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Solid State Physics for Electronics Andre Moliton Digital
Instant Download
Author(s): Andre Moliton
ISBN(s): 9781848210622, 1848210620
Edition: New
File Details: PDF, 2.29 MB
Year: 2009
Language: english
Solid-State Physics
for Electronics

André Moliton

Series Editor
Pierre-Noël Favennec
This page intentionally left blank
Solid-State Physics for Electronics
This page intentionally left blank
Solid-State Physics
for Electronics

André Moliton

Series Editor
Pierre-Noël Favennec
First published in France in 2007 by Hermes Science/Lavoisier entitled: Physique des matériaux pour
l’électronique © LAVOISIER, 2007
First published in Great Britain and the United States in 2009 by ISTE Ltd and John Wiley & Sons, Inc.

Apart from any fair dealing for the purposes of research or private study, or criticism or review, as
permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced,
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or in the case of reprographic reproduction in accordance with the terms and licenses issued by the CLA.
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ISTE Ltd John Wiley & Sons, Inc.

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UK USA

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© ISTE Ltd, 2009

The rights of André Moliton to be identified as the author of this work have been asserted by him in
accordance with the Copyright, Designs and Patents Act 1988.

Library of Congress Cataloging-in-Publication Data

Moliton, André.
[Physique des matériaux pour l'électronique. English]
Solid-state physics for electronics / André Moliton.
p. cm.
Includes bibliographical references and index.
ISBN 978-1-84821-062-2
1. Solid state physics. 2. Electronics--Materials. I. Title.
QC176.M5813 2009
530.4'1--dc22
2009016464

British Library Cataloguing-in-Publication Data

A CIP record for this book is available from the British Library
ISBN: 978-1-84821-062-2

Cover image created by Atelier Istatis.

Printed and bound in Great Britain by CPI Antony Rowe, Chippenham and Eastbourne.
 Table of Contents

Foreword. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xiii

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xv

Chapter 1. Introduction: Representations of Electron-Lattice Bonds . . . . 1

1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2. Quantum mechanics: some basics . . . . . . . . . . . . . . . . . . . . . . 2
1.2.1. The wave equation in solids: from Maxwell’s
to Schrödinger’s equation via the de Broglie hypothesis. . . . . . . . . . . 2
1.2.2. Form of progressive and stationary wave functions
for an electron with known energy (E) . . . . . . . . . . . . . . . . . . . . . 4
1.2.3. Important properties of linear operators . . . . . . . . . . . . . . . . . 4
1.3. Bonds in solids: a free electron as the zero order approximation
for a weak bond; and strong bonds . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1. The free electron: approximation to the zero order . . . . . . . . . . 6
1.3.2. Weak bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.3. Strong bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3.4. Choosing between approximations for weak and strong bonds . . . 9
1.4. Complementary material: basic evidence for the appearance of bands
in solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.4.1. Basic solutions for narrow potential wells . . . . . . . . . . . . . . . 10
1.4.2. Solutions for two neighboring narrow potential wells . . . . . . . . 14

Chapter 2. The Free Electron and State Density Functions . . . . . . . . . . 17

2.1. Overview of the free electron . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.1. The model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.2. Parameters to be determined: state density functions in
k or energy spaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
vi Solid-State Physics for Electronics

2.2. Study of the stationary regime of small scale (enabling

the establishment of nodes at extremities) symmetric wells (1D model) . . 19
2.2.1. Preliminary remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.2.2. Form of stationary wave functions for thin symmetric wells
with width (L) equal to several inter-atomic distances (L | a),
associated with fixed boundary conditions (FBC) . . . . . . . . . . . . . . 19
2.2.3. Study of energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2.4. State density function (or “density of states”) in k space . . . . . . . 22
2.3. Study of the stationary regime for asymmetric wells (1D model)
with L § a favoring the establishment of a stationary regime
with nodes at extremities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.4. Solutions that favor propagation: wide potential wells
where L § 1 mm, i.e. several orders greater than inter-atomic distances . . . 24
2.4.1. Wave function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.4.2. Study of energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.4.3. Study of the state density function in k space . . . . . . . . . . . . . 27
2.5. State density function represented in energy space for free electrons
in a 1D system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.5.1. Stationary solution for FBC . . . . . . . . . . . . . . . . . . . . . . . . 29
2.5.2. Progressive solutions for progressive boundary conditions (PBC) . 30
2.5.3. Conclusion: comparing the number of calculated states
for FBC and PBC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.6. From electrons in a 3D system (potential box) . . . . . . . . . . . . . . . 32
2.6.1. Form of the wave functions . . . . . . . . . . . . . . . . . . . . . . . . 32
2.6.2. Expression for the state density functions in k space . . . . . . . . . 35
2.6.3. Expression for the state density functions in energy space. . . . . . 37
2.7. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.7.1. Problem 1: the function Z(E) in 1D . . . . . . . . . . . . . . . . . . . 41
2.7.2. Problem 2: diffusion length at the metal-vacuum interface . . . . . 42
2.7.3. Problem 3: 2D media: state density function and the behavior
of the Fermi energy as a function of temperature for a metallic state . . . 44
2.7.4. Problem 4: Fermi energy of a 3D conductor . . . . . . . . . . . . . . 47
2.7.5. Problem 5: establishing the state density function via reasoning
in moment or k spaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.7.6. Problem 6: general equations for the state density functions
expressed in reciprocal (k) space or in energy space . . . . . . . . . . . . . 50

Chapter 3. The Origin of Band Structures within the Weak Band

Approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.1. Bloch function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3.1.1. Introduction: effect of a cosinusoidal lattice potential . . . . . . . . 55
3.1.2. Properties of a Hamiltonian of a semi-free electron . . . . . . . . . . 56
3.1.3. The form of proper functions . . . . . . . . . . . . . . . . . . . . . . . 57
 Table of Contents vii

3.2. Mathieu’s equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

3.2.1. Form of Mathieu’s equation. . . . . . . . . . . . . . . . . . . . . . . . 59
3.2.2. Wave function in accordance with Mathieu’s equation . . . . . . . 59
3.2.3. Energy calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
S
3.2.4. Direct calculation of energy when k  r . . . . . . . . . . . . . . 64
a
3.3. The band structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.3.1. Representing E f (k) for a free electron: a reminder . . . . . . . . 66
3.3.2. Effect of a cosinusoidal lattice potential on the form
of wave function and energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.3.3. Generalization: effect of a periodic non-ideally
cosinusoidal potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.4. Alternative presentation of the origin of band systems
via the perturbation method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.4.1. Problem treated by the perturbation method . . . . . . . . . . . . . . 70
3.4.2. Physical origin of forbidden bands. . . . . . . . . . . . . . . . . . . . 71
3.4.3. Results given by the perturbation theory . . . . . . . . . . . . . . . . 74
3.4.4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.5. Complementary material: the main equation . . . . . . . . . . . . . . . . 79
3.5.1. Fourier series development for wave function and potential . . . . 79
3.5.2. Schrödinger equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.5.3. Solution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.6. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.6.1. Problem 1: a brief justification of the Bloch theorem . . . . . . . . . 81
3.6.2. Problem 2: comparison of E(k) curves for free
and semi-free electrons in a representation of reduced zones . . . . . . . . 84

Chapter 4. Properties of Semi-Free Electrons, Insulators, Semiconductors,

Metals and Superlattices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.1. Effective mass (m*) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.1.1. Equation for electron movement in a band: crystal momentum . . 87
4.1.2. Expression for effective mass . . . . . . . . . . . . . . . . . . . . . . . 89
4.1.3. Sign and variation in the effective mass as a function of k . . . . . 90
4.1.4. Magnitude of effective mass close to a discontinuity . . . . . . . . . 93
4.2. The concept of holes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.2.1. Filling bands and electronic conduction. . . . . . . . . . . . . . . . . 93
4.2.2. Definition of a hole . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.3. Expression for energy states close to the band extremum
as a function of the effective mass . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.3.1. Energy at a band limit via the Maclaurin development
S
(in k = kn = n a
) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.4. Distinguishing insulators, semiconductors, metals and semi-metals . . 97
viii Solid-State Physics for Electronics

4.4.1. Required functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

4.4.2. Dealing with overlapping energy bands . . . . . . . . . . . . . . . . . 97
4.4.3. Permitted band populations . . . . . . . . . . . . . . . . . . . . . . . . 98
4.5. Semi-free electrons in the particular case of super lattices . . . . . . . . 107
4.6. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.6.1. Problem 1: horizontal tangent at the zone limit (k | S/a)
of the dispersion curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.6.2. Problem 2: scale of m* in the neighborhood
of energy discontinuities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.6.3. Problem 3: study of EF(T) . . . . . . . . . . . . . . . . . . . . . . . . . 122

Chapter 5. Crystalline Structure, Reciprocal Lattices and Brillouin Zones 123

5.1. Periodic lattices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.1.1. Definitions: direct lattice . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.1.2. Wigner-Seitz cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
5.2. Locating reciprocal planes . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
5.2.1. Reciprocal planes: definitions and properties . . . . . . . . . . . . . 125
5.2.2. Reciprocal planes: location using Miller indices . . . . . . . . . . . 125
5.3. Conditions for maximum diffusion by a crystal (Laue conditions) . . . 128
5.3.1. Problem parameters . . . . . . . . . . . . . . . . . . G. . . . .G . . . . G. 128
G
5.3.2. Wave diffused by a node located by Um ,n , p m ˜ a  n ˜ b  p ˜ c 129
5.4. Reciprocal lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
5.4.1. Definition and properties of a reciprocal lattice . . . . . . . . . . . . 133
5.4.2. Application: Ewald construction of a beam diffracted
by a reciprocal lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
5.5. Brillouin zones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
5.5.1. Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
5.5.2. Physical significance of Brillouin zone limits . . . . . . . . . . . . . 135
5.5.3. Successive Brillouin zones . . . . . . . . . . . . . . . . . . . . . . . . 137
5.6. Particular properties
G . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
5.6.1. Properties of G h ,k ,l and relation to the direct lattice . . . . . . . . 137
5.6.2. A crystallographic definition of reciprocal lattice . . . . . . . . . . . 139
5.6.3. Equivalence between the condition for maximum diffusion
and Bragg’s law. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
5.7. Example determinations of Brillouin zones and reduced zones . . . . . 141
5.7.1. Example 1: 3D lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.7.2. Example 2: 2D lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.7.3. Example 3: 1D lattice with lattice repeat unit (a) such that the base
G
vector in the direct lattice is a . . . . . . . . . . . . . . . . . . . . . . . . . . 145
5.8. Importance of the reciprocal lattice and electron filling
of Brillouin zones by electrons in insulators, semiconductors and metals . . 146
5.8.1. Benefits of considering electrons in reciprocal lattices . . . . . . . 146
 Table of Contents ix

5.8.2. Example of electron filling of Brillouin zones in simple structures:

determination of behaviors of insulators, semiconductors and metals . . . 146
5.9. The Fermi surface: construction of surfaces and properties . . . . . . . 149
5.9.1. Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.9.2. Form of the free electron Fermi surface . . . . . . . . . . . . . . . . 149
5.9.3. Evolution of semi-free electron Fermi surfaces . . . . . . . . . . . . 150
5.9.4. Relation between Fermi surfaces and dispersion curves . . . . . . . 152
5.10. Conclusion. Filling Fermi surfaces and the distinctions
between insulators, semiconductors and metals . . . . . . . . . . . . . . . . . 154
5.10.1. Distribution of semi-free electrons at absolute zero . . . . . . . . . 154
5.10.2. Consequences for metals, insulators/semiconductors
and semi-metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
5.11. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
5.11.1. Problem 1: simple square lattice . . . . . . . . . . . . . . . . . . . . 156
5.11.2. Problem 2: linear chain and a square lattice . . . . . . . . . . . . . 157
5.11.3. Problem 3: rectangular lattice . . . . . . . . . . . . . . . . . . . . . . 162

Chapter 6. Electronic Properties of Copper and Silicon . . . . . . . . . . . . 173

6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
6.2. Direct and reciprocal lattices of the fcc structure . . . . . . . . . . . . . . 173
6.2.1. Direct lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
6.2.2. Reciprocal lattice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
6.3. Brillouin zone for the fcc structure . . . . . . . . . . . . . . . . . . . . . . 178
6.3.1. Geometrical form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
6.3.2. Calculation of the volume of the Brillouin zone . . . . . . . . . . . . 179
6.3.3. Filling the Brillouin zone for a fcc structure . . . . . . . . . . . . . . 180
6.4. Copper and alloy formation . . . . . . . . . . . . . . . . . . . . . . . . . . 181
6.4.1. Electronic properties of copper . . . . . . . . . . . . . . . . . . . . . . 181
6.4.2. Filling the Brillouin zone and solubility rules . . . . . . . . . . . . . 181
6.4.3. Copper alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
6.5. Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6.5.1. The silicon crystal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6.5.2. Conduction in silicon. . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6.5.3. The silicon band structure . . . . . . . . . . . . . . . . . . . . . . . . . 186
6.5.4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.6. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
6.6.1. Problem 1: the cubic centered (cc) structure . . . . . . . . . . . . . . 190
6.6.2. Problem 2: state density in the silicon conduction band . . . . . . . 194

Chapter 7. Strong Bonds in One Dimension . . . . . . . . . . . . . . . . . . . . 199

7.1. Atomic and molecular orbitals . . . . . . . . . . . . . . . . . . . . . . . . 199
7.1.1. s- and p-type orbitals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
7.1.2. Molecular orbitals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
x Solid-State Physics for Electronics

7.1.3. V- and S-bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209

7.1.4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
7.2. Form of the wave function in strong bonds: Floquet’s theorem . . . . . 210
7.2.1. Form of the resulting potential . . . . . . . . . . . . . . . . . . . . . . 210
7.2.2. Form of the wave function . . . . . . . . . . . . . . . . . . . . . . . . 212
7.2.3. Effect of potential periodicity on the form of the wave function
and Floquet’s theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
7.3. Energy of a 1D system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
7.3.1. Mathematical resolution in 1D where x { r. . . . . . . . . . . . . . . 215
7.3.2. Calculation by integration of energy for a chain of N atoms . . . . 217
7.3.3. Note 1: physical significance in terms of (E0 – D) and E . . . . . . 220
7.3.4. Note 2: simplified calculation of the energy . . . . . . . . . . . . . . 222
7.3.5. Note 3: conditions for the appearance of permitted
and forbidden bands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
7.4. 1D and distorted AB crystals . . . . . . . . . . . . . . . . . . . . . . . . . 224
7.4.1. AB crystal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
7.4.2. Distorted chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
7.5. State density function and applications: the Peierls
metal-insulator transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
7.5.1. Determination of the state density functions . . . . . . . . . . . . . . 228
7.5.2. Zone filling and the Peierls metal–insulator transition . . . . . . . . 230
7.5.3. Principle of the calculation of Erelax (for a distorted chain). . . . . . 232
7.6. Practical example of a periodic atomic chain: concrete calculations
of wave functions, energy levels, state density functions and band filling . 233
7.6.1. Range of variation in k. . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7.6.2. Representation of energy and state density function for N = 8 . . . 234
7.6.3. The wave function for bonding and anti-bonding states . . . . . . . 235
7.6.4. Generalization to any type of state in an atomic chain . . . . . . . . 239
7.7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
7.8. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
7.8.1. Problem 1: complementary study of a chain of s-type atoms
where N = 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
7.8.2. Problem 2: general representation of the states of a chain
of V–s-orbitals (s-orbitals giving V-overlap) and a chain of V–p-orbitals . 243
7.8.3. Problem 3: chains containing both V–s- and V–p-orbitals . . . . . . 246
7.8.4. Problem 4: atomic chain with S-type overlapping of
p-type orbitals: S–p- and S*–p-orbitals . . . . . . . . . . . . . . . . . . . . . 247

Chapter 8. Strong Bonds in Three Dimensions: Band Structure

of Diamond and Silicon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
8.1. Extending the permitted band from 1D to 3D for a lattice
of atoms associated with single s-orbital nodes (basic cubic system,
centered cubic, etc.). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
 Table of Contents xi

8.1.1. Permitted energy in 3D: dispersion and equi-energy curves . . . . . 250

8.1.2. Expression for the band width . . . . . . . . . . . . . . . . . . . . . . 255
8.1.3. Expressions for the effective mass and mobility . . . . . . . . . . . . 257
8.2. Structure of diamond: covalent bonds and their hybridization . . . . . . 258
8.2.1. The structure of diamond . . . . . . . . . . . . . . . . . . . . . . . . . 258
8.2.2. Hybridization of atomic orbitals . . . . . . . . . . . . . . . . . . . . . 259
8.2.3. sp3 Hybridization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
8.3. Molecular model of a 3D covalent crystal (atoms in
sp3-hybridization states at lattice nodes) . . . . . . . . . . . . . . . . . . . . . 268
8.3.1. Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
8.3.2. Independent bonds: effect of single coupling between
neighboring atoms and formation of molecular orbitals . . . . . . . . . . . 272
8.3.3. Coupling of molecular orbitals: band formation . . . . . . . . . . . . 273
8.4. Complementary in-depth study: determination of the silicon
band structure using the strong bond method . . . . . . . . . . . . . . . . . . . 275
8.4.1. Atomic wave functions and structures. . . . . . . . . . . . . . . . . . 275
8.4.2. Wave functions in crystals and equations with proper values
for a strong bond approximation . . . . . . . . . . . . . . . . . . . . . . . . 278
8.4.3. Band structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
8.4.4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
8.5. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
8.5.1. Problem 1: strong bonds in a square 2D lattice . . . . . . . . . . . . 287
8.5.2. Problem 2: strong bonds in a cubic centered or
face centered lattices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294

Chapter 9. Limits to Classical Band Theory: Amorphous Media . . . . . . 301

9.1. Evolution of the band scheme due to structural defects (vacancies,
dangling bonds and chain ends) and localized bands . . . . . . . . . . . . . . 301
9.2. Hubbard bands and electronic repulsions. The Mott metal–insulator
transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
9.2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
9.2.2. Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
9.2.3. The Mott metal–insulator transition: estimation of
transition criteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
9.2.4. Additional material: examples of the existence and
inexistence of Mott–Hubbard transitions . . . . . . . . . . . . . . . . . . . . 309
9.3. Effect of geometric disorder and the Anderson localization . . . . . . . 311
9.3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
9.3.2. Limits of band theory application and the Ioffe–Regel conditions . 312
9.3.3. Anderson localization . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
9.3.4. Localized states and conductivity. The Anderson metal-insulator
transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
9.4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
xii Solid-State Physics for Electronics

9.5. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324

9.5.1. Additional information and Problem 1 on the Mott transition:
insulator–metal transition in phosphorus doped silicon . . . . . . . . . . . 324
9.5.2. Problem 2: transport via states outside of permitted bands
in low mobility media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331

Chapter 10. The Principal Quasi-Particles in Material Physics . . . . . . . . 335

10.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
10.2. Lattice vibrations: phonons . . . . . . . . . . . . . . . . . . . . . . . . . . 336
10.2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
10.2.2. Oscillations within a linear chain of atoms . . . . . . . . . . . . . . 337
10.2.3. Oscillations within a diatomic and 1D chain . . . . . . . . . . . . . 343
10.2.4. Vibrations of a 3D crystal . . . . . . . . . . . . . . . . . . . . . . . . 347
10.2.5. Energy of a vibrational mode . . . . . . . . . . . . . . . . . . . . . . 348
10.2.6. Phonons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
10.2.7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
10.3. Polarons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
10.3.1. Introduction: definition and origin . . . . . . . . . . . . . . . . . . . 352
10.3.2. The various polarons . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
10.3.3. Dielectric polarons . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
10.3.4. Polarons in molecular crystals . . . . . . . . . . . . . . . . . . . . . 357
10.3.5. Energy spectrum of the small polaron in molecular solids . . . . . 361
10.4. Excitons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
10.4.1. Physical origin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
10.4.2. Wannier and charge transfer excitons . . . . . . . . . . . . . . . . . 365
10.4.3. Frenkel excitons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
10.5. Plasmons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
10.5.1. Basic definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
10.5.2. Dielectric response of an electronic gas: optical plasma . . . . . . 368
10.5.3. Plasmons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
10.6. Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
10.6.1. Problem 1: enumeration of vibration modes (phonon modes) . . . 373
10.6.2. Problem 2: polaritons . . . . . . . . . . . . . . . . . . . . . . . . . . . 375

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
 Foreword

A student that has attained a MSc degree in the physics of materials or

electronics will have acquired an understanding of basic atomic physics and
quantum mechanics. He or she will have a grounding in what is a vast realm: solid
state theory and electronic properties of solids in particular. The aim of this book is
to enable the step-by-step acquisition of the fundamentals, in particular the origin of
the description of electronic energy bands. The reader is thus prepared for studying
relaxation of electrons in bands and hence transport properties, or even coupling
with radiance and thus optical properties, absorption and emission. The student is
also equipped to use by him- or herself the classic works of taught solid state
physics, for example, those of Kittel, and Ashcroft and Mermin.

This aim is reached by combining qualitative explanations with a detailed

treatment of the mathematical arguments and techniques used. Valuably, in the final
part the book looks at structures other than the macroscopic crystal, such as quantum
wells, disordered materials, etc., towards more advanced problems including Peierls
transition, Anderson localization and polarons. In this, the author’s research
specialization of conductors and conjugated polymers is discernable. There is no
doubt that students will benefit from this well placed book that will be of continual
use in their professional careers.

Michel SCHOTT

Emeritus Research Director (CNRS),

Ex-Director of the Groupe de Physique des Solides (GPS),
Pierre and Marie Curie University, Paris, France
This page intentionally left blank
 Introduction

This volume proposes both course work and problems with detailed solutions. It
is the result of many years’ experience in teaching at MSc level in applied, materials
and electronic physics. It is written with device physics and electronics students in
mind. The book describes the fundamental physics of materials used in electronics.
This thorough comprehension of the physical properties of materials enables an
understanding of the technological processes used in the fabrication of electronic
and photonic devices.

The first six chapters are essentially a basic course in the rudiments of solid-state
physics and the description of electronic states and energy levels in the simplest of
cases. The last four chapters give more advanced theories that have been developed
to account for electronic and optical behaviors of ordered and disordered materials.

The book starts with a physical description of weak and strong electronic bonds
in a lattice. The appearance of energy bands is then simplified by studying energy
levels in rectangular potential wells that move closer to one another. Chapter 2
introduces the theory for free electrons where particular attention is paid to the
relation between the nature of the physical solutions to the number of dimensions
chosen for the system. Here, the important state density functions are also
introduced. Chapter 3, covering semi-free electrons, is essentially given to the
description of band theory for weak bonds based on the physical origin of permitted
and forbidden bands. In Chapter 4, band theory is applied with respect to the electrical
and electronic behaviors of the material in hand, be it insulator, semiconductor or
metal. From this, superlattice structures and their application in optoelectronics is
described. Chapter 5 focuses on ordered solid-state physics where direct lattices,
reciprocal lattices, Brillouin zones and Fermi surfaces are good representations of
electronic states and levels in a perfect solid. Chapter 6 applies these representations
to metals and semiconductors using the archetypal examples of copper and silicon
respectively. An excursion into the preparation of alloys is also proposed.
xvi Solid-State Physics for Electronics

The last four chapters touch on theories which are rather more complex. Chapter
7 is dedicated to the description of the strong bond in 1D media. Floquet’s theorem,
which is a sort of physical analog for the Hückel’s theorem that is so widely used in
physical chemistry, is established. These results are extended to 3D media in
Chapter 8, along with a simplified presentation of silicon band theory. The huge gap
between the discovery of the working transistor (1947) and the rigorous
establishment of silicon band theory around 20 years later is highlighted. Chapter 9
is given over to the description of energy levels in real solids where defaults can
generate localized levels. Amorphous materials are well covered, for example,
amorphous silicon is used in non-negligible applications such as photovoltaics.
Finally, Chapter 10 contains a description of the principal quasi-particles in solid
state, electronic and optical physics. Phonons are thus covered in detail. Phonons are
widely used in thermics; however, the coupling of this with electronic charges is at
the origin of phonons in covalent materials. These polarons, which often determine
the electronic transport properties of a material, are described in all their possible
configurations. Excitons are also described with respect to their degree of extension
and their presence in different materials. Finally, the coupling of an electromagnetic
wave with electrons or with (vibrating) ions in a diatomic lattice is studied to give a
classical description of quasi-particles such as plasmons and polaritons.
 Chapter 1

Introduction: Representations
of Electron-Lattice Bonds

1.1. Introduction

This book studies the electrical and electronic behavior of semiconductors,

insulators and metals with equal consideration. In metals, conduction electrons are
naturally more numerous and freer than in a dielectric material, in the sense that they
are less localized around a specific atom.

Starting with the dual wave-particle theory, the propagation of a de Broglie wave
interacting with the outermost electrons of atoms of a solid is first studied. It is this
that confers certain properties on solids, especially in terms of electronic and
thermal transport. The most simple potential configuration will be laid out first
(Chapter 2). This involves the so-called flat-bottomed well within which free
electrons are simply thought of as being imprisoned by potential walls at the
extremities of a solid. No account is taken of their interactions with the constituents
of the solid. Taking into account the fine interactions of electrons with atoms
situated at nodes in a lattice means realizing that the electrons are no more than
semi-free, or rather “quasi-free”, within a solid. Their bonding is classed as either
“weak” or “strong” depending on the form and the intensity of the interaction of the
electrons with the lattice. Using representations of weak and strong bonds in the
following chapters, we will deduce the structure of the energy bands on which solid-
state electronic physics is based.
Other documents randomly have
different content
CHAP. 46. (11.)—REMEDIES FOR DISEASES OF THE HEAD, AND FOR
ALOPECY.

Bears’ grease,2315 mixed with ladanum2316 and the plant

adiantum,2317 prevents the hair from falling off; it is a cure also for
alopecy and defects in the eyebrows, mixed with the fungus from
the wick of a lamp, and the soot that is found in the nozzle. Used
with wine, it is good for the cure of porrigo, a malady which is also
treated with the ashes of deer’s horns in wine: this last substance
also prevents the growth of vermin in the hair. For porrigo some
persons employ goat’s gall, in combination with Cimolian chalk and
vinegar, leaving the preparation to dry for a time on the head. Sow’s
gall, too, mixed with bull’s urine, is employed for a similar purpose;
and when old, it is an effectual cure, with the addition of sulphur, for
furfuraceous eruptions. The ashes, it is thought, of an ass’s genitals,
will make the hair grow more thickly, and prevent it from turning
grey; the proper method of applying it being to shave the head and
to pound the ashes in a leaden mortar with oil. Similar effects are
attributed to the genitals of an ass’s foal, reduced to ashes and
mixed with urine; some nard being added to render the mixture less
offensive. In cases of alopecy the part affected is rubbed with bull’s
gall, warmed with Egyptian alum. Running ulcers of the head are
successfully treated with bull’s urine, or stale human urine, in
combination with cyclaminos2318 and sulphur: but the most effectual
remedy is calf’s gall, a substance which, heated with vinegar, has
also the effect of exterminating lice. Veal suet, pounded with salt
and applied to ulcers of the head, is a very useful remedy: the fat,
too, of the fox is highly spoken of, but the greatest value is set upon
cats’ dung, applied in a similar manner with mustard.
Powdered goats’ horns, or the horns reduced to ashes, those of
the he-goat in particular, with the addition of nitre, tamarisk-seed,
butter, and oil, are remarkably effectual for preventing the hair from
coming off, the head being first shaved for the purpose. So too, the
ashes of burnt goats’ flesh, applied the eye-brows with oil, impart to
them a black tint. By using goats’ milk, they say, lice may be
exterminated; and the dung of those animals, with honey, is thought
to be a cure for alopecy: the ashes, too, of the hoofs, mixed with
pitch, prevent the hair from coming off.
The ashes of a burnt hare, mixed with oil of myrtle, alleviate head-
ache, the patient drinking some water that has been left in the
trough after an ox or ass has been drinking there. The male organs
of a fox, worn as an amulet, are productive, if we choose to believe
it, of a similar effect: the same, too, with the ashes of a burnt deer’s
horn, applied with vinegar, rose oil, or oil of iris.
 CHAP. 47.—REMEDIES FOR AFFECTIONS OF THE EYES.

For defluxions2319 of the eyes, beef suet, boiled with oil, is applied
to the parts affected; and for eruptions of those organs, ashes of
burnt deer’s horns are similarly employed, the tips of the horns
being considered the most effectual for the purpose. For the cure of
cataract, it is reckoned a good plan to apply a wolf’s excrements: the
same substance, too, reduced to ashes, is used for the dispersion of
films, in combination with Attic honey. Bear’s gall, too, is similarly
employed; and for the cure of epinyctis, wild boar’s lard, mixed with
oil of roses, is thought to be very useful. An ass’s hoof, reduced to
ashes and applied with asses’ milk, is used for the removal of marks
in the eyes and indurations of the crystalline humours. Beef marrow,
from the right fore leg, beaten up with soot, is employed for
affections of the eyebrows, and for diseases of the eyelids and
corners of the eyes. For the same purpose, also, a sort of
calliblepharon2320 is prepared from soot, the best of all being that
made from a wick of papyrus mixed with oil of sesame; the soot
being removed with a feather and caught in a new vessel prepared
for the purpose. This mixture, too, is very efficacious for preventing
superfluous eyelashes from growing again when once pulled out.
Bull’s gall is made up into eye-salves2321 with white of egg, these
salves being steeped in water and applied to the eyes for four days
successively. Veal suet, with goose-grease and the extracted juice of
ocimum, is remarkably good for diseases of the eye-lids. Veal
marrow, with the addition of an equal proportion of wax and oil or
oil of roses, an egg being added to the mixture, is used as a liniment
for indurations of the eye-lids. Soft goats’ milk cheese is used as an
application, with warm water, to allay defluxions of the eyes; but
when they are attended with swelling, honey is used instead of the
water. In both cases, however, the eyes should be fomented with
warm whey. In cases of dry ophthalmia, it is found a very useful plan
to take the muscles2322 lying within a loin of pork, and, after
reducing them to ashes, to pound and apply them to the part
affected.
She-goats, they say, are never affected with ophthalmia, from the
circumstance that they browse upon certain kinds of herbs: the
same, too, with the gazelle. Hence it is that we find it recommended,
at the time of new moon, to swallow the dung of these animals,
coated with wax. As they are able to see, too, by night, it is a
general belief that the blood of a he-goat is a cure for those persons
affected with dimness of sight to whom the Greeks have given the
name of “nyctalopes.”2323 A similar virtue is attributed to the liver of
a she-goat, boiled in astringent wine. Some are in the habit of
rubbing the eyes with the thick gravy2324 which exudes from a she-
goat’s liver roasted, or with the gall of that animal: they recommend
the flesh also as a diet, and say that the patient should expose his
eyes to the fumes of it while boiling: it is a general opinion, too, that
the animal should be of a reddish colour. Another prescription is, to
fumigate the eyes with the steam arising from the liver boiled in an
earthen jar, or, according to some authorities, roasted.
Goats’ gall is applied for numerous purposes: with honey, for films
upon the eyes; with one-third part of white hellebore, for cataract;
with wine, for spots upon the eyes, indurations of the cornea, films,
webs, and argema; with extracted juice of cabbage, for diseases of
the eyelids, the hairs being first pulled out, and the preparation left
to dry on the parts affected; and with woman’s milk, for rupture of
the coats of the eye. For all these purposes, the gall is considered
the most efficacious, when dried. Nor is the dung of this animal held
in disesteem, being applied with honey for defluxions of the eyes.
The marrow, too, of a goat, or a hare’s lights, we find used for pains
in the eyes; and the gall of a goat, with raisin wine or honey, for the
dispersion of films upon those organs. It is recommended also, for
ophthalmia, to anoint the eyes with wolf’s fat or swine’s marrow: we
find it asserted, too, that persons who carry a wolf’s tongue,
inserted in a bracelet, will always be exempt from ophthalmia.
 CHAP. 48.—REMEDIES FOR DISEASES AND AFFECTIONS OF THE
EARS.

Pains and diseases of the ears are cured by using the urine of a
wild boar, kept in a glass vessel, or the gall of a wild boar, swine, or
ox, mixed with castor-oil and oil of roses in equal proportions. But
the best remedy of all is bull’s gall, warmed with leek juice, or with
honey, if there is any suppuration. Bull’s gall too, warmed by itself in
a pomegranate rind, is an excellent remedy for offensive exhalations
from the ears: in combination with woman’s milk, it is efficacious as
a cure for ruptures of those organs. Some persons are of opinion
that it is a good plan to wash the ears with this preparation in cases
where the hearing is affected; while others again, after washing the
ears with warm water, insert a mixture composed of the old slough
of a serpent and vinegar, wrapped up in a dossil of wool. In cases,
however, where the deafness is very considerable, gall warmed in a
pomegranate rind with myrrh and rue, is injected into the ears;
sometimes, also, fat bacon is used for this purpose, or fresh asses’
dung, mixed with oil of roses: in all cases, however, the ingredients
should be warmed.
The foam from a horse’s mouth is better still, or the ashes of fresh
horse dung, mixed with oil of roses: fresh butter too is good; beef-
suet mixed with goose-grease; the urine of a bull or she-goat; or
fullers’ lant, heated to such a degree that the steam escapes by the
neck of the vessel. For this purpose also, one third part of vinegar is
mixed with a small portion of the urine of a calf, which has not
begun to graze. They apply also to the ears calf’s dung, mixed with
the gall of that animal and sloughs of serpents, care being taken to
warm the ears before the application, and all the remedies being
wrapped in wool. Veal-suet, too, is used, with goose-grease and
extract of ocimum; or else veal marrow, mixed with bruised cummin
and injected into the ears. For pains in the ears, the liquid ejected by
a boar in copulation is used, due care being taken to receive it
before it falls to the ground. For fractures of the ears, a glutinous
composition is made from the genitals of a calf, which is dissolved in
water when used; and for other diseases of those organs, foxes’ fat
is employed, goat’s gall mixed with rose-oil warmed, or else
extracted juice of leeks: in all cases where there is any rupture,
these preparations are used in combination with woman’s milk.
Where a patient is suffering from hardness of hearing, ox-gall is
employed, with the urine of a he or she-goat; the same, too, where
there is any suppuration.
Whatever the purpose for which they are wanted, it is the general
opinion that these substances are more efficacious when they have
been smoked in a goat’s horn for twenty days. Hare’s rennet, too, is
highly spoken of, taken in Aminean2325 wine, in the proportion of
one third of a denarius of rennet to one half of a denarius of
sacopenum.2326 Bears’ grease, mixed with equal proportions of wax
and bull-suet, is a cure for imposthumes of the parotid glands: some
persons add hypocisthis2327 to the composition, or else content
themselves with employing butter only, after first fomenting the
parts affected with a decoction of fenugreek, the good effects of
which are augmented by strychnos. The testes, too, of the fox, are
very useful for this purpose; as also bull’s blood, dried and reduced
to powder. She-goats’ urine, made warm, is used as an injection for
the ears; and a liniment is made of the dung of those animals, in
combination with axle-grease.
 CHAP. 49.—REMEDIES FOR TOOTH-ACHE.

The ashes of deer’s horns strengthen loose teeth and allay tooth-
ache, used either as a friction or as a gargle. Some persons,
however, are of opinion that the horn, unburnt and reduced to
powder, is still more efficacious for all these purposes. Dentifrices are
made both from the powder and the ashes. Another excellent
remedy is a wolf’s head, reduced to ashes: it is a well-known fact,
too, that there are bones generally found in the excrements of that
animal; these bones, attached to the body as an amulet, are
productive of advantageous effects. For the cure of tooth-ache,
hare’s rennet is injected into the ear: the head also of that animal,
reduced to ashes, is used in the form of a dentifrice, and, with the
addition of nard, is a corrective of bad breath. Some persons,
however, think it a better plan to mix the ashes of a mouse’s head
with the dentifrice. In the side of the hare there is a bone found,
similar to a needle in appearance: for the cure of tooth-ache it is
recommended to scarify the gums with this bone. The pastern-bone
of an ox, ignited and applied to loose teeth which ache, has the
effect of strengthening them in the sockets; the same bone, reduced
to ashes, and mixed with myrrh, is also used as a dentifrice. The
ashes of burnt pig’s feet are productive of a similar effect, as also
the calcined bones of the cotyloïd cavities in which the hip-bones
move. It is a well-known fact, that, introduced into the throat of
beasts of burden, these bones are a cure for worms, and that, in a
calcined state, they are good for strengthening the teeth.
When the teeth have been loosened by a blow,2328 they are
strengthened by using asses’ milk, or else ashes of the burnt teeth
of that animal, or a horse’s lichen, reduced to powder, and injected
into the ear with oil. By lichen2329 I do not mean the hippomanes, a
noxious substance which I purposely forbear to enlarge upon, but an
excrescence which forms upon the knees of horses, and just above
the hoofs. In the heart2330 of this animal there is also found a bone
which bears a close resemblance to the eye-teeth of a dog: if the
gums are scarified with this bone, or with a tooth taken from the
jaw-bone of a dead horse, corresponding in place with the tooth
affected, the pain will be removed, they say. Anaxilaüs assures us
that if the liquid which exudes from a mare when covered, is ignited
on the wick of a lamp, it will give out a most marvellous
representation2331 of horses’ heads; and the same with reference to
the she-ass. As to the hippomanes, it is possessed of properties so
virulent and so truly magical, that if it is only thrown into fused
metal2332 which is being cast into the resemblance of an Olympian
mare, it will excite in all stallions that approach it a perfect frenzy for
copulation.
Another remedy for diseases of the teeth is joiners’ glue, boiled in
water and applied, care being taken to remove it very speedily, and
instantly to rinse the teeth with wine in which sweet pomegranate-
rind has been boiled. It is considered, also, a very efficacious
remedy to wash the teeth with goats’ milk, or bull’s gall. The
pastern-bones of a she-goat just killed, reduced to ashes, and
indeed, to avoid the necessity for repetition, of any other four-footed
beast reared in the farm-yard, are considered to make an excellent
dentifrice.
 CHAP. 50. (12.)—REMEDIES FOR DISEASES OF THE FACE.

It is generally believed that asses’ milk effaces wrinkles in the

face, renders the skin more delicate, and preserves its whiteness:
and it is a well-known fact, that some women are in the habit of
washing their face with it seven2333 hundred times daily, strictly
observing that number. Poppæa, the wife of the Emperor Nero, was
the first to practise this; indeed, she had sitting-baths, prepared
solely with asses’ milk, for which purpose whole troops of she-
asses2334 used to attend her on her journies.2335 Purulent eruptions
on the face are removed by an application of butter, but white lead,
mixed with the butter, is an improvement. Pure butter, alone, is used
for serpiginous eruptions of the face, a layer of barley-meal being
powdered over it. The caul of a cow that has just calved, is applied,
while still moist, to ulcers of the face.
The following recipe may seem frivolous, but still, to please the
women,2336 it must not be omitted; the pastern-bone of a white
steer, they say, boiled forty days and forty nights, till it is quite
dissolved, and then applied to the face in a linen cloth, will remove
wrinkles and preserve the whiteness of the skin. An application of
bull’s dung, they say, will impart a rosy tint to the cheeks, and not
crocodilea2337 even is better for the purpose; the face, however,
must be washed with cold water, both before and after the
application. Sun-burns and all other discolorations of the skin, are
removed by the aid of calves’ dung kneaded up by hand with oil and
gum; ulcerations and chaps of the mouth, by an application of veal
or beef-suet, mixed with goose-grease and juice of ocimum. There is
another composition, also, made of veal-suet with stag’s marrow and
leaves of white-thorn, the whole beaten up together. Marrow, too,
mixed with resin, even if it be cow marrow only, is equally good; and
the broth of cow-beef is productive of similar effects. A most
excellent remedy for lichens on the face is a glutinous substance
prepared from the genitals of a male calf, melted with vinegar and
live sulphur, and stirred together with the branch of a fig-tree: this
composition is applied twice a day, and should be used quite fresh.
This glue, similarly prepared from a decoction of honey and vinegar,
is a cure for leprous spots, which are also removed by applying a he-
goat’s liver warm.
Elephantiasis, too, is removed by an application of goats’ gall; and
leprous spots and furfuraceous eruptions by employing bull’s gall
with the addition of nitre, or else asses’ urine about the rising of the
Dog-star. Spots on the face are removed by either bull’s gall or ass’s
gall diluted in water by itself, care being taken to avoid the sun or
wind after the skin has peeled off. A similar effect is produced, also,
by using bull’s gall or calf’s gall, in combination with seed of cunila
and the ashes of a deer’s horn, burnt at the rising of Canicula.
Asses’ fat, in particular, restores the natural colour to scars and
spots on the skin caused by lichen or leprosy. A he-goat’s gall, mixed
with cheese, live sulphur, and sponge reduced to ashes, effectually
removes freckles, the composition being brought to the consistency
of honey before being applied. Some persons, however, prefer using
dried gall, and mix with it warm bran, in the proportion of one
obolus to four oboli of honey, the spots being rubbed briskly first.
He-goat suet, too, is highly efficacious, used in combination with
gith, sulphur, and iris; this mixture being also employed, with goose-
grease, stag’s marrow, resin, and lime, for the cure of cracked lips. I
find it stated by certain authors, that persons who have freckles on
the skin are looked upon as disqualified from taking any part in the
sacrifices prescribed by the magic art.
 CHAP. 51.—REMEDIES FOR DISEASES OF THE TONSILLARY
GLANDS, AND FOR SCROFULA.

Cow’s milk or goat’s milk is good for ulcerations of the tonsillary

glands and of the trachea. It is used in the form of a gargle, warm
from the udder or heated, goat’s milk being the best, boiled with
mallows and a little salt. A broth made from tripe is an excellent
gargle for ulcerations of the tongue and trachea; and for diseases of
the tonsillary glands, the kidneys of a fox are considered a sovereign
remedy, dried and beaten up with honey, and applied externally. For
quinzy, bull’s gall or goat’s gall is used, mixed with honey. A badger’s
liver, taken in water, is good for offensive breath, and butter has a
healing effect upon ulcerations of the mouth. When a pointed or
other substance has stuck in the throat, by rubbing it externally with
cats’ dung, the substance, they say, will either come up again or
pass downwards into the stomach.
Scrofulous sores are dispersed by applying the gall of a wild boar
or of an ox, warmed for the purpose: but it is only when the sores
are ulcerated that hare’s rennet is used, applied in a linen cloth with
wine. The ashes of the burnt hoof of an ass or horse, applied with
oil or water, is good for dispersing scrofulous sores; warmed urine
also; the ashes of an ox’s hoof, taken in water; cow-dung, applied
hot with vinegar; goat-suet with lime; goats’ dung, boiled in vinegar;
or the testes of a fox. Soap,2338 too, is very useful for this purpose,
an invention of the Gauls for giving a reddish2339 tint to the hair.
This substance is prepared from tallow and ashes, the best ashes for
the purpose being those of the beech and yoke-elm: there are two
kinds of it, the hard soap and the liquid, both of them much used by
the people of Germany, the men, in particular, more than the
women.
 CHAP. 52.—REMEDIES FOR PAINS IN THE NECK.

For pains in the neck, the part should be well rubbed with butter
or bears’ grease; and for a stiff neck, with beef suet, a substance
which, in combination with oil, is very useful for the cure of scrofula.
For the painful cramp, attended with inflexibility, to which people
give the name of “opisthotony,” the urine of a she-goat, injected into
the ears, is found very useful; as also a liniment made of the dung
of that animal, mixed with bulbs.
In cases where the nails have been crushed, it is an excellent plan
to attach to them the gall of any kind of animal. Whitlows upon the
fingers should be treated with dried bull’s gall, dissolved in warm
water. Some persons are in the habit of adding sulphur and alum, of
each an equal weight.
CHAP. 53.—REMEDIES FOR COUGH AND FOR SPITTING OF BLOOD.

A wolf’s liver, administered in mulled wine, is a cure for cough; a

bear’s gall also, mixed with honey; the ashes of the tips of a cow’s
horn; or else the saliva of a horse, taken in the drink for three
consecutive days—in which last case the horse will be sure to die,
they say.2340 A deer’s lights are useful for the same purpose, dried
with the gullet of the animal in the smoke, and then beaten up with
honey, and taken daily as an electuary: the spitter2341 deer, be it
remarked, is the kind that is the most efficacious for the purpose.
Spitting of blood is cured by taking ashes of burnt deer’s horns, or
else a hare’s rennet in drink, in doses of one-third of a denarius,
with Samian earth and myrtle-wine. The dung of this last animal,
reduced to ashes and taken in the evening, with wine, is good for
coughs that are recurrent at night. The smoke, too, of a hare’s fur,
inhaled, has the effect of bringing off from the lungs such humours
as are difficult to be discharged by expectoration. Purulent
ulcerations of the chest and lungs, and bad breath proceeding from
a morbid state of the lungs, are successfully treated with butter
boiled with an equal quantity of Attic honey till it assumes a reddish
hue, a spoonful of the mixture being taken by the patient every
morning: some persons, however, instead of honey prefer using
larch-resin for the purpose. In cases where there are discharges of
blood, cow’s blood, they say, is good, taken in small quantities with
vinegar; but as to bull’s blood, it would be a rash thing to believe in
any such recommendation. For inveterate spitting of blood, bull-glue
is taken, in doses of three oboli, in warm water.
 CHAP. 54. (13.)—REMEDIES FOR AFFECTIONS OF THE STOMACH.

Ulcerations of the stomach are effectually treated with asses’

milk2342 or cows’ milk. For gnawing pains in that region, beef is
stewed, with vinegar and wine. Fluxes are healed by taking the
ashes of burnt deer’s horns; and discharges of blood by drinking the
blood of a kid just killed, made hot, in doses of three cyathi, with
equal proportions of vinegar and tart wine; or else by taking kid’s
rennet, with twice the quantity of vinegar.
CHAP. 55.—REMEDIES FOR LIVER COMPLAINTS AND FOR ASTHMA.

Liver complaints are cured by taking a wolf’s liver dried, in honied

wine; or by using the dried liver of an ass, with twice the quantity of
rock-parsley and three nuts, the whole beaten up with honey and
taken with the food. The blood, too, of a he-goat is prepared and
taken with the food. For persons suffering from asthma, the most
efficient remedy of all is the blood of wild horses2343 taken in drink;
and next to that, asses’ milk boiled with bulbs, the whey being the
part used, with the addition of nasturtium steeped in water and
tempered with honey, in the proportion of one cyathus of nasturtium
to three semi-sextarii of whey. The liver or lights of a fox, taken in
red wine, or bear’s gall in water, facilitate the respiration.
 CHAP. 56.—REMEDIES FOR PAINS IN THE LOINS.

For pains in the loins and all other affections which require
emollients, frictions with bears’ grease should be used; or else ashes
of stale boars’ dung or swine’s dung should be mixed with wine and
given to the patients. The magicians, too, have added to this branch
of medicine their own fanciful devices. In the first place of all,
madness in he-goats, they say, may be effectually calmed by
stroking the beard; and if the beard is cut off, the goat will never
stray to another flock.
To the above composition they add goats’ dung, and recommend
it to be held in the hollow of the hand, as hot as possible, a greased
linen cloth being placed beneath, and care being taken to hold it in
the right hand if the pain is on the left side, and in the left hand if
the pain is on the right. They recommend also that the dung
employed for this purpose should be taken up on the point of a
needle made of copper. The mode of treatment is, for the patient to
hold the mixture in his hand till the heat is felt to have penetrated to
the loins, after which the hand is rubbed with a pounded leek, and
the loins with the same dung annealed with honey. They prescribe
also for the same malady the testes of a hare, to be eaten by the
patient. In cases of sciatica they are for applying cow-dung warmed
upon hot ashes in leaves: and for pains in the kidneys they
recommend a hare’s kidneys to be swallowed raw, or perhaps boiled,
but without letting them be touched by the teeth. If a person carries
about him the pastern-bone of a hare, he will never be troubled with
pains in the bowels, they say.
 CHAP. 57.—REMEDIES FOR AFFECTIONS OF THE SPLEEN.

Affections of the spleen are alleviated by taking the gall of a wild

boar or hog in drink; ashes of burnt deer’s horns in vinegar; or, what
is best of all, the dried spleen of an ass, the good effects being sure
to be felt in the course of three days. The first dung voided by an
ass’s foal—a substance known as “polea”2344 by the people of Syria
—is administered in oxymel for these complaints; a dried horse
tongue, too, is taken in wine, a sovereign remedy which, Cæcilius
Bion tells us, he first heard of when living among the barbarous
nations. The milt of a cow or ox is used in a similar manner; but
when it is quite fresh, the practice is to roast or boil it and take it
with the food. For pains in the liver a topical application is made by
bruising twenty heads of garlick in one sextarius of vinegar, and
applying them in a piece of ox bladder. For the same malady the
magicians recommend a calf’s milt, bought at the price set upon it
and without any haggling, that being an important point, and one
that should be religiously observed. This done, the milt must be cut
in two lengthwise, and attached to the patient’s shirt,2345 on either
side; after which, the patient must put it on and let the pieces fall at
his feet, and must then pick them up, and dry them in the shade.
While this last is doing, the diseased liver of the patient will
gradually contract, they say, and he will eventually be cured. The
lights, too, of a fox are very useful for this purpose, dried on hot
ashes and taken in water; the same, too, with a kid’s milt, applied to
the part affected.
 CHAP. 58. (14.)—REMEDIES FOR BOWEL COMPLAINTS.

To arrest looseness of the bowels, deer’s blood is used; the ashes

also of deer’s horns; the liver of a wild boar, taken fresh and without
salt, in wine; a swine’s liver roasted, or that of a he-goat, boiled in
five semisextarii of wine; a hare’s rennet boiled, in quantities the size
of a chick-pea, in wine, or, if there are symptoms of fever, in water.
To this last some persons add nut-galls, while others, again, content
themselves with hare’s blood boiled by itself in milk. Ashes, too, of
burnt horse-dung are taken in water for this purpose; or else ashes
of the part of an old bull’s horn which lies nearest the root, sprinkled
in water; the blood, too, of a he-goat boiled upon charcoal; or a
decoction made from a goat’s hide boiled with the hair on.
For relaxing the bowels a horse’s rennet is used, or else the blood,
marrow, or liver of a she-goat. A similar effect is produced by
applying a wolf’s gall to the navel, with elaterium;2346 by taking
mares’ milk, goats’ milk with salt and honey, or a she-goat’s gall with
juice of cyclaminos,2347 and a little alum—in which last case some
prefer adding nitre and water to the mixture. Bull’s gall, too, is used
for a similar purpose, beaten up with wormwood and applied in the
form of a suppository; or butter is taken, in considerable doses.
Cœliac affections and dysentery are cured by taking cow’s liver;
ashes of deer’s horns, a pinch in three fingers swallowed in water;
hare’s rennet, kneaded up in bread, or, if there is any discharge of
blood, taken with polenta;2348 or else boar’s dung, swine’s dung, or
hare’s dung, reduced to ashes and mixed with mulled wine. Among
the remedies, also, for the cœliac flux and dysentery, veal broth is
reckoned, a remedy very commonly used. If the patient takes asses’
milk for these complaints, it will be all the better if honey is added;
and no less efficacious for either complaint are the ashes of asses’
dung taken in wine; or else polea, the substance above2349-
mentioned. In such cases, even when attended with a discharge of
blood, we find a horse’s rennet recommended, by some persons
known as “hippace;” ashes of burnt horse-dung; horses’ teeth
pounded; and boiled cows’ milk. In cases of dysentery, it is
recommended to add a little honey; and, for the cure of griping
pains, ashes of deer’s horns, bull’s gall mixed with cummin, or the
flesh of a gourd, should be applied to the navel. For both complaints
new cheese made of cows’ milk is used, as an injection; butter also,
in the proportion of four semi-sextarii to two ounces of turpentine,
or else employed with a decoction of mallows or with oil of roses.
Veal-suet or beef-suet is also given, and the marrow of those
animals is boiled with meal, a little wax, and some oil, so as to form
a sort of pottage. This marrow, too, is kneaded up with bread for a
similar purpose; or else goats’ milk is used, boiled down to one half.
In cases, too, where there are gripings in the bowels, wine of the
first running2350 is administered. For the last-named pains, some
persons are of opinion that it is a sufficient remedy to take a single
dose of hare’s rennet in mulled wine; though others again, who are
more distrustful, are in the habit of applying a liniment to the
abdomen, made of goats’ blood, barley-meal, and resin.
For all defluxions of the bowels it is recommended to apply soft
cheese, and for cœliac affections and dysentery old cheese,
powdered, one cyathus of cheese being taken in three cyathi of
ordinary wine. Goats’ blood is boiled down with the marrow of those
animals for the cure of dysentery; and the cœliac flux is effectually
treated with the roasted liver of a she-goat, or, what is still better,
the liver of a he-goat boiled in astringent wine, and administered in
the drink, or else applied to the navel with oil of myrtle. Some
persons boil down the liver in three sextarii of water to half a
sextarius, and then add rue to it. The milt of a he or she-goat is
sometimes roasted for this purpose, or the suet of a he-goat is
incorporated in bread baked upon the ashes; the fat, too, of a she-
goat, taken from the kidneys more particularly, is used. This last,
however, must be taken by itself and swallowed immediately, being
generally recommended to be taken in water moderately cool. Some
persons, too, boil goats’ suet in water, with a mixture of polenta,
cummin, anise, and vinegar; and for the cure of cœliac affections,
they rub the abdomen with a decoction of goats’ dung and honey.
For both the cœliac flux and dysentery, kid’s rennet is employed,
taken in myrtle wine in pieces the size of a bean, or else kid’s blood,
prepared in the form of a dish known by the name of
“sanguiculus.”2351 For dysentery an injection is employed, made of
bull glue dissolved in warm water. Flatulency is dispelled by a
decoction of calf’s dung in wine. For intestinal affections deer’s
rennet is highly recommended boiled with beef and lentils, and
taken with the food; hare’s fur, also reduced to ashes and boiled
with honey; or boiled goat’s milk, taken with a small quantity of
mallows and some salt; if rennet is added, the remedy will be all the
more effectual. Goat suet, taken in any kind of broth, is possessed of
similar virtues, care being taken to swallow cold water immediately
after. The ashes of a kid’s thighs are said to be marvellously
efficacious for intestinal hernia; as also hare’s dung, boiled with
honey, and taken daily in pieces the size of a bean; indeed, these
remedies are said to have proved effectual in cases where a cure has
been quite despaired of. The broth too, made from a goat’s head,
boiled with the hair on, is highly recommended.
 CHAP. 59.—REMEDIES FOR TENESMUS, TAPEWORM, AND
AFFECTIONS OF THE COLON.

The disease called “tenesmus,” or in other words, a frequent and

ineffectual desire to go to stool, is removed by drinking asses’ milk
or cows’ milk. The various kinds of tapeworm2352 are expelled by
taking the ashes of deer’s horns in drink. The bones which we have
spoken2353 of as being found in the excrements of the wolf, worn
attached to the arm, are curative of diseases of the colon, provided
they have not been allowed to touch the ground. Polea, too, a
substance already mentioned,2354 is remarkably useful for this
purpose, boiled in grape juice:2355 the same too with swine’s dung,
powdered and mixed with cummin, in a decoction of rue. The antler
of a young stag, reduced to ashes and taken in wine, mixed with
African snails, crushed with the shells on, is considered a very useful
remedy.
 CHAP. 60. (15.)—REMEDIES FOR AFFECTIONS OF THE BLADDER,
AND FOR URINARY CALCULI.

Diseases of the bladder, and the torments attendant upon calculi,

are treated with the urine of a wild boar, or the bladder of that
animal taken as food; both of them being still more efficacious if
they have been thoroughly soaked first. The bladder, when eaten,
should be boiled first, and if the patient is a female, it should be a
sow’s bladder. There are found in the liver of the wild boar certain
small stones,2356 or what in hardness resemble small stones, of a
white hue, and resembling those found in the liver of the common
swine: if these stones are pounded and taken in wine, they will
expel calculi, it is said. So oppressed is the wild boar by the burden
of his urine,2357 that if he has not first voided it, he is unable to take
to flight, and suffers himself to be taken as though he were
enchained to the spot. This urine, they say, has a consuming effect
upon urinary calculi. The kidneys of a hare, dried and taken in wine,
act as an expellent upon calculi. We have already2358 mentioned
that in the gammon of the hog there are certain joint-bones; a
decoction made from them is remarkably useful for urinary
affections. The kidneys of an ass, dried and pounded, and
administered in undiluted wine, are a cure for diseases of the
bladder. The excrescences that grow on horses’ legs, taken for forty
days in ordinary wine or honied wine, expel urinary calculi. The
ashes, too, of a horse’s hoof, taken in wine or water, are considered
highly useful for this purpose; and the same with the dung of a she-
goat—if a wild goat, all the better—taken in honied wine: goats’ hair,
too, is used, reduced to ashes.
For carbuncles upon the generative organs, the brains and blood
of a wild boar or swine are highly recommended: and for serpiginous
affections of those parts, the liver of those animals is used, burnt
upon juniper wood more particularly, and mixed with papyrus and
arsenic;2359 the ashes, also, of their dung; ox-gall, kneaded to the
consistency of honey, with Egyptian alum and myrrh, beet-root
boiled in wine being laid upon it; or else beef. Running ulcers of
those parts are treated with veal-suet and marrow, boiled in wine, or
with the gall of a she-goat, mixed with honey and the extracted juice
of the bramble.2360 In cases where these ulcers are serpiginous, it is
recommended to use goats’ dung with honey or vinegar, or else
butter by itself. Swellings of the testes are reduced by using veal-
suet with nitre, or the dung of the animal boiled in vinegar. The
bladder of a wild boar, eaten roasted, acts as a check upon
incontinence of urine; a similar effect being produced by the ashes
of the feet of a wild boar or swine sprinkled in the drink; the ashes
of a sow’s bladder taken in drink; the bladder or lights of a kid; a
hare’s brains taken in wine; the testes of a male hare grilled; the
rennet of that animal taken with goose-grease and polenta;2361 or
the kidneys of an ass, beaten up and taken in undiluted wine.
The magicians tell us, that after taking the ashes of a boar’s
genitals in sweet wine, the patient must make water in a dog kennel,
and repeat the following formula—“This I do that I may not wet my
bed as a dog does.” On the other hand, a swine’s bladder, attached
to the groin, facilitates the discharge of the urine, provided it has not
already touched the ground.
 CHAP. 61.—REMEDIES FOR DISEASES OF THE GENERATIVE
ORGANS AND OF THE FUNDAMENT.

For diseases of the fundament, a sovereign remedy is bear’s gall,

mixed with the grease; to which some persons are in the habit of
adding litharge and frankincense. Butter, too, is very good, employed
with goose-grease and oil of roses. The proportions in which they
are mixed will be regulated by the circumstances of the case, care
being taken to see that they are of a consistency which admits of
their being easily applied. Bull’s gall upon lint is a remarkably useful
remedy, and has the effect of making chaps of the fundament
cicatrize with great rapidity. Swellings of those parts are treated with
veal suet—that from the loins in particular—mixed with rue. For
other affections, goats’ blood is used, with polenta. Goats’ gall too, is
employed by itself, for the cure of condylomata, and sometimes,
wolf’s gall, mixed with wine.
Bears’ blood is curative of inflamed tumours and apostemes upon
these parts in general; as also bulls’ blood, dried and powdered. The
best remedy, however, is considered to be the stone which the wild
ass2362 voids with his urine, it is said, at the moment he is killed.
This stone, which is in a somewhat liquefied state at first, becomes
solid when it reaches the ground: attached to the thigh, it disperses
all collections of humours and all kinds of suppurations: it is but
rarely found, however, and it is not every wild ass that produces it,
but as a remedy it is held in high esteem. Asses’ urine too, used in
combination with gith, is highly recommended; the ashes of a
horse’s hoof, applied with oil and water; a horse’s blood, that of a
stone-horse in particular; the blood, also, of an ox or cow, or the gall
of those animals. Their flesh too, applied warm, is productive of
similar results; the hoofs reduced to ashes, and taken in water or
honey; the urine of a she-goat; the flesh of a he-goat, boiled in
water; the dung of these animals, boiled with honey; or else a boar’s
gall, or swine’s urine, applied in wool.
 Riding on horseback, we well-know, galls and chafes the inside of
the thighs: the best remedy for accidents of this nature is to rub the
parts with the foam which collects at a horse’s mouth. Where there
are swellings in the groin, arising2363 from ulcers, a cure is effected
by inserting in the sores three horse-hairs, tied with as many knots.
CHAP. 62. (16.)—REMEDIES FOR GOUT AND FOR DISEASES OF THE
FEET.

For the cure of gout, bears’ grease is employed, mixed in equal

proportions with bull-suet and wax; some persons add to the
composition, hypocisthis2364 and nut-galls. Others, again, prefer he-
goat suet, mixed with the dung of a she-goat and saffron, or else
with mustard, or sprigs of ivy pounded and used with perdicium,2365
or with flowers of wild cucumber. Cow-dung is also used, with lees of
vinegar. Some persons speak highly in praise of the dung of a calf
which has not begun to graze, or else a bull’s blood, without any
other addition; a fox, also, boiled alive till only the bones are left; a
wolf boiled alive in oil to the consistency of a cerate; he-goat suet,
with an equal proportion of helxine,2366 and one-third part of
mustard; or ashes of goats’ dung, mixed with axle-grease. They say,
too, that for sciatica, it is an excellent plan to apply this dung
boiling2367 hot beneath the great toes; and that, for diseases of the
joints, it is highly efficacious to attach bears’ gall or hares’ feet to the
part affected. Gout, they say, may be allayed by the patient always
carrying about with him a hare’s foot, cut off from the animal alive.
Bears’ grease is a cure for chilblains and all kinds of chaps upon
the feet; with the addition of alum, it is still more efficacious. The
same results are produced by using goat-suet; a horse’s teeth
powdered; the gall of a wild boar or hog; or else the lights of those
animals, applied with their grease; and this, too, where the soles are
blistered, or the feet have been crushed by a substance striking
against them. In cases where the feet have been frozen, ashes of
burnt hare’s fur are used; and for contusions of the feet, the lights of
that animal are applied, sliced or reduced to ashes. Blisters
occasioned by the sun are most effectually treated by using asses’
fat, or else beef-suet, with oil of roses. Corns, chaps, and callosities
of the feet are cured by the application of wild boars’ dung or
swine’s dung, used fresh, and removed at the end of a couple of
days. The pastern-bones of these animals are also used, reduced to
ashes; or else the lights of a wild boar, swine, or deer. When the feet
have been galled by the shoes, they are rubbed with the urine of an
ass, applied with the mud formed by it upon the ground. Corns are
treated with beef-suet and powdered frankincense; chilblains with
burnt leather, that of an old shoe, in particular; and injuries
produced by tight shoes with ashes of goat-skin, tempered with oil.
The pains attendant upon varicose veins are mitigated by using
ashes of burnt calves’ dung, boiled with lily roots and a little honey:
a composition which is equally good for all kinds of inflammations
and sores that tend to suppurate. It is very useful, also, for gout and
diseases of the joints, when it is the dung of a bull-calf that is used
more particularly. For excoriations of the joints, the gall of a wild
boar or swine is applied, in a warm linen cloth: the dung, also, of a
calf that has not begun to graze; or else goat-dung, boiled in vinegar
with honey. Veal-suet rectifies malformed nails, as also goat-suet,
mixed with sandarach. Warts are removed by applying ashes of
burnt calves’ dung in vinegar, or else the mud formed upon the
ground by the urine of an ass.
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