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Undergraduate Lecture Notes in Physics

Rudolf P. Huebener

Conductors,
Semiconductors,
Superconductors
An Introduction to Solid-State Physics
Third Edition
Undergraduate Lecture Notes in Physics
Undergraduate Lecture Notes in Physics (ULNP) publishes authoritative texts
covering topics throughout pure and applied physics. Each title in the series is
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ULNP especially encourages new, original, and idiosyncratic approaches to physics
teaching at the undergraduate level.
The purpose of ULNP is to provide intriguing, absorbing books that will continue
to be the reader’s preferred reference throughout their academic career.

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Department of Physics, University of Virginia, Charlottesville, VA, USA

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Rudolf P. Huebener

Conductors, Semiconductors,
Superconductors
An Introduction to Solid-State Physics

Third Edition

123
Rudolf P. Huebener
Physikalisches Institut
University of Tübingen
Tübingen, Germany

ISSN 2192-4791 ISSN 2192-4805 (electronic)

Undergraduate Lecture Notes in Physics
ISBN 978-3-030-31419-4 ISBN 978-3-030-31420-0 (eBook)
https://doi.org/10.1007/978-3-030-31420-0
This book was originally published in German by Spektrum Verlag, 2013. Original title: “Leiter,
Halbleiter, Supraleiter: Eine Einführung in die Festkörperphysik”.

1st & 2nd editions: © Springer International Publishing Switzerland 2015, 2016
3rd edition: © Springer Nature Switzerland AG 2019
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt from
the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, expressed or implied, with respect to the material contained
herein or for any errors or omissions that may have been made. The publisher remains neutral with regard
to jurisdictional claims in published maps and institutional affiliations.

This Springer imprint is published by the registered company Springer Nature Switzerland AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Preface to the Third Edition

The third edition is a reprint of the second edition with a series of minor extensions.
Because of the strong recent experimental and theoretical research activities in the
field of topological materials, Sect. 11.6 has been extended considerably.
The author is grateful to Zachary Evenson from the Springer editorial office for
his effective support.

Tübingen, Germany Rudolf P. Huebener

v
Preface to the Second Edition

The second edition is an extended reprint of the first edition. In many chapters, a
more detailed mathematical treatment of the various subjects is given. A section
dealing with magnetic impurities and the Kondo effect has been added.
The author is grateful to Silvia Haindl and to Vladimir Kresin for detailed
suggestions about expanding the book.

Tübingen Rudolf P. Huebener

vii
Preface to the First Edition

Only a few scientific-technical developments from the last century have affected our
lives in such a powerful way as the spectacular advances in our knowledge of the
electronic properties of solids. Many of the present achievements are intimately
connected with these advances. To name only a few: the transistor and its extreme
miniaturization in microelectronics, the electronic processing of data and highly
developed and powerful computers, the mobile telephone and satellite communi-
cation, television and entertainment electronics, as well as numerous instruments
and systems of medical technology.
In the final analysis, the theater of all these events of dramatic progress is the
world of electrons in crystals, where the (quantized) vibrations of the crystal lattice
continuously demonstrate their influence. The revolutionary advances in knowledge
are due to many individual people. Frequently a true paradigm change has been
necessary in order to arrange and order the new perceptions properly. Hence, it is
not surprising that, as a rule, the pioneers of these new ideas initially had to
overcome great difficulties and rejection, before the new concepts slowly gained
acceptance. Also, in certain cases, highly focused research in large industrial lab-
oratories turned out to be the key to success. This is impressively illustrated in
particular by the invention of the transistor in the American Bell Laboratories.
This book represents an updated and strongly extended edition of the book
published by the same author nearly 10 years ago with the title Electrons in Action.
In particular, the physical contents were pointed out more clearly by mathematically
formulating the fundamentals. The book is aiming at students of the natural sci-
ences, and in particular of physics and materials science, as well as at engineers, as
an introduction to solid-state physics. It may serve as a motivating pre-stage and
companion of the established and very detailed textbooks.

ix
x Preface to the First Edition

In addition to the physical contents, the book treats the important role played by
many famous and often still very young scientists. The fundamental developments
are supplemented by describing their scientific and historic environment.
Marius Orlowski, Virginia Polytechnic Institute, provided important advice.

Tübingen Rudolf P. Huebener

May 2014
Contents

1 Spectacular Advances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 Well Ordered Lattice Structures in Crystals . . . . . . . . . . . . . . . . . . 15
2.1 Diffraction Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2 Reciprocal Lattice, Brillouin Zones . . . . . . . . . . . . . . . . . . . . . 23
2.3 Types of Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3 Permanent Movement in the Crystal Lattice . . . . . . . . . . . . . . . . . . 35
3.1 Quantum Theory: Max Planck and Albert Einstein . . . . . . . . . . 36
3.2 Specific Heat of the Crystal Lattice, Phonon Spectrum . . . . . . . 38
3.3 Thermal Conductivity of the Crystal Lattice . . . . . . . . . . . . . . . 44
3.4 Ballistic Phonons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4 Electric Conductor or Insulator?—Energy Bands . . . . . . . . . . . . . . 49
4.1 Approximation with Bound Electrons (Felix Bloch) . . . . . . . . . 51
4.2 Nearly-Free Electron Approximation (Rudolf Peierls) . . . . . . . . 55
5 Metals Obey the Rules of Quantum Statistics . . . . . . . . . . . . . . . . . 59
5.1 Drude-Lorentz Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5.2 Quantum Statistics, Fermi Distribution . . . . . . . . . . . . . . . . . . . 62
5.3 Fermi Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.4 Bloch-Grüneisen Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5.5 Thermoelectricity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
6 Less Can Be More: Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . 73
6.1 Intrinsic Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.2 Doped Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6.3 Excitons and Electron-Hole Droplets . . . . . . . . . . . . . . . . . . . . 81
6.4 Metal-Semiconductor Contact, P-N Junction . . . . . . . . . . . . . . . 82
6.5 Transistor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

xi
xii Contents

6.6 Photovoltaics, LED, Semiconductor Laser . . . . . . . . . . . . . . . . 89

6.7 Miniaturization, Planar Technology . . . . . . . . . . . . . . . . . . . . . 91
6.8 Thermoelectricity, Peltier Cooling . . . . . . . . . . . . . . . . . . . . . . 93
7 Circling Electrons in High Magnetic Fields . . . . . . . . ........... 97
7.1 Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........... 98
7.2 Magneto-Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
7.3 Landau Theory, Landau Cylinders, de Haas–van
Alphen Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
7.4 Integer Quantum Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . . . 107
7.5 Fractional Quantum Hall Effect . . . . . . . . . . . . . . . . . . . . . . . . 112
7.6 Generation of High Magnetic Fields . . . . . . . . . . . . . . . . . . . . 115
8 The Winner: Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
8.1 Meissner Effect, Magnetic Penetration Depth, London
Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
8.2 Type-II Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
8.3 Magnetic Flux Quantum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
8.4 BCS Theory, Energy Gap . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
8.5 Josephson Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
8.6 Motion of the Magnetic Flux Quanta . . . . . . . . . . . . . . . . . . . . 141
8.7 Technical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
9 The Big Surprise: High-Temperature Superconductivity . . . . . . . . 151
9.1 Cuprate Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
9.2 Symmetry of the Wave Function . . . . . . . . . . . . . . . . . . . . . . . 158
9.3 Grain Boundaries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
9.4 Intrinsic Josephson Junction . . . . . . . . . . . . . . . . . . . . . . . . . . 163
9.5 More New Superconductors: MgB2, Iron Pnictides . . . . . . . . . . 164
9.6 Technical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
10 Magnetism: Order Among the Elementary Magnets . . . . . . . . . . . . 169
10.1 Diamagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
10.2 Paramagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
10.3 Ferromagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
10.4 Spin Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
10.5 Antiferromagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
10.6 Technical Applications, Giant Magneto-Resistance,
Spintronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
11 Nanostructures: Superlattices, Quantum Wires, and Quantum
Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
11.1 Superlattices, Bloch Oscillations . . . . . . . . . . . . . . . . . . . . . . . 190
11.2 Mesoscopic Regime, Ballistic Electron Transport, Quantized
Conductance Value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
Contents xiii

11.3 Bottom up, Fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200

11.4 Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
11.5 Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
11.6 Topological Insulators, Metals, and Semimetals . . . . . . . . . . . . 207
11.7 Aharonov-Bohm Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
12 Defects in the Crystal Lattice: Useful or Harmful? . . . . . . . . . . . . . 213
12.1 Disorder at Thermodynamic Equilibrium . . . . . . . . . . . . . . . . . 214
12.2 Vacancies in the Crystal Lattice . . . . . . . . . . . . . . . . . . . . . . . . 214
12.3 Materials Science of Radiation Damage . . . . . . . . . . . . . . . . . . 219
12.4 Mechanical Strength of Materials . . . . . . . . . . . . . . . . . . . . . . . 220
12.5 Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
12.6 Materials Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
12.7 Magnetic Impurities, Kondo Effect . . . . . . . . . . . . . . . . . . . . . . 226

Nobel Prizes in Physics Closely Connected with the Physics

of Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Nobel Prizes in Chemistry Closely Connected with the Physics
of Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Mathematical Symbols

a Distance between the neighboring atoms or building blocks of the crystal

lattice
e Electric elementary charge
f Spring constant
fL Lorentz force
h Hour
h Planck’s constant
ħ h/2p
j Electrical current density
js Supercurrent density
k Wave number = 2p=k
k Wave vector = kX + kY + kZ
kZ Component of the wave vector in z-direction
kF Fermi wave vector
kB Boltzmann’s constant
‘ Mean free path
m me = Electron mass
mh Mass of the holes
mc Cyclotron mass of the electrons
n Electron concentration
ns Density of the superconducting electrons
p Hole concentration
r Lattice vector
r Electron coordinate
t Time
vD Drift velocity
vF Fermi velocity
z Figure of merit
mA Milliampère
mg Milligram
nm Nanometer = 10–9 Meter

xv
xvi Mathematical Symbols

µm Micrometer = 10–6 Meter

eV Electron volt (energy unit)
A Vector potential
B Magnetic flux density
CV Specific heat at constant volume
D2 Density of states in the two-dimensional case
De Density of states per volume
E Energy
F Free energy
E Electric field
G Vector in the reciprocal lattice
G Density of the Gibbs free energy
Go Quantized unit of the electrical conductance
GeV Giga-electron volt = 109 eV
GHz Giga-Hertz = 109 per second
H Magnetic field
HC Critical magnetic field of a superconductor
HC Coercive field
HC1 Lower critical magnetic field of a superconductor
HC2 Upper critical magnetic field of a superconductor
I Electrical current
Ir Recombination current
Ig Generation current
IC Critical electrical current density of a superconductor
J Exchange integral
K Kelvin
K Wave vector of the phonons
L Lorenz number
L Orbital angular momentum
M Magnetization
N Number of the crystal atoms
R Electrical resistance
RH Hall constant
S Seebeck coefficient
S Spin angular momentum
Sm Mixing entropy
T Temperature
TC Critical temperature of a superconductor
TD Debye temperature = hmD =kB
TCU Curie temperature
THz Tera-Hertz = 1012 per second
U Total vibrational energy of a crystal
U Inner energy
V Electrical voltage
V Volume
Mathematical Symbols xvii

a Polarizability
a Madelung constant
d Scattering angle
j Heat conductivity
je Heat conductivity of the electrons
jG Heat conductivity of the crystal lattice
h Debye temperature
e Electron energy
eF Fermi energy
k Wavelength
km Magnetic penetration depth of superconductors
µ Magnetic moment
µo Permeability of vacuum
µB Bohr magneton
η Damping coefficient of the motion of magnetic flux quanta
x Angular frequency
xB Bloch frequency
xc Cyclotron angular frequency
xD Debye angular frequency
xL Larmor frequency
m Frequency
mc xc/2p = Cyclotron frequency
mD xD/2p = Debye frequency
mE Einstein frequency
v Magnetic susceptibility
vp Paramagnetic susceptibility
s Mean collision time
n Coherence length of a superconductor
q Lattice vector
qf Flux-flow resistivity
r Electrical conductivity
u Phase of a wave function
uo Magnetic flux quantum
u0 Atomic wave function
w Wave function of the superconducting Cooper pairs
П Peltier coefficient
Chapter 1
Spectacular Advances

Abstract During the second half of the last century solid state physics and
materials science experienced a great advance and established itself as an important
and independent new field. In addition to X-ray diffraction, new analytical tools
such as neutron diffraction, electron microscopy, different versions of mechanical
scanning techniques, and scanning electron and laser microscopy became available.
Material fatigue, radiation damage, and the preparation of single crystals developed
into important subjects. The invention of the transistor represented perhaps the
ultimate highlight.

During the second half of the last century the physics of solids has experienced a
tremendous growth, for which many important basic steps had already been pre-
pared during the first half of the century. An early decisive impulse for these
developments came from the discovery of X-rays in 1895 in Würzburg, Germany,
by Wilhelm Conrad Röntgen. Soon afterwards, this discovery lead to the first
observation of X-ray diffraction in crystals by Max von Laue in 1912 in Munich.
William Henry Bragg, Professor in Leeds, England, together with his son William
Lawrence Bragg at the early age of only 22 years, then started the systematic
analysis of crystal structures by means of X-ray diffraction.
Today, research dealing with the physics of solids has an impressively wide
scope, if for no other reason than the fact that solids are always needed to fabricate
useful or nice things, in contrast to the totally different role of liquids and gases. The
exact knowledge of the physical properties of the materials that we use today
becomes more and more important the further we advance in the field of high
technology. The large effort of research and development within the area of solid
state physics becomes obvious if one looks at the program books for the relevant
annual meetings of, say, the German Physical Society (DPG) or the American
Physical Society (APS) which recently contained up to more than 2000 pages.
(Today, these programs of the meetings are distributed mostly electronically).
Often, the technological applications provide the key motivation for strong basic
research in solid state physics. We illustrate this by the following two examples. On
January 10, 1954, an English passenger airplane of the Comet type broke apart at

© Springer Nature Switzerland AG 2019 1

R. P. Huebener, Conductors, Semiconductors,
Superconductors, Undergraduate Lecture Notes in Physics,
https://doi.org/10.1007/978-3-030-31420-0_1
2 1 Spectacular Advances

8200 m altitude in the Mediterranean near the isle of Elba without any prior
warning and crashed into the sea. With only 3681 flight hours, the plane was
relatively new. The search for the cause of the accident turned out to be extremely
difficult, even though people worked feverishly to clarify the cause of the terrible
crash. Since the cause of the accident continued to remain unknown, it was finally
concluded that the crash must have been the result of an unfortunate combination of
several bad effects. Hence, on March 23, 1954, the grounding order for all airplanes
of the same type, immediately issued on the day of the accident, was lifted again.
Prior to this, a total of 62 modifications had been introduced in all Comet airplanes
in operation or under construction. In this way it was hoped to exclude any possible
cause of the accident (Fig. 1.1). Then a completely unexpected dramatic event
happened. On April 8, i.e., only 16 days following the resumption of the regular
flight operation, another Comet airplane with only 2704 h of flight operation cra-
shed into the Mediterranean near Naples. Again, at a high altitude of 10 000 m this
time, the plane suddenly apparently broke apart. Now the situation became extre-
mely serious. The causes had to be found at the highest level, and all available
means had to be utilized. After analysis of the many different possibilities, problems
related to what is now called material fatigue, in particular associated with the
wings, came to the center of attention. As a consequence, the complete fuselage of
an airplane was dumped into a huge tank filled with water in order to expose it to
changing, and in particular to cyclical, mechanical loads. In this way, it was found
that, after some time, fatigue effects appeared on the wings. However, the fatigue
problems on the fuselage itself were much more severe. Finally, the evidence
became clear that the mechanical load during testing caused cracks in the fuselage,
and that all the cracks originated at the rectangular corners of the cabin windows.
The causes of both plane crashes had been found. However, this event also put to an
abrupt end the British leading role in air traffic. (Today a large piece of a side of one

Fig. 1.1 Comet jet-aircraft beginning a test flight after the crash of a plane in the Mediterranean
near the isle of Elba. (Photo ullstein bild)
1 Spectacular Advances 3

of the two crashed aircrafts, recovered from the Mediterranean, is on display in the
Science Museum in London).
Because of these dramatic developments, intensive research activities were
begun at the same time at many places. Until then only little was known about the
phenomenon of material fatigue, its effect on the mechanical properties of materials,
and the mechanisms leading to the development of microcracks.
In this context of the material fatigue experienced sixty years ago with the Comet
passenger airplane, it is interesting to note that the recent development of the largest
passenger airplane, which has ever been constructed, the Airbus A 380, included an
extensive and careful mechanical material fatigue testing procedure by means of
hydraulic systems, as a critical step. Starting in 2005 the complete A 380 airplane,
consisting of the whole fuselage and the wings, has been exposed for 26 months to
mechanical loads varying with time and simulating a total number of 47500 flight
cycles (take-off and landing). This testing load program corresponds to the 25 year
lifetime of the A 380 airplane.
As a second example, we recall the possible difficulties expected more than
60 years ago during the operation of the inner components of the first nuclear
reactors. At that time hardly anything was known about the behavior of, say,
graphite when it is utilized for slowing down the neutrons which are emitted during
nuclear fission within the reactor. Would it be possible that during their irradiation
with the highly energetic neutrons the carbon atoms of the graphite lattice could be
ejected out of their regular lattice sites, eventually leading to an energetically highly
excited material, releasing abruptly its stored excess energy in an explosion like
dynamite? Such problems concerned the scientists involved in the early reactor
experiments. The American scientist Eugene Paul Wigner, originally from Hungary
(later a Nobel laureate and famous for his theoretical work on mathematical group
theory and symmetry principles and their role in atomic, nuclear, and elementary
particle physics) was one of the first who theoretically analyzed the physical
properties of lattice defects and radiation damage in crystals. At that time, a young
co-worker of Wigner, Frederick Seitz, performed the first theoretical calculations on
this subject (Fig. 1.2). Both scientists introduced the concept of the “Wigner-Seitz
cell” into solid state physics. Following these initial steps, the field of structural
lattice defects in crystals has developed into an important subfield of solid state
physics, being investigated today in many laboratories. In 1940 Frederick Seitz also
published the first general textbook on solid state physics: “The Modern Theory of
Solids”.
An enormously important development took place with respect to microelec-
tronics. Here the physics of solids has resulted in a total paradigm change in
electronic technology. It was Mervin Kelly, one of the top-level managers of the
famous American Bell Laboratories in Murray Hill in the Federal State of New
Jersey, who realized at the end of the Second World War that the old mechanical
relays and the evacuated amplifying tube made from glass had to be replaced by
something better. To Kelly a highly promising candidate appeared to be the crystal,
if it had suitable electric conduction properties. Therefore, at the Bell Laboratories a
special group of scientists was organized, which was supposed to explore the
4 1 Spectacular Advances

Fig. 1.2 Eugene P. Wigner (left photo: Deutsches Museum) and Frederick Seitz (right: private
photo)

electric conduction properties of solids. At the center of everyone’s attention then

stood the semiconductor crystals of germanium and silicon. Already, relatively
soon afterwards, an extremely momentous event had been the invention of the
transistor by John Bardeen, Walter Brattain, and William Shockley. On December
23, 1947, they demonstrated the transistor for the first time to the directors of their
company. Subsequently, as a new electronic device, the transistor underwent
intensive further development and improvement. Without a doubt, this invention
represented the start of the modern age of digital electronics.
These big advances in the field of solid state physics, of course, were accom-
panied by similar advances in instrumental techniques and methods. Here we must
mention the exploration of the regime of very low temperatures. In 1908 the Dutch
scientist Heike Kamerlingh Onnes in Leiden achieved for the first time the lique-
faction of the noble gas helium. With this success the low-temperature range down
to 4 K (−269 °C) became accessible. In this context the most spectacular event was
the subsequent discovery of superconductivity by Kamerlingh Onnes in 1911. Until
the 1930s, the number of laboratories equipped to perform experiments with liquid
helium worldwide could be counted on the fingers of one hand. In contrast, today
about 1000 helium liquefiers are operating worldwide (Fig. 1.3). Today the largest
liquefaction facility is operated at the particle accelerator Large Hadron Collider
(LHC) in Geneva. There exist eight liquefiers each having a liquefaction rate of
3600 L/h, i.e., with a total rate of 28 800 L/h. Worldwide this corresponds to about
40% of the inventory of large liquefaction facilities for helium.
Eventually, the available experimental regime was extended to lower and lower
temperatures. In particular, we mention a technique relying on the elementary
1 Spectacular Advances 5

Fig. 1.3 Modern plant for liquefying the noble gas helium. On the left we see the controls and the
cold box of the liquefier, on the right the storage vessel for liquid helium. (Photo Linde AG)

atomic magnets of a paramagnetic substance. This technique consists of the fol-

lowing sequence of steps. Initially, a paramagnetic salt pill is precooled to about
1 K, in order to reduce considerably its content of thermal energy. Subsequently,
the elementary magnets in the salt pill are all oriented in one direction by a strong
magnetic field, and simultaneously the heat of magnetization is removed, being
deposited in the environment. In the next step, the salt pill is thermally decoupled
from its environment. Then the magnetic field is turned off. Now the pill is ther-
mally isolated, and the directional disorder of the elementary magnets gradually
reappears. As a necessary consequence, the temperature of the salt pill drops at the
same time. In this way low temperatures of only a few thousandth Kelvin can be
reached. This method of “adiabatic demagnetization” was proposed in 1926 by the
Dutch scientist Peter Debye and in 1927 by the American William Francis Giauque.
In 1933 the method was demonstrated experimentally for the first time. The
extended application of this principle to the elementary magnets of the atomic
nuclei had already been proposed in 1934 by the Dutch scientist Cornelis Jacobus
Gorter and in 1935 by Nicholas Kurti and Franz Eugen Simon from Oxford. The
cooling effect due to this nuclear demagnetization was experimentally realized for
the first time in 1956. Using this technique, extremely low temperatures down to
one millionth Kelvin or lower could be reached. However, at such low temperatures
it becomes more and more difficult to establish thermal equilibrium between the
different components of the solid, namely the electrons and their elementary
magnets, the lattice vibrations, and the elementary magnets of the atomic nuclei.
6 1 Spectacular Advances

Because of their Jewish origin, Nicholas Kurti and Franz Eugen Simon had to leave
Germany in 1933 when Hitler took over the government. Earlier, both had worked first in
Berlin and then at the Technical University in Breslau (today Wroclaw), and the English
scientist Frederick Alexander Lindemann (later Viscount Cherwell) had arranged for a
position for both of them at the Clarendon Laboratory in Oxford, England. As director of
the Clarendon Laboratory Lindemann has done exactly the same at the time also for the two
brothers Fritz and Heinz London, and for Kurt Mendelssohn. After they had left Germany,
during subsequent years, all these people distinguished themselves by outstanding contri-
butions to physics at low temperatures, and Oxford gained a top position in this field.

An apparatus often used today for reaching temperatures much below 1 K is the
mixing cryostat (Fig. 1.4). In this cryostat the two isotopes of the noble gas helium,
which differ only by the number of neutrons in their atomic nuclei (3He with a
single neutron and 4He with two neutrons), are pumped through several stages of
heat exchangers, such that within the mixing chamber located at the coldest end of
the instrument an almost pure liquid 3He phase is collected directly above a liquid
mixed phase of 3He and 4He. For this technique to operate, the starting temperature
must already have been lowered to 1 K by precooling. During operation, 3He atoms
from the upper concentrated phase are dissolved continuously in the lower, much
more diluted phase. In many ways this scheme resembles a regular evaporation
process, in which the upper phase corresponds to the liquid and the lower phase to
the vapor. As the final result, a continuous cooling of liquid helium is achieved.

Fig. 1.4 Mixing cryostat for

cooling down to temperatures
well below 1 K. The coldest
end with the mixing chamber
is located at the bottom. On
the top one can see the flange
for mounting into the
cryogenic container, which
can also be evacuated. (Photo
Oxford)
1 Spectacular Advances 7

With this apparatus the attached sample to be studied can also be cooled con-
tinuously. The lowest temperatures which can be reached are a few thousandth
Kelvin. The principle of the mixing cryostat was proposed for the first time in 1951
by Heinz London. The first prototype was operated in 1965. Together with his
brother Fritz London, Heinz London also had proposed an early theory of
superconductivity.
In addition to the continuing improvements in experimental instruments and to
the refinements of measuring techniques, sample preparation and the development
of materials also saw much progress. Here an important step was the production of
single crystals with extremely high purity. It was such ultra-pure single crystals
which allowed the exact determination of many physical properties of materials and
the achievement of a theoretical understanding based on these data (Fig. 1.5). The
growing of large single crystals starts by dipping a little seed crystal under an inert
gas atmosphere into the melt of the same material and then pulling it out again at a
slow and well regulated speed. In this way, during solidification of the melt, the
exact atomic order of the seed crystal will be reproduced. Record sizes of such
cylindrical single crystals up to more than one meter in height and nearly half a

Fig. 1.5 Silicon single crystal. (Photo Wacker Chemie AG)

8 1 Spectacular Advances

meter in diameter have been achieved. The concentration of atomic impurities in

such a crystal can be reduced further by means of the “zone melting process”.
During this process the total cross-section of a short length of the crystal is heated
up to the melting temperature by means of, say, eddy current heating, while this
heating zone is slowly moved from one end of the crystal to the other. In the
resulting temperature gradient the atomic impurities are carried along to one end of
the crystal. If necessary, this process can be repeated several times. The impurity
concentration of silicon single crystals, routinely achieved today in the semicon-
ductor industry, amounts to only about a single impurity atom within one billion
silicon atoms.
The spectacular advances in our physical understanding of the microscopic
properties of solids were closely coupled to the progress of the instruments and
methods available for the analysis of materials. In addition to the investigation of
the structure of crystals by means of X-ray diffraction already mentioned, starting in
the 1950s the diffraction of neutrons was also utilized more and more for clarifying
crystal structures. For this purpose, special nuclear reactors built only for research
purposes served as neutron sources. As an example we mention the egg-shaped
research reactor (“Atomei”) built in the 1960s at the Technical University of
Munich in Garching, Germany (Fig. 1.6). In some sense as a training ground, this
reactor then turned out to become the point of origin for the much larger research
reactor of the German-French Laue-Langevin Institute in Grenoble. In 2004 the
“Atomei” was replaced by the new Research Reactor FRM II (research neutron
source Heinz Maier-Leibnitz) in Garching. Similar construction projects for
research reactors existed also in other countries with a highly developed industry.

Fig. 1.6 Egg-shaped research reactor (“Atomei”) in Garching near Munich. In the building on the
left the new research reactor FRM II, completed in 2004, is located. (Photo Albert Scharger/TU
Munich)
1 Spectacular Advances 9

In the same way as often happens with new ideas, the invention of the electron
microscope initially had to withstand great difficulties and rejection. It all began
with two Ph.D. students, namely Ernst Ruska and Bodo von Borries, who had
joined the group of Max Knoll at the Chair of High-Voltage Engineering and
Electric Plants at the Technical University of Berlin during December 1928 and
April 1929, respectively. Here, at first both worked on the improvement of the
cathode ray oscilloscope. Because of the experience gained, before long they
developed the idea that beams of fast electrons can be used for generating a
magnified image in a new type of microscope. On March 17, 1932 Ernst Ruska and
Bodo von Borries submitted their first and basic patents on the future electron
microscope. However, a few large hurdles still remained to be overcome. “Why do
we need electron microscopes, since we have light microscopes?” was the question
that people were asking. However, soon both young scientists had a breakthrough.
The Company Siemens & Halske in Berlin agreed to pick up the idea and prepared
employment contracts for Bodo von Borries and Ernst Ruska. On December 7,
1937 the first electron microscope built by Siemens was demonstrated to the
Company directors (Fig. 1.7).

Fig. 1.7 Siemens electron

microscope, a precursor of the
Siemens Elmiskop 1,
marketed in the 1950s. (Photo
TU Berlin)
10 1 Spectacular Advances

After only three years of development, in terms of its spatial resolution the
electron microscope had outpaced the light microscope. Starting in 1939, an initial
series of the Supermicroscope (“Übermikroskop”), as it was called at the time, was
offered for sale by Siemens.
Again, the underlying basic concept of this microscope is the
quantum-mechanical wave character of elementary particles, which had been pro-
posed for the first time by the French Louis de Broglie in his dissertation in 1924.
The direct experimental proof of the wave nature of electrons was provided sub-
sequently in 1927 by the two Americans Clinton Joseph Davisson and Lester
Germer of the Bell Telephone Laboratories who showed that electrons are diffracted
by the atomic lattice of crystals. During imaging based on the diffraction of waves,
the spatial resolution is always limited by the wavelength. The shorter the wave-
length, the correspondingly smaller are the structures that can be spatially resolved.
The wavelength of the beam electrons is inversely proportional to the square-root of
the accelerating voltage. At an electric voltage of 10 000 volts we have a wave
length of k = 1.2  10−2 nm (nm = nanometer = 10−9 m). On the other hand, the
wave length of visible light is much larger, k = 400–800 nm, and the achieved
spatial resolution is correspondingly much weaker.
Already in the 1950s, electron microscopy had celebrated a big success, along
with many other successes, by imaging the structural defects in the crystal lattice, as
discussed above, and by clarifying the phenomenon of material fatigue. In the latter
case the “crystal dislocations” play a central role. They were observed directly for
the first time in 1956 at the Battelle Institute in Geneva in stainless steel and at the
Cavendish Laboratory in Cambridge in aluminum. Eventually, electron micro-
scopes were built for ever increasing accelerating voltages. Today we have
instruments with an accelerating voltage of one million volts (Fig. 1.8).
For the analysis of materials, beams of fast electrons have also been utilized in
another important instrument: the scanning electron microscope. For this,
pioneering research was done again in the 1930s by Max Knoll at the Technical
University in Berlin, mentioned before, and by Manfred von Ardenne in his
Laboratory in Berlin-Lichterfelde. An electron beam collimated down to an
extremely small diameter of only 1–10 nm is scanned over the surface of the object
to be investigated. Simultaneously, a suitable signal induced by the electron beam
in the sample is recorded as a function of the spatial beam coordinates on the
sample surface within the scanning window. Correct electronic signal processing
then yields a two-dimensional image of the object. To generate the response signal
one can use several effects. For example, the emission of secondary electrons due to
the beam irradiation is quite often used. However, the beam-induced local change
of a sample property such as the electric resistivity can also provide the signal for
the image. Today, the signal based on the change in electric resistivity is often
utilized for imaging structures in thin layers of semiconductors or superconductors.
In the case of superconductors, spatially resolved images relating to their super-
conductivity can be obtained if the sample is cooled to sufficiently low temperatures
during scanning with the electron beam.
1 Spectacular Advances 11

Fig. 1.8 Modern electron microscope with an accelerating voltage of one million volts. (Photo
A. Tonomura)

Recently, the scanning principle for imaging was extended also to light beams.
However, a necessary prerequisite for this was the availability of laser beams with
their extremely narrow collimation. Today, laser scanning microscopes are widely
used in many fields.
An important milestone during the advances of the methods for the analysis of
materials has been the construction of the first scanning tunneling microscope by
Gerd Binnig and Heinrich Rohrer of the IBM Research Laboratory in Rüschlikon
near Zürich, Swizerland. Their first patent application dealing with the scanning
tunneling microscope was submitted in January 1979. In their instrument the sur-
face to be investigated is mechanically scanned with a tiny metal tip. Using
piezoelectric actuators, the metal tip can be moved in three dimensions with
12 1 Spectacular Advances

extremely high sensitivity. During the scanning process the sample surface is
approached by the tip as close as about 1 nm. Simultaneously, the
quantum-mechanical electric tunneling current is measured running between the tip
and the sample surface, if an electric voltage is applied, even though a metallic
contact between both does not exist. (The explanation of the effect of quantum
mechanical tunneling had been one of the early major successes of the new theory
of quantum mechanics). Because of the strong exponential dependence of the
tunneling current on the distance between the tip and the sample surface, one can
achieve that the tunneling current is limited only by a few or even the last single
atom sticking out of the tip. In this way, today one routinely obtains atomic res-
olution in the lateral direction with this technique (Fig. 1.9). Very recently, even
subatomic structures of silicon atoms due to the different electron orbitals, have
been observed in the images (Fig. 1.10).

Fig. 1.9 Scanning tunneling

microscope. The instrument is
mounted on a flange for
operation in ultra-high
vacuum. (Photo OMICRON
Nano Technology)

Fig. 1.10 Image of the

individual atoms of a section
of 5 nm  5 nm area on the
surface of a silicon crystal,
generated by means of atomic
force microscopy. On the
silicon atoms we can see a
subatomic structure resulting
from the electron orbitals.
(Photo F. J. Giessibl)
1 Spectacular Advances 13

Fig. 1.11 The picture shows a ring of iron atoms placed on a copper surface. In this way an
artificial coral reef consisting of 48 iron atoms has been created on an atomic scale. The circular
lines appearing within the ring are due the density of the electrons existing within the ring. (Photo
Almaden Research Center, 2000)

Soon after the invention of the scanning tunneling microscope, the mechanical
scanning principle was extended to several other types of interaction between the
probing tip and the sample surface. In particular, we mention the atomic force and
the magnetic force microscopes. In the first case, the mechanical force between the
probing tip and the sample surface is utilized. The second case is based on a
magnetic tip probing the magnetic sample properties. In recent years special
research effort has been concentrated on the extension of the techniques we have
discussed to very low temperatures and to the presence of high magnetic fields.
Today, ease of operation is emphasized by the construction of the instruments.
Finally, we point out that most of the techniques for material analysis discussed
above are restricted to the sample surface and its immediate neighborhood
(Fig. 1.11).
In many cases the developments we have outlined were accompanied by the
award of the Nobel Prize for Physics and in some cases for Chemistry to the people
involved. In order to illustrate this, in the Appendix we have listed all Nobel
Laureates who have a close relationship with the physics of solids.
Chapter 2
Well Ordered Lattice Structures
in Crystals

Abstract The lattice structure of crystals is characterized by specific symmetry

properties. Translation symmetry yields the 14 Bravais lattices. Rotation, reflection
at a mirror plane, and inversion at a point result in the 32 crystallographic point
groups. The diffraction of X-rays by a crystal, initiated in 1912 by Max von Laue,
represented the first experimental proof of the regular lattice structure of a crystal.
The elements of diffraction theory, including the reciprocal lattice and Brillouin
zones, are explained. The chapter ends with a discussion of quasi-crystals and the
different types of bonding.

Crystals have always generated a particular fascination, because of the rich variety
of their colors and shapes. While the systematic exploration of nature became
increasingly important ever since the 17th century, at the same time the science of
rocks and minerals developed into an independent branch and a collecting point for
the many different individual observations. The amateur rock collectors and the
mineralogists hiking with their tools through the mountains and hills in the early
days must be looked upon as important forerunners of the modern scientific
exploration into the properties of solids. The basic geometric crystallographic
concepts for describing the large variety of observations also originated within this
field of mineralogy.
In terms of physics, the most important property of crystals is their perfect lattice
structure with the regular periodic repetition of exactly the same elementary
building blocks in all three spatial dimensions. The elementary building blocks can
be atoms or molecules, the latter consisting either of only a few or very many
individual atoms. For example, the elementary building blocks of protein crystals
contain up to 100 000 atoms. Because of their highly regular periodic lattice
structure, crystals always possess a number of prominent symmetry properties. Of
particular importance is the “translation symmetry” resulting from the regular
periodic lattice configuration of the building blocks in all three spatial dimensions.
In a crystal the location of the building blocks of the lattice is described
mathematically by the lattice vectors.

© Springer Nature Switzerland AG 2019 15

R. P. Huebener, Conductors, Semiconductors,
Superconductors, Undergraduate Lecture Notes in Physics,
https://doi.org/10.1007/978-3-030-31420-0_2
Discovering Diverse Content Through
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implication that we were shipping loot in wholesale lots to the United States. That would
be alarming news to the countries whose stolen art works we were already returning as
rapidly as possible.
The Times story most emphatically called for a correction. But if a statement from our
office were sent through channels, it probably wouldn’t reach New York before Easter.
Edith looked up from her work. There was a glint in her eye. She asked, “Will you do me a
favor? I’d like to write the letter of correction.”
I told her to go ahead. Ten minutes later she showed me the rough draft. It covered all
the points. I reworked a phrase here and there but made no important changes and, as
soon as it was typed and cleared, I signed and mailed it. As published in the New York
Times two weeks later, on January 2, 1946, the letter read as follows:

TO THE EDITOR OF THE NEW YORK TIMES

On Dec. 7 The Times printed a report to the effect that $80,000,000 worth of
paintings, presumably from the stores of art objects stolen by the Nazis, had
arrived from Europe in the Army transport James Parker. Your Overseas Weekly
edition of Dec. 9 repeated this information but stated categorically that the
paintings were Nazi loot.
It is true that the James Parker brought to America some 200 paintings of
inestimable value, but none of them is loot or of dubious ownership. They are
the property of the Kaiser Friedrich Museum in Berlin. A press release from the
Office of Military Government for Germany (U.S.), dated Nov. 24, states that
these “priceless German-owned paintings, which might suffer irreparable
damage if left in Germany through the winter, have been selected for temporary
storage in the United States. These paintings have been gathered from various
wartime repositories in the United States Zone of Germany and are being
shipped to Washington to insure their safety and to hold them in trust for the
people of Germany. The United States Government has promised their return to
the German people.”
It cannot be stated too emphatically that the policy of the American Military
Government is to return all looted works of art to their owner nations with the
greatest possible speed. Since the restitution in August of the famous van Eyck
altarpiece, “The Mystic Lamb,” to Belgium, a steady stream of paintings,
sculpture, fine furniture and other art objects has poured from the highly
organized collecting points of the United States Zone to the liberated countries.
Few, if any, looted works of art of any importance are of unknown origin; and
though, among the vast masses of material taken from the Jews and other
“enemies of the state” for what was always described as “safekeeping” there will
undoubtedly be many pieces whose ownership will be difficult to determine, it
appears unlikely that these will be found to be of great value.
The shipment of German-owned paintings to the United States is thus a
project entirely separate from the main objectives of the Monuments, Fine Arts
and Archives Section of the Office of Military Government—namely, the
restitution of loot and the re-establishment of the German museums and other
cultural organizations. To confuse this shipment, which was directed by the
 highest national authority, with what is now the routine work of preservation,
identification and restitution performed by trained specialist personnel is to
mislead our Allies and to underrate the accomplishments of a small group of
disinterested and hard-working Americans.
Thomas C. Howe Jr.
Lieut. Comdr., USNR, Deputy Chief; Director
on Leave, California Palace of the
Legion of Honor, San Francisco.
European Theatre, Dec. 18, 1945.

The main objectives of the Monuments, Fine Arts and Archives Section of American
Military Government in Germany were defined in my letter to the New York Times as “the
restitution of loot and the re-establishment of the German museums and other cultural
institutions.” Honorable and constructive objectives. And, as expressed in that letter,
unequivocal and reassuring both to the liberated countries of Europe and to the
Germans. Yet how difficult of attainment! How difficult even to keep those objectives
clearly in mind when confronted simultaneously—as our officers often were—with a
dozen problems of equal urgency!
At close range it was impossible to look objectively at the overall record of our
accomplishments. But homeward bound in February I had that opportunity. The pieces of
the puzzle began to fit together and the picture took shape. It was possible to determine
to what extent we have realized our objectives.
So far as restitution is concerned, the record has been a success. During the summer
months our energies were devoted to obvious preliminary preparations. They included
the establishment of Central Collecting Points at Munich, Marburg and Wiesbaden.
Immediately thereafter, the contents of art repositories in the American Zone were
removed to those central depots. The Central Collecting Points, organized and directed
by Monuments officers with museum experience, were staffed with trained personnel
from German museums. The one at Munich was primarily reserved for looted art, since
the majority of the cultural booty was found in Bavaria. The Collecting Points at
Wiesbaden and Marburg, on the other hand, housed German-owned collections brought
from repositories in which storage conditions were unsatisfactory.
The process of actual restitution was inaugurated by token restitutions in the name of
General Eisenhower to Belgium, Holland, France and Czechoslovakia. Circumstances
beyond our control postponed similar gestures of good will to Poland and Greece.
Representatives of the liberated countries were invited to the American Zone to identify
and remove the loot from the collecting points. According to late reports, the restitution of
loot was continuing without interruption.
Shortly after my return, there were disquieting rumors of drastic reductions in American
personnel connected with cultural restitution in Germany. I earnestly hope that these
rumors are without foundation. Such reductions would be disastrous to the completion of
a program which has reflected so creditably on our government.
The re-establishment of German museums and other cultural institutions—our second
main objective—has been, to a large extent, sacrificed in the interests of restitution. This
brings up again the urgent need for the immediate replenishment of our dwindling Fine
Arts personnel in Germany. Our moral responsibility for the continuation of this phase of
the MFA&A program is a grave one. It was understandably neglected during the first six
months of our occupation in Germany. And it would be unfair to argue that the British
have far outdistanced us in this field. That they have done so is undeniably true.
However, the British found but little loot in their zone. Consequently, they have been able
to make rapid strides in the reconstitution of German collections and cultural institutions,
while we have been preoccupied with restitution.
Notwithstanding that preoccupation, our Monuments officers were instrumental in
arranging a series of impressive exhibitions of German-owned masterpieces. The first of
these was held at Marburg in November 1945. A second and more ambitious show,
which included many of the finest treasures of the Bavarian State Galleries, opened at
Munich in January 1946. A third, comprising paintings and sculptures from the museums
of Berlin and Frankfurt, was presented at Wiesbaden in February.
All these exhibitions were accompanied by catalogues with German and English texts.
Those of Munich and Wiesbaden were lavishly illustrated. The Munich catalogue
contained several plates showing the rooms in which the exhibition was held—lofty,
spacious galleries recalling the marble halls of our own National Gallery at Washington.
At the time of my departure from Germany, little was known of French and Russian
procedures with regard to cultural rehabilitation in their respective zones of occupation.
Their Military Governments have made provisions for personnel capable of carrying on
work similar to ours and that of the British.
The caliber of the men drawn into the project from all branches of our Armed Forces
has been cited as an important factor in the success of the Monuments, Fine Arts and
Archives program. I would like to cite another factor which I consider equally important:
There was no arbitrary drafting of personnel; participation was voluntary. The resulting
spontaneity and its value to the spirit of the work cannot be exaggerated.
APPENDIX
 APPENDIX
The following is the complete list of the paintings transferred from
Germany and now stored at the National Gallery, according to its
News Release of December 14, 1945:
Albrecht Altdorfer: Rest on the Flight into Egypt
Albrecht Altdorfer: Landscape with Satyr Family
Albrecht Altdorfer: Nativity
Albrecht Altdorfer: Christ’s Farewell to His Apostles
Christoph Amberger: Cosmographer Sebastian Münster
Jacopo Amigioni: Lady as Diana
Fra Angelico: Last Judgment
Austrian Master (ca. 1400): Christ, Madonna, St. John
Austrian Master (ca. 1410): Crucifixion
Hans Baldung Grien: Altar of Halle
Hans Baldung Grien: Graf von Löwenstein
Hans Baldung Grien: Pietà
Hans Baldung Grien: Pyramus and Thisbe
Giovanni Bellini: The Resurrection
Bohemian (ca. 1350): Glatyer Madonna
Hieronymus Bosch: St. John on Patmos
Botticelli: Giuliano de Medici, and frame
Botticelli: Madonna of the Lilies
Botticelli: St. Sebastian
Botticelli: Simonetta Vespucci
Botticelli: Venus
Dirk Bouts: Madonna and Child
Dirk Bouts: Virgin in Adoration
Peter Breughel: Dutch Proverbs
Peter Breughel: Two Monkeys
Angelo Bronzino: Portrait of a Young Man
Angelo Bronzino: Portrait of a Young Man
Angelo Bronzino: Ugolino Martelli
Hans Burgkmair: Holy Family
Giovanni Battista Caracciolo: Cosmos and Damian
Caravaggio: Cupid as Victor
Vittore Carpaccio: Entombment of Christ
Andrea del Castagno: Assumption of the Virgin
Chardin: The Draughtsman
Chardin: Still Life
Petrus Christus: Portrait of a Girl
Petrus Christus: St. Barbara and a Carthusian Monk
Joos van Cleve: Young Man
Cologne Master (ca. 1400): Life of Christ
Cologne Master (ca. 1350): Madonna Enthroned, Crucifixion
Correggio: Leda and the Swan
Francesco Cossa: Allegory of Autumn
Lucas Cranach, the Elder: Frau Reuss
Lucas Cranach, the Elder: Lucretia
Lucas Cranach, the Elder: Rest on the Flight into Egypt
Daumier: Don Quixote
Piero di Cosimo: Mars, Venus and Cupid
Lorenzo di Credi: Young Girl
Albrecht Dürer: Madonna
Albrecht Dürer: Madonna with the Goldfinch
Albrecht Dürer: Young Woman
Albrecht Dürer: Hieronymus Holzschuher
Albrecht Dürer: Cover for Portrait of Hieronymus Holzschuher
Adam Elsheimer: The Drunkenness of Noah
Adam Elsheimer: Holy Family
Adam Elsheimer: Landscape with the Weeping Magdalene
Adam Elsheimer: St. Christopher
Jean Fouquet: Etienne Chevalier with St. Stephen
French (ca. 1400): Coronation of the Virgin
French Master (ca. 1400): Triptych
Geertgen tot Sint Jans: John the Baptist
Geertgen tot Sint Jans: Madonna
Giorgione: Portrait of a Young Man
Giotto: Death of the Virgin
Jan Gossaert: Baudouin de Bourbon
Jan Gossaert: Christ on the Mount of Olives
Francesco Guardi: The Balloon Ascension
Francesco Guardi: St. Mark’s Piazza in Venice
Francesco Guardi: Piazzetta in Venice
Frans Hals: Hille Bobbe
Frans Hals: Nurse and Child
Frans Hals: Portrait of a Young Man
Frans Hals: Portrait of a Young Woman
Frans Hals: Singing Boy
Frans Hals: Tyman Oosdorp
Meindert Hobbema: Landscape
Hans Holbein: George Giesze
Hans Holbein: Old Man
Hans Holbein: Portrait of a Man
Pieter de Hooch: The Mother
Pieter de Hooch: Party of Officers and Ladies
Willem Kalf: Still Life
Willem Kalf: Still Life
Philips Konninck: Dutch Landscape
Georges de la Tour: St. Sebastian
Filippino Lippi: Allegory of Music
Fra Filippo Lippi: Adoration of the Child
Pietro Lorenzetti: St. Humilitas Raises a Nun
Pietro Lorenzetti: Death of St. Humilitas
Claude Lorrain: Italian Coast Scene
Lorenzo Lotto: Christ’s Farewell to His Mother
Bastiano Mainardi: Portrait of a Man
Manet: In the Winter Garden
Andrea Mantegna: Cardinal Mezzarota
Andrea Mantegna: Presentation in the Temple
Simon Mannion: Altar of St. Omer (two panels)
Simone Martini: Burial of Christ
Masaccio: Birth Platter
Masaccio: Three Predelle
Masaccio: Four Saints
Quentin Massys: The Magdalene
Master of the Darmstadt Passion: Altar Wings
Master of Flémalle: Crucifixion
Master of Flémalle: Portrait of a Man
Master of the Virgo inter Virgines: Adoration of the Kings
Hans Memling: Madonna Enthroned with Angels
Hans Memling: Madonna Enthroned
Hans Memling: Madonna and Child
Lippo Memmi: Madonna and Child
Antonello da Messina: Portrait of a Man
Jan Mostaert: Portrait of a Man
Aelbert Ouwater: Raising of Lazarus
Palma Vecchio: Portrait of a Man
Palma Vecchio: Young Woman
Giovanni Paolo Pannini: Colosseum.
Giovanni di Paolo: Christ on the Cross
Giovanni di Paolo: Legend of St. Clara
Joachim Patinir: Rest on the Flight into Egypt
Sebastiano del Piombo: Roman Matron
Sebastiano del Piombo: Knight of the Order of St. James
Antonio Pollaiuolo: David
Nicolas Poussin: St. Matthew
Nicolas Poussin: Amaltea
Raphael: Madonna Diotalevi
Raphael: Madonna Terranova
Raphael: Solly Madonna
Rembrandt: Landscape with Bridge
Rembrandt: John the Baptist
Rembrandt: Joseph and Potiphar’s Wife
Rembrandt: Vision of Daniel
Rembrandt: Moses Breaking the Tablets of the Law
Rembrandt: Susanna and the Elders
Rembrandt: Tobias and the Angel
Rembrandt: Minerva
Rembrandt: Rape of Proserpina
Rembrandt: Self Portrait
Rembrandt: Hendrickje Stoffels
Rembrandt: Man with Gold Helmet
Rembrandt: Old Man with Red Hat
Rembrandt: Rabbi
Rembrandt: Saskia
Rubens: Landscape (shipwreck of Aeneas)
Rubens: St. Cecilia
Rubens: Madonna Enthroned with Saints
Rubens: Andromeda
Rubens: Perseus and Andromeda
Rubens: Isabella Brandt
Jacob van Ruysdael: View of Haarlem
Andrea Sacchi(?): Allesandro del Boro
Sassetta: Legend of St. Francis
Sassetta: Mass of St. Francis
Martin Schongauer: Nativity
Seghers: Landscape
Luca Signorelli: Three Saints (altar wing)
Luca Signorelli: Three Saints (altar wing)
Luca Signorelli: Portrait of a Man
Francesco Squarcione: Madonna and Child
Jan Steen: Inn Garden
Jan Steen: The Christening
Bernardo Strozzi: Judith
Gerard Terborch: The Concert
Gerard Terborch: Paternal Advice
Giovanni Battista Tiepolo: Carrying of the Cross
Giovanni Battista Tiepolo: St. Agatha
Giovanni Battista Tiepolo: Rinaldo and Armida
Tintoretto: Doge Mocenigo
Tintoretto: Old Man
Titian: Venus with Organ Player
Titian: Self Portrait
Titian: Lavinia
Titian: Portrait of a Young Man
Titian: Child of the Strozzi Family
Cosma Tura: St. Christopher
Cosma Tura: St. Sebastian
Adriaen van der Velde: The Farm
Roger Van der Weyden: Altar with Scenes from the Life of Mary
 Roger Van der Weyden: Johannes-alter Altar with Scenes from the
Life of John the Baptist
Roger Van der Weyden: Bladelin Altar
Roger Van der Weyden: Portrait of a Woman
Roger Van der Weyden: Charles the Bold
Jan Van Eyck: Crucifixion
Jan Van Eyck: Madonna in the Church
Jan Van Eyck: Giovanni Arnolfini
Jan Van Eyck: Man with a Pink
Jan Van Eyck: Knight of the Golden Fleece
Lucas van Leyden: Chess Players
Lucas van Leyden: Madonna and Child
Velásquez: Countess Olivares
Domenico Veneziano: Adoration of the Kings
Domenico Veneziano: Martyrdom of St. Lucy
Domenico Veneziano: Portrait of a Young Woman
Vermeer: Young Woman with a Pearl Necklace
Vermeer: Man and Woman Drinking Wine
Andrea del Verrocchio: Madonna and Child
Andrea del Verrocchio: Madonna and Child
Watteau: Fête Champêtre
Watteau: French Comedians
Watteau: Italian Comedians
Westphalian Master (ca. 1250): Triptych
Konrad Witz: Crucifixion
Konrad Witz: Allegory of Redemption
 On January 15, 1946, Mr. Rensselaer W. Lee, President of the
College Art Association of America, sent the following letter to the
Secretary of State:

My dear Mr. Secretary:

The members of the College Art Association of America, a
constituent member of the American Council of Learned
Societies, have been disturbed by the removal to this country
of works of art from Berlin museums.
Information that we have received from abroad leads us to
believe that the integrity of United States policy has been
questioned as a result of this action. We have also been
informed that adequate facilities and American personnel now
exist in the American zone in Germany to assure the proper
care of art treasures in that area.
We would therefore urge that the department of State
clarify this action, and would strongly recommend that
assurances be given that no further shipments are
contemplated.

Copies of this letter were sent to members of the American

Commission for the Protection and Salvage of Artistic and Historic
Monuments in War Areas.
The State Department replied on January 25:

My Dear Mr. Lee:

Your letter of January 15, urging the Department to clarify
the action taken in removing to the United States certain
works of art from German museums, has been received. In
the absence of the Secretary, I am replying to your letter and
am glad to give you additional information on this question.
The decision to remove these works of art to this country
was made on the basis of a statement by General Clay that
he did not have adequate facilities and personnel to
safeguard German art treasures and that he could not
undertake the responsibility of their proper care.
You indicated in your letter that you have been informed
that adequate facilities and personnel now exist in the
American zone for the protection of these art treasures. I must
inform you that our information, based upon three separate
investigations, is precisely to the contrary. The redeployment
program has, as you no doubt realize, reduced American
personnel in Germany and this reduction is applied to arts
and monuments and this personnel as well as to other
branches.
The coal situation in Germany is critical and has made it
impossible to provide heat for the museums. General Clay
cannot be expected to provide heat for the museums if that
means taking it away from American forces, from hospitals, or
from essential utility needs.
We are furthermore advised that the security situation was
not such as to ensure adequate protection in Germany. In
short, the Department’s information is such that it cannot
agree with your premise.
It was realized that the “integrity of United States policy”
might be questioned by some if these works of art were
removed to this country. After a careful review of the facts, it
was decided that the most important aspect was to safeguard
these priceless treasures by bringing them to this country
where they could be properly cared for. It was hoped that the
President’s pledge that they would be returned to Germany
would satisfy those who might be critical of this Government’s
motives.
Sincerely yours,
For the Acting Secretary of State:
James W. Riddleberger
Chief, Division of Central European Affairs[6]
 In April the author of this book received from Frederick Mortimer
Clapp, director of the Frick Collection, New York, the following letter
regarding the removal of German-owned works of art to this country.
A copy of the resolution which accompanied this letter and a list of
those who subsequently signed the resolution are also printed below.

1 East 70th Street

New York 21, New York
April 24, 1946
Dear
Since we believe that it is impossible to defend on
technical, political or moral grounds the decision to ship to this
country two hundred internationally known and extremely
valuable pictures belonging indisputably, by prewar gift or
purchase, to German institutions, notably the Kaiser Friedrich
Museum of Berlin, we propose to memorialize the President
in a resolution to be signed by a group of like-minded people
interested in or associated with the arts.
We also intend to point out that no reason can be found for
even temporarily alienating these works of art from the
country to which legally they belong.
We represent no organized movement or institution. We
merely wish as American citizens to go on record by
appealing to our government to set right an ill considered
action arising from an error of judgment which, however
disinterested in intention, has already done much to weaken
our national condemnation of German sequestrations of the
artistic heritage or possessions of other nations under the
subterfuge of “protective custody,” or openly as loot.
The moral foundations of our war effort and final victories
will be subtly undermined if we, who understand the
implications, pass over in silence an action taken by our own
officials that, in outward appearance at least cannot be
distinguished from those, detestable to all right thinking
people, which the Nazis’ policy of pillage inspired and
condoned.
The Monuments Officers attached to our armed forces with
their specialized knowledge of the practical risks involved
unanimously condemned the decision. Those Americans
whose profession it is to study and preserve old paintings
deplore it. On ethical grounds it is disapproved by the opinion
of enlightened laymen.
We therefore consider the protest we will make to be our
plain and simple duty, for it is our considered judgment that no
explanation or excuse acceptable to the public conscience
can be found for sending fragile old masters across the sea to
this country. The physical hazards, the momentous
responsibilities and the intellectual ambiguities inherent in
such an act are only too grossly evident. The historical
repercussions that will follow it can be imagined in the light of
past situations of a similar kind. It is well known that the Nazis
inculcated in the German mind a fanatical belief that we are
destructive barbarians. All future deterioration of these
pictures will now, rightly or wrongly, be laid at our door.
We should be glad if you would care to join us and others,
who have already expressed to us their sense of the
unjustified impropriety of the action to which we refer in
demanding the immediate return to Germany of these panels
and canvasses, the cancellation of all plans to exhibit them in
this country and the countermanding at once of any
contemplated further shipments.
The text of the proposed resolution is enclosed. As one of
the principal reasons for submitting it to our government is to
forestall further action of a similar kind with reference to
pictures or objects of art belonging to German museums, as
well as to rectify the existing situation, may I earnestly request
you to signify your approval, if you are so minded, by signing
the resolution and returning it to me before May 6.
Sincerely yours,
 Signed: Frederick Mortimer Clapp.

On May 9, 1946, Dr. Clapp and Mrs. Juliana Force, director of the
Whitney Museum, sent President Truman the following resolution, a
copy of which was enclosed with the above letter:

RESOLUTION
Whereas in all civilized countries one of the most
significant public reactions during the recent war was the
horrified indignation caused by the surreptitious or brazen
looting of works of art by German officials in countries they
had conquered;
And Whereas that indignation and abhorrence on the part
of free peoples was a powerful ingredient in the ardor and
unanimity of their support of the war effort of democratically
governed states in which the private opinions of citizens are
the source and controlling directive of official action;
And Whereas two hundred important and valuable
pictures belonging to the Kaiser Friedrich and other Berlin
museums have been removed from Germany and sent to this
country on the still unestablished ground of ensuring their
safety;
And Whereas it is apparent that disinterested and
intelligent people believe that this action cannot be justified on
technical, political or moral grounds and that many, including
the Germans themselves, may find it hard to distinguish
between the resultant situation and the “protective custody”
used by the Nazis as a camouflage for the sequestration of
the artistic treasures of other countries;
Be It Therefore Resolved that we, the undersigned,
respectfully request the President to order the immediate safe
return to Germany of the aforesaid paintings, the cancellation
of any plans that may have been made to exhibit them in this
country and the countermanding without delay of any further
shipments of the kind that may have been contemplated.
This resolution was signed by:

Abbott, Jere
Director
Smith College Museum of Art
Northampton, Mass.
Abbott, John E.
Executive Vice-President
The Museum of Modern Art
New York, N.Y.
Adams, Philip R.
Director
Cincinnati Museum
Cincinnati, Ohio
Barber, Professor Leila
Vassar College
Poughkeepsie, N. Y.
Baker, C. H. Collins
Henry E. Huntington Library and Art Gallery
San Marino, Calif.
Barr, Alfred H.
The Museum of Modern Art
New York, N. Y.
Barzun, Jacques
History Department
Columbia University
New York, N. Y.
Baur, John I. H.
Curator of Painting
Brooklyn Museum
Brooklyn, N. Y.
Biebel, Franklin
Assistant to Director
Frick Collection
New York, N.Y.
Breeskin, Mrs. Adelyn
Acting Director
Baltimore Museum of Art
Baltimore, Md.
Burdell, Dr. Edwin S.
Director
The Cooper Union
New York, N. Y.
Chase, Elizabeth
Editor “Bulletin”
Yale University Art Gallery
New Haven, Conn.
Claflin, Professor Agnes Rindge
Vassar College
Poughkeepsie, N. Y.
Clapp, Frederick Mortimer
Director
Frick Collection
New York, N. Y.
Cole, Grover
Instructor in Ceramics
University of Michigan
Ann Arbor, Mich.
Cook, Walter W. S.
Chairman
Institute of Fine Arts
New York University, N. Y.
Courier, Miss Elodie
Dir. of Circulating Exhibitions
The Museum of Modern Art
 New York, N. Y.
Crosby, Dr. Sumner
Assistant Professor, History of Art
Yale University
New Haven, Conn.
Cunningham, Charles C.
Director
Wadsworth Atheneum
Hartford, Conn.
Dawson, John P.
Professor of Law
University of Michigan
Ann Arbor, Mich.
Faisan, Professor Lane, Jr.
Williams College
Williamstown, Mass.
Faunce, Wayne M.
Vice-Director
American Museum of Natural History
New York, N. Y.
Fisher, H. H.
Hoover Library
Stanford University
Palo Alto, Calif.
Force, Mrs. Juliana
Director
Whitney Museum of American Art
New York, N. Y.
Goodrich, Lloyd
Research Curator
Whitney Museum of American Art
New York, N. Y.
Gores, Walter J.
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