
11.2 Elements in the Gaseous State 534
11.3 Hydrogen Compounds 536
11.4 Oxygen Compounds 537
11.5 Other Substance Groups 538
Bibliography 539
12 Thermodynamic Data 541
12.1 Determination and Tabulation of Thermodynamic Data 541
12.2 Estimation of Thermodynamic Data 542
12.2.1 Thermodynamic Data of Solids 542
12.2.2 Thermodynamic Data of Gases 547
12.3 Quantum Chemical Calculation of Thermodynamic Data 550
Bibliography 552
13 Modeling of Chemical Vapor Transport Experiments: the Computer Programs TRAGMIN and CVTRANS 553
13.1 Purpose of Modeling of Chemical Vapor Transport Experiments 553
13.2 Equilibrium Calculations According to the Gmin Method 554
13.3 The Program TRAGMIN 558
13.4 The Program CVTRANS 562
Bibliography 568
14 Working Techniques 569
14.1 Transport Ampoules and Transport Furnaces 569
14.2 Preparation of Transport Ampoules 571
14.3 The Transport Experiment 576
14.4 The Transport Balance 578
14.5 High Temperature Vapor Transport: Transport under Plasma Conditions 579
Bibliography 580
15 Selected Experiments for Practical Work on Chemical Vapor Transport Reactions 581
15.1 Transport of WO2 with HgX2 (X = Cl, Br, I) 581
15.2 Transport of Zn1-xMnxO Mixed-crystals 592
15.3 Transport of Rhenium(VI)-oxide 595
15.4 Transport of Nickel 597
15.5 Transport of Monophosphides MP (M = Ti to Co) 599
Bibliography 605
16 Appendix 607
16.1 Important Thermodynamic Equations 607
16.2 Selected Physical Units, Constants, and Conversions 608
16.3 Abreviations 611
Index 615
Selected Photographs 629