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 Published by
World Scientific Publishing Co. Pte. Ltd.
5 Toh Tuck Link, Singapore 596224
USA office: 27 Warren Street, Suite 401-402, Hackensack, NJ 07601
UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

光电材料与器件
Originally published in Chinese by China Science Publishing & Media Ltd.
Copyright © China Science Publishing & Media Ltd., 2017

PHOTOELECTRIC MATERIALS AND DEVICES

Copyright © 2021 by World Scientific Publishing Co. Pte. Ltd.
All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means,
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For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance
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April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page v

Profile

This book mainly introduces the basic theory and physical character-
istics of photoelectric materials, the preparation technology of photo-
electric components, the working principle, the latest application, the
latest progress of photoelectric materials and devices technology and
the correlation with other technologies. The content mainly involves
the theoretical basis of photoelectric materials, micro-nano photo-
electric materials and devices, semiconductor luminescent materials
and devices, inorganic photoluminescence materials, LED packaging
technology, transparent conductive materials, touch screen, display
screen, solar cell materials and the basic principles and development
trend of their applications. In particular, the book gives a systematic
theoretical analysis of new photoelectric materials and devices, such
as optoelectronic materials and devices, optoelectronic materials
and devices, and transparent conductive materials, and provides
application examples.
This book can be used as a reference for undergraduate and
graduate students, majoring in engineering such as optical informa-
tion science and technology, information display and photoelectric
technology, photoelectric information engineering, and photoelectric
materials and devices, as well as for researchers and engineers.

v
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April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page vii

Preface

With the rapid development of photoelectric technologies such

as information, display, semiconductor lighting and photoelectric
sensing, the photoelectric industry will be the most attractive sunrise
industry in the 21st century and has a huge development potential.
Photoelectric materials are the foundation and the precursor of
the whole photoelectric industry. The production of new materi-
als and devices promotes the significant progress of photoelectric
technology. Without these basic materials and devices, it is difficult
to assemble high-performance photoelectric equipment and build
high-performance photoelectric system. Photoelectric materials and
devices involve many disciplines such as optics, electronics and
materials. However, there are seldom reference books.
According to the “13th Five-Year Plan” of our university and
the idea of integrated construction of disciplines and specialties,
key disciplines and specialties of materials will be built to form
a discipline and specialty system that can meet the development
needs of local pillar industries and strategic emerging industries.
At present, the school has built materials science and engineering,
microelectronics science and engineering and other majors, planning
to build photoelectric information science and engineering, optical
engineering and other majors. As the main course of the above
majors, the teaching material construction of photoelectric materials
and devices is of great significance.
This book mainly deals with the theoretical basis of photo-
electric materials, micro-nano photoelectric materials and devices,
semiconductor luminescent materials and devices, LED packaging

vii
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page viii

viii Photoelectric Materials and Devices

technology, inorganic photoluminescence materials, transparent con-

ductive materials, touch screen, display screen, solar cell materials
and the basic principles and development trends of applications.
This book is compiled by the teachers of new material technology
research institute of Chongqing University of Arts and Sciences. It
is divided into ten chapters. Tao Han organized the compilation
of the book and wrote Chapters 1 and 6, Dianyong Tang wrote
Chapters 2 and 3, Shixiu Cao wrote Chapters 4 and 5, Haibo Ruan
wrote Chapter 7, Youwei Guan wrote Chapter 8, Xin Yang and Haibo
Ruan and Tao Han wrote Chapter 9, Xin Yang wrote Chapter 10.
The writing features of this book are as follows:
(1) starting from the current situation of technology, pay attention
to the close combination with the development environment of
modern photoelectric technology, and adapt to the idea of higher
education teaching reform;
(2) pay attention to the scientific, rigorous, advanced, practical and
targeted contents in the compilation;
(3) relevant content in simple terms, step by step, strengthen the
application, the details slightly appropriate.
Thanks to the textbook project of Chongqing University of Arts
and Sciences for the publication of this book.
Limited to the level of the editor, there are inevitably omissions
and deficiencies in the book, the majority of readers are invited to
criticize and correct, so as to correct.

January 2017 Tao Han

Chongqing University
of Arts and Sciences
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page ix

Contents

Profile v

Preface vii

Chapter 1. Introduction 1
1.1 Brief Introduction of Photoelectronics
Technology . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Development course of optoelectronics
technology . . . . . . . . . . . . . . . . . . . 1
1.1.2 Related concepts of optoelectronic
technology . . . . . . . . . . . . . . . . . . . 3
1.2 The Concept, Position and Function of Photoelectric
Materials and Devices . . . . . . . . . . . . . . . . . 6
1.2.1 Basic concepts of photoelectric materials
and devices . . . . . . . . . . . . . . . . . . . 6
1.2.2 The position and function of photoelectric
materials and devices in photoelectric
technology . . . . . . . . . . . . . . . . . . . 7
1.3 The Theoretical Basis of This Book . . . . . . . . . . 8
1.3.1 Photoelectric conversion materials
and devices . . . . . . . . . . . . . . . . . . . 8
1.3.2 Electro-optical conversion materials
and devices . . . . . . . . . . . . . . . . . . . 11
1.3.3 Transparent conductive material . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

ix
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page x

x Photoelectric Materials and Devices

Chapter 2. Theoretical Basis of Photoelectric

Materials 13
2.1 Energy Band Theory . . . . . . . . . . . . . . . . . . 13
2.1.1 Schrödinger equation of crystal and its
approximate solution . . . . . . . . . . . . . 14
2.1.2 Bloch’s theorem . . . . . . . . . . . . . . . . 19
2.1.3 Periodic boundary conditions . . . . . . . . . 21
2.1.4 Energy bands and their general
properties . . . . . . . . . . . . . . . . . . . . 23
2.1.5 Brillouin zone . . . . . . . . . . . . . . . . . 26
2.1.6 Metals, semiconductors and insulators . . . . 28
2.1.7 Electrons, holes and carriers . . . . . . . . . 31
2.2 The Process of Absorption in a Material . . . . . . . 33
2.2.1 The basic absorption . . . . . . . . . . . . . 35
2.2.2 Direct transition of permission and
prohibition . . . . . . . . . . . . . . . . . . . 36
2.2.3 Indirect transition . . . . . . . . . . . . . . . 39
2.2.4 Exciton . . . . . . . . . . . . . . . . . . . . . 44
2.3 The Photoelectric Effect . . . . . . . . . . . . . . . . 46
2.3.1 External photoelectric effect . . . . . . . . . 47
2.3.2 Photoconductive effect . . . . . . . . . . . . 53
2.3.3 Photovoltage . . . . . . . . . . . . . . . . . . 59
2.3.4 Thermoelectric effect . . . . . . . . . . . . . 67
2.3.5 Pyroelectric effect . . . . . . . . . . . . . . . 68
2.3.6 Photon traction effect . . . . . . . . . . . . . 70
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

Chapter 3. Micro/Nano Photoelectric

Materials and Devices 73
3.1 Nanometer Photoelectric Materials and Devices . . . 74
3.1.1 Nano photoelectric materials . . . . . . . . . 74
3.1.2 Nanometer photoelectric devices . . . . . . . 76
3.2 Photonic Crystals and Photonic Crystal
Devices . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.2.1 Structure of photonic crystals . . . . . . . . 80
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page xi

Contents xi

3.2.2 Basic properties of photonic crystals . . . . . 81

3.2.3 Photonic crystal devices . . . . . . . . . . . . 83
3.3 Metamaterials and Related Devices . . . . . . . . . . 89
3.3.1 Metamaterials . . . . . . . . . . . . . . . . . 89
3.3.2 Negative refractive index materials
and devices . . . . . . . . . . . . . . . . . . . 89
3.3.3 Stealth cloak . . . . . . . . . . . . . . . . . . 95
3.4 Surface Plasmon Polaritons and Devices . . . . . . . 98
3.4.1 Basic principles and properties . . . . . . . . 98
3.4.2 Surface plasmon optical waveguide . . . . . . 100
3.4.3 Surface plasmon resonance sensor . . . . . . 103
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 106

Chapter 4. Semiconductor Luminescent

Materials and Devices 109
4.1 Introduction to Semiconductor Luminescent
Materials Crystals . . . . . . . . . . . . . . . . . . . 110
4.1.1 Crystal structure . . . . . . . . . . . . . . . . 110
4.1.2 Defects and their effects
on luminescence . . . . . . . . . . . . . . . . 116
4.1.3 Energy band structure . . . . . . . . . . . . 118
4.1.4 Conditions of semiconductor luminescent
materials . . . . . . . . . . . . . . . . . . . . 124
4.2 Absorption of Light by Semiconductors . . . . . . . . 128
4.2.1 Classification of light absorbing mechanisms
in semiconductors . . . . . . . . . . . . . . . 128
4.2.2 Semiconductor optical absorption
theory . . . . . . . . . . . . . . . . . . . . . . 132
4.3 Excitation and Luminescence
of Semiconductors . . . . . . . . . . . . . . . . . . . 134
4.3.1 PN junction and its characteristics . . . . . . 134
4.3.2 Recombination of injected carriers . . . . . . 144
4.4 Light-Emitting Diode Lighting Technology . . . . . . 151
4.4.1 Basic characteristics of LED . . . . . . . . . 152
4.4.2 LED luminescence principle . . . . . . . . . . 155
4.4.3 Characteristic parameters of LED . . . . . . 158
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xii Photoelectric Materials and Devices

4.4.4 LED driving technology . . . . . . . . . . . . 167

4.4.5 LED application . . . . . . . . . . . . . . . . 170
4.5 Photoluminescence and Electroluminescence
of Organic Materials . . . . . . . . . . . . . . . . . . 172
4.5.1 Photoluminescence principle
of organic materials . . . . . . . . . . . . . . 172
4.5.2 Relation between molecular structure
and luminescence properties . . . . . . . . . 176
4.5.3 Luminescence quenching phenomenon . . . . 177
4.5.4 Application of organic photoluminescent
materials . . . . . . . . . . . . . . . . . . . . 179
4.5.5 Structure and luminescence principle
of organic electroluminescent materials . . . 180
4.5.6 Advantages of organic electroluminescent
materials . . . . . . . . . . . . . . . . . . . . 181
4.5.7 Main problems of organic electroluminescent
materials . . . . . . . . . . . . . . . . . . . . 182
4.5.8 Future development trends of organic
electroluminescent materials . . . . . . . . . 182
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 183

Chapter 5. Inorganic Photoluminescent Materials 185

5.1 Inorganic Photoluminescence . . . . . . . . . . . . . 185
5.1.1 Photoluminescence process . . . . . . . . . . 185
5.1.2 Light return to ground state:
luminescence . . . . . . . . . . . . . . . . . . 187
5.1.3 Non-radiative return to ground state . . . . . 189
5.2 Luminescence Principle of Phosphor . . . . . . . . . 190
5.2.1 Basic concepts . . . . . . . . . . . . . . . . . 192
5.2.2 Characteristics of phosphors . . . . . . . . . 194
5.3 Development History and Present Situation
of Phosphors . . . . . . . . . . . . . . . . . . . . . . 197
5.3.1 Development history of fluorescent
powders for fluorescent lamps . . . . . . . . . 197
5.3.2 Rare earth tribasic phosphor . . . . . . . . . 199
5.3.3 White LED phosphor . . . . . . . . . . . . . 207
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page xiii

Contents xiii

5.4 Main Preparation Methods of Phosphors . . . . . . . 209

5.4.1 High-temperature solid-phase method . . . . 210
5.4.2 Combustion synthesis method . . . . . . . . 213
5.4.3 Solvent (hydrothermal) method . . . . . . . 215
5.4.4 Sol–gel method . . . . . . . . . . . . . . . . . 217
5.4.5 Precipitation method . . . . . . . . . . . . . 220
5.4.6 Spray pyrolysis . . . . . . . . . . . . . . . . . 221
5.4.7 Microemulsion method . . . . . . . . . . . . 224
5.4.8 Polymer network gel method . . . . . . . . . 225
5.4.9 Microwave method . . . . . . . . . . . . . . . 226
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 228

Chapter 6. Light-Emitting Diode Packaging

Technology 231
6.1 LED Packaging Mode . . . . . . . . . . . . . . . . . 231
6.1.1 Pin package . . . . . . . . . . . . . . . . . . 232
6.1.2 Surface mount packaging . . . . . . . . . . . 233
6.1.3 Power package . . . . . . . . . . . . . . . . . 234
6.1.4 Integrated multichip device packaging . . . . 235
6.1.5 Other packaging methods . . . . . . . . . . . 236
6.2 LED Packaging Technology . . . . . . . . . . . . . . 238
6.3 LED Packaging Materials and Equipment . . . . . . 244
6.3.1 LED packaging material . . . . . . . . . . . . 244
6.3.2 LED packaging equipment . . . . . . . . . . 252
6.4 Fluorescent Powder Coating Technology . . . . . . . 259
6.4.1 Mix phosphor powder . . . . . . . . . . . . . 260
6.4.2 Phosphor coating . . . . . . . . . . . . . . . 262
6.5 LED Heat Dissipation Technology . . . . . . . . . . 264
6.5.1 Source of heat . . . . . . . . . . . . . . . . . 265
6.5.2 Effect of heat on LED . . . . . . . . . . . . . 266
6.5.3 Heat dissipation mechanism and solution
of LED . . . . . . . . . . . . . . . . . . . . . 266
6.6 Optical Structure of LED . . . . . . . . . . . . . . . 274
6.6.1 LED light conversion structure . . . . . . . . 277
6.6.2 LED light distribution structure . . . . . . . 278
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xiv Photoelectric Materials and Devices

6.6.3Simulation and design of LED

packaging . . . . . . . . . . . . . . . . . . . . 279
6.7 Key Technology of Power LED Packaging . . . . . . 286
6.7.1 Ways to improve luminous efficiency . . . . . 287
6.7.2 Improving the optical characteristics
of LED . . . . . . . . . . . . . . . . . . . . . 291
6.7.3 Increase the single light flux and input power
of LED . . . . . . . . . . . . . . . . . . . . . 293
6.7.4 Reduce the cost of LED . . . . . . . . . . . . 294
6.7.5 Improving the reliability of LED . . . . . . . 294
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 294

Chapter 7. Transparent Conductive Materials 297

7.1 Brief Introduction of Transparent Conductive
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
7.2 Typical TCO Materials . . . . . . . . . . . . . . . . 298
7.3 Conductivity of TCO . . . . . . . . . . . . . . . . . . 300
7.3.1 Conductivity principle of TCO . . . . . . . . 300
7.3.2 Energy band, orbital domain
and mobility . . . . . . . . . . . . . . . . . . 302
7.3.3 N-type and P-type TCO . . . . . . . . . . . 304
7.3.4 Carrier generation . . . . . . . . . . . . . . . 305
7.3.5 The relation between the conductivity
of TCO and temperature and carrier
concentration . . . . . . . . . . . . . . . . . . 307
7.3.6 Relation between carrier scattering
and resistance in TCO . . . . . . . . . . . . 309
7.4 Optical Properties of TCO . . . . . . . . . . . . . . . 312
7.4.1 Transparency principle of TCO . . . . . . . . 312
7.4.2 Plasma vibration and plasma frequency . . . 312
7.4.3 Burstein–Moss effect . . . . . . . . . . . . . . 314
7.4.4 Carrier concentration and transparency . . . 316
7.5 Transparent Conductive Material Technology . . . . 316
7.5.1 Indium tin oxide . . . . . . . . . . . . . . . . 318
7.5.2 Other compromises between conductivity
and transparency . . . . . . . . . . . . . . . 319
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page xv

Contents xv

7.5.3 Soft ITO films . . . . . . . . . . . . . . . . . 324

7.5.4 Silver nanowires . . . . . . . . . . . . . . . . 328
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 332

Chapter 8. Touch Panel 335

8.1 Development of Touch Technology . . . . . . . . . . 335
8.1.1 The generation of touch control
technology . . . . . . . . . . . . . . . . . . . 335
8.1.2 Definition of touch panel . . . . . . . . . . . 336
8.1.3 Classification of touch panel . . . . . . . . . 338
8.2 Resistance Touch Panel . . . . . . . . . . . . . . . . 339
8.3 Capacitance Touch Panel . . . . . . . . . . . . . . . 341
8.3.1 Surface capacitance touch panel . . . . . . . 342
8.3.2 Projection capacitive touch panel . . . . . . 344
8.4 Other Touch Technology . . . . . . . . . . . . . . . . 347
8.4.1 Infrared touch panel technology . . . . . . . 347
8.4.2 Surface acoustic wave touch panel . . . . . . 349
8.5 The Frontier of Touch Control Technology . . . . . . 351
8.5.1 Embedded touch panel . . . . . . . . . . . . 351
8.5.2 Force touch technology . . . . . . . . . . . . 353
8.5.3 Flexible touch technology . . . . . . . . . . . 353
8.6 Introduction of Touch Panel Production
Technology . . . . . . . . . . . . . . . . . . . . . . . 354
8.6.1 Production technology of glass
touch panel . . . . . . . . . . . . . . . . . . . 354
8.6.2 Production technology of film
touch panel . . . . . . . . . . . . . . . . . . . 362
8.6.3 Yellow light process for film
touch panel . . . . . . . . . . . . . . . . . . . 366
8.7 Capacitive Touch Panel Production Equipment
and Materials . . . . . . . . . . . . . . . . . . . . . . 368
8.7.1 Major production equipment of capacitive
touch panel . . . . . . . . . . . . . . . . . . . 368
8.7.2 Capacitive touch panel manufacturing
auxiliary materials . . . . . . . . . . . . . . . 370
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page xvi

xvi Photoelectric Materials and Devices

Chapter 9. Display Screen 379

9.1 Introduction of Display Technology . . . . . . . . . . 379
9.2 Working Principle and Characteristic of Display . . . 383
9.2.1 Cathode ray tube (CRT) display . . . . . . . 383
9.2.2 Liquid crystal display . . . . . . . . . . . . . 384
9.2.3 Plasma display . . . . . . . . . . . . . . . . . 385
9.2.4 Organic electroluminescent display . . . . . . 386
9.2.5 LED display . . . . . . . . . . . . . . . . . . 387
9.2.6 Organic Light Emitting Diode (OLED)
display . . . . . . . . . . . . . . . . . . . . . 388
9.3 Structure and Working Principle of TFT-LCD
Device . . . . . . . . . . . . . . . . . . . . . . . . . . 389
9.3.1 Liquid crystal materials and their
properties . . . . . . . . . . . . . . . . . . . . 389
9.3.2 Structure and working principle
of panel plate . . . . . . . . . . . . . . . . . . 393
9.3.3 Structure and principle of backlight . . . . . 397
9.4 Material Technology and Technology
of TFT-LCD . . . . . . . . . . . . . . . . . . . . . . 399
9.4.1 TFT-LCD material technology . . . . . . . . 399
9.4.2 TFT-LCD technology . . . . . . . . . . . . . 414
9.5 OLED Display Screen . . . . . . . . . . . . . . . . . 422
9.5.1 Principle and application of OLED
display . . . . . . . . . . . . . . . . . . . . . 422
9.5.2 Fabrication of OLED devices . . . . . . . . . 422
9.5.3 Advantages and disadvantages of OLED . . . 425
9.5.4 Driving mode of OLED . . . . . . . . . . . . 426
9.5.5 Challenges for OLED industry . . . . . . . . 429
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 433

Chapter 10. Materials and Applications

of Solar Cells 435
10.1 Photovoltaic Technology and Solar Cells . . . . . . . 435
10.1.1 Development of solar cells . . . . . . . . . . . 435
10.1.2 Principle of solar cell . . . . . . . . . . . . . 437
10.1.3 Classification of solar cells . . . . . . . . . . 444
April 23, 2021 10:7 Photoelectric Materials and Devices 9in x 6in b4165-fm page xvii

Contents xvii

10.2 Crystalline Silicon Solar Cells . . . . . . . . . . . . . 444

10.2.1 Polycrystalline silicon thin-film
solar cells . . . . . . . . . . . . . . . . . . . . 444
10.2.2 Amorphous silicon thin-film solar cells . . . . 447
10.3 Compound Semiconductor Thin-Film Batteries . . . 448
10.3.1 CdTe solar cells . . . . . . . . . . . . . . . . 448
10.3.2 CIGS solar cells . . . . . . . . . . . . . . . . 453
10.3.3 GaAs solar cells . . . . . . . . . . . . . . . . 460
10.4 New Solar Cells . . . . . . . . . . . . . . . . . . . . . 464
10.4.1 Dye-sensitized solar cells . . . . . . . . . . . 464
10.4.2 Organic thin-film solar cells . . . . . . . . . . 468
10.4.3 Perovskite solar cells . . . . . . . . . . . . . . 471
References . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
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Chapter 1

Introduction

1.1. Brief Introduction of Photoelectronics Technology

According to the latest market analysis report of Global Industrial

Analysis, the global output value of photoelectric industry reached
932 billion US dollars in 2015. Photoelectric industry is the first
leading industry in the 21st century and the commanding point of
economic development. Its strategic position is self-evident. Photo-
electronics technology is the pillar and foundation of the photovoltaic
industry, involving the frontier theories and technologies of opto-
electronics, optics, materials, microelectronics, computer technology
and so on. It is a high-tech science formed by the infiltration
and intersection of many disciplines. Its application involves solar
photovoltaic, light-emitting diode (OLED), flat panel display screen,
laser, computer and communication. Information storage, modern
testing instruments, smart glass and many other fields.

1.1.1. Development course of optoelectronics

technology

The earliest optoelectronic devices are photodetectors, and the basis

of photodetectors is the discovery and research of photoelectric
effects. In 1873, Smith discovered the photoconductivity of selenium.
In 1888, German Hertz observed that when ultraviolet light irradi-
ated the metal, it could make the metal emit charged particles. In
1890, Lerner determined the charge–mass ratio of charged particles
and proved them to be electrons, thus clarifying the essence of
photoelectric effect. In 1900, German physicist Planck introduced

1
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch01 page 2

2 Photoelectric Materials and Devices

energy quantum into the study of blackbody radiation, and proposed

the famous Planck formula to describe the phenomenon of blackbody
radiation, which laid the foundation for quantum theory. In 1929,
Kohler made a silver–oxygen–cesium photocathode and a photocell
appeared. In 1939, Zvorakin of the Soviet Union made a practical
photomultiplier tube. In the late 1930s, lead sulfide (PbS) infrared
detectors were invented, which can detect radiation up to 3 microns.
Thermoelectric infrared detectors and radiocalorimeters made of
semiconductor materials appeared in the 1940s. In the mid-1950s,
cadmium sulfide (CdS), cadmium selenide (CdSe), photoresistors and
short-wave infrared lead sulfide photodetectors were put into use. In
1954, the first silicon-based solar cell was born at Bell Laboratory in
the United States. In 1958, HgCdTe infrared detector was invented
by Lawson et al.
In 1960, American Mayman developed ruby laser, the first laser
in the world. In 1961, the first laser rangefinder appeared. Since
then, various laser guided weapons, laser blinding weapons and laser
destructive weapons have been successfully developed.
In 1964, RCA discovered the photoelectric effect, guest-host
effect, dynamic scattering effect and phase-shift storage effect of
liquid crystal, which laid a technical foundation for the development
of liquid crystal display, liquid crystal light valve and other devices.
Since then, flat panel display technology has developed fastest with
liquid crystal display. Other flat panel displays, including plasma
display and organic electroluminescent display, have come out one
after another.
In 1966, optical fiber technology began to develop. In the same
year, British-Chinese scientist Gao Rong and others proposed the
possibility of realizing low-loss optical fibers, which opened the
way for optical fiber communication. In the 1970s, the landmark
achievements in the field of optoelectronics were the realization of
low-loss optical fibers, the maturity of semiconductor lasers and the
advent of charge coupled device (CCD). In 1970, the United States
developed a quartz optical fiber with a loss of 20 dB/km and a
semiconductor laser operating continuously at room temperature,
making optical fiber communication possible. This year is recognized
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Introduction 3

as the first year of optical fiber communication. Since then, optical

fiber communication has developed rapidly. At the same time of
technological development, applications are also developing. In the
early 1970s, the US laser-guided bomb was put into use. In 1972,
Philips of the Netherlands demonstrated an analog laser video disk.
In the mid- and late-1970s, Japan, the United States and the United
Kingdom began to build backbone optical fiber communication
networks.
In the 1990s, optoelectronic technology has achieved success in
the field of storage. CD-ROM has become an important means of
computer storage. CD and VCD have penetrated into millions of
households. DVD also entered into people’s lives in the mid-1990s. In
addition, optoelectronic technology has made great progress in light-
ing and display. In 1983, Chinese American professor Deng Qingyun
discovered organic light-emitting diode (OLED) in his laboratory. Its
low voltage and high quantum efficiency make it a new generation of
flat panel display technology. In 1993, Nishia Nakamura invented a
blue light-emitting diode (LED) with commercial application value
based on wide bandgap semiconductor materials GaN and InGaN,
which innovated the light source technology.

1.1.2. Related concepts of optoelectronic technology

Optoelectronic technology is a very broad concept. It encompasses the

generation, transmission, processing and reception of optical signals.
It covers a series of fields from basic to application, such as new mate-
rials (new light-emitting photosensitive materials, nonlinear optical
materials, substrates, transmission materials and micro-structures of
artificial materials), micro-fabrication and micro-electromechanical,
device and system integration. The science of optoelectronics technol-
ogy is the pillar and foundation of optoelectronics information indus-
try. It involves the frontier disciplines such as optoelectronics, optics,
materials science, microelectronics, computer technology and so on. It
is a high-tech discipline formed by the infiltration and intersection of
many disciplines. At present, the scope of optoelectronic technology
is shown in Table 1.1.
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4 Photoelectric Materials and Devices

Table 1.1. Overview of optoelectronic technology.

Category Industrial technical content
Optical glass, optical plastics, optical
Photoelectronic crystals, infrared materials, laser
Photoelectric
materials and materials, optical fibers, nonlinear optical
material
components materials, semiconductor optoelectronic
materials and epitaxial materials, etc.
Light-emitting devices, light detecting/
Photoelectric
receiving components, light conduits,
components
phototransistors, solar cells, etc.
LED display, liquid crystal display, plasma display,
Photoelectric organic light-emitting diode, organic light-emitting
display display, field-emitting display, laser holographic
projection, etc.
Magneto-optic effect sensor, ambient light sensor,
Optical sensor
infrared light sensor, solar light sensor
Scanner, form reader, character recognition machine,
Optical
digital camera, laser printer, laser copier, optical fax
input/output
machine, etc.
CD, VCD, DVD, optical quantum data storage,
Optical storage three-dimensional volume storage and CD-ROM,
recorder
Single-mode/multi-mode optical fibers,
optical fiber connectors, etc.
Optical amplifier, light
source-fiber coupler, light
Active
source-detector coupler, light
Components devices
source Transistor Outline (TO)
and parts
packaging device, optical pump
Optical device, etc.
communication Optical switch, optical coupler,
Passive optical attenuator, optical
devices isolator, spectrometer, wavelength
division multiplexer, etc.
Optical fiber transmission equipment,
optical fiber area network equipment,
Systems and
optical fiber communication detection
equipment
and monitoring equipment, optical fiber
radio and television (CATV) system, etc.
Semiconductor lasers, solid-state lasers,
Laser
gas lasers, dye lasers, excimer lasers, etc.
Laser and other
Laser industrial processing, laser medical
applications Laser
treatment, laser weapons, laser scientific
applications
research and other applications
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch01 page 5

Introduction 5

Photoelectronic technology is closely related to electronic tech-

nology. Electronics is a science and technology with application as
its main purpose. It mainly studies the characteristics and behavior
of electronics and the physics of electronic devices. Electronics
involves many scientific categories, including physics, chemistry,
mathematics, materials science and so on. Photoelectronics refers
to the electronics of light wave bands, namely infrared, visible,
ultraviolet and soft X-ray (wavelength range 1–10 nm). It is a science
that studies photons as information carriers and energy carriers. It
mainly studies how photons produce, move and transform. Elec-
tronic technology is a technology that studies the motion law of
electrons and is applied to electronic devices, circuits and equip-
ment. Photoelectronics technology is a technology that studies the
interaction between light and electricity, that is, photons or light
waves and electrons. It includes photoelectronics energy technology
and photoelectronics information technology. Photoelectronics tech-
nology is inseparable from electronic technology. Photoelectronics
technology needs energy–light conversion, light source needs driving
and control circuit to emit light, and photoelectric signal processing
is needed in the information field. At present, a large number of
information processing is still based on electronic technology, and
the conversion and amplification between electrical information and
optical information are still needed in the process of transmitting and
receiving. The core of future information technology is optoelectronic
technology. The advantages of optoelectronic technology in the
field of information technology are embodied in the following three
aspects.

(1) The frequency of light wave is higher and the information

capacity that can be transmitted is larger.
(2) Light wave propagation in medium has certain advantages.
(3) Great progress has been made in optoelectronic information
technology, especially after the emergence of lasers (optical
communication, optical storage).
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6 Photoelectric Materials and Devices

1.2. The Concept, Position and Function

of Photoelectric Materials and Devices

1.2.1. Basic concepts of photoelectric materials

and devices

The optoelectronic technology includes materials, devices, modules,

equipment and systems. The devices are made of materials with
certain properties (chemical, electrical, optical and mechanical prop-
erties). The modules are composed of devices suitable for specified
parameters (current, voltage, response speed or frequency). The
devices are operated by multiple functional modules in a certain
software environment. The equipment is constructed under a cer-
tain standard agreement. Therefore, the bottom and foundation of
photoelectric technology is photoelectric materials and devices.
Photoelectric materials are the foundation and pioneer of the
whole photoelectric industry. Photoelectric materials refer to mate-
rials that can generate, convert, transmit, process and store optical
signals. They mainly include semiconductor photoelectric materials
(III–V), organic semiconductor photoelectric materials, inorganic
crystals and quartz glass. Compound semiconductor materials such
as AlGaAs and InGaAsN can be formed by any combination of
III–V elements. Their lattice constants, bandgap width and absorp-
tion/emission wavelength are the three most important parameters
determining the photoelectric properties of compound semiconductor
materials. Photoelectric devices refer to devices that can realize the
conversion function between light radiation energy and signal or
the transmission, processing and storage of photoelectric signals.
At present, most commercial semiconductor optoelectronic devices
are made of GaAs-based, InP-based and GaN-based compound
semiconductor material systems. They are widely used in optical
communication network, photoelectric display, photoelectric storage,
photoelectric conversion and photoelectric detection.
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch01 page 7

Introduction 7

1.2.2. The position and function of photoelectric

materials and devices in photoelectric
technology

The emergence of new devices and materials promotes significant

advances in optoelectronic technology, including LED, OLED, solar
cells, touch screens, lasers, optical fibers, all-optical network devices
(semiconductor lasers, Erbium Doped Fiber Amplifier (EDFA),
Optical Cross Connector (OXC), Optical Add-Drop Multiplexing
(OADM)), as well as laser printers, digital cameras, VCD, DVD and so
on. Without these devices or without knowledge of them, it is difficult
to assemble high-performance optoelectronic devices and build high-
performance optoelectronic systems.
Photoelectric devices and products made of photoelectric mate-
rials are gradually applied in every important link of the information
industry. From information acquisition, processing, transmission to
information storage and display, the requirements of the information
industry for high-speed, large-capacity, high-definition, ultra-thin
and ultra-light information-related products are constantly increas-
ing, which promotes the sustained and high-speed development of the
photoelectric industry. New photoelectric materials and new products
and new technologies are emerging. Among them, optoelectronic
sensor system and its related devices, optoelectronic display, optical
communication and optical storage are the most important applica-
tion fields in the optoelectronic industry. In the field of optoelectronic
display, the flat panel display products with liquid crystal display
(LCD) as the mainstream have replaced the traditional cathode
ray tube (CRT) market and occupied half of the display market.
In photoelectric flat panel display devices and products, LCD has
penetrated into every field of display devices; OLED, known as Dream
Display, has also begun to be applied in small-scale display fields such
as mobile phones, digital cameras, personal digital assistants (PDA).
The successful development of GaN-based blue light-emitting diodes
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch01 page 8

8 Photoelectric Materials and Devices

(LED) and the appearance of commercial devices make it possible

for full-color display and white light illumination of LED products,
and set off a blue-light heat worldwide. White light has become the
fourth generation of lighting sources.
With the successful development of semiconductor lasers, digital
optical disks represented by CD ROM, VCD and DVD have become
one of the indispensable storage technologies in today’s multimedia
information age. They have been widely used in computer storage,
digital household appliances, radio and television, vehicle navigation
and electronic publishing. Optical storage is developing along the
direction of CD–DVD–3D holographic storage.
In recent years, the research and application of organic and
organic/inorganic composite optoelectronic materials and devices
have made great progress and development, which has attracted
great attention from the International Optoelectronic academia
and industry. Organic materials have become a new generation of
optoelectronic information materials with the advantages of high
speed, high density and low cost. The development and industrial-
ization of optoelectronic devices based on organic materials, such as
OLED, plastic optical fibers, organic thin-film lasers, polymer-based
holographic optical memory, organic waveguide devices, organic tran-
sistors and field effect transistors, organic optical switches, etc., will
push the optoelectronic industry to a new height.

1.3. The Theoretical Basis of This Book

1.3.1. Photoelectric conversion materials and devices

Photoelectric conversion is based on the principle of photoelectric

effect, which is the phenomenon that matter emits electrons under
the action of light radiation. The photoelectric phenomenon was first
discovered by Hertz, but Einstein was the first to successfully explain
the photoelectric effect. Einstein believed that the energy of a photon
is transmitted to a single electron in a metal. When the electron
absorbs a photon, it uses part of the energy to break away from the
metal’s bondage. The remaining part becomes the kinetic energy of
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch01 page 9

Introduction 9

the electron after it leaves the metal surface. Einstein’s photoelectric

effect equation is as follows:
1
mv 2 = hν − W, (1.1)
2
where, h is Planck constant, ν is light frequency, 12 mv 2 is photo-
electron kinetic energy, and W is the minimum energy required for
photoelectron to escape from metal surface, which is called metal
work. The emitted electrons are called photoelectrons.
The photoelectric effect can be divided into external photoelectric
effect and internal photoelectric effect. External photoelectric effect
refers to the phenomenon that the electrons in the object escape
from the surface of the object and emit outward under the action
of light, which is also called photoelectric emission effect. Internal
photoelectric effect refers to the phenomenon that illumination
changes the conductivity of an object or produces photoelectromotive
force. It is also divided into photoelectric conductivity effect and
photovoltaic effect (i.e. photovoltaic effect). Photoconductivity effect
is a phenomenon that the electron absorbs photon energy from
bonding state to free state under the action of light, which results in
the change of material conductivity. When the light irradiates on the
photoconductor, if the photoconductor is an intrinsic semiconductor
material and the radiation energy is strong enough, the electrons
in the valence band of the photoconductor will be stimulated to
the conductivity of the photoconductor, which will increase the
conductivity of the photoconductor. Photovoltaic effect refers to the
phenomenon that light causes potential difference between different
parts of inhomogeneous semiconductor or semiconductor bonding
with metal.
Photoelectric effect and photovoltaic effect are quite different.
By definition, photovoltaic effect is the precondition of photovoltaic
effect. Photovoltaic effect is a special place where photovoltaic effect
acts on semiconductor, which results in potential difference. In
materials, the materials that produce photovoltaic effect can only be
semiconductors, and photovoltaic effect materials can also be metals.
Photovoltaic effect is a minority carrier process. It is the potential
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch01 page 10

10 Photoelectric Materials and Devices

difference between the two ends of PN junction when a few carriers

absorb photons in semiconductor. The photovoltaic effect is that
semiconductor or metal emits free electrons under the excitation of
photons, and the surface emits electrons after overcoming the surface
barrier. In photovoltaic effect, carriers cannot leave the material,
while the latter can leave the material. The former has a certain
absorption spectrum for the spectrum and is related to the intensity
of light, while the latter has a cut-off wavelength of electron escape
velocity independent of the intensity of light, only related to the
frequency.
Solar energy is converted into electrical materials by photovoltaic
effect, which is mainly used to make solar cells. The working principle
of photoelectric conversion material is as follows: the same material
or two different semiconductor materials are made into PN junction
battery structure. When the solar light shines on the surface of PN
junction battery structure material, the solar energy is converted
into electricity through PN junction. The requirement of solar cells
for photoelectric conversion materials is high conversion efficiency
and large area devices, so as to better absorb sunlight. The main
photoelectric conversion materials used are monocrystalline silicon,
polycrystalline silicon and amorphous silicon. At present, the max-
imum energy conversion efficiency of inorganic silicon photovoltaic
cells (photovoltaic cells) has reached 24%, and the energy conversion
efficiency of GaAs semiconductor photovoltaic cells has even reached
32%. However, they are demanding on the purity and fabrication
process of materials, and will produce some highly toxic substances
in the manufacturing process. In addition, the non-flexibility and
difficult processing of inorganic photovoltaic cells also limit their
wide application process. The photovoltaic cells based on conjugated
polymers, or polymer solar cells, not only have the advantages of
flexible molecular design, simple fabrication method, low cost and
large area flexible devices, but also inherit the advantages of high
mobility and chemical stability of inorganic nanocrystalline carriers.
It has attracted great attention.
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Introduction 11

1.3.2. Electro-optical conversion materials and devices

Solid light-emitting materials emit light under electric field, which

is called electroluminescence. It is a process of converting electric
energy directly into light energy. Devices made from this phenomenon
are called electroluminescent devices, such as LED, liquid crystal
display, semiconductor lasers, etc. LED uses solid semiconductor chip
as luminescent material, which emits excess energy through carrier
recombination in semiconductor, and directly emits red, yellow, blue
and green light. On this basis, using the principle of three primary
colors and adding phosphor, any color of light can be emitted, such
as red, yellow, blue, green, blue, orange, purple, white, etc. It has the
characteristics of small size, low power consumption, long service life,
high brightness, low heat, environmental protection and durability.
LED lamp is a kind of illumination device which uses LED as light
source. It has been widely used in illumination, display, indication
and other fields. OLED, also known as organic electro-excitation
light, uses organic polymer materials as semiconductor materials
in light-emitting diodes. OLED technology has the characteristics
of self-luminescence. It uses very thin organic coatings and glass
substrates. When current passes through, these organic materials will
emit light, and OLED display screen has a large visual angle, and can
save electricity. OLED display technology is widely used in mobile
phones, digital cameras, DVD players, PDA, notebook computers,
car audio and television, etc.

1.3.3. Transparent conductive material

Transparent conductive materials are a kind of special materials with

high transmittance to visible light and high conductivity, such as
indium-tin oxide (ITO), nanowire, graphene and so on. Transpar-
ent conductive materials are widely used because of their unique
photoelectric properties. In many modern electronic information
technology, photoelectric technology, new energy technology and
national defense technology, the design, manufacture and use of
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12 Photoelectric Materials and Devices

transparent conductive materials is an indispensable key technology.

For example, transparent conductive materials are indispensable
electrode materials in touch screen. In photovoltaic solar cells, high
transmittance electrode materials can ensure that photovoltaic cells
can fully absorb sunlight. Coating a layer of high transparency and
high conductivity film on the surface of building glass can effectively
prevent the infrared radiation from entering or escaping, and greatly
improve the energy-saving effect of the building. Transparent con-
ductive films can also effectively shield electromagnetic radiation, so
they have important applications in aviation, communications and
other national defense industries.

References
An Y et al., 2011. Photoelectronic Technique, Beijing: Electronics Industry Press.
Hou H, 2012. Optoelectronic Materials and Devices, Beijing: National Defence
Industry Press.
Jiang W, Shi J, 2009. Photoelectronic Technique, Beijing: Science Press.
Shi S, Liu J, 2010. Optoelectronic Technology and Its Application, Beijing: Science
Press.
Wang X, Ye C, 2013. Organic Photoelectric Materials and Devices, Beijing:
Chemical Industry Press.
Zhu J, 2009. Fundamentals of Optoelectronic Technology, Beijing: Science Press.
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 13

Chapter 2

Theoretical Basis of Photoelectric Materials

2.1. Energy Band Theory

The energy spectra of electrons in a complete crystal are bands

of dense energy levels, which are called bands. The energy band
is separated from the energy band by the energy forbidden zone.
Among them, the lowest energy band completely empty at 0 K is
called conduction band, and the highest energy band completely
occupied by electrons is called valence band. The energy gap between
them is called forbidden band. Energy band theory, also known as
solid energy band theory, is a quantum mechanics theory about the
motion state of electrons in crystals. It predicts that the energy of
electrons in crystals will always fall in some limited range or “energy
band”. The electrical, optical and magnetic properties of crystals are
all related to the motion of electrons. The energy band theory is
used to study these problems. The band theory successfully explains
the difference between metals, semiconductors and insulators and the
Hall effect phenomenon. Semiconductor physics is based on energy
band theory.
With the development of experimental technology, the electronic
band structures of many crystals have been successfully determined
by means of cyclotron resonance, electro-optic, magneto-optic and
spectroscopy. Especially in recent years, due to the wide application
of computer technology, the band structure of electrons can be
calculated more accurately in theory. Nevertheless, since band theory
is a simplified approximation theory after all, it can only be applied to

13
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14 Photoelectric Materials and Devices

ordered crystals, and even for ordered crystals, when their structures
are complex, band theory is often difficult to deal with.

2.1.1. Schrödinger equation of crystal and its

approximate solution

2.1.1.1. Schrödinger equation

Crystals consist of a large number of atoms arranged periodically,

and atoms consist of nuclei and electrons. Since the inner electrons
do not participate in the physical process of the crystal, it can be
presumed that the crystal is composed of the outermost electrons of
the atom and ions that lose electrons. If r1 , r2 , r3 , . . . , rj . . . denotes
the potential vectors of electrons, R1 , R2 , R3 , . . . , Rj . . . denoting the
potential vectors of an ion that has lost its electron, then the steady-
state Schrödinger equation of the crystal is

Ĥψ = Eψ, (2.1)

where ψ is a wave function, E is an eigenvalue of energy, Ĥ is a

Hamiltonian operator, and

Ĥ = Te + TZ + ue + uZ + ueZ + V (2.2)
 h2 2
where Te = i (− 2m Δi ) is the kinetic energy operator of all
∂2 ∂2 ∂2
electrons, m is the electronic mass, and Δ2i = ∂x 2 + ∂y 2 + ∂z 2 is
i i i
the Laplacian operator of the ith electron,

  h2 2

Tz = Tα = − Δ
α α
2Mα α

is the kinetic energy operator for all ions, Mα is the mass of ions,
and Δ2∂ is the Laplace operator for the αth ion,

1  e2 1 
ûe = = ûij
2 4πε0 |ri − rj | 2
i,j=i i,j=i
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 15

Theoretical Basis of Photoelectric Materials 15

represents the interaction energy between electrons,

1  zα zβ e2 1 
ûZ = = ûαβ
2 4πε0 |Rα − Rβ | 2
α,β=α α,β=α

denotes the interaction energy between ions, and zα e and zβ e are the
charge quantities of α and β ions, respectively, and
 za e2 
ûe Z = − = ûiα
4πε0 |ri − Ra |
i,α i,α

represents the interaction energy between electrons and ions, and

V̂ = V (r1 · r2 , . . . , rn , R1 , R2 , . . . , RN )

is the potential energy of all electrons and ions in the field.

The density of atoms in crystals is about 5 × 1022 cm−3 , so
the above equation cannot be solved strictly. Generally, the single-
electron approximation method is used.

2.1.1.2. Adiabatic approximation and atomic valence

approximation

(1) Adiabatic approximation: Generally, the average kinetic energy

of heavy particles (e.g. nuclei) is the same order of magnitude
as that of light particles (e.g. extranuclear electrons). Because
Mα  m, the electron velocity is much larger than that of
the nucleus (about two orders of magnitude), so it is possible
to consider the motion of the electron in the crystal separately
from that of the nucleus. This simplification assumes that the
overall motion of atoms has a weak influence on the motion
of electrons, just as there is no exchange of energy between
the overall motion of atoms and the motion of electrons. This
simplification is usually called adiabatic approximation.
Furthermore, if we assume that the nucleus is fixed, then
the nuclear coordinates are no longer variables, but R10 , R20 , . . .
Rα0 , . . . . The form of RN 0 appears to represent the coordinates
of lattice points. In this case, the nuclear kinetic energy is zero,
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16 Photoelectric Materials and Devices

and the interaction energy uZ is constant and can be chosen as

zero. In addition, if there is no outfield, there is V = 0.
At this time, the Schrödinger equation of crystal can be
simplified to describe the electron motion equation in a fixed
nuclear field.

  2 
2
Ĥψe = (T̂e + ûe + ûe z)ψe = − ∇
2m i
i
⎤
1  e2  za e2
+ − ⎦ ψe
2 4πε0 |ri − rj | 4πε0 |ri − Ra |
i,j=i i,a

= Ee ψe . (2.3)

(2) Atomic valence approximation: To further simplify the above

equation, the so-called atomic valence approximation is adopted,
that is, all electrons except valence electrons form fixed ionic
substances with their nuclei.

2.1.1.3. Single-electron approximation — Hartree–Fock method

Crystals contain a large number of electrons, which belong to the

multi-electron system. Every electron in the system is subject to
Coulomb action of other electrons. So even if we only study the
motion of electrons, it is still very complicated. At present, the most
effective way to deal with multi-electron problems is the so-called
single-electron approximation method, which considers the motion of
each electron separately. The single-electron approximation method
is also known as the Hartree–Fock method. In this method, in order
to approximate the separation of the motion of each electron, an
appropriate simplification is adopted: when studying the motion of
an electron, the Coulomb effect of other electrons on the electron
everywhere in the crystal is considered equally according to their
probability distribution. This average consideration is achieved by
introducing a self-consistent electron field. For example, for the ith
electron, supposing that with the aid of an external potential field,
a potential field can be applied to the position of the electron at any
time with the same effect as other electrons, which is recorded as Ωi ,
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 17

Theoretical Basis of Photoelectric Materials 17

then Ωi is only related to the potential vector ri of the ith electron,

and can be recorded as Ωi = Ωi (ri ), which is called self-consistent
electron field. If all other electrons are treated in the same way, there
are
 1  1 e2
Ωi (ri ) = ûij = (2.4)
2 2 4πε0 |ri − rj |
i i,j=i

Assuming that Ωi (ri ) is known, the Hamiltonian operator of the

system can be written as

 2 2 1  
Ĥe = − ∇i + ûij + ûi,a
2m 2
i i,j=i i,a

 2 2   
= − ∇i + Ωi (ri ) + ûi,a
2m a
i i i

= Ĥi . (2.5)
i

So for the ith electron, the Hamiltonian operator is

2 2  h2 2
Ĥi = ∇i + Ωi (ri ) + ûia = − ∇ + Ωi (ri ) + ûi (ri ),
2m a
2m i
(2.6)

where ui (ri ) is the potential energy of the ith electron in all ion
fields, and Ωi (ri ) is the potential energy of the ith electron in all
other electron fields. Thus the eigenfunction of the system can be
expressed as the product of each electron wave function and the total
energy is the sum of the energy of each electron:

ψ, (r1 , r2 , . . . , ra ) = ψi (ri ), (2.7a)

i

Ee = Ei (2.7b)
i
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 18

18 Photoelectric Materials and Devices

where, ψi (ri ) and Ei satisfy the Schrödinger equation of a single

electron:

Ĥi ψi (ri ) = Ei ψi (ri ). (2.8)

By introducing the concept of self-consistent electron field, the

multi-electron problem can be transformed into a single-electron
problem. Since the ith electron can be any electron, the above single-
electron equation can be generally expressed as

Ĥψ(r) = Eψ(r). (2.9)

2
  2
Here Ĥ = − 2m ∇2 + V (r), V (r) = Ω(r) + û(r), where − 2m ∇2 is
the kinetic energy operator of a single electron; V (r) is its potential
energy operator, which contains the average Coulomb interaction
energy of all other electrons to it and the Coulomb interaction energy
of all ions to it.
For specific crystals, as long as the potential function V (r) is
written, a series of energy spectrum values E and corresponding
wave function ψ(r) can be found by solving Schrödinger equation
in principle.

2.1.1.4. Atomic orbits and lattice orbits

There are two kinds of single-electron wave functions for electrons

in crystals, one is atomic orbital and the other is lattice orbital.
In atomic orbits, electrons do not get rid of the bondage of atoms,
and basically move around atoms. Their wave functions are larger
only near individual atoms. Atomic orbits are suitable for internal
electrons in crystals. In lattice orbits, electrons move not only around
each atom, but also between atoms. They communalize in the whole
crystal, and their wave functions extend throughout the crystal.
Lattice orbits are suitable for external electrons.
The external electrons in crystals are usually concerned, and
lattice orbits are generally chosen. In addition, it is considered that
all atoms are stationary in their equilibrium positions. Therefore,
the potential energy V (r) of the external electrons should have the
symmetry of the lattice, especially the periodicity.
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 19

Theoretical Basis of Photoelectric Materials 19

2.1.1.5. State distribution of electrons

After finding all possible energy spectra and motion states of a single
electron, if we know the distribution of a large number of electrons
in these states, the problem of electron motion in a crystal will be
solved.
The distribution of electrons in states is a quantum statistical
problem. In the case of thermal equilibrium, the distribution of
electrons in the state is approximately determined by the Fermi–
Dirac distribution. New distribution functions can also be found in
unbalanced cases.

2.1.2. Bloch’s theorem

The wave equation of a single electron in a crystal is

2 2
− ∇ + V (r) ψ(r) = Eψ(r),
2m
where the potential function V (r) has the microcosmic symmetry
of the lattice, especially the periodicity of the lattice. For example,
the form of electron potential function in one-dimensional periodic
potential field is shown in Fig. 2.1.
Bloch’s theorem: If V (r) has lattice periodicity, i.e., V (r+Rm ) =
V (r), the solution of Schrödinger equation of crystal can be written

Fig. 2.1. Electrons moving in one-dimensional periodic potential field.

April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 20

20 Photoelectric Materials and Devices

in the form of Bloch’s function as follows.

ψ(r) = eik·r u(r), (2.10)

where k is called wave vector, which is a real number. Here u(r) is a

function with lattice periodicity, i.e.

u(r + Rm ) = u(r),

where Rm is the lattice vector.

Another common form of Bloch’s theorem is

ψ(r + Rm ) = eik·Rm ψ(r). (2.11)

The formula shows that the wave function ψ(r) in the periodic
potential field is translated by any lattice vector Rm , and the wave
function ψ(r + Rm ) is obtained. There is only one constant factor of
modulus 1 between the two wave functions.
In a word, the electron wave function in periodic field can be
generally expressed as the product of a plane wave and a periodic
factor. The wave vector of plane wave is the real vector k, which
can be used to indicate the motion state of electrons. Different
k represents different states. Therefore, k also acts as a quantum
number. For clarity, an index k is added to the wave function and
energy spectrum value (eigenvalue).

ψk (r) = eik·r uk (r), (2.12a)

E = E(k). (2.12b)

It can be seen from the formula that the wave vector k can
only be taken as a real value in order to make the electron wave
propagate in the whole crystal undamped. We can give a rough
explanation of the wave function: the plane wave factor eik·r is
the same as the free electron wave function, which describes the
movement of electrons among the primitive cells; the periodic factor
uk (r) describes the movement of electrons in a single cell, because it
only repeats periodically among the primitive cells. Because

|ψk (r + Rm )|2 = |eik·Rm ψk (r)|2 = |ψk (r)|2 .

April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 21

Theoretical Basis of Photoelectric Materials 21

The results show that the probability of electrons appearing at the

corresponding points in each cell is equal.
Because the momentum operator −i∇ = i ∇ and H of electrons
in crystals are not interchangeable, their wave functions are not only
plane waves, but also have a periodic factor. The product of wave
vector k and  has the dimension of momentum. For electrons moving
in periodic fields, k is usually referred to as the “quasi-momentum”
of electrons, which is expressed by p: p = k. Quasi-momentum is
also called lattice momentum.

2.1.3. Periodic boundary conditions

According to Bloch’s theorem, the wave function of an electron in a

periodic field can be expressed as the product of a plane wave and
a periodic factor. After considering the boundary conditions, k is
limited and only intermittent values can be taken. The size of the
actual crystal is always limited. The environment of the electron in
the cell near the surface is different from that in the corresponding
position of the inner cell, so it is periodically destroyed, which
brings some inconvenience to the theoretical analysis. In order to
overcome this difficulty, Born–Carmen periodic boundary conditions
are usually used: if an infinite crystal is generated by periodic
repetition of finite crystals, and requiring the motion of electrons to
repeat periodically in space with finite crystals as periodic periods.
It is assumed that the finite crystal considered is a parallel
hexahedron with N1 primordia along the a1 direction, N2 primordia
in the a2 direction and N3 primordia in the a3 direction. The total
number of primordia is N = N1 N2 N3 . According to the periodic
boundary condition, the wave function along the a1 direction is
required to take N1 a1 as the period, that is to say

ψ(r + N1 a1 ) = ψ(r) = eik·N1 a1 ψ(r) =⇒ eik·N1 a1

= 1 =⇒ k · N1 a1 = 2π.

Let k = β1 b1 + β2 b2 + β3 b3 , because bi · aj = 2πδij , there is

l1
k · N1 a1 = 2πβ1 N1 = 2πl1 ⇒ β1 = (l1 is an arbitrary integer).
N1
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 22

22 Photoelectric Materials and Devices

Similarly, there are

β2 = l2 /N2 , β3 = l3 /N3 (l2 , l3 are arbitrary integers).

So, there are

l1 l2 l3
k= b1 + b2 + b3 . (2.13)
N1 N2 N3

Under periodic boundary conditions, k can only take discontin-

uous values, so the energy E(k) corresponding to these wave vectors
can only take discontinuous values. The wave vectors k determined
by formula (2.13) are located at the top angles of some parallel
hexahedrons with three sides of b1 /N1 , b2 /N2 and b3 /N3 in the
inverted space. In inverted space, the volume of the representative
point of each wave vector k is
 
b1 b2 b3 Ωx (2π)3 /Ω (2π)3 (2π)3
· × = = = = ,
N1 N2 N3 N1 N2 N3 N NΩ V
(2.14)

where V is the volume of the whole finite crystal, so the wave vector
in the unit inverted space is V /(2π)3 , which is the distribution density
of the representative point of k in the inverted space. So the number
of representations of k in each inverted cell is

Ω∗ V (2π)3 N Ω
3
= = N. (2.15)
(2π) (2π)3 Ω

In each inverted cell, the number of representative points of k is

equal to the total number of primitive cells of crystal N . This is
an important conclusion derived from periodic boundary conditions.
Each wave vector k represents a space motion state (quantum state)
of electrons in a crystal, so that the number of states of electrons in
the range of dk = dkx dky dkz is the number of states of electrons.

V V
dk = dkx dky dkz . (2.16)
(2π)3 (2π)3
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 23

Theoretical Basis of Photoelectric Materials 23

2.1.4. Energy bands and their general properties

2.1.4.1. Energy band

The wave function of electron motion in crystal is Bloch function.

ψk (r) = eik·r uk (r). (2.17)

Given a k, the plane wave part is determined. In order to determine

uk (r), the wave equation needs to be solved.

2 2
Ĥψk (r) = − ∇ + V (r) ψk (r) = E(k)ψk (r)
2m
2 2
⇒ − ∇ + V (r) eik·r uk (r) = E(k)eik·r uk (r)
2m
2
⇒ − (∇2 + i2k · ∇ − k2 ) + V (r) uk (r) = E(k)uk (r)
2m
  2 
2 1
⇒ − ∇ + k + V (r) uk (r) = E(k)uk (r).
2m i
(2.18)

The above formula is the differential equation satisfied by uk (r), and

uk (r + Rm ) = uk (r). For a given problem, V (r) is certain. When
k is given, the form of differential equation is determined. For the
eigen equation of this property, there can be many separated energy
spectrum values:

E1 (k), E2 (k), . . . , En (k). (2.19)

By substituting these energy spectra into differential equations, the

corresponding functions uk (r) can be obtained.

u1,k (r), u2,k (r), . . . , un,k (r). (2.20)

These functions are multiplied by the plane wave factor eik·r to obtain
the corresponding wave functions:

ψ1,k (r), ψ2,k (r), . . . , ψn,k (r). (2.21)

April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 24

24 Photoelectric Materials and Devices

The above relationship can be abbreviated as

En (k), ψn,k (r) = eik·r un,k (r) (n = 1, 2, 3, . . .). (2.22)

The electronic energy spectrum value En (k) in the crystal has

the following properties.

(i) En (−k) = En (k), that is, En (k) has inversion symmetry. In

particular, for one-dimensional cases, En (k) is a dual function.
(ii) En (k + K1 ) = En (k), where K1 is a reciprocal lattice vector and
K1 = l1 b1 + l2 b2 + l3 b3 . This is because the physical meaning of
k and k + K1 is equivalent.

Therefore, two quantum numbers n and k are needed to mark

the state of electron motion and the corresponding energy spectrum
in the crystal.
Because k = Nl11 b1 + Nl22 b2 + Nl33 b3 takes the discrete value, En (k)
is a quasi-continuous energy band, that is, the relationship between
En (k) and k is quasi-continuous; index n is the label of energy band,
different n corresponds to different energy band En (k); k is the label
of different states and levels in each energy band, and each k is
represented by a point in inverted space, which is the starting point of
vector k at the origin point. The idea is at the end. For each energy
band, a point in the inverse space can represent a single-electron
state and level, and the number of k points is N . Figure 2.2 shows
the band structure of quasi-free electrons in one-dimensional case:

2 k2
En (k) = .
2m

2.1.4.2. General characteristics of energy bands

(1) V (r) has the periodicity of the lattice: V (r + Rm ) = V (r).

(2) En (k) has the periodicity of reciprocal lattice: En (k + K1 ) =
E(k), and K1 is any reciprocal lattice vector.
(3) The wave function also has the periodicity of inverted lattice:
ψn,k+K1 (r) = ψn,k (r).
(4) En (k) has inversion symmetry: En (−k) = En (k).
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 25

Theoretical Basis of Photoelectric Materials 25

Fig. 2.2. Schematic diagram of band structure of one-dimensional quasi-free

electrons.

(5) En (k) has the macroscopic point group symmetry of crystals:

En (αk) = En (k), and α is any macroscopic point group
symmetry operation of crystals. Here αk represents another wave
vector obtained by rotation or inversion of k, which is equal to
their corresponding energy spectrum. It should be noted that
although the energy spectra corresponding to αk and k are equal
here, the wave functions are generally independent. This means
that the symmetry of energy bands can cause degeneracy of
energy levels, but only the states corresponding to k and αk,
which differ from each other by one reciprocal vector K1 , are
consistent.
The wave vectors k and k  (k = k + K1 ) of a reciprocal lattice
vector differ from each other, indicating the same electronic
states and calling them equivalent, while the wave vectors k
and k  (k = αk), which are connected by the point symmetry
operation, have the same energy spectrum value and are called
symmetrical.
(6) In each energy band, the number of space wave functions ψn,k (r)
of electrons is N , and N is the total cell number of crystals.
Considering the two possible orientations of electron spin, the
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 26

26 Photoelectric Materials and Devices

Fig. 2.3. Ellipsoidal isoelectric surface near the conduction band minimum of
silicon.

number of states of each band is 2 times the total number of

crystal primitives and 2N .
(7) It can be inferred from the symmetry of the energy band that the
extreme value of the energy band is symmetrically distributed
in the inverted space, and the wave vectors are connected
by the symmetrical operation. In inverted space, the surface
composed of representative points with equal energy is called
isosurface, and the location where the minimum energy appears
is called valley. It can be seen from En (αk) = En (k) that the
isoenergetic surfaces of inverted space coincide with each other
under the macroscopic point symmetry operation of the crystal.
For example, the isoenergetic surface near the conduction band
minimum of silicon is a revolving ellipsoid. As shown in Fig. 2.3,
it has the point group symmetry of the cube and therefore has
six valleys symmetrical to each other.

2.1.5. Brillouin zone

The change of energy band En (k) in inverted space is symmetrical.

For those wave vectors associated with symmetrical operation of
macroscopic point groups of crystals, the corresponding energy
spectrum values are equal. The inverted cell can be used to analyze
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 27

Theoretical Basis of Photoelectric Materials 27

the periodicity of the band, but it is not suitable to discuss the

symmetry of the band. In inverted space, the representative points
of K linked by symmetric operations are generally not in the same
inverted cell. Therefore, it is necessary to divide the inverted space
into some periodic and symmetrical repetitive elements, Brillouin
region.

2.1.5.1. Brillouin Zoning method

In inverted space, the mid-vertical plane connecting the origin with

all inverted lattice points are shown in Fig. 2.4. These planes divide
the inverted space into several regions. The region closest to the
origin is called the first Brillouin region, and the regions closest to
the origin constitute the second Brillouin region. By analogy, we can
get the third and fourth Brillouin zone. It can also be said that the
area surrounded by the interface near the origin is the first Brillouin
zone, the area entering through an interface from the origin is the
second Brillouin zone, and the area entering after passing through
the interface (n−1) is the n Brillouin zone. The representative points
of k on the boundary of Brillouin zone are located on the mid-vertical
plane of the inverted lattice vector Kn and satisfy the plane equation.
 
Kn 1 1
k· = Kn or k · Kn = Kn2 . (2.23)
Kn 2 2

Fig. 2.4. Mid-vertical plane.

April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 28

28 Photoelectric Materials and Devices

2.1.5.2. Characteristics of Brillouin region

(1) The volume of each Brillouin region is equal and equal to that
of an inverted cell.
(2) After translating the proper inverse lattice vector Kn , the parts
of each Brillouin region can coincide with another Brillouin
region.
(3) Each Brillouin region is symmetrically distributed around the
origin, and has the point group symmetry of positive and inverse
lattices.

2.1.5.3. Simple Brillouin zone

In order to find the independent states in each band, it is only

necessary to limit k to a Brillouin region. The first Brillouin zone
is the most convenient to use. It is usually called the simple Brillouin
zone.

2.1.6. Metals, semiconductors and insulators

An important aspect of the band theory’s success lies in its ability

to explain why some elements combine into crystals to form good
conductors, while others form semiconductors or insulators. The
physical properties of conductors and insulators are very different.
For example, at 1 K, the resistivity of good conductors (excluding
superconductors) can be as low as 10−10 Ω · cm, while the resistivity
of good insulators can be as high as 1022 Ω · cm.
Metals are generally conductors, and the conductivity decreases
with the increase of temperature. Semiconductors have poor con-
ductivity, and the conductivity increases rapidly with the increase of
temperature. Insulators have the worst conductivity and are basically
non-conductive. These differences can be well explained by using
energy band theory.

2.1.6.1. Full-filled band and partially-filled band

The contribution of an electron to the current density in the crystal

is jk = −e 2
V v, and the total current density is j = −e (2π)3 f v dk.
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 29

Theoretical Basis of Photoelectric Materials 29

Because E(−k) = E(k), for a pair of electrons in the ±k0 state, their
velocities are equal and opposite. According to the formula of average
electron velocity, there are
1 1
v(−k0 ) = [∇k E(k)]k=−k0 = [∇−k E(−k )]k =k0
 
1
= − [∇k E(k )]k =k0 = −v(k0 ).

(1) In the absence of an external field, the electrons are in thermal
equilibrium, and the distribution function f is only a function
of energy E. The wave vector is in the state of ±k, and the
corresponding energy is equal, so the probability of occupation
by electrons is equal. In this pair of states, the electron velocities
are equal in magnitude and opposite in direction, so the contri-
butions to the current cancel each other out. There is no current
flow in the crystal, as shown in Fig. 2.5.
(2) When there is an electric field ε,
dk 1 −e
= F = ε.
dt h h
For full-filled band case, the change of electrons in Brillouin
region under the action of electric field is shown in Fig. 2.6,

(a) (b)

Fig. 2.5. E(k) and v(k) diagrams without outfield: (a) full-filled band condition
and (b) partial-filled band condition.
April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 30

30 Photoelectric Materials and Devices

(a) (b)

Fig. 2.6. E(k) and v(k) diagrams with outfield: (a) Full-filled band condition
and (b) partial-filled band condition.

±k states occupy electrons at the same time, so the contribution

to current is zero.
For partial-filled cases, there are more electrons in the state of
wave vector k opposite to the electric field, less electrons in the
same state as the electric field, or more electrons in the opposite
direction of υ and ε, and fewer electrons in the same direction
of ε. Electrons are negatively charged, resulting in a net current
along the electric field in the crystal.

2.1.6.2. Metals, semiconductors and insulators

The difference between semiconductor, insulator and metal depends

on whether there is a partially filled unsatisfactory band at 0 K.
The two basic conditions for determining whether a crystal is a
semiconductor or an insulator are as follows.

(1) Electrons are sufficient to fill integer bands. If there are N

primitive cells in a crystal, considering the two orientations of
electrons, each band can hold 2N electrons, and the total number
of electrons in a crystal is multiplied by the number of primitive
cells, the condition can be expressed as

Number of electrons in each cell ∗ N/2N = integer,

April 23, 2021 10:6 Photoelectric Materials and Devices 9in x 6in b4165-ch02 page 31

Theoretical Basis of Photoelectric Materials 31

that is, the number of electrons in each cell should be even.

(2) There is an energy gap between the highest energy of occupied
band by electrons and the higher energy band, which does not
overlap. If this condition is not satisfied, electrons can be filled
into overlapping bands so that they cannot be full-filled.

One of the above two items is not satisfied, that is, it may be
metal.
The difference between semiconductor and insulator lies in the
narrow bandgap of the former, which is generally less than 3 eV.
The above discussion is applicable to most crystals, but not
to some transition metal oxides. For example, cobalt oxide (CoO)
is a semiconductor material rather than a metal. Although the
number of electrons in each cell of cobalt oxide is odd, the single-
electron approximation and the shared motion model cannot be
simply applied to the case where the d-electron motion is tightly
bound by atoms in such materials. This shows that the band theory
has limitations.

2.1.7. Electrons, holes and carriers

For semiconductors and insulators, when the temperature rises from

0 K, there will always be a small number of electrons, which jump
from the highest occupied band to the adjacent empty band due to
thermal excitation. There are also a few electrons in the previously
empty adjacent energy bands that can conduct electricity. Usually,
the lowest empty band on the highest full band is called conduction
band; the former full maximum band is now in empty state, and
electrons have room to move and can conduct electricity. The highest
occupied bands are usually called valence bands because they are
the bands occupied by valence electrons forming chemical bonds.
The void state in the valence band is called a void. Electrons in
conduction band and holes in valence band can conduct current, so
they are collectively called carriers.

(i) Holes: Thermal excitation causes a part of the valence band

electrons to jump to the conduction band and form an empty state.
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After several manœuvres on the part of each vessel, Captain
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6. ALLIANCE, ATALANTA, AND TREPASSEY.

In February, 1781, Captain Barry, of the frigate Alliance, of thirty-two

guns, sailed from Boston for l'Orient, having on board Colonel
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The advantage was, both as to men and guns, on the side of the
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opposing vessels had sweeps, and were therefore able to choose
their positions. And the most advantageous positions they did
choose—they lay on the quarters, and athwart the stern of the
Alliance. Consequently, but few of her guns could be brought to
bear.
Added to these untoward circumstances, there soon occurred, on
board the Alliance, a still greater misfortune. A grape-shot struck the
shoulder of Captain Barry, inflicting a severe and dangerous wound.
But he neither heeded its pain nor its danger, but continued on the
quarter-deck, marking the progress of the action, and giving his
orders as occasion required. At length, however, by reason of loss of
blood, he was obliged to be borne below. At this time, the American
flag was shot away, and fell. There was a momentary pause on
board the Alliance, which the enemy construing into a surrender,
they filled the air with loud rejoicings.
But they mistook. The flag had been shot down, not hauled down.
The supposed pause was only the needful interval occupied in
rëloading. The colors were soon rëinstalled, and again floated as
proudly as before; and a full broadside from the Alliance showed to
her foes how the interval had been occupied. That broadside
rëcalled them to their quarters. Fortunately, about this time, a
welcome breeze, though still light, sprung up. The sails of the
Alliance, which had scarcely served any purpose during the
engagement, and seemed destined to acquire no honor in the
coming victory—the sails were no longer idle. They soon brought the
vessel into a more favorable position. This circumstance added to
the confidence and rëdoubled the efforts of the seamen. Broadside
followed broadside in quick succession, and did all desirable
execution. At three o'clock in the afternoon the action terminated:
the Alliance was the victor.
On being ushered into the presence of Barry, Captain Edwards
presented his sword; which, however, the former declined taking,
observing, "that he richly merited it, and that his king ought to give
him a better ship."
The importance of firmness and perseverance, in a commander, was
well illustrated during the above engagement. Soon after Barry
received his wound, and had been obliged to go below, one of his
lieutenants, disheartened by the misfortune which had befallen his
commander, and appalled by the fearful devastation which seemed
to be making by the enemy with the ship's spars and rigging,
repaired to him, and proposed that the colors should be struck.
Barry started. The colors be struck! no such thought had entered his
mind. The colors be struck! "No!" said he; "if the ship can't be
fought without me, carry me at once on deck." The lieutenant, if
ashamed, was also rëanimated. He repaired on deck, went round
among the crew, and made known Barry's courage and
determination. There was but one response among the brave tars.
They decided to "stick to him manfully." And they did. From that
moment "the ship was fought"—and fought without the presence of
Barry. But no sooner was his wound dressed, than he insisted on
being aided in ascending to the deck; before reaching it, however,
the enemy had struck. Brave seamen! brave commander!
The Alliance had eleven killed during the action, and twenty-one
wounded. Among the latter, were several officers. She had suffered
terribly in her spars and rigging. The loss of the enemy was eleven
killed and thirty wounded.

7. CONGRESS AND SAVAGE.

The Savage was a British sloop, carrying twenty guns and about one
hundred and fifty men. In September, 1781, while on a cruise along
the Southern coast of the United States, she entered the Potomac,
and plundered the estate of Washington, then in another quarter,
commanding the American army. It was an expedition unworthy a
high-minded and honorable officer, and a well-merited rebuke was
soon after meted out to him.
On leaving the Potomac, the Savage fell in with the American
privateer Congress, Captain Geddes, off Charleston. The vessels
were of the same force. On board the Congress, at the time, was
Major McLane, a distinguished American officer, who with a part of
his command had volunteered to serve as marines. As the crew of
the Savage were all seamen, she had decidedly the advantage, in
respect to the Congress, whose crew, in part, were landsmen,
unacquainted with marine warfare.
The vessels were now within cannon distance. The Congress
commenced by firing her bow-chasers. This was at half-past ten in
the morning. At eleven, they had approximated so near each other,
that the landsmen employed their musketry, and with effect. A sharp
and destructive cannonade followed on both sides.
At the commencement of the engagement, the advantage lay with
the Savage. Her position being on the Congress' bows, was favorable
for raking. But a closer engagement followed, and the tide turned in
favor of the privateer. So well did she manœuvre, so promptly, so
dextrously, that she soon disabled her enemy. At the expiration of an
hour, the braces and bowlines of the Savage were shot away. Not a
rope was left by which to trim the sails. The musketry of the
Americans had cleared her decks. In this situation, it was deemed
impossible that she could much longer continue the contest. Indeed,
she was already nearly a wreck—her sails, rigging, and yards were
so shattered as to forbid her changing her position, but with the
greatest difficulty. She would not, however, surrender, but
rëcommenced a vigorous cannonade. Again her quarter-deck and
forecastle were cleared by the fatal musketry of the American
landsmen. Three guns on her main deck were rendered useless. The
vessels were now so near each other, that the fire from the guns
scorched the men opposed to them in the other. At length, the
mizen-mast of the Savage was shot away. At this instant, the
boatswain of the Savage appeared forward, with his hat off, calling
for quarter. But it was half an hour before the crew of the Congress
could board her, by reason of the loss of their boats. But, on
reaching her, she was found to be scarcely more than a wreck. Her
decks were covered with blood, and killed and wounded men.
The Congress had thirty men killed and wounded. The Savage had
twenty-three killed and thirty-one wounded. Among the latter, was
her commander, Captain Sterling.
The marine service often furnished examples of great heroism and
most patriotic endurance. Such an instance occurred on board the
Congress. After the action terminated, Major McLane went forward
to ascertain what had become of his sergeant, Thomas. He found
the poor fellow lying on his back in the netting, near the foot of the
bowsprit, with his musket loaded, but both legs broken. "Poor
fellow!" thought the major, as he beheld him; "poor fellow!" But the
poor fellow began huzzaing lustily for the victory achieved; and
followed his exulting and even vociferous huzzas by a corresponding
exclamation addressed to his major: "Well, major, if they have
broken my legs, my hands and my heart are still whole."
Sergeant Thomas was terribly wounded, but the kind-hearted major
did not neglect him. The best care was taken of him; ultimately, he
recovered; and, nothing deterred by the painful experience he had
had of the sometimes ill-fortune of war, he entered on board the
Hyder Ali, commanded by Captain Barney.
It is ever delightful to record instances of high-minded and
magnanimous conduct on the part of victors towards the
vanquished. This engagement furnishes one most honorable to the
American character. The officers and crew of the Savage were
treated with the greatest kindness and attention. Major McLane even
accompanied Captain Sterling into Pennsylvania, to secure him from
insult, his treatment of American prisoners having rendered him
highly obnoxious to the patriots.
Such is a brief account of some of the exploits of the American
marine during the war of the Revolution. There were others perhaps
equally honorable to the skill and enterprise of our naval officers, but
which our limits forbid us to notice. On the breaking out of the war,
the country was poorly prepared to enter the lists with the mistress
of the ocean. Indeed, it was not until 1776, that the forbearing
policy of congress was abandoned, and the nautical enterprise of the
country was let loose upon British commerce. From that time,
however, American valor was exhibited in its true and persevering
spirit, and contributed, as far as it had scope, in inducing the
mother-country to acknowledge the independence of her wayward
child—which she did on the 20th of January, 1783.
Upon this most desirable event, orders of recall were issued to all
naval commanders; and the commissions of privateers and letters of
marque were annulled. On the 11th of April following, a
proclamation from the proper authorities announced the cessation of
hostilities. From this time, as the glad intelligence spread, the helms
of our warlike ships were turned towards our home ports, leaving
the merchantmen again to the peaceful possession of that element,
which for years they had traversed, if at all, at the greatest hazard.
 XV. EMINENT FOREIGNERS,
CONNECTED WITH THE REVOLUTION.

George III. King of England—General Burgoyne—Sir Henry

Clinton—Colonel Barre—Charles Townshend—Lord Cornwallis—
William Pitt—Marquis of Bute—George Grenville—Duke of
Grafton—Lord North—Colonel Tarleton—Sir Peter Parker—Sir
William Meadows—Sir Guy Carlton—General Gage—Marquis of
Rockingham—Edmund Burke—Kosciusko—Count Pulaski—Baron
de Kalb—Baron Steuben—Count Rochambeau—Count D'Estaing.

In the preceding pages, we have had occasion to trace the causes

and events of that struggle which resulted in the independence of
the United States; and, in so doing, incidental mention has been
made of some of the leading men of England, who figured in the
cabinet, in the field, and on the ocean; with the part they acted
either in favor of, or in opposition to the grand object of the colonies
in their contest with the mother-country. Judging from his own early
desires, the author persuades himself that he will be conferring a
favor upon his readers by giving some brief sketches, in this place,
of those distinguished men, and of others, who contributed to retard
or accelerate the final result. Such notices of the most prominent,
we proceed to give, beginning with the monarch, the great fountain
of power and law, then on the throne of Great Britain.

GEORGE III.

George III. was born in 1738, and succeeded to the throne on the
death of his grandfather, George II., October 25, 1760, about the
time the troubles with America began. At this period, principally
through the lofty spirit and political sagacity of Pitt, afterwards Earl
of Chatham, who was, and for some time had been, at the head of
the administration, the affairs of the nation were in a most
prosperous state. The army and navy were highly efficient, and
flushed with recent conquests; the revenue flourished; commerce
was increasing; the people were loyal; and, perhaps, no prince had
ascended the throne of his ancestors with more flattering prospects
than George the Third.
Soon after ascending the throne, the king evinced a determination to
procure a general peace. In this measure he differed from his great
minister, Pitt, who, on that account, retired from office, October 5,
1761. Peace, however, contrary to the wishes and designs of the
king could not be obtained on a just basis, and the war proceeded.
In May, 1762, Lord Bute, a particular favorite of the king, who had
contrived to gain a remarkable ascendancy over him, succeeded the
Duke of Newcastle, as first lord of the treasury. Preliminaries of
peace between England, France, and Spain, were signed on the 3d
of November, and the definite treaty followed, February 10th, 1763.
The people, however, were by no means pacifically inclined, or
contented with the political ascendancy of Lord Bute, whose
administration was attacked with unsparing severity by several
popular writers, particularly by the celebrated John Wilkes, in his
periodical paper, called the North Briton. The arrest of Wilkes, and
the seizure of his papers under a general warrant, issued by the
secretary of state for the home department, increased the
indignation and clamors of the people; Lord Bute was execrated
throughout the country, and the king himself became exceedingly
unpopular. The removal of the favorite, and the appointment of
George Grenville to the head of the treasury, having failed to allay
the national irritation, Pitt, it is asserted, was at length summoned to
court, and requested to make arrangements for forming a new
ministry; but he presumed, it is added, to dictate such arrogant
terms, that, rather than submit to them, the king said he would
place the crown on Pitt's head, and submit his own neck to the axe.
In 1764, the king suggested to Grenville the taxation of America, as
a grand financial measure for relieving the mother-country from the
heavy war expenses, which, it was unjustly claimed, had chiefly
been incurred for the security of the colonies. The minister was
startled, and raised objections to the proposal, which, however, were
overruled by the king, who plainly told him that, if he were afraid to
adopt such a measure, others might easily be found who possessed
more political courage. At length, Grenville reluctantly brought the
subject before parliament; and, in spite of a violent opposition, the
stamp act, so important in its consequences, was passed in the
following year. The most alarming irritation prevailed among the
colonists of America.
The Rockingham party, which now came into power, procured the
repeal of the stamp act; but, notwithstanding this and some other
popular measures of the new cabinet, it was dissolved in the
summer of 1766. The Duke of Grafton succeeded Lord Rockingham,
as first lord of the treasury, and Pitt (then Earl of Chatham) took
office as lord privy seal. In the following year, Charles Townshend,
chancellor of the exchequer, proposed the taxation of certain articles
imported by the American colonists; and, early in 1768, Lord
Chatham retired in deep disgust from the administration, which,
during the preceding autumn, had been weakened by the succession
of Lord North to Charles Townshend, as chancellor of the exchequer.
Some other official changes took place; one of the most important of
which, perhaps, was the appointment of Lord Hillsborough to the
new colonial secretaryship.
The aspect of affairs in America grew more serious every hour: the
deputies of Massachusetts declared taxation by the British
parliament to be illegal; a scheme for a general congress of the
different states was proposed, and an open rupture with the mother-
country was evidently approaching. Blind to the consequences of
their fatal policy, the king and his ministers, however, persisted in
those measures, with regard to the trans-Atlantic colonies, which
eventually produced a dismemberment of the empire.
In January, 1770, the Duke of Grafton resigned all his employments;
but, unfortunately for America, he was succeeded by Lord North,
who increased rather than alleviated the national calamities, and
was decidedly with the king in his determination never to yield to the
demands of the colonists, but to coerce them to submission,
however unjustly, by the arm of power.
In 1782, Lord North was compelled to resign, and the Rockingham
party, friendly to the independence of America, came into office; but
the new administration soon afterwards broke up, on account of the
sudden death of the premier. Lord Shelburne was now placed at the
head of the treasury, and Pitt, son of the great Earl of Chatham,
became chancellor of the exchequer.
In 1783, a general peace was concluded, and the United States
procured a formal acknowledgment of their independence. When
Adams, the first American envoy, attended at the levee, the king, to
whom he was personally disagreeable, received him with dignified
composure, and said, "I was the last man in England to acknowledge
the independence of America, but having done so, I shall also be the
last to violate it." This was highly honorable to the king. America was
a jewel in the British crown which was increasing in lustre, to part
with which was truly painful to royal ambition. Nor did George III.
consent to any acts which tended to this relinquishment, only as he
was compelled to it by the ill success of his armies in America, and
the clamorous demands for peace by his subjects at home. But
having, at length, parted with this jewel, and having acknowledged
the independence of America, he nobly declared his intention to live
in peace with this newborn empire.

JOHN BURGOYNE.

General Burgoyne was the natural son of Lord Bingley. At an early

age he entered the army; and while quartered with his regiment at
Preston, married Lady Charlotte Stanley, whose father, the Earl of
Derby, was so incensed at the match, that he threatened utterly to
discard her; but a reconciliation at length took place, and the earl
allowed her three hundred pounds a-year during his life, and, by his
will, bequeathed her a legacy of twenty-five thousand pounds. The
influence of the family to which Burgoyne had thus become allied,
tended materially to accelerate his professional advance. In 1762, he
acted as brigadier-general of the British forces which were sent out
for the defence of Portugal against France and Spain.
In 1775, he was appointed to a command in America; whence he
returned in the following year, and held a long conference with the
king on colonial affairs. Resuming his post in 1777, he addressed a
proclamation to the native Indians, in which he invited them to his
standard, but deprecated, with due severity, the cruel practice of
scalping. The pompous turgidity of style, in which this address was
couched, excited the ridicule of the Americans, and procured for
General Burgoyne the soubriquet of "Chrononhotonthologos." His
first operations were successful: he dislodged the enemy from
Ticonderoga and Mount Independence, and took a large number of
cannon, all their armed vessels and batteries, as well as a
considerable part of their baggage, ammunition, provisions, and
military stores. But his subsequent career was truly disastrous; his
troops suffered much from bad roads, inclement weather, and a
scarcity of provisions; the Indians, who had previously assisted him,
deserted; and the Americans, under General Gates, surrounded him
with a superior force, to which, although victorious in two
engagements, he was, at length, compelled to capitulate at
Saratoga, with the whole of his army. This event, which rendered
him equally odious to ministers and the people, was, for some time,
the leading topic of the press; and numberless lampoons appeared,
in which the general's conduct was most severely satirized. The
punsters of the day, taking advantage of the American general's
name, amused themselves unmercifully at Burgoyne's expense; but
of all their effusions, which, for the most part, were virulent rather
than pointed, the following harmless epigram, poor as it is, appears
to have been one of the best:
 "Burgoyne, unconscious of impending fates,
Could cut his way through woods, but not through
Gates."

In May, 1778, he returned to England, on his parole, but the king

refused to see him. Burgoyne solicited a court-martial, but in vain. In
1779, he was dismissed the service for refusing to return to America.
Three years after, however, he was restored to his rank in the army,
appointed commander-in-chief in Ireland, and sworn in one of the
privy-council of that kingdom. He died suddenly of a fit of the gout,
at his house in Hertford street, on the 4th of August, 1792; and his
remains were interred in the cloisters of Westminster abbey.
It would, perhaps, be rash to pronounce a positive opinion of the
merits of Burgoyne, as a commander. He boldly courted a scrutiny
into the causes which led to his surrender at Saratoga, which
ministers refused, because, as it has been insinuated, such a
proceeding might expose the absurd imprudence and inefficiency of
their own measures with regard to the American war. Prior to the
capitulation, his military career, as well in America as Portugal, had
been rather brilliant; his misfortune was precisely that which befel
Cornwallis; but, unlike the latter, Burgoyne was not allowed an
opportunity of redeeming his reputation.
In parliament, he was a frequent and fluent, but neither a sound nor
an impressive speaker. While in employment, he appears to have
been a staunch advocate for the American war; which, however, he
severely reprobated, from the time that he ceased to hold a
command. He was a writer, chiefly dramatic, of considerable merit.

SIR HENRY CLINTON.

This distinguished general was a grandson of the Earl of Clinton, and

was born about the year 1738. After having received a liberal
education, he entered the army, and served for some time in
Hanover. In the early part of the revolutionary struggle he came to
America, and was present at the battle of Bunker's hill; from which
time to the close of the American war, he continued to aid the British
cause. In 1777, he was made a Knight of the Bath, and in January,
1778, commander-in-chief of the British forces in America. On his
return to England, a pamphlet war took place between him and
Cornwallis, as to the surrender of the latter, the entire blame of
which each party attributed to the other. In 1793, he obtained the
governorship of Gibraltar, in possession of which he died on the 23d
of December, 1795.
 Sir Henry Clinton.

The merits of Sir Henry Clinton, as a commander, have been variously estimated; and,
as is usually the case, the truth seems to be intermediate between the panegyric of his
friends and the censure of his enemies. That he was endowed with bravery, and
possessed a considerable share of military skill, cannot, in fairness, be denied; but he
was decidedly unequal to the great difficulties of his situation and unfit to contend
against so lofty a genius as Washington, supported by a people resolved on obtaining
their independence, and fighting on their native soil.

ISAAC BARRE.
 Colonel Barre.

Colonel Barre was born in Ireland, about the year 1726. He served at Quebec, under
Wolfe, in the picture of whose death, by Benjamin West, his figure is conspicuous. The
Earl of Shelburne procured him a seat in parliament, where, acting in opposition to
government, he was not only deprived of his offices of adjutant-general and governor
of Stirling castle, which he had received as a reward for his services in America, but
dismissed from the service. During the Rockingham administration, he was
compensated for the loss which he had sustained, by being voted a pension of three
thousand two hundred pounds per annum; which he subsequently relinquished,
pursuant to an arrangement with Pitt, on obtaining a lucrative, but not distinguished
office. He usually took office when his party predominated; and was, in the course of
his career, a privy counsellor, vice treasurer of Ireland, paymaster of the forces, and
treasurer of the navy. His best speeches were delivered during North's administration,
on the American war, to which he appears to have been inflexibly opposed. His oratory
was powerful, but coarse; his manner, rugged; his countenance, stern; and his stature,
athletic. He was suspected, but apparently without reason, of having assisted in writing
the letters of Junius. For the last twenty years of his life, he was afflicted with
blindness, which, however, he is said to have borne with cheerful resignation. His death
took place on the 20th of July, 1792.
 CHARLES TOWNSHEND.

Charles Townshend, son of Viscount Townshend, was born 1725. From his youth, he
was distinguished for great quickness of conception and extraordinary curiosity. In
1747, he went into parliament, and continued a member till he died. He held various
offices in the government. In 1765, he was paymaster general, and chancellor of the
exchequer; and a lord of the treasury in August, 1766, from which period he remained
in office until his decease, which took place on the 4th of September, 1767.
In person, Charles Townshend was tall and beautifully proportioned; his countenance
was manly, handsome, expressive, and prepossessing. He was much beloved in private
life, and enjoyed an unusual share of domestic happiness.
Burke, in his speech on American taxation, thus admirably depicted the general
character of Charles Townshend: "Before this splendid orb (alluding to the great Lord
Chatham) had entirely set, and while the western horizon was in a blaze with his
descending glory, on the opposite quarter of the heavens arose another luminary, and
for his hour he became lord of the ascendant. This light, too, is passed, and set for
ever! I speak of Charles Townshend, officially the rëproducer of this fatal scheme
(American taxation); whom I cannot even now remember, without some degree of
sensibility. In truth, he was the delight and ornament of this house, and the charm of
every private society which he honored with his presence. Perhaps there never arose in
this country, nor in any country, a man of more pointed and finished wit, and (where
his passions were not concerned) of a more refined, exquisite, and penetrating
judgment. If he had not so great a stock, as some have had who flourished formerly, of
knowledge long treasured up, he knew better by far, than any man I ever was
acquainted with, how to bring together, within a short time, all that was necessary to
establish, to illustrate, and to decorate that side of the question he supported. He
stated his matter skillfully and powerfully; he particularly excelled in a most luminous
explanation and display of his subject."

CHARLES CORNWALLIS, MARQUIS.

Lord Cornwallis, eldest son of the fifth lord, and first Earl Cornwallis, was born 1738. At
the age of twenty, he entered the army, and obtained a captaincy. In 1762, on the
death of his brother, he took his seat in the house of lords. In 1770, he and three other
young peers, having protested, with Lord Camden, against the taxation of America,
Mansfield, the chief justice, is said to have sneeringly observed, "Poor Camden could
only get four boys to join him!"
Although he had opposed the measures of the government with regard to the
disaffected colonies, yet when hostilities commenced, he did not scruple to accept of
active employment against the Americans. His history, during the war, will be found in
the preceding pages. He was a proud man, and most humiliating was it when he was
obliged to surrender to Washington at Yorktown.
But his failure in America did not impair his reputation. On his return to England, he
was made governor of the Tower. In 1786, he was sent to Calcutta, as governor-general
and commander-in-chief. Having terminated, successfully, a war in that country, he
returned to England. In 1799, he became lord-lieutenant of Ireland. Soon after the
expiration of his vice-regency, he was sent to France as plenipotentiary for Great
Britain, in which capacity he signed the treaty of Amiens. In 1804, he succeeded the
Marquis Wellesley, as governor-general of India. On his arrival at Calcutta, he
proceeded, by water, to take the command in the upper provinces. The confinement of
the boat, the want of exercise, and the heat of the weather, had a most serious effect
on his health. Feeling, soon after he had landed, that his dissolution was at hand, he
prepared some valuable instructions for his successor; and the last hours of his life
were passed in taking measures to lessen the difficulties which his decease would
produce. He expired at Ghazepoore, in Benares, on the 5th of October, 1805.
Lord Cornwallis was not endowed with any brilliancy of talent. He had to contend with
no difficulties, on his entrance into life: high birth procured him a military station, which
his connexions enabled him to retain, after he had committed an error, or, at least, met
with a mischance, that would have utterly ruined a less influential commander.
Although ambitious, he appears to have possessed but little ardor. He manifested no
extraordinary spirit of enterprise; he hazarded no untried manœuvres; and yet, few of
his contemporaries passed through life with more personal credit or public advantage.
He had the wisdom never to depute to others what he could perform himself. His
perseverance, alacrity, and caution, procured him success as a general, while his strong
common sense rendered him eminent as a governor. He always evinced a most anxious
desire to promote the welfare of those who were placed under his administration;
Ireland and Hindostan still venerate his memory. His honor was unimpeachable; his
manners, devoid of ostentation; and his private character, altogether amiable.
Napoleon Buonaparte, in his conversations with Barry O'Meara, declared that Lord
Cornwallis, by his integrity, fidelity, frankness, and the nobility of his sentiments, was
the first who had impressed upon him a favorable opinion of Englishmen. "I do not
believe," said the ex-emperor, "that he was a man of first-rate abilities; but he had
talent, great probity, sincerity, and never broke his word. Something having prevented
him from attending at the Hôtel de Dieu, to sign the treaty of Amiens, pursuant to
appointment, he sent word to the French ministers that they might consider it
completed, and that he would certainly execute it the next morning. During the night,
he received instructions to object to some of the articles; disregarding which, he signed
the treaty as it stood, observing that his government, if dissatisfied, might refuse to
ratify it, but that, having once pledged his word, he felt bound to abide by it. There was
a man of honor!" added Napoleon; "a true Englishman."

LORD CHATHAM.

William Pitt, Earl of Chatham, was born November 15, 1708. His father was Robert Pitt,
of Boconnock, in the county of Cornwall. He received his education at Trinity college,
Cambridge. He took a seat in parliament as early as 1735, as a member for Old Sarum.
His exalted talents, his lofty spirit, and commanding eloquence, soon rendered him
singularly conspicuous. Under George II., in 1757, he became premier of that
celebrated war administration, which raised England to a proud prëeminence over the
other nations of Europe. His energy was unbounded. "It must be done," was the reply
he often made, when told that his orders could not be executed. After which, no excuse
was admitted. Under his auspices, England triumphed in every quarter of the globe. In
America, the French lost Quebec; in Africa, their chief settlements fell; in the East
Indies, their power was abridged; in Europe, their armies suffered defeat; while their
navy was nearly annihilated, and their commerce almost reduced to ruin.
On the accession of George the Third, Pitt, who felt strongly impressed with the policy
of declaring war against Spain, was thwarted in his wishes by the influence of Lord
Bute; and, disdaining to be nominally at the head of a cabinet which he could not
direct, he resigned his office in October, 1761.

Lord Chatham.

In 1764, he greatly distinguished himself by his opposition to general warrants, which,

with all his accustomed energy and eloquence, he stigmatized as being atrociously
illegal. A search for papers, or a seizure of the person, without some specific charge,
was, he contended, repugnant to every principle of true liberty. "By the British
constitution," said he, "every man's house is his castle! not that it is surrounded by
walls and battlements; it may be a straw-built shed; every wind of heaven may whistle
round it; all the elements of nature may enter it; but the king cannot; the king dare
not."
He invariably opposed, with the whole force of his eloquence, the measures which led
to the American war: and long after his retirement from office, he exerted himself most
zealously to bring about a reconciliation between the mother-country and her colonies;
But when the Duke of Portland, in 1778, moved an address to the crown, on the
necessity of acknowledging the independence of America, Lord Chatham, although he
had but just left a sick bed, opposed the motion with all the ardent eloquence of his
younger days. "My lords," said he, "I lament that my infirmities have so long prevented
my attendance here, at so awful a crisis. I have made an effort almost beyond my
strength to come down to the house on this day, (and perhaps it will be the last time I
shall be able to enter its walls,) to express my indignation at an idea which has gone
forth of yielding up America. My lords: I rejoice that the grave has not yet closed upon
me; that I am still alive to lift up my voice against the dismemberment of this ancient
and most noble monarchy. Pressed down, as I am, by the hand of infirmity, I am little
able to assist my country in this most perilous conjuncture; but, my lords, while I have
sense and memory, I will never consent to deprive the royal offspring of the house of
Brunswick of their fairest inheritance."
The Duke of Richmond having replied to this speech, Lord Chatham attempted to rise
again, but fainted, and fell into the arms of those who were near him. The house
instantly adjourned, and the earl was conveyed home in a state of exhaustion, from
which he never recovered. His death took place at Hayes, early in the following month,
namely, on the 11th of May, 1778. The House of Commons voted the departed patriot,
who had thus died gloriously at his post, a public funeral, and a monument in
Westminster abbey at the national expense. An income of four thousand pounds per
annum was annexed to the earldom of Chatham, and the sum of twenty thousand
pounds cheerfully granted to liquidate his debts: for, instead of profiting by his public
employments, he had wasted his property in sustaining their dignity, and died in
embarrassed circumstances.
In figure, Lord Chatham was eminently dignified and commanding. "There was a
grandeur in his personal appearance," says a writer, who speaks of him when in his
decline, "which produced awe and mute attention; and, though bowed by infirmity and
age, his mind shone through the ruins of his body, armed his eye with lightning, and
clothed his lips with thunder." Bodily pain never subdued the lofty daring, or the
extraordinary activity of his mind. He even used his crutch as a figure of rhetoric. "You
talk, my lords," said he, on one occasion, "of conquering America—of your numerous
friends there—and your powerful forces to disperse her army. I might as well talk of
driving them before me with this crutch."

CHARLES JAMES FOX.

Charles James Fox was the third son of Henry Fox, Lord Holland, and was born January
24th, 1749. His mother was a daughter of the Duke of Richmond, and his sister the
wife of Lord Cornwallis. Lord Holland made it a rule, in the tuition of his children, to
follow and regulate, but not to restrain nature. This indulgence was a sad error, as it
always is on the part of parents. On arriving to maturity, Charles used to boast that he
was, when young, never thwarted in any thing. Two instances are related of this
indulgence of the father, before the son was six years old. One day, standing by his
father, while he was winding up a watch—"I have a great mind to break that watch,
papa," said the boy. "No, Charles; that would be foolish." "Indeed, papa," said he, "I
must do it." "Nay," answered the father, "if you have such a violent inclination, I won't
baulk it." Upon which, he delivered the watch into the hands of the youngster, who
instantly dashed it on the floor.
At another time, while Lord Holland was secretary of state, having just finished a long
dispatch which he was going to send, Mr. Charles, who stood near him, with his hand
on the inkstand, said, "Papa, I have a good mind to throw this ink over the paper." "Do,
my dear," said the secretary, "if it will give you any pleasure." The young gentleman
immediately threw on the ink, and his father sat down very composedly to write the
dispatch over again.
Such a course of education, we should anticipate, would work the moral ruin of a child.
Its baleful influence was seen in after years, in gambling, horse-racing, drinking, and
kindred vices, carried to a fearful extent on the part of this son, whose training was so
inauspiciously begun and persevered in.
 Fox.

But, despite of these most degrading and ruinous practices, Fox proved to be one of
the most accomplished and effective orators, and perhaps we may add, statesman of
his times. He was the rival of Pitt; and, though not so finished in his elocution, he not
unfrequently equalled him in the effect produced.
By what means he attained to such eminence, it scarcely appears; for the younger part
of his life seems to have been so exclusively devoted to his pleasures, as scarcely to
have time left for the cultivation of his intellect. His genius, however, was brilliant; and
from his earliest years he was in the society of men distinguished for their cultivated
intellect, and the eminent part they took in the government of the country. It is related
of Fox, that he would not unfrequently spend the entire night at his favorite
amusement, gambling, and thence proceed to the House of Commons, when he would
electrify the whole assembly with some cogent and brilliant speech.
Fox was a firm, steadfast friend to the Americans and their independence. At the time
the measures which led to the American war had come to a crisis, a formidable party
existed in England, opposed to the unjust and illiberal policy of the government. To this
party, Fox united himself; and, from his conspicuous talents, soon acquired the
authority of a leader. In 1773, he opposed the Boston port bill, and apologized for the
conduct of the colonies. In his speech on that occasion, he arraigned the measures of
the ministers in bold and energetic language, and explained the principles of the
constitution with masculine eloquence. The session of 1775, opened with a speech from
the king, declaring the necessity of coercion. On this occasion, Fox poured forth a
torrent of his powerful eloquence. In that plain, forcible language, which formed one of
the many excellencies of his speeches, he showed what ought to have been done, what
ministers had promised to do, and what they had not done. He affirmed that Lord
Chatham, the king of Prussia—nay, even Alexander the Great—never gained more in
one campaign than Lord North had lost.
When the news of the disastrous defeat of Burgoyne reached England, Fox loudly
insisted upon an inquiry into the causes of his failure. And in like manner, when the fate
of Cornwallis' army at Yorktown was made known, the oppositionists were loud in their
denunciations of the proceedings of ministers in regard to the war. Mr. Fox designed to
make a motion for an investigation into the conduct of Lord Sandwich, who was at the
head of the admiralty. But he was, for a time, too much indisposed to make the
attempt. It was on this occasion, that Burke is reported to have said, "that if Fox died,
it would be no bad use of his skin, if, like John Ziska's, it should be converted into a
drum, and used for the purpose of sounding an alarm to the people of England."
The death of Mr. Fox occurred 13th of August, 1806.
Walpole thus compares the two great orators of England: "Mr. Fox, as a speaker, might
be compared to the rough, but masterly specimen of the sculptor's art; Mr. Pitt, to the
exquisitely finished statue. The former would need a polish to render him perfect; the
latter possessed, in a transcendent degree, every requisite of an accomplished orator.
The force of Mr. Fox's reasoning flashed like lightning upon the mind of the hearer: the
thunder of Mr. Pitt's eloquence gave irresistible effect to his powerful and convincing
arguments."
The sympathy and support of such men as Fox, during our Revolutionary struggle,
served to sustain and animate our patriotic fathers. They felt that while they were in
the field, engaged in defeating the armies of England, they had friends in the House of
Commons, who were making every possible effort to defeat the impolitic and
oppressive measures of the king and his ministers.

JOHN STUART.

John Stuart, Marquis of Bute, was born in 1715. In the ninth year of his age, he
succeeded his father as Marquis of Bute. On the accession of George the Third, the
highest dignities in the state were supposed to be within the grasp of Lord Bute; but,
however he might have swayed the king's mind in private, he took no public part in the
direction of public affairs until 1761, when he accepted the secretaryship resigned in
that year by Lord Holderness. At length, he became prime minister; and, immediately
on coming into power, determined, if possible, to effect a peace, which had for some
time been negotiating. He accomplished his object, but his success rendered him
exceedingly unpopular. He was accused, by some weak-minded persons, of having been
bribed by the enemies of his country; and it was added, that the princess dowager had
shared with him in the price at which peace had been purchased by the French
government.
He quitted office in April, 1763, but continued to exert a powerful influence over the
mind of the king, especially in relation to America. Several measures, the object of
which was to humble the colonies, and continue them in subjection to the crown, are
said to have been suggested by this nobleman. He died in 1792.

GEORGE GRENVILLE.

Grenville.

George Grenville was born 1712. In 1741, he was returned to parliament for the town
of Buckingham, for which place he served during the remainder of his life. He held
several important offices. In April, 1763, he became first lord of the treasury and
chancellor of the exchequer. He resigned his office in July, 1765, and died in November,
1770. During his premiership, the project of imposing internal taxes in America was
carried into effect. The project was first named to him by the king, and urged upon
him. At first, the minister was opposed to the idea, but after having adopted it as a
measure of his administration, which he was compelled to do by royal authority, he
urged and supported it by all the means in his power.

DUKE OF GRAFTON.

Henry Augustus Fitzroy, Duke of Grafton, was born 1735. He was educated at
Cambridge, where he was notoriously profligate. In July, 1766, the Rockingham
administration was dissolved, and the Duke of Grafton was made first lord
commissioner of the treasury, which office he held until January, 1770. He has received
an unenviable notoriety from the strictures of Junius. His administration was composed
of men of different political principles and parties. Junius, in a letter addressed to the
duke, thus narrates, and severely animadverts upon, the circumstances of his grace's
appointment to the premiership: "The spirit of the favorite (Lord Bute) had some
apparent influence upon every administration; and every set of ministers preserved an
appearance of duration as long as they submitted to that influence; but there were
certain services to be performed for the favorite's security, or to gratify his resentments,
which your predecessors in office had the wisdom, or the virtue, not to undertake. A
submissive administration was, at last, gradually collected from the deserters of all
parties, interests, and connexions; and nothing remained but to find a leader for these
gallant, well-disciplined troops. Stand forth, my lord, for thou art the man! Lord Bute
found no resource of dependence or security in the proud, imposing superiority of Lord
Chatham's abilities; the shrewd, inflexible judgment of Mr. Grenville; nor in the mild,
but determined integrity of Lord Rockingham. His views and situation required a
creature void of all these properties; and he was forced to go through all his division,
resolution, composition, and refinement of political chemistry, before he happily arrived
at the caput mortuum of vitriol in your grace. Flat and insipid in your retired state, but
brought into action, you become vitriol again. Such are the extremes of alternate
indolence or fury, which have governed your whole administration!"

FREDERICK NORTH, EARL OF GUILFORD.

This nobleman, better known as Lord North, was the minister of George III., under
whose administration England lost her American colonies. He succeeded Charles
Townshend, as chancellor of the exchequer; and, in 1770, the Duke of Grafton, as first
lord of the treasury, and continued in that high, but laborious office, till the conclusion
of the war. As a public character, Lord North was a flowing and persuasive orator, well
skilled in argumentation, and master of great presence and coolness of mind; and, in
private life, he was very amiable, cheerful, and jocose in conversation, the friend of
learned men, and correct in conduct. In his policy towards America, he was stern and
uncompromising. On first coming into power, he was inclined to be conciliatory; but
soon he adopted restrictive and oppressive measures, more so than his predecessors,
and, at length, declared that he would omit no means but that he would bring America
in humility at his feet. The faithful warnings of Pitt, Burke, Fox, and others, had no
restraining influence, and the consequence was, that America was lost to the British
crown. Lord North, in the latter years of his life, was afflicted with blindness. He died
July, 1792, aged sixty.

BARRASTRE TARLETON.

Colonel Tarleton was born in Liverpool, on the 21st of August, 1754, and at first
commenced studying law, but, on the breaking out of war in America, he entered the
army, and, having arrived in that country, he was permitted to raise a body of troops
called the "British Legion," which he commanded in several successful excursions
against the enemy. Such was the daring intrepidity, energy, and skill, with which he
conducted his corps, that he may be said to have greatly accelerated, if not secured,
some of the most important victories under Lord Cornwallis. On his return to England,
he was made a colonel, and became so popular that, in 1790, he was returned, free of
expense, as a member for Liverpool, which he represented in three subsequent
parliaments.
In 1818, previously to which he had been raised to the rank of general, he was created
a baronet, and, on the coronation of George the Fourth, was made a K. C. B. He was
one of the bravest officers of his time, and is described as having been to the British, in
the American war, what Arnold, in his early career, was to the Americans.

SIR PETER PARKER.

Sir Peter Parker, son of Rear-admiral Christopher Parker, was born in 1723, and entered
the navy under the auspices of his father. Having served with great reputation on
several occasions, in 1775 he hoisted his broad pendant on board the Bristol, of fifty
guns, in which he proceeded, with a squadron under his command, to the American
station. On account of bad weather and other impediments, he did not reach Cape Fear
until May, 1776. In the following month, he made an unsuccessful attack on Charleston,
in South Carolina. Shortly afterwards, he joined Lord Howe, the commander-in-chief, at
New York, whence he was dispatched, with the Asia, Renown, and Preston, to distract
the attention of the enemy, while the army attacked the lines on Long Island. Towards
the close of the same year, he proceeded, in command of a small squadron, to make an
attempt on Rhode Island, of which he obtained possession without loss. He was now
advanced to the rank of rear-admiral of the blue; and, a few months after, appointed to
the chief command on the Jamaica station, where he served with signal success until
1782, in which year he returned with a convoy to England. Before his death, which
occurred in 1811, he became admiral of the blue and admiral of the white.

SIR WILLIAM MEADOWS.

Sir William Meadows was born in 1738. In 1775, he repaired with his regiment to
America, where he distinguished himself, particularly at the battle of Brandywine,
during which he was wounded.
In 1792, he served under Cornwallis in India. On returning to England, he was
appointed governor of the Isle of Wight, and, afterwards, governor of Hull. He died at
Bath, 1813.
As a military man, he was highly distinguished. He was invariably cheerful, during an
engagement; and his troops, by whom he was much beloved, are said, on more than
one occasion, to have mounted the breach, laughing at their general's last joke. His
hilarity scarcely ever deserted him; one day, while on a reconnoitering party, he
observed a twenty-four-pound shot strike the ground, on his right, in such a direction
that, had he proceeded, it would, in all probability, have destroyed him; he, therefore,
stopped his horse, and, as the ball dashed across the road in front of him, gracefully
took off his hat, and said: "I beg, sir, that you will continue your promenade; I never
take the precedence of any gentleman of your family."

GENERAL GAGE.

General Thomas Gage, second son of Viscount Gage, was born about the year 1721,
and entered the army at an early age. Having served with considerable credit, he was
commissioned as lieutenant-general; soon after which, (April, 1774,) he was appointed
to succeed Mr. Hutchinson, as governor of Massachusetts Bay. In May, he sailed for
Boston with four regiments, where, contrary to his expectations, he was received with
great ceremony and outward respect.
About this time, serious troubles of the colonies with England began. General Gage
took strong and decided measures, and hastened, rather than retarded, an open
contest. By his order it was that the military stores at Concord were destroyed, which
led to the skirmish at Lexington, and which opened the war.
On the 10th of October, 1775, he resigned his command to Sir William Howe, and
departed for England. At the time of his death, which took place on the 2d of April,
1788, he was a general in the army. His talents for command are said to have been
respectable.

SIR GUY CARLTON.

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