CONTENTS
Preface = Ⅶ
Introduction = Ⅷ
List of Contributors = XXI
1 Structure, Defects and Electronic Properties of Amorphous Semiconductors / M. Popescu = 1
1.1 Structural States of Solids = 1
1.1.1 Ordered State = 1
1.1.2 Disordered (Non-Crystalline) State = 2
1.2 Atomic Scale Ordering in Crystalline and Non-Crystalline Solids = 2
1.2.1 Long-Range Order = 2
1.2.2 Short-Range Order = 2
1.2.3 Medium-Range Order = 3
1.3 Fundamental Problems of Structure of Non-Crystalline Semiconductors = 4
1.3.1 Tetrahedrally Bonded Amorphous Semiconductors = 4
1.3.2 Amorphous Non-Tetrahedrally Bonded Semiconductors = 7
1.4 Defects in Non-Crystalline Solids = 10
1.4.1 Local Defects = 11
1.4.2 The Diffuse or Collective Defects (Extended Defects) = 12
1.4.3 Chemical Defects = 13
1.4.4 Electronic-Structural Defects = 14
1.4.5 Macrodefects = 16
1.5 Electronic States in Amorphous Semiconductors = 16
1.5.1 Electronic States in Tetrahedrally Bonded Semiconductors = 16
1.5.2 Electronic States in Non-Tetrahedrally Bonded Semiconductors = 18
References = 20
2 Photo-Induced Phenomena in Amorphous and Glassy Chalcogenides / M. Frumar ; B. Frumarov a ´ ; T. W a ´ gner ; P. N e ∨ mec = 23
2.1 Introduction = 23
2.2 Photo-Induced Effects in Amorphous and Glassy Chalcogenides = 24
2.2.1 Irreversible Photo-Induced Changes = 26
2.2.2 Reversible Photo-Induced Changes = 32
2.3 Applications = 37
2.4 Summary = 39
References = 39
3 Short-, Medium- and Long-Range-Order Structural Transformations in Amorphous Semiconductors / E. Mytilineou ; A. Kolobov = 45
3.1 Introduction = 45
3.2 Short-Range-Order (SRO) Effects = 46
3.3 Medium-Range-Order (MRO) Effects = 51
3.4 Long-Range-Order (LRO) Effects = 53
3.5 Conclusion = 55
References = 55
4 Dynamics of Photo-Induced Metastability in Amorphous Chalcogenides / K. Shimakawa = 58
4.1 Introduction = 58
4.2 Light-Induced Metastable Defect (LMID) Creation = 59
4.3 Photostructural Changes = 62
4.4 Discussion = 65
4.5 Conclusions = 67
References = 68
5 Sub-Gap Photo-Induced Phenomena in Chalcogenide Glasses / K. Tanaka = 69
5.1 Introduction = 69
5.2 Chalcogenide Glass = 69
5.3 Photo-Induced Phenomena = 70
5.4 Sub-Gap Photo-Induced Phenomena = 72
5.4.1 Background = 73
5.4.2 Photo-Induced Bragg Grating = 73
5.4.3 Photo-Induced Persistent Self-Focusing Structure = 75
5.4.4 Photo-Induced Fluidity = 75
5.4.5 Giant Photoexpansion = 77
5.4.6 Spectral Light-Intensity Dependence = 78
5.5 Mechanism = 79
5.5.1 Temperature Rise = 79
5.5.2 Two-Photon Absorption = 80
5.5.3 Gap States and Microscopic Structure = 80
5.5.4 Refractive-Index Change = 81
5.5.5 Fluidity and Volume Expansion = 82
5.6 Summary = 86
References = 86
6 Photo-Induced Anisotropy in Chalcogenide Glassy Semiconductors / V.M. Lyubin ; M.L. Klebanov = 91
6.1 Introduction = 91
6.2 Samples and Experimental Procedures = 92
6.3 Photo-Induced Optical Anisotropy = 94
6.3.1 Above-Bandgap Light Excitation = 94
6.3.2 Sub-Bandgap Light Excitation = 98
6.3.3 Super-Bandgap Light Excitation = 100
6.4 Photo-Induced Anisotropy of Other Properties of ChGS = 102
6.4.1 Polarization-Dependent Photocrystallization = 102
6.4.2 Polarization-Dependent Photodoping of ChGS Films by Silver = 103
6.4.3 Photo-Induced Anisotropy of Photoconductivity = 104
6.4.4 Anisotropic Opto-Mechanical Effect and Ionic Transport = 105
6.5 Conclusion = 105
References = 106
7 The Optomechanical Effect in Amorphous Chalcogenide Films / M. Stuchlik ; P. Krecmer ; S.R. Elliott = 109
7.1 Introduction = 109
7.2 Experimental = 110
7.3 Results = 111
7.3.1 Polarization Dependence = 111
7.3.2 Light-Intensity Dependence = 112
7.3.3 Wavelength Dependence = 113
7.4 Discussion = 115
7.5 Conclusions = 117
References = 117
8 Photo-Plastic Effects in Chalcogenide Glasses : Raman Scattering Studies / S.N. Yannopoulos = 119
8.1 Preamble = 119
8.2 The Photo-Induced Fluidity Effect : A Synopsis = 120
8.3 Changes of Vibrational Modes in the Athermal PiF Regime at Ambient Temperature = 121
8.3.1 High-Frequency Modes : Intramolecular Vibrations = 121
8.3.2 Medium Range Structure : the Boson Peak Region = 123
8.4 Temperature Dependence of the Photo-Induced Fluidity Effect = 124
8.5 PiF in Non-Stoichiometric A sx Glasses = 128
8.5.1 The Role of Illumination-to-Bandgap Energy Ratio in PiF = 129
8.5.2 The Role of the Glass Transition Temperature = 131
8.6 Microscopic Models Related to PiF = 131
8.6.1 Intramolecular Structural Models for PiF = 132
8.6.2 Implications of Intermolecular Structural Modifications = 133
8.7 Summary and Outlook = 135
References = 136
9 Photo-Induced Non-Linearity and Transmittance Oscillation in GeSe₂and As₂S₃ / J. Hajto ; I. J a ´ nossy = 138
9.1 Introduction = 138
9.2 Experimental Technique = 139
9.3 Laser-Induced Optical Anisotropy = 140
9.3.1 Experimental Results on Laser-Induced Birefringence and Dichroism = 140
9.3.2 Theoretical Results on Laser-Induced Optical Anisotropy = 143
9.3.3 Comparison of the Model with the Experiments = 148
9.3.4 Application of the Optical Anisotropy Effect = 149
9.4 Optical Bistability and Light-Induced Transmittance Oscillations in Amorphous Semiconductor Films = 149
9.4.1 Experimental Results = 150
9.4.2 Theoretical Considerations = 152
9.5 Conclusion = 157
References = 158
10 Optically-Induced Diffusion and Dissolution of Metals in Amorphous Chalcogenides / T. W a ´ gner ; M. Frumar = 160
10.1 Introduction = 160
10.2 Preparation of Bulk Glasses and Thin Films = 161
10.3 Kinetics = 162
10.3.1 Kinetic Measurement Methods and Kinetics of OIDD Process = 162
10.3.2 Kinetic Curves of the OIDD Process = 163
10.3.3 Mechanism of the OIDD Process = 164
10.3.4 Location of Actinic Light Absorption During OIDD = 166
10.3.5 Diffusion Profiles = 168
10.4 Reaction Products and Their Properties = 168
10.4.1 Optical Properties = 169
10.4.2 Mechanical and Thermal Properties = 171
10.4.3 Structure = 173
10.5 Applications = 177
References = 177
11 Photo-Induced Deposition of Silver Particles on Amorphous Semiconductors / T. Kawaguchi = 182
11.1 Introduction = 182
11.2 Photodeposited Ag Particles = 184
11.3 Compositional Dependence of Photodeposition = 185
11.4 Effect of Light Intensity, Photon Energy and Temperature = 188
11.5 Erasing, Rewriting and Fixing of Ag Patterns = 189
11.6 Mechanism of Photodeposition = 191
11.6.1 Photoelectro-Ionic Processes = 192
11.6.2 Thermodynamic Aspect = 195
11.7 Other Observations = 196
11.8 Concluding Remarks = 197
References = 198
12 Photo-Induced Changes in Liquid Sulfur and Selenium / Y. Sakaguchi ; K. Tamura = 199
12.1 Introduction = 199
12.2 Experimental = 201
12.2.1 Optical Cells = 201
12.2.2 Measurement Set-Up = 201
12.3 Photo-Induced Changes in Liquid Sulfur = 202
12.3.1 Transient Absorption Measurements = 202
12.3.2 Short- and Long-Living Products = 204
12.3.3 What is a Short-Living Product? = 204
12.3.4 What is a Long-Living Product? = 205
12.3.5 Temperature Variation of Relaxation Time = 207
12.3.6 Photo-Induced Polymerization as a Cooperative Phenomenon = 208
12.4 Ab Initio Molecular-Dynamics Simulation for Liquid Sulfur = 209
12.4.1 Photo-Induced Bond Breaking In Isolated S8 Ring = 209
12.4.2 Photo-Induced Structural Change in Liquid Sulfur = 211
12.4.3 Relaxation Process. A New Candidate for Long-Living Product = 211
12.4.4 Polymerization = 212
12.5 Photo-Induced Changes in Liquid Selenium = 212
12.5.1 Transient DC Conductivity Measurements = 212
12.5.2 Maximum Voltage = 214
12.6 Ab Initio Molecular-Dynamics Simulation for Liquid Selenium = 215
12.6.1 Bond Breaking in an Infinite Selenium Chain = 215
12.7 Final Remarks = 216
References = 217
13 Staebler-Wronski Effect : Physics and Relevance to Devices / P. Stradins ; M. Kondo = 220
13.1 Introduction = 220
13.2 Creation of Si Dangling Bond Defects = 222
13.2.1 Defect Creation at Low Exposure Temperatures and Their Thermal Stability. Effect of High Electric Fields on Defect Creation = 222
13.2.2 Defect Creation at Very High Photocarrier Generation Rates = 225
13.2.3 Influence Between Groups of Defects with Different Stability = 228
13.3 Effect of H-Content and Microstructure. Defect Precursors. Structural Changes = 229
13.4 Light-Induced Degradation of Photoconductivity = 231
13.4.1 Photodegradation of Solar Cells = 236
13.5 Summary = 239
References = 240
14 Photo-Induced Structural Metastability in a-Si:H / S. Nonomura = 244
14.1 Introduction = 244
14.2 Experimental Details = 245
14.3 Fundamental Properties of Photo-Induced Structural Metastability = 247
14.4 Effect of Deposition Conditions and Cyanide Treatment on Photo-Induced Structural Metastability = 251
14.4.1 Effect of Deposition Conditions on Photo-Induced Structural Metastability = 251
14.4.2 Effect of Cyanide Treatment on Photo-Induced Structural Metastability = 256
14.5 Summary = 257
References = 257
15 First Principles Molecular Dynamics and Photo Structural Response in Amorphous Silicon and Chalcogenide Glasses / D.A. Drabold ; X. Zhang ; J. Li = 260
15.1 Introduction = 261
15.2 Method = 261
15.2.1 Making the Structural Model of the Glass = 262
15.2.2 Density Functional Theory and Molecular Dynamics = 263
15.2.3 Photostructural Change from Molecular Dynamics = 265
15.3 Applications = 266
15.3.1 Amorphous Silicon = 267
15.3.2 Amorphous Selenium = 268
15.3.3 As₂Se₃ = 272
15.3.4 Discussion = 276
References = 276
16 Soft Atomic Modes and Negative-U Centers as Sources of Metastable Transformations in the Structure and Dynamics of Glasses / M.I. Klinger = 279
16.1 Introduction = 279
16.2 The Soft-Mode Dynamics of Glasses = 281
16.3 Negative-U Centers in Glassy Semiconductors = 284
16.4 Photo-Induced Metastable Transformations in Structure (Photostructural Changes) = 286
16.4.1 Photostructural Changes as Metastable "Defects" Due to Excited Negative-U Centers = 286
16.4.2 Kinetics and Transition Probabilities = 290
16.4.3 Concluding Remarks = 292
16.5 On Correlations Between Photo-Induced Transformations in Atomic Dynamics and Photostructural Changes = 292
16.5.1 Are Pronounced Metastable Transformations Available in Atomic Tunneling Dynamics? = 292
16.5.2 Can Pronounced Metastable Transformations be Available in the HFD Related to Soft Modes? = 293
16.6 Suppression of Photostructural Changes at High Pressure = 295
16.7 Conclusions = 295
References = 296
17 Hypervalent Bonds as Active Centers Providing Photo-Induced Transformations in Glasses / S.A. Dembovsky ; E.A. Chechetkina = 299
17.1 Introduction = 299
17.2 What Kind of Bond is Needed? = 300
17.3 A Quantum-Chemistry Study : HVB versus VAP = 301
17.4 General Model of PSC and Related Phenomena = 302
17.5 Self-Organization of HVB : a Bond-Wave Model = 305
17.6 Conclusions = 307
References = 308
18 Phase-Change Optical Storage Media / T. Ohta ; S.R. Ovshinsky = 310
18.1 Introduction = 310
18.2 Phase-Change Overwrite Optical Disc = 310
18.2.1 Phase-Change Optical Memory Phenomena = 310
18.2.2 The Phase-Change Memory Mechanism = 311
18.2.3 Phase-Change Overwriting Method = 311
18.3 Phase-Change Materials = 313
18.3.1 Bonding Features of Chalcogenide Phase-Change Materials = 313
18.3.2 Phase-Change Optical Disc Materials for Optical Disc Memory = 313
18.4 Breakthrough Technologies of the Phase-Change Optical Disc Media = 316
18.4.1 Basic Layer Structure = 316
18.4.2 Million Overwrite Cycle Phase Change Optical Disc [6] = 316
18.5 Thin Substrate Technology of Phase Change Optical Disc Promotes DVD = 318
18.6 High-Density Recording Technologies for Phase Change Optical Discs = 319
18.6.1 Short-Wavelength Blue Laser and High Numerical Aperture Lens Recording = 319
18.6.2 Dual-Layer Recording = 319
18.6.3 Multi-Level Recording = 320
18.6.4 Near-Field Recording and Super-RENS Recording = 320
18.6.5 High Data Rate, High-Density Recording on Phase-Change Disc = 321
18.6.6 Combination Technology = 321
18.7 Future Directions of the Phase-Change Storage Media = 322
18.7.1 Ultra Short Pulse (Femtosecond) Laser Recording = 322
18.8 Conclusion = 323
References = 324
19 Application of Ge-Sb-Te Glasses for Ultrahigh-Density Optical Storage / J. Tominaga = 327
19.1 Introduction = 327
19.2 Optical Near-Field and Surface Plasmons = 328
19.3 GeSbTe Glass and its Characteristics for NFR = 330
19.4 NFR Optical Disc Using GeSbTe Glass = 333
19.5 Summary = 336
References = 337
20 Evaluation of Multiplexing in High-Density Holographic Memories / J.M. Gonz a ´ lez-Leal ; P. Krecmer ; J. Prokop ; S.R. Elliott = 338
20.1 Introduction = 338
20.2 Holographic Data-Storage Media = 341
20.3 HOLOMETER = 342
20.3.1 Concept = 342
20.3.2 Implementation = 342
20.3.3 Performance = 344
20.4 Diffraction of Light by a Volume Grating = 345
20.5 Testing the Holographic Data-Storage Potential of Chalcogenide Glasses = 351
20.6 Summary = 354
References = 355
21 Optical Waveguides Photo-Written in Glasses with a Femtosecond Laser / K. Hirao ; K. Miura = 357
21.1 Introduction = 357
21.2 Experimental Details = 357
21.3 Experimental Results = 358
21.3.1 Photo-Written Waveguides = 358
21.3.2 Power Dependence = 359
21.3.3 Guided Light Intensity Profiles = 360
21.4 Discussion = 362
21.5 Conclusions = 363
References = 364
22 Applications of the Photodissolution Effect in Chalcogenide Glasses / P.J.S. Ewen = 365
22.1 Introduction = 365
22.2 The MPD Effect and its Imaging Properties = 365
22.2.1 The Basic Effect = 365
22.2.2 Material Systems Exhibiting the Effect = 366
22.2.3 The Metal Concentration Profile = 366
22.2.4 Spectral Sensitivity = 368
22.2.5 Imaging Properties = 368
22.3 Applications of the Effect = 368
22.3.1 High-Resolution Lithography = 368
22.3.2 IR Diffractive Optical Elements = 371
22.3.3 IR Optical Components = 374
22.3.4 Miscellaneous Applications = 376
22.4 Comparison of MPD and Photodarkening as Techniques for Producing Structures = 378
22.5 Conclusions = 379
References = 380
23 Engineering Glassy Chalcogenide Materials for Integrated Optics Applications / K. Richardson ; T. Cardinal ; M. Richardson ; A. Schulte ; S. Seal = 383
23.1 Introduction = 383
23.2 Chalcogenide Glasses for Near-Infrared (NIR) Optics = 383
23.3 Bulk Chalcogenide Glasses (ChG) : Composition and Optical Properties = 384
23.4 Chalcogenide Thin Films and Comparison with Bulk Glass = 389
23.5 Structural Characterization of Chalcogenide Glasses = 390
23.5.1 Raman Spectroscopy = 390
23.5.2 NIR Raman Spectroscopy of Bulk Chalcogenide Glasses = 392
23.5.3 NIR Waveguide and Micro-Raman Spectroscopy of Chalcogenide Films = 394
23.6 Photo-Induced Changes in Glassy Chalcogenides = 395
23.6.1 Exposure Sensitivity of Chalcogenide Glasses = 396
23.6.2 Photo-Induced Waveguides in Bulk ChG Materials = 397
23.6.3 Photo-Induced Changes in ChG Films = 399
23.6.4 Grating Fabrication in As₂S₃ Glassy Films = 400
23.7 Conclusions and Outlook = 401
References = 402
Index = 407
