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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
6.1 Introduction 157
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
7.1 Introduction 203
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
8.1 Introduction 241
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
9.1 Introduction 251
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
10.1 Introduction 269
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
10.5 Conclusions 285
10.A Addendum: Perspectives on Optical Devices 286
References 288

11 Optical Properties of Organic Semiconductors 295


Takashi Kobayashi and Hiroyoshi Naito
11.1 Introduction 295
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
11.9 Conclusions 320
References 321

12 Organic Semiconductors and Applications 323


Furong Zhu
12.1 Introduction 323
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


12.5 Conclusions 368
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
13.4 Conclusions 400
References 400

14 Optical Properties of Thin Films 403


V.-V. Truong, S. Tanemura, A. Haché, and L. Miao
14.1 Introduction 403
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
14.6 Conclusions 430
References 430

15 Optical Characterization of Materials by Spectroscopic Ellipsometry 435


J. Mistrík
15.1 Introduction 435
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
15.9 Conclusions 462
Acknowledgments 463
References 463

16 Excitonic Processes in Quantum Wells 465


Jai Singh and I.-K. Oh
16.1 Introduction 465
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
16.7 Conclusions 499
References 500

17 Optoelectronic Properties and Applications of Quantum Dots 503


Jørn M. Hvam
17.1 Introduction 503
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


17.6 Conclusions 533
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 Introduction 537
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
18.5 Conclusions 582
Acknowledgments 583
References 583

19 Optical Properties and Spin Dynamics of Diluted Magnetic Semiconductor


Nanostructures 589
Akihiro Murayama and Yasuo Oka
19.1 Introduction 589
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
19.6 Conclusions 607
Acknowledgments 608
References 609
xiv Contents

20 Kinetics of the Persistent Photoconductivity in Crystalline III-V


Semiconductors 611
Ruben Jeronimo Freitas and Koichi Shimakawa
20.1 Introduction 611
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
20.5 Conclusions 623
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,
Winston-Salem, North Carolina, USA
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
Darwin University, Darwin, Australia
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
Darwin University, Darwin, Australia
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,
Winston-Salem, North Carolina, USA
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
1.2 Optical Constants n and K 3

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
4 1 Fundamental Optical Properties of Materials I

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
1.2 Optical Constants n and K 5

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
6 1 Fundamental Optical Properties of Materials I

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
1.3 Refractive Index and Dispersion 7

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,
8 1 Fundamental Optical Properties of Materials I

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.
1.3 Refractive Index and Dispersion 9

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.
10 1 Fundamental Optical Properties of Materials I

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.
1.3 Refractive Index and Dispersion 11

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.
12 1 Fundamental Optical Properties of Materials I

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
1.3 Refractive Index and Dispersion 13

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
14 1 Fundamental Optical Properties of Materials I

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
1.3 Refractive Index and Dispersion 15

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.
16 1 Fundamental Optical Properties of Materials I

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.
18 1 Fundamental Optical Properties of Materials I

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
STRONG ABSORPTION REGION

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.
1.4 The Swanepoel Technique: Measurement of n and α for Thin Films on Substrates 19

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
20 1 Fundamental Optical Properties of Materials I

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
STRONG ABSORPTION REGION

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
1.4 The Swanepoel Technique: Measurement of n and α for Thin Films on Substrates 21

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
STRONG ABSORPTION REGION

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.


22 1 Fundamental Optical Properties of Materials I

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
1.4 The Swanepoel Technique: Measurement of n and α for Thin Films on Substrates 23

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
STRONG ABSORPTION REGION

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.
24 1 Fundamental Optical Properties of Materials I

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
STRONG ABSORPTION REGION

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),
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Sie werden erraten, daß in diesem Tale ein Mann lebt, der diese
Erfolge begründet hat. Sein Name ist George F. Johnson, aber
jedermann nennt ihn »George F.«.
Er lebt in einem netten Hause in der Nähe des Parks. Er ist immer
sichtbar. Er lebt, bewegt sich und hat sein Dasein inmitten seiner
Leute.
Jeder Arbeiter kann ihn in seinem Bureau sprechen. Ist er nicht in
seinem Bureau, so kann man ihn auf der Rennbahn, im Tanzpavillon
oder bei einem Ballspiel antreffen.
Für gewöhnlich ist er umgeben von einer Schar von Kindern oder
von einer Arbeitermenge. Ununterbrochen fragen die Leute ihn um
Rat in allen erdenklichen Angelegenheiten. »Er ist der Papa unserer
Familie,« sagen sie.
Jedes Kind auf der Straße nennt ihn »George F.«. Denkt daran
und erschauert, ihr steifgeborenen Direktoren mit den versteinerten
Gesichtern! Hier ist ein Mann, der 28 000 000 Pfund Sterling im Jahr
umsetzt, und der Zeit hat, Drachen steigen zu lassen und Puppen zu
flicken.
Am letzten Maitage hatten die Arbeiter seines Tales eine große
Parade von 20 000 Mann, und wer glauben Sie, führte sie? George
F. Er ging an der Spitze seiner Leute, wie jedermann es von ihm
erwartete.
»Sie wissen, ich liebe alle diese Leute«, sagte er zu einem
Freund, als sie zusammen auf der Tribüne saßen und auf das
nächste Pferderennen warteten. »Und ich hoffe,« fügte er hinzu,
»daß einige von ihnen auch mich lieben.«
Er ist kein Philantrop, dieser George F., weder ist er ein Genie
noch ein Übermensch. Er ist nichts weiter als
ein großer, einsichtsvoller, gutherziger Mann,
der es liebt, inmitten geschäftiger, frohsinniger Menschen zu leben.
In diesem Tal gibt es keine Verdächtigung und keinen Snobismus.
Es gibt dort kein »Klassenbewußtsein«, weil es keine Klassen gibt.
Jeder Arbeiter hat die Möglichkeit, Teilhaber zu sein, und jeder
Kapitalist arbeitet.
Die sämtlichen 15 000 Arbeiter von George F. abwärts bis zu dem
kleinsten Jungen in der Gerberei gehören alle den »E.-J. Workers«,
der dortigen Gewerkschaft an.
Alles geschieht offen. Jedermann kann seine Meinung äußern. Es
gibt keine Maßregelungen. Alle Arbeiter scheinen zu fühlen, daß die
ganze Anlage ihnen gehört.
George F. Johnson ist jetzt über 70 Jahre alt. Er ist der
erfolgreichste unter allen Schuhfabrikanten, aber vor 35 Jahren war
er noch nichts als ein Vorarbeiter in einer kleinen Schuhfabrik, die
zusammengebrochen war. Damals erzielt er weniger als 20 Dollar
wöchentlichen Lohn.
Der Hauptgläubiger dieser kleinen bankrotten Fabrik war ein
Finanzmann namens Endicott, der in Boston lebte. Er kam
nachzusehen, was man tun könne. Er lernte dort F. Johnson kennen,
und Johnsons Vernunft und Ernst machten ihm einen tiefen
Eindruck.
»Ich habe kein Geld,« sagte Johnson, »aber ich kann aus dieser
Fabrik einen Erfolg machen. Mir liegt nichts an einem Gehalt, aber
wenn Sie mir den halben Anteil an der Fabrik für 150 000 Dollar
verkaufen wollen, will ich Ihnen meinen Wechsel dafür geben.«
Das war ein erstaunlicher Vorschlag. Er war absurd und riskant,
aber Endicott war ein weiser Mann, und er stimmte zu. Er wettete
150 000 Dollar auf Johnson.
Die kleine Fabrik machte ihre Fortschritte in Riesensprüngen. Sie
wuchs, bis Johnson sich als Vater einer Familie von 15 000 fand.
Die Arbeiter seiner Fabrik leben jetzt in zwei Städten, die gänzlich
ihnen gehören und die sie »Endicott« und »Johnson« genannt
haben.
Sie sind nicht Angestellte im gewöhnlichen Sinne. Sie sind
Teilhaber.
Gerade so wie Endicott Johnson zu seinem Teilhaber machte, ohne
von ihm Bezahlung für seine Aktien zu verlangen, so hat Johnson
aus seinen Arbeitern Teilhaber gemacht.
Vier Fünftel von ihnen arbeiten im Akkord und alle nehmen an
dem Nutzen teil, sobald sie ein Jahr lang in der Fabrik tätig gewesen
sind.
Alljährlich werden auf die Vorzugsaktien sieben Prozent und auf
die Stammaktien zehn Prozent Dividende gezahlt; der gesamte dann
noch verbleibende Nutzen wird zu gleichen Teilen zwischen den
Arbeitern und den Inhabern der Stammaktien geteilt.
Die Gesellschaft beschließt jedes Jahr, ob der Nutzen in Geld oder
in Stammaktien auszuzahlen ist. Für gewöhnlich beträgt der
Nutzanteil der Arbeiter 50 Prozent ihres gesamten Lohnes.
Der Hauptunterschied zwischen dieser Endicott-Johnson-
Gesellschaft und anderen guten Firmen scheint zu sein, daß die
Arbeiter auch ihrerseits volle Leistung geben. Sie geben ebenso wie
sie bekommen.
So hat zum Beispiel vor kurzem George F. Johnson die beiden
Städte mit einem prachtvollen Denkmal beschenkt, das der
Bildhauer Moretti zur Erinnerung an die 1692 Angestellten des
Werkes ausgeführt hat, die in dem großen Kriege gekämpft hatten.
Dann wiederum beschenkten die Arbeiter ihrerseits Johnson mit
einem schönen Marmorportal. Die gesamten Kosten dieses
Bauwerkes trugen die Arbeiter.
Oft hält George F., der Vater dieser beiden Städte, Ansprachen an
seine Leute — klare, einfache Ansprachen von eindringlicher
Wirkung. So sagte er unter anderem:
»Wenn Sie Besseres leisten, gehört der Nutzen in dieser
Gesellschaft Ihnen. Niemand steht da und wartet darauf, ihn Ihnen
wegzunehmen.«
»Jeder von uns auf dieser Welt braucht jemand, der uns
veranlaßt, unser Bestes zu tun.«
»Wir können unsere Erzeugungskosten herabsetzen, ohne unsere
Löhne zu vermindern,
wenn wir alle zusammenwirken wollen, um die Nichtproduzierenden
auszuscheiden, die Bremser und die Schmarotzer.«
»Ich bitte euch nicht, irgend etwas für mich zu tun. Ich bitte euch
nur, euer Bestes für euch zu tun. Und das Beste, das ihr heute tun
könnt, ist noch nicht das Beste, das ihr morgen tun könnt.«
»In diesem demokratischen Geschäft müssen wir uns alle selbst
fragen: Wieviel Arbeiter haben wir angestellt, die wir entbehren
könnten? Wie viele sind nur eine Belastung und eine Ausgabe für
uns?«
»Seid keine Bürde! Schafft keine Hindernisse! Faßt euer Ruder
und zieht fest an. Seid der Mühe wert! Tut euer Bestes! Gebt dem
alten Geschäft seine Chancen!«
Thomas A. Edison.
Edison ist jetzt bald 80 Jahre alt. Er wurde in Ohio von englisch-
holländischen Eltern geboren. Sein Vater war ein Landwirt und
Getreidehändler ohne besondere Erfolge.
Mit acht Jahren wurde Edison zur Schule geschickt. Drei Monate
später schickte ihn der Lehrer mit der Bemerkung nach Hause, daß
er zu dumm sei, um unterrichtet zu werden. (Was für ein Narr war
dieser Lehrer.)
Edison hatte niemals mehr Schulunterricht. Seine Mutter, eine
kluge und gute Frau, unterrichtete ihn selbst.
Er war immer ein eigentümlicher Junge. Mit sechs Jahren fand
man ihn einmal auf Gänseeiern sitzen, die er auszubrüten versuchte.
Bei einem anderen Anlaß machte er ein großes Experiment in der
Scheune und steckte sie in Brand, wofür er eine gute Tracht Prügel
erhielt.
Von Anfang an hatte er eine Neigung für Chemie. In seinem
räumlichen Hause richtete er sich ein Laboratorium mit 200 Flaschen
ein. Er versah jede einzelne davon mit der Aufschrift »Gift«, damit
niemand sie berühren sollte.
Mit 14 Jahren wurde er Zeitungsjunge und verkaufte Magazine
und Zeitungen auf Eisenbahnzügen.
Er hatte auf dem Zuge ein kleines Laboratorium. Schließlich
steckte er damit den Zug in Brand, und der Schaffner warf ihn hinaus
und ließ seine Flaschen folgen. Auch gab er dem Jungen eine so
mächtige Ohrfeige, daß er seit damals taub wurde.
Mit 16 Jahren wurde er in Kanada Telegraphenbote. Er verlor aber
seine Anstellung, weil er eine arbeitsparende Erfindung machte —
sein Vorgesetzter sagte, er wäre faul. Aus ähnlichen Gründen verlor
er später noch drei weitere Anstellungen.
Mit 23 Jahren wanderte er nach Neuyork. Dort kam er ohne einen
Heller an. Er erhielt eine Stellung in dem Bureau einer
Börsentelegraphenfirma mit 300 Dollar monatlich. Das war seine
erste Chance. Er erhielt dieses hohe Gehalt, weil er es
zustandegebracht hatte, eine wertvolle Maschine zu reparieren, die
in Unordnung geraten war.
Im nächsten Jahre erfand er einen Telegraphenapparat, den er der
Western Union Telegraphen-Gesellschaft für 40 000 Dollar verkaufte.
Er hätte auch ganz gerne 400 000 Dollar dafür genommen, da er von
dem Wert seiner Erfindung zu jener Zeit keine Ahnung hatte.
Er benutzte diese 40 000 Dollar, um eine Maschinenwerkstatt zu
eröffnen. Im Jahre 1873 kam er das erstemal nach England und
verkaufte einige seiner Erfindungen.
Eine englische Firma machte ihm ein Angebot von
»dreißigtausend« für eines seiner Patente. Edison dachte, es
bedeutete 30 000 Dollar — er sagte: »Ja.« Zu seiner Überraschung
erhielt er 30 000 Pfund — fünfmal so viel. Seit jener Zeit hat Edison
ein warmes Gefühl für England.
Edison ist der fruchtbarste Erfinder der Welt. Er hat über 1000
Patente erworben. 45 Jahre lang ist er ein berufsmäßiger Erfinder.
Er ist der ausdauerndste aller Experimentierer. Er arbeitete schwerer
und schläft weniger als irgendein anderer Mensch. Es liegt ihm
nichts am Geld. Er raucht und kaut Tabak.
Er haßt neue Kleider. Seit 30 Jahren ist ihm nicht für einen neuen
Anzug Maß genommen worden. Vor 30 Jahren hat ihm irgendein
gewisser Schneider Maß genommen und seither geht er immer
wieder zu diesem und sagt: »Ich möchte einen anderen Anzug von
dem gleichen Stoff.«
Er hat viele Mißerfolge und einige wunderbare Erfolge
aufzuweisen. Einmal wendete er zwei Jahre und 2 000 000 Dollar an
eine Erfindung, die sich als ziemlich wertlos herausstellte.
Er macht sich nichts aus Ehren. Eine englische Universität bot ihm
ein Ehrendoktorat — er hat sich niemals die Mühe genommen,
hinzukommen, um es in Empfang zu nehmen. Vor einiger Zeit wurde
ihm in Neuyork eine Goldene Medaille verliehen. Er verlor sie
unterwegs auf dem Fährboot. »Was liegt daran«, sagte er zu seiner
Frau. »Ich habe mindestens zwei Liter solcher Medaillen in meinem
Zimmer.«
Als er das letztemal in Frankreich war, erhielt er das Kreuz der
Ehrenlegion. Er nahm das Kreuz an, aber als man ihm auch die
Schärpe anlegen wollte, zog er sich zurück und ließ es nicht zu.
Nach seiner Denkungsart ist eine Schärpe an einem Mann ungefähr
so töricht wie ein Band an einem Frosch.
Seine Erfindungen haben viel zur Bequemlichkeit und
Annehmlichkeit der Welt beigetragen. Tatsächlich war sein ganzes
Leben sozialer Dienstleistung gewidmet.
Sein intimster Freund ist vielleicht Henry Ford — ein anderer
Erfinder von gleichem Typus. Diese beiden Männer gehen
gemeinsam mit John Burroughs, dem führenden Naturforscher
Amerikas, jeden Winter auf eine Pflanzung nach Florida.
Edison hat niemals einen unbeschäftigten Augenblick. Selbst
wenn er spielt, erfindet er. Ich habe ihn bei verschiedenen
Gelegenheiten in seinem langen schmalen Laboratorium in
Neujersey beobachtet, wie er grübelte und grübelte und grübelte,
immer in irgendein schweres Problem vertieft.
Edison glaubt selten etwas, bevor er den Beweis dafür hat. Er hat
eine Fülle von Zweifeln in Bezug auf die Meinungen und die
Praktiken der Menschen auf Lager.
In seiner Bibliothek hat er mehr als zehntausend Bücher, meist
wissenschaftliche Gegenstände. Aber Edison glaubt selten
irgendeine Feststellung in irgendeinem dieser Bücher, bevor er sie
selbst ausprobiert und bewiesen hat.
Bei seiner Arbeit nimmt er ein Buch lediglich als Ausgangspunkt,
um anzufangen. Es bedeutet keineswegs einen Abschluß.
Sein ganzes Leben hat er damit zugebracht, jenes Niemands-
Land zu erforschen, das außerhalb der Bücher besteht.
Edison ist zuerst und vor allem ein harter Arbeiter. Er verabscheut
Faulheit als die schlimmste von allen Krankheiten. Er wird unter
Umständen einen dummen Menschen beschäftigen, aber niemals
einen faulen.
Edison nimmt nichts als vorausgesetzt an. Er hat eine Abneigung
gegen Menschen, die sprunghaft und oberflächlich sind. In jeder
Sache gräbt er bis an die Wurzeln. Er hat sein ganzes Leben damit
zugebracht, das Warum herauszufinden.
Lord Rhondda.
Dies ist die Geschichte des Mannes, der, ohne ein Redner zu sein,
sein Leben lang der »ungekrönte König von Wales« war — D. A.
Thomas, der in den letzten beiden Jahren seines Lebens als Lord
Rhondda bekannt war.
»D. A.«, wie seine Freunde ihn nannten, war der größte
Geschäftsschöpfer, den Wales jemals hervorgebracht hat.
Er war der Schöpfer der »Cambrian Coal Combine« — einer
Gartenstadt von 12 000 gutbezahlten Bergleuten. Er gründete mehr
als 30 Gesellschaften, und was immer er anfaßte, wurde ein Erfolg.
Als er im Jahre 1918 starb, betrug sein Vermögen gegen 685 000
Pfund — aber er hätte leicht doppelt so viel haben können. Er war
immer mehr darauf bedacht, ein Geschäft aufzubauen, als seinen
Anteil an dessen Nutzen hereinzubekommen.
D. A. Thomas war ein kaufmännischer Abenteurer von der Art, die
das britische Weltreich aufgebaut hat. Er war mehr als das — er war
ein unabhängiger Denker.
Er war so unabhängig, daß er noch nicht seinem vollen Werte
nach gewürdigt worden ist, wie Sie beim Lesen der folgenden kurzen
Skizze seiner Laufbahn sehen werden.
Er wurde vor 70 Jahren in einem kleinen Dorfe in Wales, dessen
Namen ich nicht buchstabieren kann, geboren. Sein Vater war ein
Krämer, der ein Kohlengeschäft angefangen hatte und dies sehr
bedauerte.
Man erzählt, daß sein Vater vor seinem Kohlenlager stand und
sich von seinen Verlusten sehr bedrückt fühlte, als ein Nachbar mit
der Nachricht zu ihm kam: »Es ist ein Junge.«
»Gut«, sagte der Vater. »Ich weiß zwar nicht, was aus ihm werden
soll. Für uns gibt es nur noch das Armenhaus.«
Der junge D. A. war anfangs ein zarter Knabe, aber er trainierte
sich zu einem Athleten. Er wurde ein guter Geher, Schwimmer und
Radfahrer. Er war auch ein geschickter Boxer, und ungeachtet seiner
Kurzsichtigkeit wurde er Mittelgewichts-Champion von Cambridge.
Er war immer mutig. Als junger Bursche gewann er die Medaille
der »Royal Humane Society« für eine Lebensrettung. Er sprang in
einen eisigen See und zog einen Mann aus dem Wasser.
Als er 21 Jahre alt war, starb sein Vater, und er begann ein
selbständiges Geschäft. Mit 26 Jahren heiratete er Sybill Haig, die
Tochter eines Kohlenbergwerksbesitzers. Sie hatten ein Kind, die
gegenwärtige Viscountesse Rhondda, die jetzt die
weitausgedehnten Interessen ihres Vaters verwaltet.
D. A. beschäftigte sich mit Politik nicht weniger als mit dem
Geschäft. Aber als Politiker hatte er keinen Erfolg, oder besser
gesagt, er war nicht der Mann, sich in den schlüpfrigen Winkelzügen
des Parlaments zurecht zu finden.
Er war ein Liberaler, aber er ließ sich durch keine Führung
beeinflussen. Er war kein angestelltes Parlamentsmitglied mit dem
Namen seines Meisters auf seinem Halsband.
Er war unabhängig. Das ist das Wort, das in diesen Tagen der
Maschinenmenschen besonders betont werden muß.
Die kunstreichen Ränkemacher der Politik fürchteten und haßten
ihn. Er war zu tüchtig — zu ehrenhaft — zu furchtlos, um ein Mitglied
der Mitglieder zu werden.
Wie Leverhulme wurde er von den Kabinettsmachern vollkommen
vernachlässigt. Es ist eine auffallende Tatsache, daß D. A. Thomas
25 Jahre lang dem Parlament angehört hat und niemals ein
wichtiges Amt bekleidet hat.
Im Jahre 1910 gab er die Politik auf. Es wurde ihm klar, daß er
vollständig ungeeignet war, das Spiel der Politik mitzumachen. Er
war kein guter Redner. Seine Stimme war schwach, und er hatte nie
daran gedacht, sie auszubilden. Er hatte eher eine Verachtung für
fließendes Reden: in einem Lande, das stets von redegewandten
Leuten regiert worden war, entschieden ein Fehler!
Stets zog er das Geschäft der Politik vor. Das Geschäft war sein
Leben. Er liebte seine Aufregungen und seine Nützlichkeit.
Immerwährend las er Bücher über Geschäft.
Er war kein Zuschauer. Er war voll Energie — durchaus
Tatmensch. Er liebte seinen großen Schreibtisch in seinem großen
Bureau in dem Cambrian-Gebäude in Cardiff.
Er hatte einen stahlharten Willen, aber er war weder grob noch
laut. Er war ein ruhiger, zäher, schlauer Mann, der alles
vorauszusehen schien.
Er hatte auch Streiks, natürlich. Niemand kann die Bergleute von
Süd-Wales beschäftigen, ohne Streiks zu haben. Aber selbst die
Streikleiter achteten D. A. und sympathisierten mit ihm, wenn die
Schlacht einmal vorüber war.
Sein ganzes Leben lang war er ein Gegner der Staatskontrolle.
Sein einziger Fehler in dieser Hinsicht war sein Vorschlag, ein
Gesundheitsamt zu errichten. Er widersprach der Staatsidee amtlich
fixierter Löhne, ohne Rücksicht auf seine persönlichen Vor- oder
Nachteile.
Er hatte eine Menge Feinde — Leute, die versucht hatten, ihn zu
narren, ihn zu betrügen oder ihn zu bedrohen. »Kein Mann ist sein
Salz wert,« sagte er, »der keine Feinde hat.«
Er verachtete langsame, verschlagene und unverläßliche Leute.
Er war kein Idealist. Er wußte, was Menschennatur ist. Aber er war
durchaus für ein faires Spiel und Festhalten an seinen Regeln.
Als er reich wurde, verdarb ihn sein Geld nicht. Er wurde niemals
ein Nabob. Er war immer gesellig. Er liebte die Arbeiter und zog
jederzeit ein Kohlenbergwerk dem Hause der Lords vor.
Er liebte die Landwirtschaft, aber er konnte sie nie einträglich
gestalten. Wer kann es? Er hatte eine große Herde von Hereford-
Schafen und einen großen Landsitz in Monmouthshire.
Während des Krieges legte er alle Privatangelegenheiten beiseite
und stellte seine volle Energie der Regierung zur Verfügung.
Er und seine Tochter waren an Bord der »Lusitania« bei ihrem
Untergang, wurden aber aufgefischt und gerettet. Kaum in England
angelangt, wurde er ersucht, wieder den Ozean zu kreuzen — und
er tat es. Er war ein Mann ohne Furcht.
Als Nahrungsmittelkontrolleur hatte er mehr Erfolg als irgendein
anderer Träger dieses Amtes in irgendeinem andern Land.
Jedermann fühlte, daß er vollkommen gewissenhaft vorging und
daß, was immer er tat, das Rechte war.
Schließlich, im Jahre 1918, wurde er von seiner Bürde erdrückt. Er
starb — 20 Jahre zu früh. Er gab sein Leben für sein Land, so gut
wie irgendein Kämpfer.
Er war ein charakteristischer britischer Geschäftsmann vom
vornehmsten Typ. Er liebte Wales, seine Bergleute und das ganze
Land. Seinen Adelstitel nahm er von dem Rhonddatal, wo seine
Bergleute lebten. Und er überschüttete Cardiff mit Geschenken.
Sir Swire Smith.
Vor ungefähr zehn Jahren gab es in der Stadt Keighley in
Yorkshire ein bemerkenswertes Begräbnis. Mehr als 700
Trauergäste schritten hinter einer Bahre einher, während Tausende
die Straßen säumten.
Der beste Maßstab, um den Erfolg eines Menschen im Leben zu
beurteilen, ist die Größe seines Begräbnisses. Es ist eine endgültige
Demonstration seiner Fähigkeit, Freunde zu gewinnen.
Demgemäß war Sir Swire Smith erfolgreich. Er hatte 76 Jahre
menschlicher Zeitrechnung gelebt — in der Wertung seines Lebens
war er einer der Höchststehenden seiner Generation.
Sir Swire Smith war ein Meisterspinner. Er war auch ein
Sportsmann — ein Witzbold — ein Sänger — ein Weltreisender —
ein Erzieher — ein guter Kamerad — ein Pionier.
Er war der »Peter Pan« von Yorkshire. Mit 76 Jahren war er
jünger, als die meisten Menschen mit 30.
Er war im Jahre 1842 in einem kleinen Häuschen von Keighley
geboren. Sein Vater hatte ein kleines Maschinengeschäft. Auch war
er Methodist, und der junge Swire wurde nach den strengen Regeln
von John Wesley erzogen.
Er war ein lustiger Junge mit blauen Augen und gelocktem Haar.
Wie alle normalen Jungen, war er voll Übermut. Mit 16 Jahren
begann er in einer Spinnerei zu arbeiten.
Mit 20 Jahren fing er seine eigene Wollspinnerei mit einem Kapital
von 360 Pfund Sterling an. Er hatte keinen besonderen Erfolg, weil
er zu keiner Zeit sehr eifrig auf Gelderwerb bedacht war. Das
Wollgeschäft war matt und unbeständig und voll Unsicherheit.
Swire Smith fand sich selbst nicht früher, als in seinem 25. Jahr.
Um diese Zeit hörte er eine Vorlesung von Samuel Smiles, dem
Verfasser von »Hilf dir selbst«.
Damals bereiste Samuel Smiles England und Schottland nach
allen Richtungen, schrieb und sprach über wirksamen Betrieb und
die Notwendigkeit technischer Ausbildung. Er war ein Rufer in der
Wüste. Er zeigte Britannien, daß Deutschland und Amerika im
Begriff seien, vorzustoßen.
Diese Warnungen entflammten Swire Smith. Er wurde sofort
Sekretär des »Mechanics Institute«.
Zu jener Zeit lebten in Keighley nur gegen 20 000 Menschen, und
die wenigsten von ihnen kümmerten sich auch nur im mindesten um
technische Erziehung — aber der junge Swire ließ nicht nach. Er
brachte 11 000 Pfund Sterling für eine technische Schule auf, die im
Jahre 1870 eröffnet wurde. Ihr Zweck war, die Prinzipien von
Wissenschaft und Kunst auf die Betätigung in Handel und Wandel
anzuwenden. Keighley wies den Weg, aber England folgte nicht.
Hätte es gefolgt, es wäre heute in einer viel glücklicheren Lage.
Die kleine Schule von Keighley brachte Northrop, den Erfinder des
automatischen Webstuhls hervor. Aus ihr kam W. H. Watkimson, der
die »Husch-Husch-Boote« erfand, und Alfred Fogler von dem Kgl.
Kollegium der Wissenschaften.
Sie brachte Leben in das Parlament, und das Ergebnis war das
Gesetz vom Jahre 1889 über technische Ausbildung. Dieses Gesetz
gab ähnlichen Schulen Millionen Pfund Sterling. Zu dieser Zeit führte
die Keighley-Schule mit 1400 Schülern.
Die Vereinigten Staaten folgten ebenso dem Beispiel von Keighley
wie England. Andrew Carnegie, ein lebenslanger Freund von Swire
Smith, besuchte Keighley, sah die Schule und gründete sofort nach
seiner Rückkehr nach Pittsburgh die größte technische Schule
Amerikas.
Wie Sie sehen, entsprang alles dieses dem Enthusiasmus eines
jungen 24jährigen Mannes, der eine Vorlesung von Samuel Smiles
über wirksamen Betrieb gehört hatte.
Mit 39 Jahren überredete Swire Smith die Regierung, eine
königliche Kommission für technische Erziehung zu ernennen. Er
und sechs andere wurden ihre Mitglieder.
Diese Kommission ging nach Deutschland und entdeckte viele
überraschende Tatsachen: sie fand 8000 Schüler in den
Gewerbeschulen von Hamburg; sie fand, daß die Technische
Hochschule von Stuttgart, einer keineswegs sehr großen Stadt,
mehr Studenten hatte als Liverpool.
Sie ging nach Frankreich, der Schweiz, Amerika und Kanada, und
ihr Bericht brachte Fortschritt und Bewegung in die meisten
britischen Industrien. Wie die Regierung zugab, war dieser Bericht
zum größten Teil aus den Notizen von Sir Swire Smith
zusammengestellt worden.
Als Arbeitgeber gab Sir Swire Smith ein gutes Beispiel. Sein Plan
war, »die besten Leistungen durch Zahlung der höchsten Löhne« zu
erzielen. Er begann die Ausbildung seiner Angestellten in seiner
eigenen Spinnerei und zahlte die halben Kosten einer besseren
technischen Schulung für jeden Arbeiter, der sie wünschte.
Wenn er zu Hause war, ging er täglich zweimal durch seine
Werke. Er kannte alle seine Arbeiter bei Namen und frühstückte
zusammen mit ihnen in der Kantine.
Einmal war er entzückt, als ein kleiner Junge auf der Straße
einmal zu einem anderen sagte: »Sieh mal, der Mann arbeitet in
unserer Spinnerei.«
Swire Smith war ein Anhänger des Grundsatzes: »Vergnügen und
40 Prozent«, aber er schätzte das Vergnügen höher als die vierzig.
Sein Glaubensbekenntnis war: »Wenn dein Geschäft deine
Lebensfreude beeinträchtigt, dann gib lieber dein Geschäft auf.«
Sein größter Fehler vom finanziellen Standpunkt war, daß er seine
Ersparnisse vollständig in Florida und in Texas anlegte. Hätte er sie
in Keighley angelegt, so wäre er aller Wahrscheinlichkeit nach ein
Millionär geworden. Im ganzen verlor er gegen 60 000 Pfund Sterling
dadurch, daß er sie in den Wildnissen der Vereinigten Staaten
anlegte.
Im Anekdotenerzählen hatte er kaum seinesgleichen. Wo immer
er war, gab es Gelächter. Sein Anekdotenschatz war unerschöpflich.
Er hatte eine sehr schöne Baritonstimme und war immer bereit,
eine alte Ballade oder eine Stelle aus einer Oper zu singen.
Als Sprecher war er lebhaft, unterhaltend und praktisch. Er war
nicht im geringsten steifleinen. Ehrungen machten ihm keinen
Eindruck. Bis an seines Lebens Ende blieb er ein Junge — kurz vor
seinem Tode lernte er noch einen neuen Tanz und schrieb ein paar
Kindern lustige Briefe.
Er blieb unverheiratet, obwohl er sehr oft verliebt war. Er war
niemals einsam. Die Welt war seine Familie. Keighley sollte ihm ein
vornehmes Denkmal setzen.
Henry Ford.
Hören Sie die staunenerregende Geschichte von Henry Ford, der
jetzt für nahezu das ganze Menschengeschlecht Motore und
Traktoren baut.
Urteilt man nach Ergebnissen, so ist Henry Ford der erfolgreichste
Fabrikant der Welt.
Er zahlt die höchsten Löhne.
Er macht die höchsten Profite.
Er verkauft zu den billigsten Preisen.
Henry Ford ist die lebendige Antwort auf die törichte Theorie, ein
Kapitalist könne nur dadurch Geld verdienen, daß er seine
Angestellten oder das Publikum beraubt.
Henry Ford beraubt niemanden, er ist kein Ausbeuter des
Proletariats.
Er ist ein Millionär — und jeder Pfennig seines Geldes ist rein.
Seine beispiellosen Profite sind nur ein Teil dessen, was er der
Öffentlichkeit erspart. Und er zahlt seinen Arbeitern weit mehr, als
sie selbständig verdienen können.
Henry Ford ist ein Kapitalist und er zeigt allen Kapitalisten einen
besseren Weg zum Reichtum.
Er hat sich seinen eigenen Erfolg geschaffen — er, zusammen mit
seinen Leuten. Er hat keinen Titel. Er würde niemals einen
annehmen. Er ist nicht einmal ein »Herr«. Seine Freunde nennen ihn
kurzweg Henry.
Er ist 64 Jahre alt. Er wurde auf einer kleinen Farm in der Nähe
von Detroit geboren. Sein Vater war ein irischer Auswanderer.

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