Contributors

xvii

Preface

xxi

Part I TOPOLOGICAL MODELS FOR THE CRYSTALLINE AND AMORPHOUS PHASES

(a) Description of the Atomic Arrangement in SiO2 Polymorphs

The Topology of Silica Networks

(46)

L. W. Hobbs

C. E. Jesurum

B. Berger

Introduction

(3)

Graph Properties of Networks

(10)

Primary and Secondary Graph Properties

(1)

Tessellations

(2)

Rings

(5)

Local Clusters

(2)

Network Constraint and Structural Freedom

(4)

Structural Stability and Rigidity Constraints

(1)

Structural Freedom and Amorphizability

(3)

Local-Rules Basis for Structural Assembly

(22)

Assembling Crystalline Polymorphs

(1)

Quartz

(3)

Cristobalite and Tridymite

(2)

Moganite

(1)

Keatite

(1)

Coesite

(1)

Generating Amorphous Networks

(2)

Local Rules Self-Assembly

(2)

Reassembly of Disordered Collision Cascades

(3)

Refinement of Topological Models

(1)

Local Cluster Analysis

(1)

Crystalline Polymorphs

(2)

Topologically Disordered Silicas

(3)

Topology of Silica Surfaces

(1)

Conclusions

(1)

Acknowledgements

(1)

References

(5)

Low-Pressure Crystalline Phases of SiO2

(20)

G. Dolino

Introduction

(1)

Quartz

(8)

Crystalline Properties at Room Temperature

(1)

Occurrence

(1)

Atomic Structure

(1)

Chemical Composition

(1)

Electromechanical Properties

(1)

Optical Properties

(1)

Dislocations

(1)

Twins

(1)

α--β Transition and High-Temperature Properties

(1)

Order Parameter

(2)

Temperature Variation of Physical Properties in η2

(1)

Thermal Properties

(1)

Incommensurate Phase

(1)

Soft Mode and Lattice Vibrations of Quartz

(2)

Other Low-Pressure Polymorphs

(7)

Cristobalite

(1)

Structure and Properties of the α Phase

(1)

α--β Transition and High-Temperature Properties

(1)

Disorder in the β Phase

(1)

Tridymite

(1)

Phase Relations

(3)

Temperature Variation in Physical Properties

(1)

Conclusion

(1)

References

(4)

Theoretical Investigations of the Structure of Amorphous SiO2 at Elevated Pressure

(38)

L. Stixrude

Introduction

(3)

Theoretical Methods

(11)

Statistical Mechanical Simulations

(2)

Electronic Structure Methods

(1)

Semi-Empirical Potentials

(8)

Structure and Compression Mechanisms of Tectosilicates

(4)

Compression of SiO2 Glass

(13)

Overview

(1)

Elastic Regime

(4)

Anelastic Regime

(2)

Permanent Densification

(2)

Coordination Changes

(4)

Conclusions and Future Directions

100

(1)

Acknowledgment

101

(1)

References

101

(6)

(b) Experimental Analysis of SiO2 Atomic Networks

Nuclear Magnetic Resonance as a Structural Probe of SiO2

107

(14)

R. Dupree

Introduction

107

(1)

29Si Chemical Shifts in SiO2 Polymorphs

108

(6)

Shift Structure Correlations for Tetrahedrally Coordinated Polymorphs

109

(2)

Some Examples of the Use of 29Si NMR for Giving Structural Information about Crystalline SiO2 Phases

111

(1)

Tridymite Orthorhombic Phase

111

(2)

Oxygen Positions in High-Temperature SiO2 Phases

113

(1)

29Si as Probe of Amorphous SiO2 Structure

114

(1)

17O NMR in SiO2

115

(4)

Quadrupolar Effects

115

(1)

17O NMR in Crystalline Systems

116

(1)

Quartz

116

(1)

Cristobalite

117

(1)

Coesite

118

(1)

Stishovite

118

(1)

17O NMR in Glassy SiO2

118

(1)

Acknowledgment

119

(1)

References

119

(2)

Neutron and X-Ray Scattering Studies of Vitreous Silica

121

(32)

A. C. Wright

R. N. Sinclair

Introduction

121

(3)

Traditional Theories of Glass Structure

122

(1)

Ranges of Order

123

(1)

Neutron and X-Ray Scattering Techniques

124

(1)

Modern Diffraction Data

125

(2)

X-Ray Diffraction

125

(1)

Neutron Diffraction

126

(1)

Methods of Interpretation

127

(2)

General Data Characteristics

127

(2)

Accuracy and Comparison with Models

129

(1)

The SiO4 Tetrahedral Structural Unit (Range I)

129

(3)

The Si--O--Si and Bond Torsion Angles (Range II)

132

(2)

Network Topology and Structural Theories/Models (Range III)

134

(8)

Crystal-Based Models

135

(2)

Random Network Models

137

(2)

Computer Simulation

139

(2)

First Diffraction Peak

141

(1)

Long-Range Density Fluctuations (Range IV)

142

(1)

Fast Neutron Irradiated Vitreous Silica

143

(1)

Inelastic Neutron Scattering Studies

144

(3)

Conclusions

147

(1)

References

148

(5)

Part II ELECTRONIC STRUCTURE OF THE SI-O2 BOND AND THE EXTENDED NETWORK

(a) Calculations and Modelling of the Electronic Structure

Molecules as a Basis for Modeling the Force Field of Silica

153

(14)

G. V. Gibbs

F. C. Hill

M. B. Boisen, Jr.

R. T. Downs

Introduction

153

(1)

Connection Between the Force Field of Silica and Small Molecules

153

(5)

Structural Evidence

153

(2)

Evidence Provided by Electron Density Distributions

155

(2)

Evidence Provided by Molecular Modeling of the Structure of Silica

157

(1)

Generation of Silica Structure Types Using a Molecular-Based Potential

158

(4)

Discussion

162

(1)

References

163

(4)

First Principles Calculation of the Electronic Structures of Crystalline and Amorphous Forms of SiO2

167

(14)

W. Y. Ching

Introduction

167

(1)

Method and Approach

168

(2)

Results on Crystalline Phases

170

(3)

Results on Amorphous Phases

173

(4)

Conclusions

177

(1)

Acknowledgements

178

(1)

References

178

(3)

The Electronic Structure of Silica Using Ab Initio Pseudopotentials

181

(20)

J. R. Chelikowsky

N. Binggeli

Introduction

181

(2)

Pseudopotentials

183

(4)

Crystalline Forms of Silica

187

(1)

Structural Energies of Crystalline Silica

188

(1)

Electronic Structure of α-Quartz

189

(3)

Electronic Structure of α-Quartz at High Pressure

192

(4)

Conclusions

196

(1)

Acknowledgements

196

(1)

References

196

(5)

(b) Experimental Analysis of the Electronic Structure

X-Ray Absorption Near Edge Structures of SiO2

201

(26)

F. Jollet

Introduction

201

(1)

Principle of XANES

202

(5)

Presentation of XANES

202

(2)

Dependence on the Electronic Structure

204

(1)

Interpretation

205

(2)

The Si K, Si L2.3 and O K XANES Signatures and their Relation to the Electronic Structure in SiO2

207

(11)

Crystalline SiO2

207

(1)

α-Quartz

207

(5)

Polarization Effects in α-Quartz

212

(1)

Other Crystalline Phases

213

(2)

Amorphous SiO2

215

(3)

Other Silicon Oxides

218

(1)

Knowledge of Empty States: Examples

218

(4)

SiO2 Under Pressure

218

(3)

Radiation Damage Produced by High Energy Ions

221

(1)

Conclusion

222

(1)

Acknowledgements

223

(1)

References

223

(4)

Electron Energy Loss Structures of SiO2

227

(26)

M. Gautier-Soyer

Introduction

227

(1)

Physical Basis of REELS

228

(6)

Dielectric Approach to REELS

228

(1)

Deriving the Electron Energy Loss Function from the REELS Spectra

229

(1)

Removing Multiple Losses

230

(1)

Validity of the Dipole Approximation (k ∼ 0)

231

(1)

Influence of Surface Effects

232

(1)

Obtaining the Complex Dielectric Function from the Single Scattering Inelastic Cross-Section: the Model of Yubero and Tougaard

232

(1)

Interpretation of the ELF in Terms of Electronic Structure---Comparison with Optical Data

233

(1)

Application to SiO2: Optical Properties Derived from Optical Measurements, TEELS, REELS and Electronic Structure Calculation

234

(2)

The REELS Spectrum of SiO2

236

(11)

Band Gap

238

(1)

Origin of the Structures above the Band Gap in the REELS Spectrum of SiO2

239

(2)

Origin of the 5.1 and 7.2 eV Structures Observed in the Band Gap Region

241

(2)

Comparison with Previous Optical Absorption Measurements

243

(1)

Comparison with Calculated Electronic Transitions

244

(1)

Origin of the 5.1 and 7.2 Structures Observed in the REELS Spectrum

245

(2)

Conclusion

247

(1)

Acknowledgments

247

(1)

References

247

(6)

Part III MACROSCOPIC AND POINT DEFECTS

Theory of Electronic and Structural Properties of Point Defects in SiO2

253

(40)

A. H. Edwards

W. B. Fowler

J. Robertson

Introduction

253

(1)

Theory

254

(4)

General Methodological Requirements

254

(1)

Equilibrium Geometries and Potential Energy Surfaces

254

(1)

Optical Properties

254

(1)

Hyperfine Parameters

255

(1)

Electrical Level Positions

256

(1)

Specific Methods

256

(1)

Termination Issues

256

(1)

Ab Initio Methods

257

(1)

Intrinsic Defects

258

(12)

E' Centers

258

(1)

E' Centers in α-Quartz

259

(2)

E' Centers in Silica Glass

261

(1)

Similarities and Differences

262

(1)

Superoxide Radical and the Non-Bridging Oxygen in a-SiO2

263

(1)

Theoretical Hyperfine Results

263

(2)

Transformation Mechanisms

265

(1)

Metastable Structure of Transient Defects

266

(1)

Self-Trapped Hole

266

(2)

Self-Trapped Exciton (STE)

268

(1)

Other Oxygen Deficiency Centers

268

(1)

Twofold Silicon

269

(1)

Oxygen Divacancy

269

(1)

Valence-Alternation Pairs

269

(1)

Extrinsic Defects

270

(2)

Phosphorus Defect

270

(1)

Germanium Defect

270

(1)

Aluminum Defact

271

(1)

Nitrogen Defect

271

(1)

Current Problems

272

(15)

E' Center in Silica

272

(1)

Lelis Experiments and the E' Center as a Switching Trap

272

(7)

Interaction of Hydrogen with Defects in a SiO2

279

(5)

Optical Properties of Silica Glass

284

(1)

2 and 4.8 eV Absorption and 1.9 eV Luminescence

285

(1)

5.85 eV Absorption

285

(1)

3.8 and 8 eV Absorption

285

(1)

5 and 7.6 eV Absorption and 4.4 and 2.7 eV Emission

285

(2)

Acknowledgements

287

(1)

References

287

(6)

Radiation-Induced Defects and Electronic Modification

293

(36)

P. Paillet

J. L. Leray

H. J. von Bardeleben

Introduction

293

(1)

Characterization of Radiation-Induced Defects by Electrical and Optical Techniques

294

(11)

Origin of Hole and Electron Traps in Oxide Layers

294

(3)

Electrical Characterization of Defects

297

(1)

Post-Irradiation Evolution of the Net Trapped Charge

297

(2)

Thermally Stimulated Current

299

(2)

Thermally Stimulated Luminescence

301

(4)

ERP Characterization of Radiation-Induced Point Defects in Crystalline and Amorphous SiO2

305

(19)

Defects in Crystalline α-SiO2

307

(1)

Intrinsic Defects

307

(3)

Impurity Related Defects

310

(1)

Defects in Bulk Silica

310

(1)

Intrinsic Defects

311

(7)

Defects in Thermal Silica

318

(3)

Defects at Si/SiO2 Interfaces: Pb, Pb0 and Pb1 Centres

321

(3)

Conclusions

324

(1)

Acknowledgements

325

(1)

References

325

(4)

Transient Defects and Electronic Excitation

329

(20)

N. Itoh

A. M. Stoneham

K. Tanimura

Introduction

329

(2)

Electrons, Holes and Excitons in Fused Silica and α-Quartz

331

(3)

Mobility of Electrons

331

(1)

Mobilities of Holes

332

(1)

Dynamics of Excitons and Exciton Formation

332

(2)

Self-Trapping of Excitons and Holes in Fused Silica and α-Quartz

334

(3)

Theory of the Self-Trapped Exciton

335

(1)

Is the Hole Self-Trapped?

336

(1)

Transient Atomic Defects

337

(4)

Transient Defects at Surfaces and Interfaces

341

(2)

Pb Centres at a Moving Silicon/Oxide Interface

342

(1)

Defects Associated with Telegraph Noise

342

(1)

Transient Defects in Silica-Based Glasses

343

(1)

Charge Transfer: Colours of Silicas

343

(1)

Gratings Produced in Ge-Doped Optical Fibres

343

(1)

References

344

(5)

Radiation-Induced Defects and Structural Modifications

349

(76)

E. Dooryhee

J.-P. Duraud

R. A. B. Devine

Basic Irradiation Processes and Formation Yields of Point Defects

349

(33)

Introduction

349

(3)

Basic Irradiation Concepts

352

(1)

Macroscopic Description of the Beam-Solid Interaction

352

(3)

Elastic Nuclear Scattering

355

(5)

Inelastic Scattering

360

(1)

Experimental Observations of the Damage

361

(2)

Defect Creation by Elastic Collisions

363

(1)

Primary Knock-ons and Collisional Cascades

363

(3)

Irradiation of SiO2 by Fast Neutrons (E < 100 KeV)

366

(1)

Ion Implantation in SiO2

367

(4)

Defect Creation by Inelastic Processes

371

(1)

High-Energy Ion Irradiation of SiO2

372

(1)

Electron Irradiation of SiO2

373

(2)

Photon Irradiation of SiO2

375

(1)

High-Energy Photolysis

375

(4)

Sub-Band Gap Photolysis

379

(1)

Post-Irradiation Annealing of Point Defects

379

(3)

Effect of Dense Electronic Excitations

382

(11)

Introduction

382

(1)

Track Formation in SiO2

383

(1)

Microscopic and Macroscopic Studies of Tracks in SiO2

384

(4)

Mechanisms for Latent Track Formation

388

(2)

Defect Generation in SiO2 by Laser Irradiation

390

(1)

Remarks on Energy Absorption and Relaxation by SiO2

390

(1)

Defect Formation under Subpicosecond UV Laser Pulses

391

(2)

Radiation-Induced Structural Modification

393

(10)

Structural Modification of α-Quartz

393

(1)

Amorphization under Irradiation

393

(3)

Structural Analysis of Particle-Amorphized α-Quartz

396

(2)

Structural Evolution

398

(2)

Point Defect Model for the Metamictization of Quartz

400

(3)

Conclusion

403

(1)

Structural Modifications of Amorphous SiO2

403

(13)

The Structural Nature of Amorphous SiO2

403

(2)

Infrared Spectroscopy and the Si--O--Si Bridging Bond Angle

405

(2)

Interpretation of Radiation-Induced Changes

407

(3)

Dose Dependence of Radiation-Induced Modifications

410

(2)

Nature of the Radiation-Induced Densification

412

(3)

Densification Maximization and Radiation-Induced Viscous Flow

415

(1)

References

416

(9)

Part IV PROCESSING AND APPLICATIONS OF CRYSTALLINE AND AMORPHOUS PHASES

Quartz Oscillators

425

(24)

J. R. Vig

Introduction

425

(1)

Applications

426

(1)

Oscillator Basics

426

(5)

Quartz Resonators

427

(3)

Equivalent Circuit of Crystal Unit

430

(1)

Oscillator Circuits

431

(1)

Factors Affecting Frequency Stability

431

(10)

Temperature

432

(2)

Aging and Drift

434

(1)

Short-Term Stability

435

(1)

Thermal Hysteresis and Retrace

436

(1)

Drive Level

436

(1)

Acceleration, Vibration, and Shock

436

(1)

Magnetic Field Effects

437

(1)

Radiation Effects

437

(2)

Other Effects on Stability

439

(1)

Interactions Among the Influences on Stability

440

(1)

Filters

441

(1)

Sensors

441

(1)

Oscillator Comparison

442

(2)

Future of Quartz Oscillator Technology

444

(1)

References

444

(5)

Science and Technology of Silica Lightguides for Telecommunications

449

(26)

C. R. Kurkjian

D. M. Krol

Introduction

449

(2)

History

451

(2)

First Low-Loss Lightguide Fiber, 1970

453

(1)

Composition

454

(3)

Optical Behaviour

457

(4)

Optical Loss

457

(4)

Lightguide Design

461

(1)

Solitions

462

(1)

Processing

463

(1)

Vapour Deposition Processes

463

(1)

MCVD

463

(1)

Fiber Drawing

464

(1)

Defects

465

(1)

Mechanical Properties

465

(1)

New Devices

466

(5)

Erbium-Doped Fiber Amplifiers

466

(2)

Fiber Bragg Gratings

468

(1)

Photoinduced Second Harmonic (χ(2)) Gratings in Fibers

468

(2)

Electric Field Poling of Glass

470

(1)

Feedback of Lightguide Results to Glass Science

471

(1)

References

471

(4)

Microstructure, Surface Chemistry, and Properties of Silica Gels

475

(20)

C. J. Brinker

W. L. Warren

S. Wallace

Sol--Gel Processing

475

(2)

High Surface Area Silica Gels

477

(2)

Unique Properties of High Surface Area, Bulk Sol-Gel Silica as Compared with Amorphous Silica

479

(1)

Three-Membered Rings in Sol-Gel Glasses

480

(2)

Consequences of Three-Membered Rings

482

(4)

Enhanced Surface Reactivity

482

(2)

Enhanced Defect Creation

484

(1)

Membranes

485

(1)

Sol--Gel Thin Films

486

(5)

Introduction

486

(1)

Sol--Gel Film Deposition

486

(2)

Control of Microstructure

488

(1)

Dense Insulating Films on Si

489

(1)

Porous Sol--Gel Films

490

(1)

Summary

491

(1)

Bulk Gels

491

(1)

Thin Films

491

(1)

Acknowledgments

491

(1)

References

491

(4)

Index

495

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Structure and Imperfections in Amorphous and Crystalline Silicon Dioxide

9780471975366

0471975362

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