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Optical Properties of Materials and Their Applications
Wiley Series in Materials for Electronic and
Optoelectronic Applications
www.wiley.com/go/meoa
Series Editors
Professor Arthur Willoughby, University of Southampton, Southampton, UK
Dr Peter Capper, Ex-Leonardo MW Ltd, Southampton, UK
Professor Sofa Kasap, University of Saskatchewan, Saskatoon, Canada
Published Titles
Bulk Crystal Growth of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper
Properties of Group-IV, III—V and II—VI Semiconductors, S. Adachi
Charge Transport in Disordered Solids with Applications in Electronics, Edited by S. Baranovski
Optical Properties of Condensed Matter and Applications, Edited by J. Singh
Thin Film Solar Cells: Fabrication, Characterization, and Applications, Edited by J. Poortmans and V.
Arkhipov
Dielectric Films for Advanced Microelectronics, Edited by M. R. Baklanov, M. Green, and K. Maex
Liquid Phase Epitaxy of Electronic, Optical and Optoelectronic Materials, Edited by P. Capper and M. Mauk
Molecular Electronics: From Principles to Practice, M. Petty
Luminescent Materials and Applications, A. Kitai
CVD Diamond for Electronic Devices and Sensors, Edited by R. S. Sussmann
Properties of Semiconductor Alloys: Group-IV, III—V and II—VI Semiconductors, S. Adachi
Mercury Cadmium Telluride, Edited by P. Capper and J. Garland
Zinc Oxide Materials for Electronic and Optoelectronic Device Applications, Edited by C. Litton, D. C.
Reynolds, and T. C. Collins
Lead-Free Solders: Materials Reliability for Electronics, Edited by K. N. Subramunian
Silicon Photonics: Fundamentals and Devices, M. Jamal Deen and P. K. Basu
Nanostructured and Subwavelength Waveguides: Fundamentals and Applications, M. Skorobogatiy
Photovoltaic Materials: From Crystalline Silicon to Third-Generation Approaches, Edited by G. Conibeer
and A. Willoughby
Glancing Angle Deposition of Thin Films: Engineering the Nanoscale, Matthew M. Hawkeye, Michael T.
Taschuk, and Michael J. Brett
Physical Properties of High-Temperature Superconductors, R. Wesche
Spintronics for Next Generation Innovative Devices, Edited by Katsuaki Sato and Eiji Saitoh
Inorganic Glasses for Photonics: Fundamentals, Engineering and Applications, Animesh Jha
Amorphous Semiconductors: Structural, Optical and Electronic Properties, Kazuo Morigaki, Sandor Kugler,
and Koichi Shimakawa
Microwave Materials and Applications, Two volume set, Edited by Mailadil T. Sebastian, Rick Ubic, and Heli
Jantunen
Molecular Beam Epitaxy: Materials and Applications for Electronics and Optoelectronics, Edited by Hajime
Asahi and Yoshiji Korikoshi
Metalorganic Vapor Phase Epitaxy (MOVPE): Growth, Materials Properties, and Applications, Edited by
Stuart Irvine and Peter Capper
Optical Properties of Materials and Their
Applications
Edited by
Jai Singh
College of Engineering, IT and Environment
Charles Darwin University, Darwin, Australia
Second Edition
This edition first published 2020
© 2020 John Wiley & Sons Ltd
Edition History
John Wiley & Sons Inc. (1e, 2006)
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Library of Congress Cataloging-in-Publication Data
Names: Singh, Jai, editor.
Title: Optical properties of materials and their applications / edited by
Jai Singh (College of Engineering, IT, and Environment, Charles Darwin
University, Darwin, Australia)
Other titles: Optical properties of condensed matter and applications. |
Optical properties of condensed matter and applications.
Description: Second edition. | Hoboken, NJ : John Wiley & Sons, 2020. |
Series: Wiley series in materials for electronic and optoelectronic
applications | Previous edition: Optical properties of condensed matter
and applications, 2006. | Includes bibliographical references and index.
Identifiers: LCCN 2019023895 (print) | LCCN 2019023896 (ebook) | ISBN
9781119506317 (cloth) | ISBN 9781119506065 (adobe pdf ) | ISBN
9781119506058 (epub)
Subjects: LCSH: Condensed matter–Optical properties. | Materials–Optical
properties. | Electrooptics–Materials.
Classification: LCC QC173.458.O66 O68 2020 (print) | LCC QC173.458.O66
(ebook) | DDC 530.4/12–dc23
LC record available at https://lccn.loc.gov/2019023895
LC ebook record available at https://lccn.loc.gov/2019023896
Cover Design: Wiley
Cover Images: © mitchFOTO / Shutterstock
Set in 10/12pt WarnockPro by SPi Global, Chennai, India
10 9 8 7 6 5 4 3 2 1
v
Contents
List of Contributors xv
Series Preface xvii
Preface xix
1 Fundamental Optical Properties of Materials I 1

S.O. Kasap, W.C. Tan, Jai Singh, and Asim K. Ray
1.1 Introduction 1
1.2 Optical Constants n and K 2
1.2.1 Refractive Index and Extinction Coefficient 2
1.2.2 n and K, and Kramers–Kronig Relations 5
1.3 Refractive Index and Dispersion 7
1.3.1 Cauchy Dispersion Relation 7
1.3.2 Sellmeier Equation 8
1.3.3 Refractive Index of Semiconductors 10
1.3.3.1 Refractive Index of Crystalline Semiconductors 10
1.3.3.2 Bandgap and Temperature Dependence 11
1.3.4 Refractive Index of Glasses 11
1.3.5 Wemple–DiDomenico Dispersion Relation 14
1.3.6 Group Index 15
1.4 The Swanepoel Technique: Measurement of n and 𝛼 for Thin Films
on Substrates 16
1.4.1 Uniform Thickness Films 16
1.4.2 Thin Films with Non-uniform Thickness 22
1.5 Transmittance and Reflectance of a Partially Transparent Plate 25
1.6 Optical Properties and Diffuse Reflection: Schuster–Kubelka–Munk
Theory 27
1.7 Conclusions 31
Acknowledgments 31
References 32
2 Fundamental Optical Properties of Materials II 37

S.O. Kasap, K. Koughia, Jai Singh, Harry E. Ruda, and Asim K. Ray
2.1 Introduction 37
2.2 Lattice or Reststrahlen Absorption and Infrared Reflection 40
2.3 Free Carrier Absorption (FCA) 42
vi Contents
2.4 Band-to-Band or Fundamental Absorption (Crystalline Solids) 45

2.5 Impurity Absorption and Rare-Earth Ions 48
2.6 Effect of External Fields 54
2.6.1 Electro-Optic Effects 54
2.6.2 Electro-Absorption and Franz–Keldysh Effect 55
2.6.3 Faraday Effect 56
2.7 Effective Medium Approximations 58
2.8 Conclusions 61
Acknowledgments 61
References 62
3 Optical Properties of Disordered Condensed Matter 67

Koichi Shimakawa, Jai Singh, and S.K. O’Leary
3.1 Introduction 67
3.2 Fundamental Optical Absorption (Experimental) 69
3.2.1 Amorphous Chalcogenides 69
3.2.2 Hydrogenated Nano-Crystalline Silicon (nc-Si:H) 72
3.3 Absorption Coefficient (Theory) 74
3.4 Compositional Variation of the Optical Bandgap 79
3.4.1 In Amorphous Chalcogenides 79
3.5 Conclusions 80
References 80
4 Optical Properties of Glasses 83

Andrew Edgar
4.1 Introduction 83
4.2 The Refractive Index 84
4.3 Glass Interfaces 86
4.4 Dispersion 88
4.5 Sensitivity of the Refractive Index 90
4.5.1 Temperature Dependence 90
4.5.2 Stress Dependence 91
4.5.3 Magnetic Field Dependence—The Faraday Effect 92
4.5.4 Chemical Perturbations—Molar Refractivity 94
4.6 Glass Color 95
4.6.1 Coloration by Colloidal Metals and Semiconductors 95
4.6.2 Optical Absorption in Rare-Earth-Doped Glass 96
4.6.3 Absorption by 3d Metal Ions 99
4.7 Fluorescence in Rare-Earth-Doped Glass 102
4.8 Glasses for Fiber Optics 104
4.9 Refractive Index Engineering 106
4.10 Glass and Glass–Fiber Lasers and Amplifiers 109
4.11 Valence Change Glasses 111
4.12 Transparent Glass Ceramics 114
4.12.1 Introduction 114
4.12.2 Theoretical Basis for Transparency 116
Contents vii
4.12.3 Rare-Earth-Doped Transparent Glass Ceramics for Active

Photonics 120
4.12.4 Ferroelectric Transparent Glass Ceramics 121
4.12.5 Transparent Glass Ceramics for X-ray Storage Phosphors 121
4.13 Conclusions 124
References 124
5 Concept of Excitons 129

Jai Singh, Harry E. Ruda, M.R. Narayan, and D. Ompong
5.1 Introduction 129
5.2 Excitons in Crystalline Solids 130
5.2.1 Excitonic Absorption in Crystalline Solids 133
5.3 Excitons in Amorphous Semiconductors 135
5.3.1 Excitonic Absorption in Amorphous Solids 137
5.4 Excitons in Organic Semiconductors 139
5.4.1 Photoexcitation and Formation of Excitons 140
5.4.1.1 Photoexcitation of Singlet Excitons Due to
Exciton–Photon Interaction 141
5.4.1.2 Excitation of Triplet Excitons 142
5.4.2 Exciton Up-Conversion 147
5.4.3 Exciton Dissociation 148
5.4.3.1 Conversion from Frenkel to CT Excitons 151
5.4.3.2 Dissociation of CT Excitons 152
5.5 Conclusions 153
References 154
6 Photoluminescence 157
Takeshi Aoki
6.2 Fundamental Aspects of Photoluminescence (PL) in Materials 158
6.2.1 Intrinsic Photoluminescence 159
6.2.2 Extrinsic Photoluminescence 160
6.2.3 Up-Conversion Photoluminescence (UCPL) 162
6.2.4 Other Related Optical Transitions 163
6.3 Experimental Aspects 164
6.3.1 Static PL Spectroscopy 164
6.3.2 Photoluminescence Excitation Spectroscopy (PLE) and
Photoluminescence Absorption Spectroscopy (PLAS) 167
6.3.3 Time Resolved Spectroscopy (TRS) 168
6.3.4 Time-Correlated Single Photon Counting (TCSPC) 171
6.3.5 Frequency-Resolved Spectroscopy (FRS) 172
6.3.6 Quadrature Frequency Resolved Spectroscopy (QFRS) 173
6.4 Photoluminescence Lifetime Spectroscopy of Amorphous
Semiconductors by QFRS Technique 175
6.4.1 Overview 175
6.4.2 Dual-Phase Double Lock-in (DPDL) QFRS Technique 176
viii Contents
6.4.3 Exploring Broad PL Lifetime Distribution in a-Si:H by

Wideband QFRS 178
6.4.3.1 Effects of Excitation Intensity, Excitation, and
Emission Energies 179
6.4.3.2 Temperature Dependence 184
6.4.3.3 Effect of Electric and Magnetic Fields 185
6.4.4 Residual PL Decay of a-Si:H 189
6.5 QFRS on Up-Conversion Photoluminescence (UCPL) of RE-Doped
Materials 192
6.6 Conclusions 197
Acknowledgments 198
References 198
7 Photoluminescence, Photoinduced Changes, and Electroluminescence in

Noncrystalline Semiconductors 203
Jai Singh
7.2 Photoluminescence 205
7.2.1 Radiative Recombination Operator and Transition Matrix
Element 206
7.2.2 Rates of Spontaneous Emission 211
7.2.2.1 At Nonthermal Equilibrium 212
7.2.2.2 At Thermal Equilibrium 214
7.2.2.3 Determining E0 215
7.2.3 Results of Spontaneous Emission and Radiative Lifetime 216
7.2.4 Temperature Dependence of PL 222
7.2.5 Excitonic Concept 223
7.3 Photoinduced Changes in Amorphous Chalcogenides 225
7.3.1 Effect of Photo-Excitation and Phonon Interaction 226
7.3.2 Excitation of a Single Electron–Hole Pair 228
7.3.3 Pairing of Like Excited Charge Carriers 229
7.4 Radiative Recombination of Excitons in Organic Semiconductors 232
7.4.1 Rate of Fluorescence 233
7.4.2 Rate of Phosphorescence 233
7.4.3 Organic Light Emitting Diodes (OLEDs) 234
7.4.3.1 Second- and Third-Generation OLEDs: TADF 235
7.5 Conclusions 236
Acknowledgments 236
References 237
8 Photoinduced Bond Breaking and Volume Change in Chalcogenide Glasses 241

Sandor Kugler, Rozália Lukács, and Koichi Shimakawa
8.2 Atomic-Scale Computer Simulations of Photoinduced Volume
Changes 243
8.3 Effect of Illumination 244
8.4 Kinetics of Volume Change 245
Contents ix
8.4.1 a-Se 245

8.4.2 a-As2 Se3 246
8.5 Additional Remarks 248
8.6 Conclusions 249
References 249
9 Properties and Applications of Photonic Crystals 251

Harry E. Ruda and Naomi Matsuura
9.2 PC Overview 252
9.2.1 Introduction to PCs 252
9.2.2 Nanoengineering of PC Architectures 253
9.2.3 Materials Selection for PCs 255
9.3 Tunable PCs 255
9.3.1 Tuning PC Response by Changing the Refractive Index of
Constituent Materials 256
9.3.1.1 PC Refractive Index Tuning Using Light 256
9.3.1.2 PC Refractive Index Tuning Using an Applied
Electric Field 256
9.3.1.3 Refractive Index Tuning of Infiltrated PCs 257
9.3.1.4 PC Refractive Index Tuning by Altering the
Concentration of Free Carriers (Using Electric
Field or Temperature) in Semiconductor-Based PCs 257
9.3.2 Tuning PC Response by Altering the Physical Structure
of the PC 258
9.3.2.1 Tuning PC Response Using Temperature 258
9.3.2.2 Tuning PC Response Using Magnetism 258
9.3.2.3 Tuning PC Response Using Strain 258
9.3.2.4 Tuning PC Response Using Piezoelectric Effects 259
9.3.2.5 Tuning PC Response Using MEMS Actuation 260
9.4 Selected Applications of PC 260
9.4.1 Waveguide Devices 261
9.4.2 Dispersive Devices 262
9.4.3 Add/Drop Multiplexing Devices 262
9.4.4 Applications of PCs for Light-Emitting Diodes (LEDs) and
Lasers 263
9.5 Conclusions 265
Acknowledgments 265
References 265
10 Nonlinear Optical Properties of Photonic Glasses 269

Keiji Tanaka
10.2 Photonic Glass 271
10.3 Nonlinear Absorption and Refractivity 272
10.3.1 Fundamentals 272
10.3.2 Two-Photon Absorption 275
x Contents
10.3.3 Nonlinear Refractivity 278

10.4 Nonlinear Excitation-Induced Structural Changes 280
10.4.1 Fundamentals 280
10.4.2 Oxides 281
10.4.3 Chalcogenides 283
10.A Addendum: Perspectives on Optical Devices 286
References 288
11 Optical Properties of Organic Semiconductors 295

Takashi Kobayashi and Hiroyoshi Naito
11.2 Molecular Structure of π-Conjugated Polymers 296
11.3 Theoretical Models 298
11.4 Absorption Spectrum 300
11.5 Photoluminescence 304
11.6 Non-Emissive Excited States 306
11.7 Electron–Electron Interaction 309
11.8 Interchain Interaction 314
References 321
12 Organic Semiconductors and Applications 323

Furong Zhu
12.1.1 Device Architecture and Operation Principle 324
12.1.2 Technical Challenges and Process Integration 325
12.2 Anode Modification for Enhanced OLED Performance 327
12.2.1 Low-Temperature High-Performance ITO 327
12.2.1.1 Experimental Methods 328
12.2.1.2 Morphological Properties 329
12.2.1.3 Electrical Properties 331
12.2.1.4 Optical Properties 333
12.2.1.5 Compositional Analysis 336
12.2.2 Anode Modification 339
12.2.3 Electroluminescence Performance of OLEDs 340
12.3 Flexible OLEDs 345
12.3.1 Flexible OLEDs on Ultrathin Glass Substrate 346
12.3.2 Flexible Top-Emitting OLEDs on Plastic Foils 347
12.3.2.1 Top-Emitting OLEDs 348
12.3.2.2 Flexible TOLEDs on Plastic Foils 350
12.4 Solution-Processable High-Performing OLEDs 353
12.4.1 Performance of OLEDs with a Hybrid MoO3 -PEDOT:PSS
Hole Injection Layer (HIL) 353
12.4.2 Morphological Properties of the MoO3 -PEDOT:PSS HIL 361
Contents xi
12.4.3 Surface Electronic Properties of MoO3 -PEDOT:PSS HIL 363

References 369
13 Transparent White OLEDs 373

Choi Wing Hong and Furong Zhu
13.1 Introduction—Progress in Transparent WOLEDs 373
13.2 Performance of WOLEDs 374
13.2.1 Optimization of Dichromatic WOLEDs 374
13.2.2 J-L-V Characteristics of WOLEDs 377
13.2.3 Electron-Hole Current Balance in Transparent WOLEDs 384
13.3 Emission Behavior of Transparent WOLEDs 386
13.3.1 Visible-Light Transparency of WOLEDs 386
13.3.2 L-J Characteristics of Transparent WOLEDs 390
13.3.3 Angular-Dependent Color Stability of Transparent WOLEDs 395
References 400
14 Optical Properties of Thin Films 403

V.-V. Truong, S. Tanemura, A. Haché, and L. Miao
14.2 Optics of Thin Films 404
14.2.1 An Isotropic Film on a Substrate 404
14.2.2 Matrix Methods for Multi-Layered Structures 406
14.2.3 Anisotropic Films 407
14.3 Reflection-Transmission Photoellipsometry for Determination of
Optical Constants 408
14.3.1 Photoellipsometry of a Thick or a Thin Film 408
14.3.2 Photoellipsometry for a Stack of Thick and Thin Films 410
14.3.3 Remarks on the Reflection-Transmission Photoellipsometry
Method 412
14.4 Application of Thin Films to Energy Management and
Renewable-Energy Technologies 412
14.4.1 Electrochromic Thin Films 413
14.4.2 Pure and Metal-Doped VO2 Thermochromic Thin Films 414
14.4.3 Temperature-Stabilized V1-x Wx O2 Sky Radiator Films 417
14.4.4 Optical Functional TiO2 Thin Film for Environmentally
Friendly Technologies 420
14.5 Application of Tunable Thin Films to Phase and Polarization
Modulation 424
References 430
15 Optical Characterization of Materials by Spectroscopic Ellipsometry 435

J. Mistrík
15.2 Notions of Light Polarization 436
xii Contents
15.3 Measureable Quantities 438

15.4 Instrumentation 441
15.5 Single Interface 442
15.6 Single Layer 448
15.7 Multilayer 454
15.8 Linear Grating 458
Acknowledgments 463
References 463
16 Excitonic Processes in Quantum Wells 465

Jai Singh and I.-K. Oh
16.2 Exciton–Phonon Interaction 466
16.3 Exciton Formation in QWs Assisted by Phonons 467
16.4 Nonradiative Relaxation of Free Excitons 474
16.4.1 Intraband Processes 475
16.4.2 Interband Processes 479
16.5 Quasi-2D Free-Exciton Linewidth 485
16.6 Localization of Free Excitons 491
References 500
17 Optoelectronic Properties and Applications of Quantum Dots 503

Jørn M. Hvam
17.2 Epitaxial Growth and Structure of Quantum Dots 504
17.2.1 Self-Assembled Quantum Dots 504
17.2.2 Site-Controlled Growth on Patterned Substrates 505
17.2.3 Natural or Interface Quantum Dots 506
17.2.4 Quantum Dots in Nanowires 507
17.3 Excitons in Quantum Dots 508
17.3.1 Quantum-Dot Bandgap 509
17.3.2 Optical Transitions 510
17.4 Optical Properties 513
17.4.1 Radiative Lifetime, Oscillator Strength, and Internal
Quantum Efficiency 514
17.4.2 Linewidth, Coherence, and Dephasing 516
17.4.3 Transient Four-Wave Mixing 517
17.5 Quantum Dot Applications 520
17.5.1 Quantum Dot Lasers and Optical Amplifiers 520
17.5.1.1 Gain Dynamics 522
17.5.1.2 Homogeneous Broadening and Dephasing 524
17.5.1.3 Long-Wavelength Lasers 526
17.5.1.4 Nano Lasers 527
17.5.2 Single-Photon Emitters 527
17.5.2.1 Micropillars and Nanowires 530
Contents xiii
17.5.2.2 Photonic Crystal Waveguide 531

Acknowledgments 534
References 534
18 Perovskites – Revisiting the Venerable ABX3 Family with Organic

Flexibility and New Applications 537
Junwei Xu, D.L. Carroll, K. Biswas, F. Moretti, S. Gridin, and R.T. Williams
18.1.1 Review 537
18.1.2 The Structures 538
18.1.2.1 Simple Cubic Frameworks 538
18.1.2.2 The Multiplicity of Hybrids 539
18.1.2.3 Structural Variation 540
18.2 Hybrid Perovskites in Photovoltaics 544
18.2.1 Review 544
18.2.2 The Phenomena Characterized as “Defect Tolerance” 548
18.3 Light-Emitting Diodes Using Solution-Processed Lead Halide
Perovskites 549
18.3.1 Review 549
18.3.2 Construction and Characterization of LEDs Utilizing
CsPbBr3 Nano-Inclusions in Cs4 PbBr6 as the
Electroluminescent Medium 553
18.4 Ionizing Radiation Detectors Using Lead Halide Perovskite
Materials: Basics, Progress, and Prospects 562
Acknowledgments 583
References 583
19 Optical Properties and Spin Dynamics of Diluted Magnetic Semiconductor

Nanostructures 589
Akihiro Murayama and Yasuo Oka
19.2 Quantum Wells 591
19.2.1 Spin Injection 591
19.2.2 Study of Spin Dynamics by Pump-Probe Spectroscopy 594
19.3 Fabrication of Nanostructures by Electron-Beam Lithography 596
19.4 Self-Assembled Quantum Dots 599
19.5 Hybrid Nanostructures with Ferromagnetic Materials 604
Acknowledgments 608
References 609
xiv Contents
20 Kinetics of the Persistent Photoconductivity in Crystalline III-V

Semiconductors 611
Ruben Jeronimo Freitas and Koichi Shimakawa
20.2 A Review of PPC in III-V Semiconductors 613
20.3 Key Physical Terms Related to PPC 615
20.3.1 Dispersive Reaction 615
20.3.2 SEF and Power Law 616
20.3.3 Waiting Time Distribution 617
20.4 Kinetics of PPC in III-V Semiconductors 617
Acknowledgments 623
20.A On the Reaction Rate Under the Uniform Distribution 623
References 625
Index 627
xv
List of Contributors
Takeshi Aoki Joint Research Center of High-technology, Department of Electronics and

Information Technology, Tokyo Polytechnic University, Atsugi, Japan
K. Biswas Department of Chemistry and Physics, Arkansas State University, Jonesboro,
USA
D.L. Carroll Department of Physics and Nanotechnology Center, Wake Forest University,
Winston-Salem, North Carolina, USA
Andrew Edgar School of Chemical and Physical Sciences, Victoria University of
Wellington, New Zealand
Ruben Jeronimo Freitas Department of Electrical and Electronic Engineering, National
University of Timor Lorosae, Díli, East Timor
S. Gridin Department of Physics and Nanotechnology Center, Wake Forest University,
A. Haché Département de physique et d’astronomie, Université de Moncton, New
Brunswick, Canada
Jørn M. Hvam Department of Photonics Engineering, Technical University of Denmark,
Kongens Lyngby, Denmark
S.O. Kasap Department of Electrical and Computer Engineering, University of
Saskatchewan, Saskatoon, Canada
Takashi Kobayashi Department of Physics and Electronics, Osaka Prefecture University,
Sakai, Japan
K. Koughia Department of Electrical and Computer Engineering, University of
Saskatchewan, Saskatoon, Canada
Sandor Kugler Department of Theoretical Physics, Budapest University of Technology
and Economics, Hungary
Rozália Lukács Norwegian University of Life Sciences, Ås, Akershus, Norway
Naomi Matsuura Centre for Nanotechnology, University of Toronto, Canada
L. Miao Guilin University of Electronic Technology, Guangxi, P.R. China
xvi List of Contributors
J. Mistrík Center of Materials and Nanotechnologies, Faculty of Chemical Technology,

University of Pardubice, Czech Republic
F. Moretti Lawrence Berkeley National Laboratory, Berkeley, California, USA
Akihiro Murayama Graduate School of Information Science and Technology, Hokkaido
University, Sapporo, Japan
Hiroyoshi Naito The Research Institute for Molecular Electronic Devices, Osaka
Prefecture University, Sakai, Japan
M.R. Narayan College of Engineering, Information Technology and Environment,
Charles Darwin University, Darwin, Australia
S.K. O’Leary School of Engineering, The University of British Columbia, Kelowna,
Canada
I.-K. Oh College of Engineering, Information Technology and Environment, Charles
Darwin University, Darwin, Australia
Yasuo Oka Institute of Multidisciplinary Research for Advanced Materials, Tohoku
University, Sendai, Miyagi, Japan
D. Ompong College of Engineering, Information Technology and Environment, Charles
Asim K. Ray Department of Electrical & Computer Engineering, Brunel University
London, Uxbridge, UK
Harry E. Ruda Centre for Nanotechnology and Electronic and Photonic Materials Group,
Department of Materials Science, University of Toronto, Ontario, Canada
Koichi Shimakawa Department of Electrical and Electronic Engineering, Gifu University,
Japan
Jai Singh College of Engineering, Information Technology and Environment, Charles
W.C. Tan Department of Electrical & Computer Engineering, National University of
Singapore, Kent Ridge, Singapore
Keiji Tanaka Department of Applied Physics, Graduate School of Engineering, Hokkaido
University, Sapporo, Japan
S. Tanemura Japan Fine Ceramics Centre, Mutsuno, Atsuta-ku, Nagoya, Japan
V.-V. Truong Physics Department, Concordia University, Montreal, Quebec, Canada
R.T. Williams Department of Physics and Nanotechnology Center, Wake Forest
University, Winston-Salem, North Carolina, USA
Choi Wing Hong, Department of Physics, Hong Kong Baptist University, Kowloon Tong,
China
Junwei Xu Department of Physics and Nanotechnology Center, Wake Forest University,
Furong Zhu Department of Physics, Hong Kong Baptist University, Kowloon Tong, China
xvii
Series Preface
Wiley Series in Materials for Electronic and Optoelectronic

Applications
This book series is devoted to the rapidly developing class of materials used for elec-
tronic and optoelectronic applications. It is designed to provide much-needed infor-
mation on the fundamental scientific principles of these materials, together with how
these are employed in technological applications. These books are aimed at (postgradu-
ate) students, researchers, and technologists engaged in research, development, and the
study of materials in electronics and photonics, and at industrial scientists developing
new materials, devices, and circuits for the electronic, optoelectronic, and communica-
tions industries.
The development of new electronic and optoelectronic materials depends not only
on materials engineering at a practical level, but also on a clear understanding of the
properties of materials and the fundamental science behind these properties. It is the
properties of a material that eventually determine its usefulness in an application. The
series therefore also includes such titles as electrical conduction in solids, optical prop-
erties, thermal properties, and so on, all with applications and examples of materials in
electronics and optoelectronics. The characterization of materials is also covered within
the series as much as it is impossible to develop new materials without the proper char-
acterization of their structure and properties. Structure–property relationships have
always been fundamentally and intrinsically important to materials science and engi-
neering.
Materials science is well known for being one of the most interdisciplinary sciences.
It is the interdisciplinary aspect of materials science that has led to many exciting dis-
coveries, new materials, and new applications. It is not unusual to find scientists with
a chemical engineering background working on materials projects with applications in
electronics. In selecting titles for the series, we have tried to maintain the interdisci-
plinary aspect of the field, and hence its excitement to researchers in this field.
Arthur Willoughby
Peter Capper
Safa Kasap
xix
Preface
The second edition, being published more than 10 years after the first edition, presents
state-of-the-art developments in almost all topics related to the optical properties of
materials and their applications presented in the first edition. Since the publication of the
first edition in 2006, many advances have been made in fields such as the optical prop-
erties of materials, electroluminescence in organic light-emitting devices, organic solar
cells, opto-electronic devices, etc. It is hence very timely to update all the chapters in
the first edition by adding developments since 2006 to produce the second edition. This
second edition contains 15 of the original 16 chapters, all of which have been updated,
as well as 5 brand new chapters, contributed by very experienced and well-known sci-
entists and groups available on different aspects of the optical properties of materi-
als. The study of optical properties of materials has now become an interdisciplinary
field, and scientists of physical, chemical, and biological sciences; nanotechnology engi-
neers; and industry researchers have strong interests in this field. The field offers one of
the fastest-growing research platforms in material sciences. The second edition covers
many examples and applications in the field of electronic and optoelectronic properties
of materials, and in photonics. Most chapters are presented to be relatively indepen-
dent with minimal cross-referencing, and chapters with complementary contents are
arranged together to facilitate a reader with cross-referencing.
Books written in this field mostly follow one of the two pedagogies: chapters are either
based on (i) physical processes, or (ii) the various classes of materials. This book com-
bines the two approaches by first identifying the processes that should be described
in detail, and then introducing the relevant classes of materials. Many books also miss
the details of how various optical properties are measured. This book presents a com-
prehensive review of experimental techniques, including recent advances in ultrafast
(femtosecond) spectroscopy of materials. Not many books are currently available with
such a wide coverage of the field with clarity and levels of readership in a single volume
as this book.
In Chapters 1 and 2 by Kasap et al., the fundamental optical properties of materials
are reviewed, and as such these chapters are expected to refresh the readers with the
basics by providing useful optical relations. In Chapter 3, Shimakawa et al. present an
up-to-date review of the optical properties of disordered inorganic solids, and Chapter 4
by Edgar presents an extensive discussion on the optical properties of glasses. Chapter
5 by Singh and co-workers presents the concept of excitons in inorganic and organic
semiconductors, both crystalline and non-crystalline variants. In Chapter 6, Aoki has
presented a comprehensive review of the experimental advances in the techniques of
xx Preface
measuring photoluminescence together with updates in luminescence results in amor-

phous semiconductors, and Chapter 7 by Singh complements the theoretical advances
in the field of photoluminescence and photoinduced changes in non-crystalline semi-
conductors. In Chapter 8 by Kugler et al., recent advances in the simulation of pho-
toinduced bond breaking and volume changes in chalcogenide glasses are presented. In
Chapter 9, Ruda and Matsuura present a comprehensive review of the properties and
applications of photonic crystals. In Chapter 10, Tanaka has presented an up-to-date
review of the nonlinear optical properties of photonic glasses.
Chapter 11 by Kobayashi and Naito discusses the fundamental optical properties of
organic semiconductors. In Chapter 12, Zhu has presented a comprehensive review
of the applications of organic semiconductors, in particular, in developing organic
light-emitting diodes (OLEDs). In Chapter 13, Hong and Zhu have reviewed the recent
developments in the fabrication of transparent white light-emitting diodes (WOLEDs).
This is a new chapter added in the second edition. In Chapter 14, Truong and Tanemura
have presented an up-to-date review of the optical properties of thin films and their
applications, and Chapter 15 by Mistrik deals with the optical characterization of
materials by spectroscopic ellipsometry. This is the second new chapter in the second
edition. In Chapter 16, Singh and Oh have discussed the excitonic processes in quantum
wells. In Chapter 17, the third new chapter in this edition, Hvam has presented an
up-to-date comprehensive review of the optoelectronic properties and applications
of quantum dots. Chapter 18 by Xu et al. presents up-to-date developments in the
applications of perovskites. This is the fourth new chapter in the second edition.
In Chapter 19, Murayama and Oka have presented the optical properties and spin
dynamics of diluted magnetic semiconductor nanostructures. In the final Chapter 20,
the fifth new chapter in this edition, Freitas and Shimakawa have discussed the kinetics
of the persistent photoconductivity in Crystalline III–V semiconductors. Thus, the
addition of the five new chapters on transparent WOLELDs, ellipsometry, quantum
dots, perovskites, and persistent photoconductivity widens the scope of the second
edition to a new level. One of the chapters on the negative index of refraction in the
first edition has not been included in the second edition at the request of the authors.
The readership of the book is expected to be the senior undergraduate and post-
graduate students, and teaching and research professionals in the field. In conclusion, I
am very grateful to all the contributing authors of the second edition for their utmost
co-operation in meeting the deadlines, without which this project would not have con-
cluded. I also would like to acknowledge the technical support from Drs Stefanija Klaric
and Luis Herrera Diaz in preparing my chapters. I would also like to thank my friend
Beth Woof for her support throughout the course of preparation of this volume.
Darwin, Australia Jai Singh

1
Fundamental Optical Properties of Materials I

S.O. Kasap 1 , W.C. Tan 2 , Jai Singh 3 , and Asim K. Ray 4
1
Department of Electrical and Computer Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, Canada
2
Department of Electrical & Computer Engineering, National University of Singapore, Kent Ridge, Singapore
3
College of Engineering, IT and Environment, Purple 12, Charles Darwin University, Ellengowan Drive, Darwin, Australia
4 Department of Electrical & Computer Engineering, Brunel University London, Kingston Lane, Uxbridge, UK
CHAPTER MENU
Introduction, 1
Optical Constants n and K, 2
Refractive Index and Dispersion, 7
The Swanepoel Technique: Measurement of n and 𝛼 for Thin Films on Substrates, 16
Transmittance and Reflectance of a Partially Transparent Plate, 25
Optical Properties and Diffuse Reflection: Schuster–Kubelka–Munk Theory, 27
Conclusions, 31
References, 32
1.1 Introduction
Optical properties of a material change or affect the characteristics of light passing
through it by modifying its propagation vector or intensity. Two of the most important
optical parameters are the refractive index n and the extinction coefficient K, which are
generically called optical constants, although some authors include other optical coeffi-
cients within this terminology. The latter is related to the attenuation or absorption coef-
ficient 𝛼. In Part I, in this chapter, we present the complex refractive index, the frequency
or wavelength dependence of n and K, so-called dispersion relations, how n and K are
inter-related, and how n and K can be determined by studying the transmission as a
function of wavelength through a thin film of the material. Physical insights into n and K
are provided in Part II (Chapter 2). In addition, there has been a strong research inter-
est in characterizing the optical properties of inhomogeneous media, such as porous
media, in which both light absorption and scattering take place so that the reflectance
is not specular but diffuse. The latter problem is now included in this second edition.
The optical properties of various materials, with n and K being the most important,
are available in the literature in one form or another, either published in journals,
books, and handbooks, or posted on websites of various researchers, organizations
(e.g. NIST), or companies (e.g. Schott Glass). Nonetheless, the reader is referred to the
Optical Properties of Materials and Their Applications, Second Edition. Edited by Jai Singh.
© 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.
2 1 Fundamental Optical Properties of Materials I
works of Greenway and Harbeke [1], Wolfe [2], Klocek [3], Palik [4, 5], Ward [6],
Efimov [7], Palik and Ghosh [8], Nikogosyan [9], and Weaver and Frederikse [10]
for the optical properties of a wide range of materials. Adachi’s books on the optical
constants of semiconductors are highly recommended [11–13], along with Madelung’s
third edition of Semiconductors: Data Handbook [14]. There are, of course, other books
and handbooks that also contain optical constants in various chapters; see, for example,
references [15–20]. There are also various books that describe optical properties
of solids at the senior undergraduate and introductory graduate levels, such as those
by Tanner [21], Jimenez and Tomm [22], Stenzel [23], Fox [24], Simmons and Potter
[25], Toyozawa [26], Wooten [27], and Abeles [28], which are highly recommended.
A number of experimental techniques are available for measuring n and K, some
of which have been summarized by Simmons and Potter [25]. For example, ellipsom-
etry measures changes in the polarization of light incident on a sample to sensitively
characterize surfaces and thin films (see Chapter 23 in this volume). The interaction
of incident polarized light with the sample causes a polarization change in the light,
which may then be measured by analyzing the light reflected from the sample. Collins
has also provided an extensive in-depth review of ellipsometry for optical measure-
ments [29]. One of the most popular and convenient optical experiments involves a
monochromatic light passing through a thin sample, and measuring the transmitted
intensity as a function of wavelength, T(𝜆), using a simple spectrophotometer. For thin
samples on a thick transparent substrate, the transmission spectrum shows oscillations
in T(𝜆) with the wavelength due to interferences within the thin film. Swanepoel’s tech-
nique uses the T(𝜆) measurement to determine n and K, as described in Section 1.4.
1.2 Optical Constants n and K

One of the most important optical constants of a material is its refractive index, which in
general depends on the wavelength of the electromagnetic (EM) wave, through a rela-
tionship called dispersion. In materials where an EM wave loses its energy during its
propagation, the refractive index becomes complex. The real part is usually the refrac-
tive index, n, and the imaginary part is called the extinction coefficient, K. In this section,
the refractive index and extinction coefficient will be presented in detail, along with
some common dispersion relations. A more practical and a semiquantitative approach
is taken along the lines in [30] rather than a full dedication to rigor and mathematical
derivations. More analytical approaches can be found in other texts, such as [25, 26].
1.2.1 Refractive Index and Extinction Coefficient

The refractive index of an optical or dielectric medium, n, is the ratio of the velocity
of light c in vacuum to its velocity v in the medium; n = c/v. Using this and Maxwell’s
equations, one obtains
√ the well-known Maxwell’s formula for the refractive index of a
substance as n = 𝜀r 𝜇r , where 𝜀r is the static dielectric constant or relative permittiv-
ity and 𝜇r the relative magnetic
√ permeability of the medium. As 𝜇r = 1 for nonmagnetic
substances, one gets n = 𝜀r , which is very useful in relating the dielectric properties to
optical properties of materials at any particular frequency of interest. As 𝜀r depends on
the wavelength of light, the refractive index also depends on the wavelength of light, and
this dependence is called dispersion. In addition to dispersion, an EM wave propagating

through a lossy medium experiences attenuation, which means it loses its energy, due to
various loss mechanisms such as the generation of phonons (lattice waves), photogen-
eration, free carrier absorption, scattering, etc. In such materials, the refractive index
becomes a complex function of the frequency of the light wave. The complex refractive
index in this chapter is denoted by n*, with real part n, and imaginary part K, called the
extinction coefficient, is related to the complex relative permittivity, 𝜀r = 𝜀′r + i𝜀′′r , by,
√ √
n∗ = n + iK = 𝜀r = 𝜀′r + i𝜀′′r (1.1a)
where 𝜀′r and 𝜀′′r are, respectively, the real and imaginary parts of 𝜀r . Eq. (1.1a) gives:
n2 − K 2 = 𝜀′r and 2nK = 𝜀′′r . (1.1b)
In explicit terms, n and K can be obtained as
√
r + 𝜀r ) + 𝜀′r ]1∕2
′′2 1∕2
n = (1∕ 2)[(𝜀′2 (1.2a)
√
r + 𝜀r ) − 𝜀′r ]1∕2
′′2 1∕2
K = (1∕ 2)[(𝜀′2 (1.2b)
Some books (particularly in electrical engineering) use 𝜀r = 𝜀′r − i𝜀′′r and n* = n − iK
instead of 𝜀r = 𝜀′r + i𝜀′′r and n* = n + iK. The preference lies in what was assumed for the
propagating electric field, whether it is represented by expi(𝜔t − kx) or expi(kx − 𝜔t),
where k is the propagation constant. In a lossy medium, the imaginary part of√ n* must
lead to a traveling wave whose amplitude decays. Notice that, for 𝜀r ≪ 𝜀r , n = 𝜀′r and
′′ ′
K = 𝜀′′r ∕2n—that is, the refractive index is essentially determined by the real part of 𝜀r
and K is determined by the imaginary part of 𝜀r , which is known to represent losses in
a dielectric medium.
The extinction coefficient K represents loss from the energy carried by the propagat-
ing EM wave by conveniently including this loss as the imaginary part in the complex
refractive index. The optical attenuation coefficient 𝛼 gauges the rate of this loss from
the propagating EM wave. In the absence of scattering, the attenuation would be due
to absorption within the medium. For an EM wave that is propagating along x with an
intensity I, 𝛼 is defined by
dI
𝛼=− (1.3)
Idx
We can relate 𝛼 and K quite easily by taking a plane wave traveling along x for which
the electric field in the wave propagates as E = Eo expi(kx − 𝜔t), where Eo is a constant,
𝜔 is the angular frequency and k is the complex propagation constant in the medium,
related to n* by its definition k = n*𝜔/c = (n + iK)(𝜔/c). In free space k = k o = 𝜔/c = 2𝜋/𝜆,
where 𝜆 is the free space wavelength. We can substitute for n* and then use I is pro-
portional to |E|2 to find I ∝ exp[−2(𝜔/c)Kx)]—that is, I decays exponentially with the
distance propagated. We can substitute for I in (1.3) to find
2𝜔
𝛼= K (1.4)
c
The optical constants n and K can be determined by measuring the reflectance from
the surface of a material as a function of polarization and the angle of incidence. For
normal incidence, the reflection coefficient, r, is obtained as
1 − n∗ 1 − n − iK
r= = (1.5)
1 + n∗ 1 + n + iK
The reflectance R is then defined by:

| 1 − n − iK |2 (1 − n)2 + K 2
R = |r|2 = || | =
| . (1.6)
| 1 + n + iK | (1 + n)2 + K 2
Notice that whenever K is large, for example, over a range of wavelengths, the absorp-
tion is strong, and the reflectance is almost unity. The light is then reflected, and any
light in the medium is highly attenuated (typical sample calculations may be found in
[24, 30]).
Optical properties of materials are typically presented either by showing the frequency
dependences (dispersion relations) of n and K or 𝜀′r and 𝜀′′r . An intuitive guide to explain-
ing dispersion in insulators is based on a single oscillator model in which the electric
field in the light induces forced dipole oscillations in the material (displaces the electron
shells in an atom to oscillate about the positive nucleus) with a single resonant frequency
𝜔o . The frequency dependences of 𝜀′r and 𝜀′′r are then obtained as:
Nat ′ N
𝜀′r = 1 + 𝛼 and 𝜀′′r = 1 + at 𝛼e′′ , (1.7)
𝜀o e 𝜀o
where N at is the number of atoms per unit volume, 𝜀o is the vacuum permittivity, and
𝛼e′ and 𝛼e′′ are, respectively, the real and imaginary parts of the electronic polarizability,
given respectively by:
1 − (𝜔∕𝜔o )2
𝛼e′ = 𝛼eo (1.8a)
[1 − (𝜔∕𝜔o )2 ]2 + (𝛾∕𝜔o )2 (𝜔∕𝜔o )2
and
(𝛾∕𝜔o )(𝜔∕𝜔o )
𝛼e′′ = 𝛼eo (1.8b)
[1 − (𝜔∕𝜔o )2 ]2 + (𝛾∕𝜔o )2 (𝜔∕𝜔o )2
where 𝛼 eo is the DC polarizability corresponding to 𝜔 = 0 and 𝛾 is the loss coefficient that
characterizes the EM wave losses within the material system. Using Eqs. (1.1)–(1.2) and
(1.7)–(1.8), the frequency dependence of n and K can be studied. Figure 1.1a shows the
dependence of n and K on the normalized frequency 𝜔/𝜔o for a simple single electronic
dipole oscillator of resonance frequency 𝜔o .
(a) n, K Figure 1.1 Refractive index n and extinction
8 Complex refractive index coefficient K obtained from a single electronic
dipole oscillator model. (a) n and K versus
6 normalized frequency, and (b) reflectance
versus normalized frequency.
4 n γ/ωo = 0.1
2 K εDC1/2 = 3
K n
0 ω/ωo
0 1 2 3
(b) R
1 Reflectance
0.5
0 ω/ωo
0 1 2 3
It is seen from Figure 1.1 that √ n and K peak close to 𝜔 = 𝜔o . If a material has a 𝜀′′r
≫ 𝜀r , then 𝜀r ≈ i𝜀r , and n ≈ K ≈ 𝜀′′r ∕2 is obtained from Eq. (1.1b). Figure 1.1b shows
′ ′′
the dependence of the reflectance R on the frequency. It is observed that R reaches its
maximum value at a frequency slightly above 𝜔 = 𝜔o , and then remains high until 𝜔
reaches nearly 3𝜔o ; thus, the reflectance is substantial while absorption is strong. The
normal dispersion region is the frequency range below 𝜔o , where n falls as the frequency
decreases; that is, n decreases as the wavelength 𝜆 increases. Anomalous dispersion
region is the frequency range above 𝜔o where n decreases as 𝜔 increases. Below 𝜔o ,
K is small and, if 𝜀DC is 𝜀r (0), the DC permittivity, then
𝜔2o
n2 ≈ 1 + (𝜀DC − 1) ; 𝜔 < 𝜔o . (1.9)
𝜔2o − 𝜔2
Since, 𝜆 = 2𝜋c/𝜔, defining 𝜆o = 2𝜋c/𝜔o as the resonance wavelength, one gets:
𝜆2
n2 ≈ 1 + (𝜀DC − 1) ; 𝜆 > 𝜆o . (1.10)
𝜆2
− 𝜆2o
While intuitively useful, the dispersion relations in Eq. (1.8) are far too simple. More
rigorously, we have to consider the dipole oscillator quantum mechanically, which
means a photon excites the oscillator to a higher energy level—see, for example, Fox [24]
or Simmons and Potter [25]. The result is that we would have a series of 𝜆2 /(𝜆2 − 𝜆i 2 )
terms with various weighting factors Ai that add to unity, where 𝜆i represent different
resonance wavelengths. The weighting factors Ai involve quantum mechanical matrix
elements.
Figure 1.2 shows the complex relative permittivity and the complex refractive index
of crystalline silicon in terms of photon energy h𝜈 [31, 32]. For photon energies below
the bandgap energy (1.1 eV), both 𝜀′′r and K are negligible and n is close to 3.7. Both 𝜀′′r
and K increase and change strongly as the photon energy becomes greater than 3 eV,
far beyond the bandgap energy. Notice that both 𝜀′′r and K peak at h𝜈 ≈ 3.5 eV, which
corresponds to a direct photoexcitation processes, electrons excited directly from the
valence band to the conduction band, as discussed in Chapter 2.
1.2.2 n and K, and Kramers–Kronig Relations

If we know the frequency dependence of the real part, 𝜀′r , of the relative permittivity of a
material, we can, using the Kramers–Kronig relations between the real and the imaginary
parts, determine the frequency dependence of the imaginary part 𝜀′′r , and vice versa.
The transform requires that we know the frequency dependence of either the real or
imaginary part over as wide a range of frequencies as possible, ideally from zero (DC)
to infinity, and that the material has linear behavior, that is, it has a relative permittivity
that is independent of the applied field. The Kramers–Kronig relations for the relative
permittivity 𝜀r = 𝜀′r + i𝜀′′r are given by [33–35] (see also Appendix 1C in [25] as well
as [27])
2
∞
𝜔′ 𝜀′′ r (𝜔′ ) ′
𝜀′r (𝜔) = 1 + P d𝜔 (1.11a)
𝜋 ∫ 0 𝜔′ 2 − 𝜔2
and
2𝜔
∞
𝜀′r (𝜔′ ) − 1
𝜀′′r (𝜔) = − P d𝜔′ (1.11b)
𝜋 ∫0 𝜔′ 2 − 𝜔2
50
40
8
ε r″
30 7
Real Imaginary
6
20 Real
εr′
5
10 4 n
εr″ Imaginary
0 3
εr′ 2 K
–10 K n
1
–20 0
1.5 2 3 4 5 6 0 2 4 6 8 10
Photon energy (ћω) Photon energy (ћω)
(a) (b)
Figure 1.2 (a) Complex relative permittivity of a silicon crystal as a function of photon energy plotted
in terms of real (𝜀′r ) and imaginary (𝜀′′r ) parts. (b) Optical properties of a silicon crystal vs. photon
energy in terms of real (n) and imaginary (K) parts of the complex refractive index. Source: Adapted
from D. E. Aspnes and A. A. Studna, 1983 [32] and H.R. Philipp and E.A. Taft, 1960 [31].
where 𝜔′ is the integration variable, P represents the Cauchy principal value of the inte-
gral, and the singularity at 𝜔 = 𝜔′ is avoided.
Similarly, one can relate the real and imaginary parts of the polarizability, 𝛼 ′ (𝜔) and
𝛼 (𝜔), and those of the complex refractive index, n(𝜔) and K(𝜔), as well. For a complex
′′
refractive index written as n* = n(𝜔) + iK(𝜔),

2
∞
𝜔′ K(𝜔′ ) ′ 2
∞
n(𝜔′ ) − 1 ′
n(𝜔) = 1 + P d𝜔 and K(𝜔) = − P d𝜔 (1.12)
𝜋 ∫0 𝜔 −𝜔
′ 2 2 𝜋 ∫ 0 𝜔′ 2 − 𝜔2
Although it appears, in theory, that one needs to integrate the spectrum of n or K from
DC to infinite frequencies, this is obviously not feasible, and is unnecessary. It should
be noted that the experimental setup usually has low- and high-frequency limitations
that truncate the preceding integrations. Moreover, in many cases, we are interested in
the spectrum of n and K in and around an absorption band. Thus, before and after the
absorption frequency range, K would be negligibly small, and we can use this absorption
frequency range in the preceding integrals in Eq. (1.12). There are numerous studies in
the literature that use the preceding Kramers–Kronig relations in extracting the wave-
length dependence of n from that of K, and vice versa, especially around clear absorption
bands; a few selected examples can be found in [36–40], and there are many others in the
literature. There are also several useful approaches in which the absorption spectrum,
or K(𝜔), is described in terms of a particular physical model with a particular expres-
sion, and the corresponding refractive index n(𝜔) is derived from the Kramers–Kronig
transformation for both amorphous and crystalline solids—for examples, see [41, 42].
It should be emphasized that the optical constants n and K have to obey what are
called f-sum rules [43]. For example, the integration of [n(𝜔) – 1] over all frequencies
must be zero, and the integration of 𝜔K(𝜔) over all frequencies gives (𝜋/2)𝜔p 2 , where
𝜔p = ℏ(4𝜋NZe2 /me )1/2 is the free electron plasma frequency in which N is the atomic
concentration, Z is the total number of electrons per atom, and e and me are the charge
and mass of the electron, respectively. The f -sum rules provide a consistency check and
enable various constants to be interrelated.
1.3 Refractive Index and Dispersion

There are several popular models describing the spectral dependence of refractive index
n in a material. Most of these are described in the following text, although some, such
as the infrared refractive index, is covered in the discussion on Reststrahlen absorption
in Part II, since it is closely related to the coupling of the EM wave to lattice vibrations.
The most popular dispersion relation in optical materials is probably the Sellmeier rela-
tionship, since one can sum any number of resonance-type terms to get as wide a range
of wavelength dependence as possible. However, its main drawback is that it does not
accurately represent the refractive index when there is a contribution arising from free
carriers in narrow bandgap or doped semiconductors.
There are many handbooks, books, and websites that now provide empirical equations
for the refractive index of a wide range of solids, for example as in references [1–19, 44].
1.3.1 Cauchy Dispersion Relation

In the Cauchy relationship, the dispersion relationship between the refractive index (n)
and the wavelength of light (𝜆) is commonly stated in the following form:
B C
n=A+ + 4 (1.13)
𝜆 2 𝜆
where A, B, and C are material-dependent specific constants. Equation (1.13) is known
as Cauchy’s formula; it is typically used in the visible spectrum region for various optical
glasses, and it applies to normal dispersion, when n decreases with increasing 𝜆 [45, 46].
The third term is sometimes dropped for a simpler representation of n versus 𝜆 behavior.
The original expression was a series in terms of the wavelength, 𝜆, or frequency, 𝜔, or
photon energy ℏ𝜔 of light as:
n = a0 + a2 𝜆−2 + a4 𝜆−4 + a6 𝜆−6 + … 𝜆 > 𝜆th , (1.14a)
or
n = n0 + n2 (ℏ𝜔)2 + n4 (ℏ𝜔)4 + n6 (ℏ𝜔)6 + … ℏ𝜔 < ℏ𝜔th , (1.14b)
where ℏ𝜔 is the photon energy; ℏ𝜔th = hc/𝜆th is the optical excitation threshold (e.g.
bandgap energy); and a0 , a2 ,… and n0 , n2 ,… are constants. It has been found that a
Cauchy relation in the following form [47]:
n = n−2 (ℏ𝜔)−2 + n0 + n2 (ℏ𝜔)2 + n4 (ℏ𝜔)4 , (1.15)
can be used satisfactorily over a wide range of photon energies. The dispersion parame-
ters of Eq. (1.15) are listed in Table 1.1 for a few selected materials over specific photon
energy ranges.
Cauchy’s dispersion relations given in Eqs. (1.13)–(1.14) were originally called the
elastic ether theory of the refractive index. It has been widely used for many materials,
Table 1.1 Cauchy’s dispersion parameters of Eq. (1.15) for Ge, Si, and Diamond from [43].
Material ℏ𝝎(eV) Min ℏ𝝎(eV) Max n−2 (eV2 ) n0 n2 (eV−2 ) n4 (eV−4 )
Diamond 0.0500 5.4700 −1.07 × 10−5 2.378 0.00801 0.000104

Si 0.0020 1.08 −2.04 × 10−8 3.4189 0.0815 0.0125
−8
Ge 0.0020 0.75 −1.00 × 10 4.0030 0.220 0.140
although, in recent years, many researchers have preferred to use the Sellmeier equation,
described in the following text.
1.3.2 Sellmeier Equation

The Sellmeier equation [48] is an empirical relation between the refractive index n of
a substance and wavelength 𝜆 of light in the form of a series of single dipole oscillator
terms, each of which has the usual 𝜆2 /(𝜆2 − 𝜆i 2 ) dependence as in
A1 𝜆2 A2 𝜆2 A3 𝜆2
n2 = 1 + + + (1.16)
𝜆2 − 𝜆21 𝜆2 − 𝜆22 𝜆2 − 𝜆23
where A1 , A2 , A3 and 𝜆1 , 𝜆2 , and 𝜆3 are constants, called Sellmeier coefficients, which
are determined by fitting this expression to the experimental data. The actual Sellmeier
formula is more complicated. It has more terms of similar form, such as Ai 𝜆2 /(𝜆2 – 𝜆i 2 ),
where i = 4, 5, ..., but these can generally be neglected in representing n vs. 𝜆 behavior
over typical wavelengths of interest and by ensuring that the three terms included in
Eq. (1.16) correspond to the most important or relevant terms in the summation [49].
The Sellmeier coefficients for some materials, including pure Silica (SiO2 ) and 86.5 mol%
SiO2 –13.5 mol% GeO2 , are given in Table 1.2 as examples. A quantitative analysis of the
application of the Sellmeier dispersion relation to a range of materials, from glasses to
semiconductors, has been discussed by Tatian [49].
There are two methods for determining the refractive index of silica–germania
glass (SiO2 )1-x (GeO2 )x . The first is a simple, but approximate, linear interpolation of
the refractive index between known compositions, for example, n(x) − n(0.135) =
(x − 0.235)[n(0.135) − n(0)]/0.135, where n(x) is for (SiO2 )1−x (GeO2 )x ; n(0.135) is for
86.5 mol% SiO2 –13.5 mol% GeO2 ; and n(0) is for SiO2 . The second is an interpolation
for coefficients Ai and 𝜆i between SiO2 and GeO2 as [50]:
{A1 (S) + X[A1 (G) − A1 (S)]}𝜆2
n2 − 1 = + …, (1.17)
𝜆2 − {𝜆1 (S) + X[𝜆1 (G) − 𝜆1 (S)]}𝜆21
where S and G in parentheses refer to silica and germania, respectively. The theoreti-
cal basis of the Sellmeier equation lies in representing the solid as a sum of N lossless
(frictionless) Lorentz oscillators such that each has the usual form of 𝜆2 /(𝜆2 – 𝜆i 2 ) with
different 𝜆i and each has a different strength, or weighting factor; Ai , i = 1 to N [51, 52].
Such dispersion relationships are essential in designing photonic devices such as waveg-
uides. (Note that although Ai weighs different Lorentz contributions, they do not sum to
1 since they include other parameters besides the oscillator strength f i .) The refractive
indices of most optical glasses have been extensively modeled by the Sellmeier equation.
Table 1.2 Sellmeier coefficients of a few materials, where 𝜆1 , 𝜆2 , 𝜆3 are in μm.
Material A1 A2 A3 𝝀1 𝝀2 𝝀3
SiO2 (fused silica) 0.696749 0.408218 0.890815 0.0690660 0.115662 9.900559

86.5% SiO2 –13.5% 0.711040 0.451885 0.704048 0.0642700 0.129408 9.425478
GeO2
GeO2 0.80686642 0.71815848 0.85416831 0.068972606 0.15396605 11.841931
Barium fluoride 0.3356 0.506762 3.8261 0.057789 0.109681 46.38642
Sapphire 1.023798 1.058264 5.280792 0.0614482 0.110700 17.92656
Diamond 0.3306 4.3356 0.175 0.106
Quartz, no 1.35400 0.010 0.9994 0.092612 10.700 9.8500
Quartz, ne 1.38100 0.0100 0.9992 0.093505 11.310 9.5280
KTP, no 1.2540 0.0100 0.0992 0.09646 6.9777 5.9848
KTP, ne 1.13000 0.0001 0.9999 0.09351 7.6710 12.170
Source: From various sources.
Various optical glass manufacturers such as Schott Glass normally provide the Sellmeier
coefficients for their glasses [53]. The optical dispersion relations for glasses have been
discussed by a number of authors [7, 25, 54].
There are other Sellmeier–Cauchy-like dispersion relationships that inherently take
account of various contributions to the optical properties, such as the electronic and
ionic polarization and the interaction of photons with free electrons. For example, for
many semiconductors and ionic crystals, two useful dispersion relations are,
B𝜆2 D𝜆2
n2 = A + + 2 , (1.18)
𝜆2−C 𝜆 −E
and
B C
n2 = A + + + D𝜆2 + E𝜆4 , (1.19)
𝜆2 − 𝜆o (𝜆 − 𝜆2o )2
2 2
where A, B, C, D, E, and 𝜆o are constants particular to a given material. Eq. (1.18) is

equivalent to the Sellmeier equation. Eq. (1.19) is known as the Herzberger dispersion
relation [52]. Table 1.3 provides a few examples. Both Cauchy and Sellmeier equations
are strictly applicable in wavelength regions where the material is transparent, that is,
the extinction coefficient is relatively small. The refractive index dispersion relations
Table 1.3 Parameters of Eq. (1.19) for some selected materials.
Material 𝝀o (𝛍m) A B (𝛍m)2 C (𝛍m)4 D (𝛍m)−2 E (𝛍m)−4
Silicon 0.028 3.41983 0.159906 −0.123109 1.269 × 10−6 −1.951 × 10−9

−2
MgO 0.11951 2.95636 0.021958 0 −1.0624 × 10 −2.05 × 10−5
−5 −3
LiF 0.16733 1.38761 0.001796 −4.1 × 10 −2.3045 × 10 −5.57 × 10−6
−4
AgCl 0.21413 4.00804 0.079009 0 −8.5111 × 10 −1.976 × 10−7
Source: Si data from D.F. Edwards and E. Ochoa, Appl. Optics 19, 4130 (1980), others from W. L. Wolfe, The
Handbook of Optics, W.G. Driscoll and W. Vaughan, McGraw-Hill, New York, 1978.
for a wide range of semiconductors have been compiled by Madelung in [14]. There
are many application-based articles in the literature that provide empirical dispersion
relations for a variety of materials; a recent example on far infrared substrates (Ge, Si,
ZnSe, ZnS, ZnTe) is given in reference [55]. There are both websites and various journal
articles in the literature that give the refractive index of numerous materials as a function
of wavelength.
1.3.3 Refractive Index of Semiconductors

1.3.3.1 Refractive Index of Crystalline Semiconductors
A particular interest in the case of semiconductors is in n and K for photon ener-
gies greater than the bandgap Eg for optoelectronics applications. Due to various
features and singularities in the E-k diagrams of crystalline semiconductors, the
optical constants n and K for ℏ𝜔 > Eg are not readily expressible in simple terms.
Various authors, for example, Forouhi and Bloomer [42, 56] and Chen et al. [57], have
nonetheless provided useful and tractable expressions for modeling n and K in this
regime. In particular, Forouhi–Bloomer (FB) equations express n and K in terms of the
photon energy ℏ𝜔 in a consistent way that obey the Kramers–Kronig relations [42],
that is
∑
q
Ai (ℏ𝜔 − Eg )2 ∑
q
Boi (ℏ𝜔) + Coi
K= and n = n(∞) + , (1.20)
i=1
(ℏ𝜔)2 − Bi (ℏ𝜔) + Ci i=1
(ℏ𝜔)2 − Bi (ℏ𝜔) + Ci
where (ℏ𝜔) is the photon energy; q is an integer that represents the number of terms
needed to suitably model experimental n, K; Eg is the bandgap and Ai , Bi , C i , Boi , C oi are
constants; Boi and C oi depend on Ai , Bi , C i , and Eg —only the latter four are independent
parameters; and Boi = (Ai /Qi )[−(1/2)Bi 2 + Eg Bi – Eg 2 + C i ], C oi = (Ai /Qi )[(1/2)(Eg 2 + C i )
Bi − 2Eg C i ], and Qi = (1/2)(4C i − Bi 2 )1/2 . Forouhi and Bloomer provide a table of
FB coefficients, Ai , Bi , C i , and Eg for four terms in the summation in Eq. (1.20) [42] for
a number of semiconductors; an example that shows an excellent agreement between
the FB dispersion relation and the experimental data is shown in Figure 1.3. Table 1.4
provides the FB coefficients for a few selected semiconductors.
Other useful theoretical or somewhat semiempirical dispersion relationships have
also been proposed, for example, by Afromowitz [58], Adachi [59–63], Campi and
Papuzza [64], and others [65]. These models have been applied to various semiconduc-
tors and their alloys with relative success over certain photon energy ranges. One of the
useful and straightforward approaches to modeling the dispersion has been based on
writing the complex relative permittivity 𝜀r (ℏ𝜔) as a finite sum of a number of damped
harmonic oscillators (the so-called harmonic oscillator approximation), and fitting this
expression to the experimental data as in references [66, 67], even though many terms
may be needed and the curve fit process has to be carefully chosen to ensure a reliable
representation of the data. One of best models considered so far, however, has involved
parametric modeling [68–70], in which not only a sum of harmonic oscillators are used
but also Gaussian broadened polynomials to represent the dispersion of the complex
relative permittivity, and hence n and K.
5
SiC
3 n
n, K
2
1
K
0
0 2 4 6 8 10 12 14
Photon energy (eV)
Figure 1.3 n and K versus photon energy for crystalline SiC. The solid line is obtained from the FB
equation with four terms with appropriate parameters, and the points represent the experimental
data. See original reference [42] for the data and details. Source: Reprinted with permission, from
Figure 2c, A.R. Forouhi and I. Bloomer, Phys. Rev. B, 38, 1865. Copyright (1988) by the American Physical
Society.
1.3.3.2 Bandgap and Temperature Dependence

The refractive index of a semiconductor (typically for ℏ𝜔 < Eg ) typically decreases with
increasing bandgap Eg . There are various empirical and semi-empirical rules and expres-
sions that relate n to Eg . Based on an atomic model, Moss has suggested that n and Eg are
related by n4 Eg = K = constant [71, 72] (K is about ∼100 eV). In the Hervé–Vandamme
relationship [73],
( )2
A
2
n =1+ , (1.21)
Eg + B
where A and B are constants as A ≈ 13.6 eV and B ≈ 3.4 eV. The temperature dependence
of n arises from the variation of Eg with the temperature T, and it typically increases
with increasing temperature. The temperature coefficient of refractive index (TCRI) of
semiconductors can be found from the Hervé–Vandamme relationship as:
[ ]
1 dn (n2 − 1)3∕2 dEg dB
TCRI = • =− + (1.22)
n dT 13.6n2 dT dT
where dB/dT ≈ 2.5 × 10−5 eV K−1 . TCRI is typically found to be positive (n increasing
with temperature) and in the range of 10−6 to 10−4 K−1 .
Although Eqs. (1.21) and (1.22) are popular, there are other very useful empirical and
semiempirical relationships (see, e.g., [74]), some of which are summarized in Table 1.5
with appropriate references.
1.3.4 Refractive Index of Glasses

The Sellmeier equation with three terms have been found to represent the dispersion
of n reasonably well for most glasses and ceramics. The coefficients in the Sellmeier
equation have been listed at several websites [44] and handbooks.
Table 1.4 FB coefficients for selected semiconductors [42] for four terms (i = 1 to 4).
Ai Bi (eV) C i (eV2 ) n(∞) E g (eV)
Si 0.00405 6.885 11.864 1.950 1.06

0.01427 7.401 13.754
0.06830 8.634 18.812
0.17488 10.652 29.841
Ge 0.08556 4.589 5.382 2.046 0.60
0.21882 6.505 11.486
0.02563 8.712 19.126
0.07754 10.982 31.620
GaP 0.00652 7.469 13.958 2.070 2.17
0.14427 7.684 15.041
0.13969 10.237 26.567
0.00548 13.775 47.612
GaAs 0.00041 5.871 8.619 2.156 1.35
0.20049 6.154 9.784
0.09688 9.679 23.803
0.01008 13.232 44.119
GaSb 0.00268 4.127 4.267 1.914 0.65
0.34046 4.664 5.930
0.08611 8.162 17.031
0.02692 11.146 31.691
InP 0.20242 6.311 10.357 1.766 1.27
0.02339 9.662 23.472
0.03073 10.726 29.360
0.04404 13.604 47.602
InAs 0.18463 5.277 7.504 1.691 0.30
0.00941 9.130 20.934
0.05242 9.865 25.172
0.03467 13.956 50.062
InSb 0.00296 3.741 3.510 1.803 0.12
0.22174 4.429 5.447
0.06076 7.881 15.887
0.04537 10.765 30.119
Note: First entry in the box is for i = 1, and the fourth is for i = 4.
Gladstone–Dale formula [82, 83] is an empirical equation that allows the average
refractive index n of an oxide glass to be calculated from its density 𝜌 and its constituents
as:
n−1 ∑ N
= p1 k1 + p2 k2 + · · · = pi ki = CGD , (1.23)
𝜌 i=1
Table 1.5 Various selected simple relationships proposed between n and the bandgap E g .
Relationship Comment/Reference
n4 Eg = K; K = constant Widely used, but has limitations. K ≈ 95 eV; 173 eV for Group IV
elements [75]; K = 108 eV [76]. For a theoretical derivation and
discussion of Moss’s rule, see [77].
( )2
2 A
n =1+ A ≈ 13.6 eV and B ≈ 3.4 eV. Hervé–Vandamme relationship. See text.
Eg + B
n = 4.084 + 𝛽Eg 𝛽 = −0.62 eV−1 . Proposed by Ravindra et al. [76], but has serious
limitations for small and large n.
n = − ln(0.027Eg ) The Reddy Equation [78]. Based on the Duffy relationship
Eg = 3.72Δ𝜒 op [79] and Δ𝜒 op = 9.8exp(−n) in [80], where Δ𝜒 op is
optical electronegativity.
12.417
n2 = √ See [81]. Equivalent to n4 (Eg − 0.365 eV) = 154. Similar to the Moss
Eg − 0.365 relation. Eg > 0.365 eV
Note: Eg is in eV.
where the summation is for various oxide components (each a simple oxide), pi is the
weight fraction of the i-th oxide in the compound, and k i is the refraction coefficient
that represents the polarizability of the i-th oxide. The right-hand side of Eq. (1.23) is
called the Gladstone–Dale coefficient C GD . In more general terms, as a mixture rule for
the overall refractive index, the Gladstone–Dale formula is frequently written as:
n − 1 n1 − 1 n −1
= w1 + 2 w2 + · · · , (1.24)
𝜌 𝜌1 𝜌2
where n and 𝜌 are the effective refractive index and effective density, respectively, of the
whole mixture; n1 , n2 ,… are the refractive indices of the constituents; 𝜌1 , 𝜌2 ,… represent
the density of each constituent; and w1 , w2 … are the weight fractions of the constituents.
Gladstone–Dale equations for the polymorphs of SiO2 and TiO2 give the average n,
respectively, as:
n(SiO2 ) = 1 + 0.21𝜌 and n(TiO2 ) = 1 + 0.40𝜌 (1.25)
It is generally assumed that the refractive index can be related to the polarizability 𝛼
through the well-known Lorentz–Lorenz equation (equivalent to the Clausius–Mossotti
equation in dielectrics), which involves the local field as
n2 − 1 1 ∑
= N𝛼 (1.26)
n + 2 3𝜀o j j j
2
in which 𝛼 j is the polarizability of a given type (species) (j) of atoms in the structure,
and N j is the concentration of this species of atoms. Equation (1.26) includes both elec-
tronic and ionic polarizability and assumes that the local field is the Lorentz field, which
depends on polarization through P/3𝜀o in the standard model for cubic crystals and
noncrystalline solids. Ritland [84] assumed that the local field depends on the polariza-
tion as bP/𝜀o , where b is a numerical constant, and reformulated Eq. (1.26) in SI units
as
n2 − 1 b ∑
= N𝛼 (1.27)
n2 − 1 + (1∕b) 𝜀o j j j
and b is kept as a variable fitting parameter to the experimental data. Obviously, b = 1/3 is
the usual Lorentz–Lorenz equation, but the best fits do not necessarily lead to 1/3 [84].
Most recent work on the refractive index of glasses has invariably used the Sellmeier
equation, given its excellent fit to the dispersion data on glasses, as well as the adoption
of the Sellmeier equation by some industrial glass manufacturers such as Schott [85].
Further, in some cases, the temperature dependence of the Sellmeier coefficients are
also evaluated, so that dn/dT can be determined at different wavelengths [86–90]. While
dn/dT is positive for many semiconductors, this is not generally true for glasses.
1.3.5 Wemple–DiDomenico Dispersion Relation

Based on the single oscillator model, the Wemple–DiDomenico (WD) model is a
semi-empirical dispersion relation for determining the refractive index at photon
energies below the interband absorption edge in a variety of materials [91, 92]. It is
given by
Eo Ed
n2 = 1 + , (1.28)
Eo2 − (h𝜈)2
where 𝜈 is the frequency, h is the Planck constant, Eo is the single oscillator energy, and
Ed is the dispersion energy, which is a measure of the average strength of interband
optical transition. Ed can be written as Ed = 𝛽N c Za N e (eV), where N c is the effective
coordination number of the cation nearest-neighbor to the anion (e.g. N c = 6 in NaCl,
N c = 4 in Ge), Za is the formal chemical valency of the anion (Za = 1 in NaCl, 2 in Te, and
3 in GaP), N e is the effective number of valence electrons per anion excluding the cores
(N e = 8 in NaCl, Ge; 10 in TlCl; 12 in Te; 91 /3 in As2 Se3 ), and 𝛽 is a constant that depends
on whether the interatomic bond is ionic (𝛽 i ) or covalent (𝛽 c ): 𝛽 i = 0.26 ± 0.04 eV (e.g.
halides NaCl, ThBr, etc., and most oxides, Al2 O3 , etc.), and 𝛽 c = 0.37 ± 0.05 eV (e.g. tetra-
hedrally bonded AN B8−N zinc blende and diamond type structures, GaP, ZnS, etc., and
wurtzite crystals have a 𝛽 that is intermediate between 𝛽 i and 𝛽 c ). Further, empirically,
Eo = CEg (D), where Eg (D) is the lowest direct bandgap and C is a constant, typically
C ≈ 1.5. Eo has been associated with the main peak in the 𝜀′′r (h𝜈) versus h𝜈 spectrum.
The parameters required for calculating n from Eq. (1.28) are listed in Table 1.6 [91].
It should be apparent that one can improve on the single oscillator model by adding a
second oscillator term to Eq. (1.28) [93], and so on; although one loses the simplicity of
the model, which the experimentalists like.
Since its publication in 1971, the WD model has also been successfully applied to var-
ious amorphous semiconductors and glasses in addition to crystals, following the origi-
nal arguments of Wemple [92]. In their original work, WD provided the single oscillator
parameters for an extensive list of materials, some of which are summarized in Table 1.6,
with further discussion in [94]. The ratio Eo /Eg has been observed by researchers to be
very roughly in the range 1.5–2.5. The simple WD model is expected to hold in the small
absorption region of the spectrum, that is, away from absorption bands due to inter-
band transitions (h𝜈 < Eg ) or Reststrahlen absorption, etc. While it is apparent that the
Table 1.6 Examples of parameters for Wemple–DiDomenico dispersion relationship in various

materials.
Material Nc Za Ne E o (eV) E d (eV) 𝜷 (eV) 𝜷 Comment
NaCl 6 1 8 10.3 13.6 0.28 𝛽i Halides, LiF, NaF, etc.

CsCl 8 1 8 10.6 17.1 0.27 𝛽i CsBr, CsI, etc.
TlCl 8 1 10 5.8 20.6 0.26 𝛽i TlBr
CaF2 8 1 8 15.7 15.9 0.25 𝛽i BaF2 , etc.
CaO 6 2 8 9.9 22.6 0.24 𝛽i Oxides, MgO, TeO2 , etc.
Al2 O3 6 2 8 13.4 27.5 0.29 𝛽i
LiNbO3 6 2 8 6.65 25.9 0.27 𝛽i
TiO2 6 2 8 5.24 25.7 0.27 𝛽i
ZnO 4 2 8 6.4 17.1 0.27 𝛽i
ZnSe 4 2 8 5.54 27 0.42 𝛽c II-VI, Zinc blende, ZnS, ZnTe,
CdTe
GaAs 4 3 8 3.55 33.5 0.35 𝛽c III-V, Zinc blende, GaP, etc.
Si (Crystal) 4 4 8 4.0 44.4 0.35 𝛽c Diamond, covalent bonding; C
(diamond), Ge, 𝛽-SiC, etc.
SiO2 (Crystal) 4 2 8 13.33 18.10 0.28 𝛽i Average crystalline form
SiO2 (Amorphous) 4 2 8 13.38 14.71 0.23 𝛽i Fused silica
CdSe 4 2 8 4.0 20.6 0.32 𝛽 i –𝛽 c Wurtzite
Note: Values extracted and combined from tables in [91].
WD relation can only be approximate, it has nonetheless found wide acceptance among
experimentalists due to its straightforward simplicity. For example, in 2018 alone, it has
been applied nearly 200 times to a wide variety of inorganic and organic material sys-
tems, particularly to semiconductor films.
1.3.6 Group Index

Group index is a factor by which the group velocity of a group of waves in a dielectric
medium is reduced with respect to propagation in free space. It is denoted by N g and
defined by N g = vg /c, where vg is the group velocity, defined by vg = d𝜔/dk, where k is
the wave vector or the propagation constant. The group index can be determined from
the ordinary refractive index n through [95]
dn
Ng = n − 𝜆 (1.29)
d𝜆
where 𝜆 is the wavelength of light (in free space). Figure 1.4 illustrates the relation
between N g and n in SiO2 . The group index N g is the quantity that is normally used in
calculating dispersion in optical fibers, since it is N g that determines the group velocity
of a propagating light pulse in a glass or transparent medium. It should be remarked
that, although n vs. 𝜆 can decrease monotonically with 𝜆 over a range of wavelengths,
N g can exhibit a minimum in the same range where the dispersion, dN g /d𝜆, becomes
zero. The point dN g /d𝜆 = 0 is called the zero-material dispersion wavelength, which is
around 1300 nm for silica, as apparent in Figure 1.4.
1.49 Figure 1.4 Refractive index n and the group

index Ng of pure SiO2 (silica) glass as a
function of wavelength. Source: Adapted
1.48
from S.O. Kasap, 2017 [30].
1.47 Ng
1.46
n
1.45
1.44
500 700 900 1100 1300 1500 1700 1900
Wavelength (nm)
1.4 The Swanepoel Technique: Measurement of n and 𝜶

for Thin Films on Substrates
1.4.1 Uniform Thickness Films
In many instances, the optical constants are conveniently measured by examining the
transmission through a thin film of the material deposited on a transparent glass or
other (e.g. sapphire) substrate. The classic reference on the optical properties of thin
films has been the book by Heavens [96]; the book is still useful in clearly describing
what experiments can be carried out, and has a number of useful derivations such as
the reflectance and transmittance through thin films in the presence of multiple reflec-
tions. Since then, numerous research articles and reviews have been published. Poelman
and Smet [97] have critically reviewed how a single transmission spectrum measure-
ment can be used to extract the optical constants of a thin film. In general, the amount
of light that gets transmitted through a thin film material depends on the amount of
reflection and absorption that takes place along the light path. If the material is a thin
film with a moderate absorption coefficient 𝛼, then there will be multiple interferences
at the transmitted side of the sample, as illustrated in Figure 1.5.
In this case, some interference fringes will be evident in the transmission spectrum
obtained from a spectrophotometer, as shown in Figure 1.6. One very useful method
that makes use of these interference fringes to determine the optical properties of the
material is called the Swanepoel method [98] which is based on earlier works of Mani-
facier et al. [99] and Hall and Ferguson [100].
Swanepoel has shown that the optical properties of a uniform thin film of thickness
d, refractive index n, and absorption coefficient 𝛼, deposited on a thick substrate with
a refractive index s, as shown in Figure 1.5, can be obtained from the transmittance T
given by
Ax
T= (1.30)
B − Cx cos 𝜑 + Dx2
where A = 16n2 s, B = (n + 1)3 (n + s2 ), C = 2(n2 − 1)(n2 − s2 ), D = (n − 1)3 (n − s2 ),
𝜑 = 4𝜋nd/𝜆, x = exp(−𝛼d) is an absorbance-type parameter, and n, s, and 𝛼 are all
1.4 The Swanepoel Technique: Measurement of n and α for Thin Films on Substrates 17
Incident
monochromatic
wave Monochromatic
light
nair = 1 T=1
nfilm = n d Thin film α>0

Thin film n* = n + iK
Glass
nsubstrate = s substrate
α=0
Substrate
T
Detector
Figure 1.5 Schematic sketch of the typical behavior of light passing through a thin film on a substrate.
On the left, oblique incidence is shown to demonstrate the multiple reflections. In most
measurements, the incident beam is nearly normal to the film, as shown on the right.
Full Transmission Spectrum from an a-Se Thin Film

1
0.9
0.8
STRONG ABSORPTION REGION
0.7
TRANSPARENT REGION
0.6
Transmittance
0.5
Interference Fringes
0.4
0.3
ABSORPTION REGION
0.2
0.1 Expt data

Substrate
0
600 800 1000 1200 1400 1600 1800 2000
λ in nm
Figure 1.6 An example of a typical transmission spectrum of a 0.969-μm-thick amorphous Se thin film
that has been vacuum coated on a glass substrate held at a substrate temperature of 50∘ C during the
deposition.
functions of wavelength 𝜆. Although x (with values of 1 under no absorption and

approaching 0 under strong absorption) has been called “absorbance” in most studies
using the Swanepoel technique as in the original papers, the usual definition of
absorbance, however, is log10 (1/T), so that x, strictly, is not true absorbance. Eq. (1.30)
assumes K 2 < < n2 , where n + iK is the complex refractive index of the film and normal
incidence. What is very striking and useful is that all the important optical properties
can be determined from the application of this equation; this will be introduced in the
subsequent paragraphs. Before the optical properties of any thin film can be extracted,
the refractive index of their substrate must first be calculated. For a glass substrate with
very negligible absorption, that is, K ≤ 0.1 and 𝛼 ≤ 10−2 cm−1 , in the range of operating
wavelengths, the refractive index s is,
√( )
1 1
s= + −1 (1.31)
Ts Ts2
where T s is the transmittance value measured from the spectrophotometer. This expres-
sion can be derived from the transmittance equation for a bulk sample with little atten-
uation. With this refractive index s known, the next step is to construct two envelopes
around the maxima and minima of the interference fringes in the transmission spec-
trum, as indicated in Figure 1.7.
There will altogether be two envelopes that have to be constructed before any of the
expressions derived from Eq. (1.30) can be used to extract the optical properties. This
Full Transmission Spectrum
1
TS TM
0.9
Maxima
0.8 T
0.7
0.6
TRANSPARENT REGION
Transmittance
Tm
0.5 Extreme Points Minima

ABSORPTION REGION
0.4
0.3
0.2
Expt data
Substrate
0.1 Maxima Envelope
Minima Envelope
0
600 800 1000 1200 1400 1600 1800 2000
λ in nm
Figure 1.7 The construction of envelopes in the transmission spectrum of the thin a-Se film in
Figure 1.6.
can be done by locating all the extreme points of the interference fringes in the trans-
mission spectrum and then making sure that the respective envelopes, T M (𝜆) for the
maxima and T m (𝜆) for the minima, pass through these extremes, the maxima and min-
ima, of T(𝜆) tangentially. From Eq. (1.30), it is not difficult to see that, at cos 𝜑 = ± 1,
the expressions that describe the two envelopes are,
Ax
Maxima∶TM = , (1.32a)
B − Cx + Dx2
Ax
Minima∶Tm = . (1.32b)
B + Cx + Dx2
Figure 1.7 shows two envelopes constructed for a transmission spectrum of an a-Se
thin film. It can also be seen that the transmission spectrum is divided into three spe-
cial regions according to their transmittance values: (i) the transparent region, where
T(𝜆) ≥ 99.99% of the substrate’s transmittance value of T s (𝜆), (ii) the strong absorption
region, where T(𝜆) is typical smaller than 20%, and (iii) the absorption region, in between
the two latter regions as shown in Figure 1.7.
The refractive index of the thin film can be calculated from the two envelopes, T M (𝜆)
and T m (𝜆), and the refractive index of the substrate s through
[ ]
[ ]
2 1∕2 1∕2
TM − Tm s2 + 1
2
n = N + (N − s ) ; N = 2s + , (1.33)
TM Tm 2
where N is defined by the second equation on the right hand side of Eq. (1.33). T M
and T m are assumed to be continuous functions of 𝜆 and x, so that values have to be
at the same wavelength for use in Eq. (1.33). The derivation of Eq. (1.33) is based on
considering 1/T m − 1/T M , which is 2C/A, and then substituting for C and A from earlier,
and then solving for n. Since the equation is not valid in the strong absorption region,
where there are no maxima and minima, the calculated refractive index has to be fitted
to a well-established dispersion model for extrapolation to shorter wavelengths before it
can be used to obtain other optical constants. Usually either the Sellmeier or the Cauchy
dispersion equation is used to fit n vs 𝜆 experimental data in this range. Figure 1.8 shows
the refractive indices extracted from the envelopes and fitted to the Sellmeier dispersion
model with two terms.
With the refractive index of the thin film corresponding to two adjacent maxima (or
minima) at points 1 and 2, given as n1 at 𝜆1 and n2 at 𝜆2 , the thickness can be easily
calculated from the basic interference equation of waves as follows:
𝜆 1 𝜆2
dcrude = (1.34)
2(𝜆1 n2 − 𝜆2 n1 )
where dcrude refers to the thickness obtained from the maxima (minima) at points 1, 2.
As other adjacent pairs of maxima or minima points are used, more thickness values can
be deduced, and hence an average value calculated. It is assumed the film has an ideal
uniform thickness.
The absorption coefficient 𝛼 can be obtained once x is extracted from the transmission
spectrum. This can be done as follows:
ln(x)
𝛼=− (1.35)
dave
Refractive index of the a-Se film in Figure 1.7

4
Fitted To Sellmeier Equation
3.8 Crude Calculation From Envelopes
Improved Calculation
3.6
3.4
3.2
3
n
TRANSPARENT REGION
2.8
2.6
2.4
ABSORPTION REGION
2.2
2
600 800 1000 1200 1400 1600 1800 2000
λ in nm
Figure 1.8 Determination of the refractive index from the transmission spectrum maxima and minima
shown in Figure 1.7. The solid black curve shows the fitted Sellmeier n vs. 𝜆 curve, which follows
n2 = 3.096 + 2.943𝜆2 /[𝜆2 − (402.31)2 ], where 𝜆 is in nm.
√
2
EM − EM −(n2 −1)3 (n2 −s4 ) 2
where x = (n−1)3 (n−s2 )
; EM = 8n
TM
s
+ (n2 − 1)(n2 − s2 ); and dave is the average
thickness of dcrude .
The accuracy of the thickness, the refractive index, and the absorption coefficient can
all be further improved in the following manner. The first step is to determine a new
set of interference orders, represented by m′ , for the interference fringes from the basic
interference equation of waves; that is,
2ne dave
m′ = , (1.36a)
𝜆e
where ne and 𝜆e are values taken at any extreme point, and m′ is an integer if the extremes
taken are maxima or a half-integer if the extremes taken are minima.
The second step is to get a new corresponding set of thickness values, d′ , from this
new set of order numbers m′ , by rearranging Eq. (1.36a) as:
m′ 𝜆e
d′ = (1.36b)
2ne
From this new set of thickness values, d′ , a new average thickness, dnew , must be cal-
culated before it can be applied to improve the refractive index. This can be done by
ignoring those d′ that have values very different from the rest during averaging. With
this new average thickness, a more accurate refractive index ne can be obtained from
the same equation,
m′ 𝜆 e
ne = (1.36c)
2dnew
This new refractive index can then be fitted to the previous dispersion model again,
so that an improved absorption coefficient 𝛼 can be calculated from Eq. (1.35). All these
parameters can then be used in Eq. (1.30) to regenerate a calculated transmission spec-
trum T cal (𝜆), so that the root mean square error (RMSE) can be determined from the
experimental spectrum T exp . The RMSE is calculated as follows:
√
√ q
√∑
√ (T − T )2
√ exp cal
√ i=1
RMSE = , (1.37)
q
where T exp is the transmittance of the experimental or measured spectrum, T cal is the
transmittance of the regenerated spectrum obtained through the Swanepoel calcula-
tion method, and q is the range of the measurement. Figure 1.9 shows the regenerated
transmission spectrum of the a-Se thin film that appeared in Figure 1.6 using the optical
constants calculated from the envelopes (as quoted in the caption of Figure 1.8).
Full Spectrum of the a-Se Film in Figure 1.6 by the Swanepoel Method
1
0.9
0.8
0.7
TRANSPARENT REGION
0.6
Transmittance
0.5 RMSE = 1.02%
0.4
0.3
ABSORPTION REGION
0.2
Expt data
0.1 Regenerated Spectrum by Sellmeier Fitted n
Substrate
0
600 800 1000 1200 1400 1600 1800 2000
λ in nm
Figure 1.9 Regenerated transmission spectrum of the sample in Figure 1.6.

1.4.2 Thin Films with Non-uniform Thickness

The Swanepoel technique in the case of a film with a wedge-like cross-section, as shown
in Figure 1.10, involves the integration of Eq. (1.30) over the thickness of the film in order
for it to more accurately describe the transmission spectrum [101]. The transmittance
then becomes,
𝜑
1 2
Ax
TΔd = dx (1.38)
𝜑2 − 𝜑1 ∫𝜑1 B − Cx cos 𝜑 + Dx2
with
4𝜋n(d − Δd) 4𝜋n(d + Δd)
𝜑1 = , and 𝜑2 = ,
𝜆 𝜆
where A = 16n2 s, B = (n + 1)3 (n + s2 ), C = 2(n2 − 1)(n2 − s2 ), D = (n − 1)3 (n − s2 ), 𝜑
has been defined after Eq. (1.30), x = exp(−𝛼d) corresponds x to the absorbance-type
parameter calculated using the average film thickness d over the illumination region, n
and s are the refractive index of the film and substrate, respectively, 𝛼 is the absorption
coefficient, and Δd is the thickness variation throughout the illumination area, which
has been called the roughness of the film (This nomenclature is actually confusing, since
the film may not be truly “rough,” but may just have a continuously increasing thickness
as in a wedge from one end to the other.)
The first parameter to be extracted before the rest of the optical properties is Δd.
Consider the transmission region where absorption is very small, that is, x is almost
unity, and the spectrum exhibits clear maxima and minima. Eq. (1.38) can be modified
by considering the maxima and minima, which are both continuous functions of 𝜆. In
this way, we have,
[ ( )]
𝜆 a 1+b 2𝜋nΔd
Maxima∶TMd = √ tan−1
√ tan , (1.39a)
2𝜋nΔd 1 − b2 1 − b 2 𝜆
[ ( )]
𝜆 a 1−b 2𝜋nΔd
Minima∶Tmd = √ tan −1
√ tan , (1.39b)
2𝜋nΔd 1 − b2 1 − b2 𝜆
A C
where a = B+D
, and b = B+D
.
Monochromatic Figure 1.10 System of an absorbing thin film

light with a variation in thickness on a thick finite
T=1 transparent substrate.
Δd
Nonuniform film α>0 d

n* = n + iK
Glass
substrate
α=0
Refractive index = s
T
Detector
Notice that there is no x in these equations, since x = 1 was used. As long as

0 < Δd < 𝜆/4n, the refractive index, n and Δd, can both can be obtained by simultane-
ously solving Eqs. (1.39a) and (1.39b) numerically at various wavelengths.
Since Eqs. (1.39a) and (1.39b) are only valid in the region of zero absorption, the refrac-
tive index, outside of the transparent region, must be obtained in another way. Theoret-
ically, a direct integration of Eq. (1.38) over both Δd and x can be performed, although
this would be analytically too difficult. Nevertheless, over the wavelength region where
absorption is small (where one can still distinguish interference fringes), an approxima-
tion to the integration, according to Swanepoel, is as follows:
[ ( )]
𝜆 ax 1 + bx 2𝜋nΔd
Maxima∶TMx = √ tan−1
√ tan , (1.40a)
2𝜋nΔd 1 − b2 1 − b 2 𝜆
x [ x
( )]
𝜆 ax 1 − bx 2𝜋nΔd
Minima∶Tmx = √ tan −1
√ tan , (1.40b)
2𝜋nΔd 1 − b2 1 − b2 𝜆
x x
Ax Cx
where ax = and bx = As long as 0 < x ≤ 1, numerically, there will only be
B+Dx2 B+Dx2
.
one unique solution. Therefore, the two desired optical properties, refractive index, n
and x (and hence 𝛼), can both be obtained when Eqs. (1.40a) and (1.40b) are solved
simultaneously using the calculated average Δd. Eqs. (1.40a) and (1.40b) are valid for
Δd ≪ d.
As before, the calculated refractive index can be fitted to a well-established disper-
sion model, such as the Cauchy or Sellmeier equation, as shown in Figure 1.11, for
Refractive Index of a Simulated Sample with Non-Uniform Thickness

4
Fitted To cauchy Equation
3.8 Crude Calculation From Envelopes
Improved Calculation
3.6
3.4
3.2
3
n
2.8
2.6
ABSORPTION REGION
2.4 n(λ) = 2.587 + (2.461 × 10–8 )λ–1 + (2.876 × 10–13)λ–2
2.2
2
600 800 1000 1200 1400 1600 1800 2000
λ in nm
Figure 1.11 The refractive index of a sample with d = 1 μm and Δd = 30 nm, and n fitted to a Cauchy
equation in the figure. Eqs. (1.40a) and (1.40b) were used for the determination of n.
extrapolation to shorter wavelengths. The thickness is calculated from any two adjacent
maxima (or minima) using Eq. (1.34), and the absorption coefficient can be calculated
from
ln(xweak )
𝛼weak = − (1.41)
d
where 𝛼 weak is the absorption coefficient in the weak and medium absorption region;
xweak is the absorbance-like parameter (x) obtained from Eqs. (1.40a) and (1.40b); and d,
as before, is the average thickness.
According to Swanepoel, in the region of strong absorption, the interference fringes
are smaller, and the spectrum approaches the interference-free transmission sooner.
Since the transmission spectra in this region are the same for any film with the same
average thickness, regardless of its uniformity, the absorption coefficient in the strong
absorption region will thus be,
ln(xstrong )
𝛼strong = − (1.42)
d
√
A− (A2 −4Ti2 BD) 2T T
where xstrong = 2Ti D
, Ti = T M+Tm , and T M and T m are the envelopes of maxima
M m
and minima, respectively, constructed from the measured spectrum.
The accuracy of the thickness and refractive index can be further improved in exactly
the same way as that for a film with uniform thickness for the computation of the new
absorption coefficient, using Eqs. (1.40a) and (1.40b). Figure 1.12 shows the regenerated
Transmission Spectrum of a Simulated Sample with Non-Uniform Thickness

1
0.9
0.8
0.7
0.6
Transmittance
0.5
RMSE = 0.25%
0.4
ABSORPTION REGION
0.3
0.2
Expt data
0.1 Regenerated T
Substrate
0
600 800 1000 1200 1400 1600 1800 2000
λ in nm
Figure 1.12 A regenerated transmission spectrum of a sample with an average thickness of 1 μm and
average Δd of 30 nm, and a refractive index fitted to a Cauchy equation in Figure 1.11.
1.5 Transmittance and Reflectance of a Partially Transparent Plate 25
transmission spectrum of a simulated sample with nonuniform thickness using the opti-
cal constants calculated from the envelopes. Marquez et al. [102] have discussed the
application of Swanepoel technique to wedge-shaped As2 S3 thin film and made use
of the fact that a non-uniform wedge-shaped thin film has a compressed transmission
spectrum. Figure 1.13 shows a flow chart that highlights the various steps involved in
the extraction of the optical coefficients of thin film for both uniform and a nonuniform
film thicknesses.
Various computer algorithms based on the Swanepoel technique are available in the
literature [103]. Further discussions and enhancements are also available [97, 104–106].
For example, one improvement in the strong absorption region is based on a so-called
tangencypoint method as described in [106]. There are numerous useful applications of
the Swanepoel technique for extracting the optical constants of thin films; some selected
recent examples are given in [107–118].
1.5 Transmittance and Reflectance of a Partially Transparent

Plate
The transmittance of the thin film in Figure 1.6 is based on the interference of light waves
within the thin film; it assumes that waves have a much longer coherence length than
the thickness of the film, so that we may suitably add the optical fields of the waves.
A film would be too thick if the coherence length of the waves is shorter than the thick-
ness of the film. When we pass light through a transparent (or partially transparent)
plate, we typically do not observe interference effects. Even if we have a thin film, we
may not observe interference effects if the light source is incoherent. In these cases, we
cannot add the electric fields to calculate the reflected and transmitted light irradiances;
instead, we need to use reflectance and transmittance of the surfaces. Consider the mul-
tiple reflections shown in Figure 1.14. The first transmitted light intensity into the plate
is (1 − R), and the first transmitted light out is (1 − R)(1 − R) = (1 − R)2 . However, there
are internal reflections, so that the second transmitted light is R2 (1 − R)2 , so that the
transmitted intensity through the plate is T plate = (1 − R)2 [1 + R2 + R4 + …], or
(1 − R)2 1−R 2nno

Tplate = = = (1.43)
1 − R2 1 + R n2 + n2o
where R = (n – no )/(n + no ), and n is the refractive index of the plate and no that of the
surrounding, as in Figure 1.14. One of the simplest ways to determine the refractive
index of a medium as a plate is to measure the transmittance T plate , and then use
√
n −1 −2
= Tplate + Tplate −1 (1.44)
no
The overall reflectance is 1 – T plate , so that
(n − no )2
Rplate = (1.45)
n2 + n2o
If the plate is partially transparent with some attenuation coefficient 𝛼, then, each time
light traverses the thickness L of the plate, it experiences an attenuation factor exp(−𝛼L),
Another random document with
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A. D. 1897 (Zanzibar).
Abolition of slavery.
Under pressure from the British government, the Sultan of

Zanzibar issued a decree, on the 6th or April, 1897,
terminating the legal status of slavery, with compensation to
be awarded on proof of consequent loss.
AFRICA: A. D. 1897 (Zululand).

Annexation to Natal.
By act of the Natal Parliament in December, 1897, Zululand

(with Amatongaland already joined to it) was annexed to Natal
Colony, and Dinizulu, son of the last Zulu king, was brought
from captivity in St. Helena and reinstated.
AFRICA: A. D. 1897-1898 (Sudan).

Completion of the Anglo-Egyptian conquest.
See (in this volume)

EGYPT: A. D. 1897-1898.
AFRICA: A. D. 1897-1898 (Uganda).

Native insurrections and mutiny of Sudanese troops in Uganda.

UGANDA: A. D. 1897-1898.
AFRICA: A. D. 1898 (Abyssinia).

Treaty of King Menelek with Great Britain.

ABYSSINIA: A. D. 1898.
AFRICA: A. D. 1898 (British South Africa Company).

Reorganization.

SOUTH AFRICA (RHODESIA):
A. D. 1898 (FEBRUARY).
AFRICA: A. D. 1898 (Egypt).

The Nile question between England and France.
Marchand's expedition at Fashoda.

EGYPT: A. D. 1898 (SEPTEMBER-NOVEMBER).
AFRICA: A. D. 1898 (Nigeria and the French Sudan).

Definition of French and English possessions in
West and North Africa.

NIGERIA: A. D. 1882-1899.
AFRICA: A. D. 1898 (Rhodesia).
Reorganization of the British South Africa Company and
the administration of its territories.

SOUTH AFRICA
(RHODESIA AND THE BRITISH SOUTH AFRICA COMPANY):
A. D. 1898 (FEBRUARY).
AFRICA: A. D. 1898 (Tunis).

Results of the French Protectorate.

TUNIS: A. D. 1881-1898.
AFRICA: A. D. 1899.
Railway development.
"Railroad development in Africa has been rapid in the past few

years and seems but the beginning of a great system which must
contribute to the rapid development, civilization, and
enlightenment of the Dark Continent. Already railroads run
northwardly from Cape Colony about 1,400 miles, and
southwardly from Cairo about 1,100 miles, thus making 2,500
miles of the 'Cape to Cairo' railroad complete, while the
intermediate distance is about 3,000 miles. Mr. Rhodes, whose
recent visit to England and Germany in the interest of the
proposed through line from the Cape to Cairo is a matter of
record, and whose visit to Germany was made necessary by the
fact that in order to pass from the southern chain of British
territory to the northern chain he must cross German or
Belgian territory, is reported as confident that the through
line will be completed by the year 1910. Certainly it may
reasonably be assumed that a continuous railway line will be
in operation from the southern to the northern end of Africa
in the early years of the twentieth century. Toward this line,
present and prospective, which is to stretch through the
eastern part of the continent, lateral lines from either coast
are beginning to make their way. A line has already been
constructed from Natal on the southeast coast: another from
Lourenço Marquez in Portuguese territory and the gold and
diamond fields: another from Beira, also in Portuguese
territory, but considerably farther north, and destined to
extend to Salisbury in Rhodesia, where it will form a junction
with the 'Cape to Cairo' road; still another is projected from
Zanzibar to Lake Victoria Nyanza, to connect, probably, at
Tabora, with the transcontinental line; another line is under
actual construction westward from Pangani just north of
Zanzibar, both of these being in German East Africa; another
line is being constructed northwestwardly from Mombasa, in
British territory, toward Lake Victoria Nyanza, and is
completed more than half the distance, while at the entrance
to the Red Sea a road is projected westwardly into Abyssinia,
and is expected to pass farther toward the west and connect
with the main line. At Suakim, fronting on the Red Sea, a road
is projected to Berber, the present terminus of the line
running southwardly from Cairo. On the west of Africa lines
have begun to penetrate inward, a short line in the French
Sudan running from the head of navigation on the Senegal
eastwardly toward the head of navigation on the Niger, with
the ultimate purpose of connecting navigation on these two
streams. In the Kongo Free State a railway connects the Upper
Kongo with the Lower Kongo around Livingstone Falls; in
Portuguese Angola a road extends eastwardly from Loanda, the
capital, a considerable distance, and others are projected
from Benguela and Mossamedes with the ultimate purpose of
connecting with the 'Cape to Cairo' road and joining with the
lines from Portuguese East Africa, which also touch that road,
thus making a transcontinental line from east to west, with
Portuguese territory at either terminus. Farther south on the
western coast the Germans have projected a road from Walfisch
Bay to Windhoek, the capital of German Southwest Africa, and
this will probably be extended eastwardly until it connects
with the great transcontinental line from 'Cape to Cairo,'
which is to form the great nerve center of the system, to be
contributed to and supported by these branches connecting it
with either coast. Another magnificent railway project, which
was some years ago suggested by M. Leroy Beaulieu, has been
recently revived, being no less than an east and west
transcontinental line through the Sudan region, connecting the
Senegal and Niger countries on the west with the Nile Valley
and Red Sea on the east and penetrating a densely populated
and extremely productive region of which less is now known,
perhaps, than of any other part of Africa. At the north
numerous lines skirt the Mediterranean coast, especially in
the French territory of Algeria and in Tunis, where the length
of railway is, in round numbers, 2,250 miles, while the
Egyptian railroads are, including those now under
construction, about 1,500 miles in length.
{4}
Those of Cape Colony and Natal are nearly 3,000 miles, and
those of Portuguese East Africa and the South African Republic
another thousand. Taking into consideration all of the roads
now constructed, or under actual construction, their total
length reaches nearly 10,000 miles, while there seems every
reason to believe that the great through system connecting the
rapidly developing mining regions of South Africa with the
north of the continent and with Europe will soon be pushed to
completion. A large proportion of the railways thus far
constructed are owned by the several colonies or States which
they traverse, about 2,000 miles of the Cape Colony system
belonging to the Government, while nearly all that of Egypt is
owned and operated by the State."
United States Bureau of Statistics,

Monthly Summary, August, 1899.
See, also, (in this volume),

RAILWAY, CAPE TO CAIRO.
AFRICA: A. D. 1899 (June).

International Convention respecting the liquor traffic.
Representatives of the governments of Great Britain, Germany,
Belgium, Spain, the Congo State, France, Italy, the
Netherlands, Portugal, Russia, Sweden and Norway, and Turkey,
assembled at Brussels, in June, 1899, with due authorization,
and there concluded an international convention respecting the
liquor traffic in Africa. Subsequently the governments of
Austria-Hungary, the United States of America, Liberia and
Persia, gave their adhesion to the Convention, and
ratifications were deposited at Brussels in June, 1900. The
Convention is, in a measure, supplemental to what is known as
"the General Act of Brussels," relative to the African slave
trade, which was framed at a conference of the representatives
of European, American, African, and Asiatic states, at
Brussels. The treaty known as the General Act of Brussels was
signed July 2, 1890, but did not come into force until April
2, 1894. The text of it may be found in (United States) House
Doc. Number 276, 56th Congress, 3d Session. The Convention of
1899 provides:
"Article I.
From the coming into force of the present Convention, the
import duty on spirituous liquors, as that duty is regulated
by the General Act of Brussels, shall be raised throughout the
zone where there does not exist the system of total
prohibition provided by Article XCI, of the said General Act,
to the rate of 70 fr. the hectolitre at 50 degrees centigrade,
for a period of six years. It may, exceptionally, be at the
rate of 60 fr. only the hectolitre at 50 degrees centigrade in
the Colony of Togo and in that of Dahomey. The import duty
shall be augmented proportionally for each degree above 50
degrees centigrade; It may be diminished proportionally for
each degree below 50 degrees centigrade. At the end of the
above-mentioned period of six years, the import duty shall be
submitted to revision, taking as a basis the results produced
by the preceding rate. The Powers retain the right of
maintaining and increasing the duty beyond the minimum fixed
by the present Article in the regions where they now possess
that right.
Article II.
In accordance with Article XCIII of the General Act of
Brussels, distilled drinks made in the regions mentioned in
Article XCII of the said General Act, and intended for
consumption, shall pay an excise duty. This excise duty, the
collection of which the Powers undertake to insure as far as
possible, shall not be lower than the minimum import duty
fixed by Article I. of the present Convention.
Article III.
It is understood that the Powers who signed the General Act of
Brussels, or who have acceded to it, and who are not
represented at the present Conference, preserve the right of
acceding to the present Convention."
Great Britain, Parliamentary Publication.

(Papers by Command: Treaty Series, Number 13, 1900).
AFRICA: A. D. 1899.
Progress of the Telegraph line from the Cape to Cairo.

TELEGRAPH, CAPE TO CAIRO.
AFRICA: A. D. 1899 (German Colonies).

Cost to Germany, trade, etc.

GERMANY: A. D. 1899 (JUNE).
AFRICA: A. D. 1899 (Nigeria).

Transfer of territory to the British Crown.

NIGERIA: A. D. 1899.
AFRICA: A. D. 1899 (Orange Free State).

Treaty of alliance with the Transvaal.
Making common cause.

SOUTH AFRICA (ORANGE FREE STATE):
A. D. 1897 (APRIL); and 1899 (SEPTEMBER-OCTOBER).
AFRICA: A. D. 1899 (The Sudan).

Anglo-Egyptian Condominium established.

EGYPT: A. D. 1899 (JANUARY).
AFRICA: A. D. 1899 (Transvaal and Orange Free State).

Outbreak of war with Great Britain.

SOUTH AFRICA (TRANSVAAL AND ORANGE FREE STATE):
A. D. 1899 (SEPTEMBER-OCTOBER).
AFRICA: A. D. 1899 (West Africa).

Definition of British and German frontiers.

SAMOAN ISLANDS.
AFRICA: A. D. 1899 (Zanzibar).

Renunciation of rights of extra-territoriality by Germany.

SAMOAN ISLANDS.
AFRICA: A. D. 1899-1900.
Summary of the partition of the Continent.
"Seven European nations, as before remarked, now control
territories in Africa, two of them having areas equal in each
case to about the entire land area of the United States, while
a few small territories remain as independent States.
Beginning at the northeast, Egypt and Tripoli are nominally at
least tributaries of Turkey, though the Egyptian Government,
which was given large latitude by that of Turkey, has of late
years formed such relations with Great Britain that, in
financial matters at least, her guidance is recognized; next
west, Algeria, French; then Morocco on the extreme northwest,
an independent Government and an absolute despotism; next on
the south, Spain's territory of Rio de Oro; then the Senegal
territories, belonging to the French, and connecting through
the desert of Sahara with her Algeria; then a group of small
divisions controlled by England, along the Gulf of Guinea;
then Liberia, the black Republic; Togoland, controlled by the
Germans; Dahomey, a French protectorate; the Niger territory,
one-third the size of the United States, controlled by
England; Kamerun, controlled by Germany; French Kongo; then
the Kongo Free State, under the auspices of the King of
Belgium, and occupying the very heart of equatorial Africa;
then Portuguese Angola; next, German South west Africa; and
finally in the march down the Atlantic side, Cape Colony,
British.
{5}
Following up the eastern side comes the British colony of
Natal; then just inland from this the two Boer Republics, the
Orange Free State and the South African Republic, both of
which are entirely in the interior, without ocean frontage;
next, Portuguese Africa, and west of this the great territory
known as 'Rhodesia'; then German Africa, which extends almost
to the equator; north of these, British East Africa, fronting
on the Indian Ocean, and merging northwardly with the Egyptian
Sudan, which was recently recovered from the Mahdi by the joint
operation of British and Egyptian troops, and the British flag
placed side by side with that of Egypt; next north, upon the
coast, Italian territory and a small tract opposite the
entrance to the Red Sea controlled by England; and a few
hundred miles west of the entrance to the Red Sea, the
independent Kingdom of Abyssinia. This division of African
territory, nearly all of it made within the memory of the
present generation, forms the present political map of Africa.
With England and France controlling an area equal in each case
to that of the United States; Germany, a territory one-third
the size of the United States; Portugal, with an area somewhat
less; the Kongo Free State in the great equatorial basin, but
having a frontage upon the Atlantic with an area nearly
one-third that of the United States; Italy and Spain, each
with a comparatively small area of territory; Egypt, with
relations quite as much British as Turkish; Tripoli, Turkish,
and the five independent States of Morocco, Liberia,
Abyssinia, and the two Boer Republics—nothing remains
unclaimed, even in the desert wastes, while in the high
altitudes and subtropical climate of southeast Africa
civilization and progress are making rapid advancement."
United States Bureau of Statistics,
Monthly Summary, August, 1899.
The following table, given in an article in "The Forum,"

December, 1899, by Mr. O. P. Austin, Chief of the United
States Bureau of Statistics, shows the area, total population,
foreign population, and imports and exports of the territory
in Africa held by each European Government and by the
independent States of that continent, at the time of its
compilation so far as could be ascertained; but the statistics
of area and population, especially the latter, are in many
cases necessarily estimates:
POP.
TOTAL FOREIGN PER SQ.
AREA. POPULATION. POPULATION MILE IMPORTS.
EXPORTS.
French Africa. 3,028,000 28,155,000 922,000 9.3
$70,116,000 $69,354,000
British Africa. 2,761,000 35,160,000 455,000 12.8
131,398,000 131,835,000
Turkish Africa. 1,760,000 21,300,000 113,000 12.2
54,091,000 62,548,000
German Africa. 944,000 11,270,000 4,000 12.0
4,993,000 2,349,000
Belgian Africa. 900,000 30,000,000 2,000 33.3
4,522,000 3,309,000
Portuguese Africa. 790,000 8,059,000 3,000 10.2
11,863,000 6,730,000
Spanish Africa. 243,000 36,000 … 0.5
… …
Italian Africa. 188,000 850,000 … 4.5
… …
Independent States.
Morocco. 219,000 5,000,000 … 22.8

6,402,000 6,261,000
Abyssinia. 150,000 3,500,000 … 23.3
… …
South African Republic. 120,000 1,096,000 346,000 9.2
104,703,000 53,532,000
Orange Free State. 48,500 208,000 78,000 4.3
5,994,000 8,712,000
Liberia. 48,000 1,500,000 25,000 31.3
1,217,000 1,034,000
Total. 11,189,500 146,133,000 1,948,000 …

$395,299,000 $345,714,000
According to a statistical table in the twentieth volume of
Meyer's Konversations-Lexicon (third annual supplement), based
upon the latest data furnished by the boundary treaties
between the Powers, it would appear that all but about
one-seventh of the African continent is now (A. D. 1900)
included in some "protectorate" or "sphere of influence." The
French sphere is the largest, comprising about 3,700,000
square miles (about the extent of Europe) out of a total area
of 11,600,000. England comes next with 2,400,000 (including
the Boer territories). Then follow in order Germany, Belgium
(Congo Free State), and Portugal, each with somewhat less than
a million square miles. The Egyptian sphere (about 400,000
square miles) may properly be regarded as part of the British.
The extent of the French sphere will appear less imposing on
consulting the map of Africa here given, which shows that it
takes in the greater part of the sands of the Sahara. The
British sphere (including Egypt and her dependencies) is
estimated to contain in round numbers about 50,000,000 souls;
the French, 35,000,000; the Belgian, 17,000,000; the German,
9,000,000; the Portuguese, 8,000,000.
AFRICA: A. D. 1900 (Ashanti).

Revolt of the tribes.
Siege and relief of Kumasai.

ASHANTI.
AFRICA: A. D. 1900 (Togoland and Gold Coast).

Demarcation of the Hinterland.
Late in November it was announced from Berlin that conferences

regarding the British and German boundaries in West Africa
were then in progress in the Colonial Department of the German
Foreign Office, their principal object being the demarcation
of the Hinterland of Togoland and of the Gold Coast, and in
particular the partition of the neutral zone of Salaga as
arranged in Article 5 of the Samoa Agreement between Great
Britain and Germany.

SAMOAN ISLANDS.
AFRIDIS, British Indian war with the.

INDIA: A. D. 1897-1898.
AFRIKANDER BUND, The.

SOUTH AFRICA (CAPE, COLONY):
A. D. 1881-1888; 1898; and 1898 (MARCH-OCTOBER).
AFRIKANDER CONGRESS.
SOUTH AFRICA (Cape Colony): A. D. 1900 (DECEMBER).
AFRIKANDERS:
Joining the invading Boers.

SOUTH AFRICA (THE FIELD OF WAR):
A. D. 1899 (OCTOBER-NOVEMBER.).
AFRIKANDERS:
Opposition to the annexation of the Boer Republics.

SOUTH AFRICA (CAPE COLONY): A. D. 1900 (MAY).
{6}
AGRARIAN PROTECTIONISTS, The German.

GERMANY: A. D. 1895-1898; 1899 (AUGUST); and 1901 (FEBRUARY).
AGRICULTURAL LAND BILL, The.

ENGLAND: A. D. 1896.
AGUINALDO y FAMY, Emilio.

First appearance in the Filipino insurrection.
His treaty with the Spaniards and departure from the Islands.

PHILIPPINE ISLANDS: A. D. 1896-1898.

Circumstances in which he went to Manila to co-operate with
American forces.

UNITED STATES OF AMERICA:
A. D. 1898 (APRIL-MAY: PHILIPPINES).

Arrival at Manila, May 19, 1898.
His organization of insurgent forces.
His relations with Admiral Dewey.

UNITED STATES OF AMERICA: A. D. 1898 (APRIL-JULY).

Correspondence with General Anderson.

A. D. 1898 (JULY-AUGUST: PHILIPPINES).

Relations with American commander at Manila.
Declared President of the Philippine Republic.

A. D. 1898 (JULY-SEPTEMBER).

Conflict of his army with American forces.

PHILIPPINE ISLANDS:
A. D. 1898 (AUGUST-DECEMBER), and after.
ALABAMA: A. D. 1899.
Dispensary Laws.
Acts applying the South Carolina "dispensary" system of

regulation for the liquor traffic to seventeen counties, but
not to the State at large, were passed by the Legislature.
See, in this volume,

SOUTH CAROLINA: A. D. 1892-1899.
ALASKA: A. D. 1898-1899.
Discovery of the Cape Nome gold mining region.
"The Cape Nome mining region lies on the western coast of

Alaska, just beyond the military reservation of St. Michael
and about 120 miles south of the Arctic Circle. It can be
reached by an ocean voyage of ten or twelve days from Seattle.
It has long been known that gold exists in the general vicinity
of Cape Nome, and during the last five or six years a few
adventurous miners have done more or less prospecting and
claim staking throughout the district lying between Norton and
Kotzebue sounds. During the winter of 1898-99, a large number
of miners entered the Kotzebue country, while others spent the
season in the vicinity of Golofnin Bay." On the 15th of
October, 1898, a party of seven men reached Snake River in a
schooner. "Between that date and the 18th a miners' meeting
was held, the boundaries of a district 25 miles square were
established, local mining regulations were formulated, and Dr.
Kittleson was elected recorder for a term of two years. After
organizing the district natives were hired to do the necessary
packing, and a camp was established on Anvil Creek. The
prospecting outfits were quickly brought into service. In one
afternoon $76 was panned out on Snow Creek. Encouraged by this
showing lumber was carried up from the schooner and two
rockers were constructed. … In four or five days over $1,800
was cleaned up with these two rockers. … The weather turned
cold and the water was frozen up. As it was impossible to do
any more work with the rockers the party broke camp on the 3d
of November and returned to the schooner, which they found
frozen solid in 2 feet of ice. They then made their way in a
small boat to an Indian village, near Cape Nome, where they
obtained dogs and sleds, and a little farther on they were met
by reindeer from the Swedish Mission, with which they returned
to Golofnin Bay.
"The lucky miners had agreed among themselves that their

discovery should be held secret, but the news was too good to
keep, and soon leaked out. A general stampede commenced at
once and continued all winter. Every available dog and
reindeer was pressed into the service, and they were soon
racing with each other for the valuable claims which had been
left unstaked in the vicinity of Anvil Creek. As soon as that
creek had been all taken up the stampede extended to the
neighboring streams and gulches, and Glacier and Dexter
creeks, as well as many others which have not proved equally
valuable, were quickly staked and recorded. By the 25th of
December a large party armed with numerous powers of attorney
had entered the district, and as the local regulations allowed
every man to stake on each creek one claim of the full legal
dimensions (660 by 1,320 feet), it was not long until the
whole district had been thoroughly covered, and nearly every
stream had been staked with claims, which in some cases were
'jumped' and the right of possession disputed.
"The news of a rich strike at Nome worked its way up the Yukon
River during the winter, and as soon as the ice broke in June
a large crowd came down from Rampart City, followed by a
larger crowd from Dawson. The 'Yukoners,' as these people were
called, were already disgusted with the hardships,
disappointments, and Canadian misgovernment which they had met
with on the upper river. … Those to whom enough faith had been
given to go over to Cape Nome were disgusted and angered to
find that pretty much the whole district was already staked,
and that the claims taken were two or three times as large as
those commonly allowed on the upper river. Another grievance
was the great abuse of the power of attorney, by means of
which an immense number of claims had been taken up, so that
in many cases (according to common report) single individuals
held or controlled from 50 to 100 claims apiece. …
"A miners' meeting was called by the newcomers to remedy their

grievances. Resolutions were prepared, in which it was
represented that the district had been illegally organized by
men who were not citizens of the United States and who had not
conformed with the law in properly defining the boundaries of
the district with reference to natural objects, in enacting
suitable and sufficient mining regulations, and in complying
with any of the details of organization required by law. It
was intended by the promoters of this meeting to reorganize
the district in such a way as would enable them to share the
benefits of the discovery of a new gold field with the men who
had entered it the previous winter, and, as they expressed it,
'gobbled up the whole country.' It is, of course, impossible
to say what would have been the result if their attempt had
not been interfered with. … On the 28th of June Lieutenant
Spaulding and a detachment of 10 men from the Third Artillery
had been ordered to the vicinity of Snake River, and on the
7th of July their numbers were increased by the addition of 15
more.
{7}
As soon as it was proposed to throw open for restaking a large
amount of land already staked and recorded an appeal was made
to the United States troops to prevent this action by
prohibiting the intended meeting, which was called to assemble
July 10. It was represented to them that if the newcomers
should attempt, under the quasi-legal guise of a miners'
meeting, to take forcible possession of lands already claimed
by others, the inevitable consequence would be a reign of
disorder and violence, with the possibility of considerable
bloodshed. On the strength of this representation and appeal
the army officers decided to prevent the adoption of the
proposed resolutions. The miners were allowed to call their
meeting to order, but as soon as the resolutions were read
Lieutenant Spaulding requested that they be withdrawn. He
allowed two minutes for compliance with his request, the
alternative being that he would clear the hall. The
resolutions were not withdrawn, the troops were ordered to fix
bayonets, and the hall was cleared quietly, without a
conflict. Such meetings as were subsequently attempted were
quickly broken up by virtue of the same authority. The light
in which this action is regarded by the people at Nome
depends, of course, upon the way in which their personal
interests were affected. …
"The great discontent which actually did exist at this time

found sudden and unexpected relief in the discovery of the
beach diggings. It had long been known that there was more or
less gold on the seashore, and before the middle of July it
was discovered that good wages could be taken out of the sand
with a rocker. Even those who were on the ground could hardly
believe the story at first, but its truth was quickly and
easily demonstrated. Before the month was over a great army of
the unemployed was engaged in throwing up irregular
intrenchments along the edge of the sea, and those who had
just been driven nearly to the point of desperation by the
exhaustion of all their resources were soon contentedly
rocking out from $10 to $50 each per day and even more than
that. This discovery came like a godsend to many destitute
men, and was a most fortunate development in the history of
the camp.
"Meantime the men who were in possession of claims on Anvil

and Snow creeks were beginning to sluice their ground and
getting good returns for their work, while others were
actively making preparations to take out the gold which they
knew they had discovered. More sluice boxes were constructed
and put into operation as rapidly as possible. A town site was
laid off at the mouth of Snake River, and on the 4th of July a
post-office was established. The town which has sprung so
suddenly into existence is called 'Nome' by the Post-Office
Department, but at a miners' meeting held February 28, it was
decided to call it 'Anvil City,' and this is generally done by
the residents of the district, as well as in all official
records. At a meeting held in September, however, the name was
again changed to 'Nome.'"
United States, 56th Congress, 1st session,

Senate Document Number 357, pages. 1-4.
"A year ago [that is, in the winter of 1898-1899] a few Eskimo
huts and one or two sod houses of white men were the only
human habitations along 60 miles of the present Nome coast.
Last June [1899] a dozen or score of tents contained the whole
population. By October a town of 5,000 inhabitants fronting
the ocean was crowded for a mile or more along the beach.
Hundreds of galvanized-iron and wooden buildings were
irregularly scattered along two or three thoroughfares,
running parallel with the coast line. There is every
description of building, from the dens of the poor
prospectors, built of driftwood, canvas, and sod, to the large
companies' warehouses, stores, and the army barracks—a city,
as it were, sprung up in the night, built under the most
adverse circumstances on the barren seacoast, a coast without
harbor, all the supplies being landed through the surf. … The
country contributes nothing toward the support of the
population except a few fish and a limited supply of
driftwood.
"The city is of the most cosmopolitan type and contains

representatives of almost every nationality on the globe:
Germans, Canadians, Frenchmen, Englishmen, Russians, Swedes,
Norwegians, Poles, Chinese, negroes, Italians, Spaniards,
Greeks, Jews, and Americans. The dominant type is the
American, through whose efforts, with that inherent talent of
the Anglo-Saxon race for self-government, this isolated
community at once organized a city government. Before the
close of the summer Nome had a mayor, councilmen, a police
force, a deputy United States marshal, a United States
post-office, a fire department with town well, a board of
health, a hospital corps, and charitable organizations. A
majority of the people consists of the shifting population of
the Yukon country, which, upon hearing the news of the
discovery of gold, poured itself into Nome. … Along with the
shifting population of the Yukon from Dawson and other camps
came also many would-be explorers, adventurers, and especially
gamblers, but good order prevails throughout. Drunkenness,
disorderly conduct, and theft are promptly tried before the
police justice and punished by fine and imprisonment. Copies
of the official rules and regulations are kept posted before
the city hall and in other conspicuous places, as a warning to
all: 'Ignorance of the law is no excuse.' Some of the well-known
'toughs' and most undesirable characters are reported to have
been rounded up by the authorities late in the fall and
exported to the States. … There are several printing presses
and three newspapers—the Nome News, Nome Herald, and Nome Gold
Digger. … There are at least 2,500 people now [February, 1900]
wintering at Nome, and, by estimate, at least several thousand
are on their way there by winter routes. …
"Since, according to the conservative estimate of those who

are best situated to judge, it is believed that the Nome
region will have a population of at least 30,000 or 40,000
people this year (1900), some public improvements there seem
not only commendable but urgently necessary. Among these the
most important are: Some municipal form of government, water
supply, land-office service, and harbor facilities. As the
General Government had never made provision for any form of
municipal government in Alaska, the people of Nome, in
response to the urgency of the hour, called a mass meeting,
and organized the present government of Nome, with a complete
corps of city officers, as aforesaid, though they were
conscious at the time that it was without authority from the
United States Government."
F. C. Schrader and A. H. Brooks,

Preliminary Report on the Cape Nome Gold Region, Alaska
(United States Geological Survey), pages 45-47.
{8}
ALASKA: A. D. 1900.
Civil Government.
Better provision for the civil government of Alaska was made

by an Act which passed Congress after much debate and was
approved by the President on the 6th of June, 1900. It
constitutes Alaska a civil and judicial district, with a
governor who has the duties and powers that pertain to the
governor of a Territory, and a district court of general
jurisdiction, civil and criminal, and in equity and admiralty,
the court being in three divisions, each with a district
judge. The act provides a civil code for the district.
ALASKA: A. D. 1900.
Exploration of Seward peninsula.

POLAR EXPLORATION, 1900.
ALASKA BOUNDARY QUESTION, The.
The boundary between Alaska, when it was Russian territory,

and the British possessions on the western side of the
American continent, was settled by an Anglo-Russian treaty in
1825. The treaty which ceded the Russian territory to the
United States, in 1867, incorporated the definition of
boundary given in Articles III. and IV. of the above-mentioned
convention, which (translated from French to English) read as
follows:
"III.
The line of demarcation between the possessions of the High
Contracting Parties upon the Coasts of the Continent and the
Islands of America to the North-West, shall be drawn in the
following manner: Commencing from the southernmost point of
the Island called Prince of Wales Island, which point lies in
the parallel of 54 degrees 40 minutes, North Latitude, and
between the 131st and 133d Degree of West Longitude (Meridian
of Greenwich), the said line shall ascend to the North along
the Channel called Portland Channel, as far as the Point of
the Continent where it strikes the 56th Degree of North
Latitude; from this last mentioned Point the line of
demarcation shall follow the summit of the mountains situated
parallel to the coast, as far as the point of intersection of
the 141st Degree of West Longitude (of the same meridian),
and, finally, from the said point of intersection, the said
Meridian Line of the 141st Degree, in its prolongation as far
as the Frozen Ocean, shall form the limit between the Russian
and British Possessions on the Continent of America to the
North West.
"IV.
With reference to the line of demarcation laid down in the
preceding Article, it is understood:
1st.
That the Island called Prince of Wales Island shall belong
wholly to Russia.
2d.
That wherever the summit of the mountains which extend in a
direction parallel to the Coast, from the 56th Degree of North
Latitude to the point of intersection of the 141st Degree of
West Longitude, shall prove to be at the distance of more than
ten marine leagues from the Ocean, the limit between the
British Possessions and the line of Coast which is to belong
to Russia, as above mentioned, shall be formed by a line
parallel to the windings of the Coast, and which shall never
exceed the distance of ten marine leagues therefrom."
When attempts to reduce this description in the treaty to an

actually determined boundary-line were begun, disagreements
arose between Canada and the United States, which became
exceedingly troublesome after the Klondike gold discoveries
had given a new importance to that region and to its
communications with the outside world. The Alaska boundary
question proved, in fact, to be considerably the most
difficult of settlement among all the many subjects of
disagreement between the United States and Canada which a
Joint High Commission was created in 1898 (see—in this
volume—CANADA: A. D. 1898-1900) to adjust. It was the one
question on which no ground of compromise could then be found,
and which compelled the Commission to adjourn in February,
1899, with its labors incomplete. The disputable points in the
definition of the boundary by the Anglo-Russian treaty of 1825
are explained as follows by Professor J. B. Moore,
ex-Assistant Secretary of State, in an article contributed to
the "North American Review" of October, 1899: "An examination
of the boundary defined in Articles III. and IV. of the
convention of 1825 shows," says Professor Moore, "that it is
scientifically divisible into two distinct sections, first,
the line from the southernmost point of Prince of Wales
Island, through Portland Channel and along the summit of the
mountains parallel to the coast, to the point of intersection
of the 141st meridian of longitude; and, second, the line from
this point to the Arctic Ocean. With the latter section, which
is merely a meridian line, and as to which the United States
and Canadian surveys exhibit no considerable difference, we
are not now concerned. The section as to which material
differences have arisen is the first. The principal
differences in this quarter are two in number, first, as to
what channel is meant by Portland Channel (sometimes called
Portland Canal); and, second, as to what is the extent of the
line or strip of coast (la lisière de côte) which was assigned
to Russia."
Map of Alaska.
The following is an English statement of the situation of the

controversy at the time the Joint High Commission adjourned:
"The adjournment of the Commission with nothing accomplished
is fresh in all our memories. Nor is it easy to determine on
whose shoulders lies the blame of this unfortunate break down.
America has been blamed for her stubbornness in refusing to
submit to an arbitration which should take into consideration
the possession of the towns and settlements under the
authority of the United States and at present under their
jurisdiction; while they have also been charged with having
made no concessions at all to Canada in the direction of
allowing her free access to her Yukon possessions. I am
enabled to say, however, in this latter respect the Americans
have not been so stiff-necked as has been made to appear.
Although it was not placed formally before the Commission, it
was allowed clearly to be understood by the other side, that
in regard to Skagway, America was prepared to make a very
liberal concession. They were ready, that is, to allow of the
joint administration of Skagway, the two flags flying side by
side, and to allow of the denationalisation, or
internationalisation as it might otherwise be termed, of the
White Pass and the Yukon Railroad, now completed to Lake
Bennett, and the only railroad which gives access to the
Yukon. They were even prepared to admit of the passage of
troops and munitions of war over this road, thus doing away
with the Canadian contention that, should a disturbance occur
in the Yukon, they are at present debarred from taking
efficient measures to quell it.
{9}
This proposition, however, does not commend itself to the
Canadians, whose main object, I think I am justified in
saying, is to have a railroad route of their own from
beginning to end, in their own territory, as far north as
Dawson City. At one time, owing to insufficient information
and ignorance of the natural obstacles in the way, they
thought they could accomplish this by what was known as the
Stikine route. They even went so far as to make a contract
with Messrs. McKenzie and Mann to construct this road, the
contractors receiving, as part of their payment, concessions
and grants of territory in the Yukon, which would practically
have given them the absolute and sole control of that
district. The value of this to the contractors can hardly be
overestimated. However, not only did the natural obstacles I
have referred to lead to the abandonment of the scheme, but
the Senate at Ottawa threw out the Bill which had passed
through the Lower House, affording a striking proof that there
are times when an Upper House has its distinct value in
legislation. It has been suggested (though I am the last to
confirm it) that it was the influence of the firm of railroad
contractors, to whose lot it would probably fall to construct
any new line of subsidised railway, which caused the Canadian
Commission to reject the tentative American proposal regarding
Skagway, and to put forward the counter claim to the
possession of Pyramid Harbour (which lies lower down upon the
west coast of the Lynn Canal), together with a two mile wide
strip of territory reaching inland, containing the Chilcat
Pass, and through it easy passage through the coast ranges,
and so by a long line of railroad to Fort Selkirk, which lies
on the Yukon River, to the south and east of Dawson City. It
is said also, though of this I have no direct evidence, that
the Canadians included the right to fortify Pyramid Harbour.
It is not surprising that the Americans rejected this
proposal, for they entered into the discussion convinced of
the impossibility of accepting any arrangement which would
involve the surrender of American settlements, and though it
is not so large or important as Skagway or Dyea, Pyramid
Harbour is nevertheless as much an American settlement as the
two latter. I am bound to point out that just as the Dominion
of Canada, as a whole, has a keener interest in this dispute
than has the Home Government, so the Government of British
Columbia is more closely affected by any possible settlement
than is the rest of the Dominion. And British Columbia is as
adverse to the Pyramid Harbour scheme as the United States
themselves. This is due to the fact that when finished the
Pyramid Harbour and Fort Selkirk railroad would afford no
access to the British Columbia gold fields on Atlin Lake,
which would still be reached only by way of Skagway and the
White Pass, or by Dyea and the Chilcat Pass. But quite apart
from this view of the matter, we may take it for granted that
the United States will never voluntarily surrender any of
their tide-water settlements, while the Canadian Government,
on the other hand, are no more disposed to accept any
settlement based on the internationalisation of Skagway, their
argument probably being that, save as a temporary 'modus
vivendi,' this would be giving away their whole case to their
opponents."
H. Townsend,
The Alaskan Boundary Question
(Fortnightly Review, September, 1899).
Pending further negotiations on the subject, a "modus vivendi"

between the United States and Great Britain, "fixing a
provisional boundary line between the Territory of Alaska and
the Dominion of Canada about the head of Lynn Canal," was
concluded October 20, 1899, in the following terms:
"It is hereby agreed between the Governments of the United

States and of Great Britain that the boundary line between
Canada and the territory of Alaska in the region about the
head of Lynn Canal shall be provisionally fixed as follows
without prejudice to the claims of either party in the
permanent adjustment of the international boundary: In the
region of the Dalton Trail, a line beginning at the peak West
of Porcupine Creek, marked on the map No. 10 of the United
States Commission, December 31, 1895, and on Sheet No. 18 of
the British Commission, December 31, 1895, with the number
6500; thence running to the Klehini (or Klaheela) River in the
direction of the Peak north of that river, marked 5020 on the
aforesaid United States map and 5025 on the aforesaid British
map; thence following the high or right bank of the said
Klehini river to the junction thereof with the Chilkat River,
a mile and a half, more or less, north of Klukwan,—provided
that persons proceeding to or from Porcupine Creek shall be
freely permitted to follow the trail between the said creek
and the said junction of the rivers, into and across the
territory on the Canadian side of the temporary line wherever
the trail crosses to such side, and, subject to such
reasonable regulations for the protection of the Revenue as
the Canadian Government may prescribe, to carry with them over
such part or parts of the trail between the said points as may
lie on the Canadian side of the temporary line, such goods and
articles as they desire, without being required to pay any
customs duties on such goods and articles; and from said
junction to the summit of the peak East of the Chilkat river,
marked on the aforesaid map No. 10 of the United States
Commission with the number 5410 and on the map No. 17 of the
aforesaid British Commission with the number 5490. On the Dyea
and Skagway Trails, the summits of the Chilcoot and White
Passes. It is understood, as formerly set forth in
communications of the Department of State of the United
States, that the citizens or subjects of either Power, found
by this arrangement within the temporary jurisdiction of the
other, shall suffer no diminution of the rights and privileges
which they now enjoy. The Government of the United States will
at once appoint an officer or officers in conjunction with an
officer or officers to be named by the Government of Her
Britannic Majesty, to mark the temporary line agreed upon by
the erection of posts, stakes, or other appropriate temporary
marks."
In his Annual Message to Congress, December 3, 1900, the

President of the United States stated the situation as
follows:
"The work of marking certain provisional boundary points, for

convenience of administration, around the head of Lynn Canal,
in accordance with the temporary arrangement of October, 1899,
was completed by a joint survey in July last.
{10}
The modus vivendi has so far worked without friction, and the
Dominion Government has provided rules and regulations for
securing to our citizens the benefit of the reciprocal
stipulation that the citizens or subjects of either Power
found by that arrangement within the temporary jurisdiction of
the other shall suffer no diminution of the rights and
privileges they have hitherto enjoyed. But however necessary
such an expedient may have been to tide over the grave
emergencies of the situation, it is at best but an
unsatisfactory makeshift, which should not be suffered to
delay the speedy and complete establishment of the frontier
line to which we are entitled under the Russo-American treaty
for the cession of Alaska. In this relation I may refer again
to the need of definitely marking the Alaskan boundary where
it follows the 141st meridian. A convention to that end has
been before the Senate for some two years, but as no action
has been taken I contemplate negotiating a new convention for
a joint determination of the meridian by telegraphic
observations. These, it is believed, will give more accurate
and unquestionable results than the sidereal methods
heretofore independently followed, which, as is known, proved
discrepant at several points on the line, although not varying
at any place more than seven hundred feet."
ALEXANDRIA:
Discovery of the Serapeion.

ARCHÆOLOGICAL RESEARCH:
EGYPT: DISCOVERY OF THE SERAPEION.
ALEXANDRIA:
Patriarchate re-established.

PAPACY: A. D. 1896 (MARCH).
ALIENS IMMIGRATION LAW, The Transvaal.

SOUTH AFRICA (THE TRANSVAAL):
A. D. 1896-1897 (MAY-APRIL).
ALPHABET, Light on the origin of the.

ARCHÆOLOGICAL RESEARCH: CRETE.
AMATONGALAND:
Annexed, with Zululand, to Natal.

AFRICA: A. D. 1897 (ZULULAND).
AMERICA:
The Projected Intercontinental Railway.

RAILWAY, THE INTERCONTINENTAL.
AMERICA, Central.

CENTRAL AMERICA.
AMERICAN ABORIGINES.

INDIANS, AMERICAN.
AMERICAN REPUBLICS, The Bureau of the.
"The idea of the creation of an international bureau, or

agency, representing the Republics of the Western Hemisphere,
was suggested to the delegates accredited to the International
American Conference held in Washington in 1889-90, by the
conference held at Brussels in May, 1888, which planned for an
international union for the publication of customs tariffs,
etc. … On March 29, 1890, the International American
Conference, by a unanimous vote of the delegates of the
eighteen countries there represented, namely: The Argentine
Republic, Bolivia, Brazil, Chile, Colombia, Costa Rica,
Ecuador, Guatemala, Haiti, Honduras, Mexico, Nicaragua,
Paraguay, Peru, Salvador, United States, Uruguay, and
Venezuela, provided for the establishment of an association to
be known as 'The International Union of American Republics for
the Prompt Collection and Distribution of Commercial
Information,' which should be represented at the capital of
the United States by a Bureau, under the title of 'The Bureau
of the American Republics.' This organ, so to speak, of the
independent governments of the New World was placed under the

Optical Properties of Materials and Their Applications Second Edition Singh Full Chapter

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Optical properties of materials and their

applications Second Edition Singh

1 Fundamental Optical Properties of Materials I 1

2 Fundamental Optical Properties of Materials II 37

2.4 Band-to-Band or Fundamental Absorption (Crystalline Solids) 45

3 Optical Properties of Disordered Condensed Matter 67

4 Optical Properties of Glasses 83

4.12.3 Rare-Earth-Doped Transparent Glass Ceramics for Active

5 Concept of Excitons 129

6.4.3 Exploring Broad PL Lifetime Distribution in a-Si:H by

7 Photoluminescence, Photoinduced Changes, and Electroluminescence in

8 Photoinduced Bond Breaking and Volume Change in Chalcogenide Glasses 241

8.4.1 a-Se 245

9 Properties and Applications of Photonic Crystals 251

10 Nonlinear Optical Properties of Photonic Glasses 269

10.3.3 Nonlinear Refractivity 278

11 Optical Properties of Organic Semiconductors 295

12 Organic Semiconductors and Applications 323

12.4.3 Surface Electronic Properties of MoO3 -PEDOT:PSS HIL 363

13 Transparent White OLEDs 373

14 Optical Properties of Thin Films 403

15 Optical Characterization of Materials by Spectroscopic Ellipsometry 435

15.3 Measureable Quantities 438

16 Excitonic Processes in Quantum Wells 465

17 Optoelectronic Properties and Applications of Quantum Dots 503

17.5.2.2 Photonic Crystal Waveguide 531

18 Perovskites – Revisiting the Venerable ABX3 Family with Organic

19 Optical Properties and Spin Dynamics of Diluted Magnetic Semiconductor

20 Kinetics of the Persistent Photoconductivity in Crystalline III-V

Takeshi Aoki Joint Research Center of High-technology, Department of Electronics and

J. Mistrík Center of Materials and Nanotechnologies, Faculty of Chemical Technology,

Wiley Series in Materials for Electronic and Optoelectronic

measuring photoluminescence together with updates in luminescence results in amor-

Darwin, Australia Jai Singh

Fundamental Optical Properties of Materials I

1.2 Optical Constants n and K

1.2.1 Refractive Index and Extinction Coeﬃcient

this dependence is called dispersion. In addition to dispersion, an EM wave propagating

The reﬂectance R is then deﬁned by:

1.2.2 n and K, and Kramers–Kronig Relations

refractive index written as n* = n(𝜔) + iK(𝜔),

1.3 Refractive Index and Dispersion

1.3.1 Cauchy Dispersion Relation

Material ℏ𝝎(eV) Min ℏ𝝎(eV) Max n−2 (eV2 ) n0 n2 (eV−2 ) n4 (eV−4 )

Diamond 0.0500 5.4700 −1.07 × 10−5 2.378 0.00801 0.000104

1.3.2 Sellmeier Equation

Table 1.2 Sellmeier coeﬃcients of a few materials, where 𝜆1 , 𝜆2 , 𝜆3 are in μm.

SiO2 (fused silica) 0.696749 0.408218 0.890815 0.0690660 0.115662 9.900559

where A, B, C, D, E, and 𝜆o are constants particular to a given material. Eq. (1.18) is

Table 1.3 Parameters of Eq. (1.19) for some selected materials.

Material 𝝀o (𝛍m) A B (𝛍m)2 C (𝛍m)4 D (𝛍m)−2 E (𝛍m)−4

Silicon 0.028 3.41983 0.159906 −0.123109 1.269 × 10−6 −1.951 × 10−9

1.3.3 Refractive Index of Semiconductors

1.3.3.2 Bandgap and Temperature Dependence

1.3.4 Refractive Index of Glasses

Ai Bi (eV) C i (eV2 ) n(∞) E g (eV)

Si 0.00405 6.885 11.864 1.950 1.06

1.3.5 Wemple–DiDomenico Dispersion Relation

Table 1.6 Examples of parameters for Wemple–DiDomenico dispersion relationship in various

Material Nc Za Ne E o (eV) E d (eV) 𝜷 (eV) 𝜷 Comment

NaCl 6 1 8 10.3 13.6 0.28 𝛽i Halides, LiF, NaF, etc.

Note: Values extracted and combined from tables in [91].

1.3.6 Group Index