Lynton Superconductivity

GO
a
w
o
SUPER-
CONDUCTIVITY
3
Ernest A. Lynton
METHUENS MONOGRAPHS ON
PHYSICAL SUBJECTS
Superconductivity
ERNEST
A.
LYNTON
Although the fascinating phenomenon of

superconductivity has been known for fifty
years, it is largely through the concentrated
experimental and theoretical work of the last
decade that a basic (though at present very
incomplete) understanding of the effect has
been reached. This monograph is a largely
descriptive introduction to superconductivity, requiring little more than an undergraduate physics background. It is written to
serve two functions ; first as a stepping stone
towards more intensive study for those who
intend to work in the field of research and
development of superconductivity and its
applications and, secondly, as a basic refer-
ence on the present state of the subject of

superconductivity.
The book
contains a description of the
principal characteristics of a superconductor,
together with a detailed discussion of the most

useful phenomenological models which have
been applied to superconductors. The second
monograph describes the fundamental microscopic properties in terms of the

theory of Bardeen, Cooper and Schrieffer. It
is shown how remarkably successful this
theory has been in explaining the behaviour
of an idealized superconductor. There is a
chapter on superconducting devices, a subject index and a bibliography of more than
330 books and articles.
part of the
SECOND EDITION
LONDON
METHUEN & CO. LTD
NEW YORK
JOHN WILEY & SONS INC
methuen's monographs
on physical subjects
General Editor: B. L.
WORSNOP,
b.sc, ph.d.
SUPERCONDUCTIVITY
Superconductivity
E. A. Lynton
Professor of Physics
Rutgers, The State University
New Brunswick, N.J., U.S.A.
Powder patterns of the intermediate stale, showing thesbrinking of the superconducting (dark) regions as /; takes on the
values (left to right, top to bottom) 0, 008, 027, 053, 0-79, and
0-90.
(After Faber, 1958. Reproduced by kind permission of the
Royal Society and the author.) Proc. Roy. Soc. A248 464,
plate 25.
LONDON: METHUEN & CO LTD

NEW YORK: JOHN WILEY & SONS INC
First published in 1962
Second edition 1964
1962 and 1964 by E. A. Lynton

Printed
in
Great Britain by
Spottiswoode, Ballantyne
London
&
& Co Ltd
Colchester
Catalogue No. Methuen 12/4081/66

2-1
CHRJS.
i
For Carla
Acknowledgements
Contents
This book has grown, beyond recognition, from a set of lecture notes
written and used during my stay at the Institut Fourier of the Univerof Grenoble in 1959-60.
sity
hosts, Professors Neel
and pleasant year.
should like once again to thank
and Weil and Dr Goodman, for a stimulating
Basic Characteristics
am very grateful to a large number of people who
have helped me with written or oral comments, with news of their unpublished work, with preprints, and with copies of graphs. In particular I thank Drs Coles, Collins, Cooper, Douglass, Faber, Garfunkel,
Goodman, Masuda,
Olsen, Pippard, Schrieffer, Shapiro,
Swihart, Tinkham, Toxen, and
Waldram.
My colleagues Lindenfeld,
McLean, and Weiss provided much helpful discussion. Above all my

gratitude is due to Bernard Serin, from whose guidance and friendship
I
all
Perfect conductivity
and the critical magnetic field
Superconducting elements and compounds
1.3
1.4
The Meissner effect

The specific heat
1.5
Theoretical treatments
9
11
Phenomcnological Thermodynamic Treatment
13
16
the time to read the entire
and suggested many improvements, not

have been wise enough to incorporate.
2.2
2.3
Interrelation
many
years.
He found
September 1961
E. A.
2.4
Preface to the Second Edition
The Gorter-Casimir
This edition contains revisions and additions which bring the monograph essentially up to date, as of the end of June 1964. The treatment
3.3
Trapped
of superconductors of the second kind has been considerably amplia discussion of the Josephson effect has been added, and a num-
3.4
3.5
The perfect conductor

The London equations
3.6
Quantized flux
incor-
Dr
Nozieres, for his valuable
lation, edited with
many
unfortunately reached
comments and
Russian transilluminating footnotes by Dr. Gor'kov,
me too
late for these
help.
comments
to be included
in the present edition.
IV
E. A.
LYNTON
22
and the intermediate
state
4.1
4.2
4.3
23
26
flux
27
for a superconductor
28
32
The Pippard Non-local Theory
4.4
August 1964
19
22
Influence of geometry
fied,
model
Static Field Description
3.2
porated in the excellent French translation of Mme Nozieres, which

was published early this year. I am very grateful to her, as well as to
thermal
17
two-fluid
Perfect diamagnetism
Many of these were also
magnetic and
between
3.1
ber of other changes have been made.
13
effects
properties
LYNTON
1.2
The phase transition

Thermodynamics of mechanical
draft of the manuscript
of which
2.1
have profited for
first
page
Introduction
my
The penetration depth, A

The dependence of A on temperature and
The range of coherence
The Pippard non-local relations
The Ginzburg-Landau Phenomcnological Theory
vi
vii
34
34
field
36
40
41
48
VI
Contents
Contents
Vlll
The Surface Energy

The
The
page 55
,.
IX
Microscopic Theory of Superconductivity
page 116
55
11.1
Introduction
59
11.2
6.3
and the range of coherence

surface energy and the intermediate state
Phase nucleation and propagation
61
.3
6.4
Supercooling in ideal specimens
65
1 1
.4
6.5
Superconductors of the second kind
67
11.5
6.6
The mixed
71
The
The
The
The
The
6.7
Surface Superconductivity
74
11.7
Experimental verification of predicted thermal
75
11.8
The
75
11.10 Electromagnetic properties
6.1
6.2
surface energy
state or
Shubnikov phase
1.6
116
electron-phonon interaction
117
Cooper
pairs
118
ground
state energy
energy gap at
120
0K
superconductor at
126
finite
temperatures
129
properties
vn Low Frequency Magnetic Behaviour of Small Specimens

7.1
Vffl
Increase in the critical field
7.2
High
threads and superconducting magnets
77
7.3
Variation of the order parameter and the energy

gap with magnetic field
78
The Isotope
8.1
8.2
field
Effect
XII
81
12.1
Introduction
12.2
Dilute solid solutions with non-magnetic im-
12.3
Compounds
83
Thermal Conductivity
87
9.2
Electronic conduction
9.3
Lattice conduction
9.4
Thermal conductivity in the intermediate
temperature thermal conductivity
139
141
141
141
Superconducting Devices
145
150
153
153
89
13.2
Superconducting magnets
154
Superconducting computer elements
157
3.3
94
95
10.2
The
96
10.3
Electromagnetic absorption in the far infrared
10.4
Microwave absorption
100
10.5
Nuclear spin relaxation
104
10.6
The tunnel
10.7
Far infrared transmission through thin
10.8
The Ferrell-Glover sum
specific heat
98
106
films
Superimposed metals
Research devices
95
effect
XIII
2.4
with magnetic impurities
13.1
Introduction
rule
136
87
93
state
The Energy Gap

10.1
134
81
Precise threshold field measurements
Low
Coherence properties and ultrasonic attenuation
purities
Discovery and theoretical considerations
9.1
specific heat
Superconducting Alloys and Compounds
IX
1.9
127
109
1
14
Bibliography
165
Index
183
Introduction
Although the fascinating phenomenon of superconductivity has been
known for fifty years, it is largely through the concentrated experimental and theoretical work of the past decade that a basic (though
as yet very incomplete) understanding of the effect has been reached.
Far from being an oddity of little physical
interest it has been shown

phenomenon of basic importance and with close
a number of fields. At the present time one important
to be a co-operative
analogies in
period in the development of the subject has been completed, and the
next is already well under way, with much effort in theory and experi-
ment to carry our understanding from the general to the particular,

from the idealized superconductor to the specific metal. Somewhat
coincidentally, there
now
also
is
great interest in possible practical
applications of superconductivity.
This
monograph
is
a largely descriptive introduction to super-
more than an undergraduate physics background, and written to serve two functions. It can be a first survey and
a stepping stone toward more intensive study for those who intend to
conductivity, requiring no
become actively engaged

tivity,
in the further development of superconducbe it in basic research or in technical applications. Such readers
from the extensive bibliography, listing more than 450

At the same time the book is sufficiently complete
description both of experimental details and of theoretical
will benefit
books and
in its
articles.
approaches to be a basic reference for those who wish to be acquainted

with the present state of superconductivity. It will enable them to
follow further developments as they appear in the scientific and
technical literature.
The contents of the book can be grouped into a number of sections

which treat the subject of superconductivity in successive layers with
increasing resolution of detail. The first three chapters introduce the
reader to the principal characteristics of bulk superconductors, and
treat these in
terms of the basic phenomenological models of London

and of Gorter-Casimir. With this section the reader thus acquires a
broad outline and a general understanding of the thermodynamic and
1
Superconductivity
the static electromagnetic behaviour of idealized, bulk superconductors. The treatment of the subject is then pursued in greater detail
along two essentially parallel directions. In the section comprising
Chapters IV-VII are discussed those aspects of the behaviour of
CHAPTER
Basic Characteristics
superconductors which lead to the non-local treatments of Pippard
and of Ginzburg and Landau. These more sophisticated phenomenological models account for an interphase surface energy, in terms of
which the later chapters of this section describe the intermediate state,
phase nucleation, propagation, and supercooling, superconductors
of the second kind, and the magnetic behaviour of specimens of
small dimensions. Chapters VIII-X can be read without a study of
the preceding section (IV-VII)
and
characteristics of a superconductor
describe in
much
detail those
which during the past decade
Perfect conductivity and critical magnetic field

behaviour
of electrical resistivity was among the first problems
The
investigated by Kamerlingh Onnes after he had achieved the liquefaction of helium. In 1911, measuring the resistance of a mercury
sample as a function of temperature, he found that at about 4K the
resistance falls abruptly to a value which Onnes' best efforts could not
1.1.
distinguish
zero. This extraordinary
from
phenomemon he
called
have indicated the microscopic nature of superconductivity, and

have led to the theory of Bardeen, Cooper, and Schrieffer. The
fundamental aspects of this theory are presented with a minimum of
superconductivity,
mathematics.
current will be induced which attempts to maintain the magnetic flux
The book closes with a chapter on the behaviour of alloys and compounds, and with one on superconducting devices.
In describing the principal empirical characteristics of supercon-
temperature,
When
Tc
and the temperature at which

(Kamerlingh Onnes, 1913).
a metallic ring
through the ring
at
have
tried to include only the
tinent experiments, or in the description of superconducting be-
to emphasize
has been slighted.
My
what aspects of the latter

whose work
The choice was not a judgement of the scientific
detail.
may appear
critical
field,
a constant value. For a body of resistance
R and
self-inductance L, this induced current will decay as
(LI)
7(0)exp(-i?//L).
key experiments through
which the phenomenon in question was established, as well as more

recent work which gives the most detailed or the most precise information. It is both unnecessary and impossible in a monograph of this
small size to be encyclopaedic either in the enumeration of all perhaviour in minute
appears the
exposed to a changing magnetic
is
/(/)
ductors
it
selection of
arbitrary, especially to those
value of such work, but rather of its didactic usefulness in illuminating

the elementary characteristics of superconductors.
/(/)
can be measured with great precision, for example, by observing
the torque exerted by the ring

carries
known
upon another, concentric one which
current. This allows the detection of
much
smaller
any potentiometric method. A long series of such

measurements on superconducting rings and coils by Kamerlingh
Onnes and Tuyn (1924), Grassman (1936), and others recently culminated in an experiment by Collins (1956), in which a superconducting ring carrying an induced current was kept below Tc for about two
and a half years. The absence of any detectable decay of the current
-21
during this period allowed Collins to place an upper limit of 10
ohm-cm on the resistivity of the superconductor.! This can be com-9
pared to the value of 10
ohm-cm for the low temperature resistivity
resistance than
of the purest copper.
There
is,
therefore,
little
doubt that a superconductor
is
indeed a
23
ohm-cm
t Quinn and Ittner (1962) have lowered this upper limit to 10"
by looking for the time decay of a current circulating in a thin film tube.
Basic characteristics
Superconductivity
perfect conductor, in the interior of which

field vanishes.
any slowly varying electric
A current induced in a superconducting ring will persist
indefinitely without dissipation.
Below Tc the superconducting behaviour can be quenched and

normal conductivity restored by the application of an external mag,
netic field. This field,

field,
and, as
shown
c , is
thick so that surface effects can be ignored, the critical current is that
which creates at the surface of the specimen a field equal to
c.
Smaller samples remain superconducting with much higher currents
than those calculated from this criterion, which
1 ,
it
1.2.
varies approximately as
Superconducting elements and compounds

I lists all
characteristic
(1.2)
investigators,
Alekseevskii
presently
and
Tc
known superconducting elements and their

In addition there have been found by many
in particular by Matthias and co-workers, by

and co-workers, and by Zhdanov and Zhuravlev (see
Table
Element
Normal
119
Cadmium
0-56
Gallium
Indium
3-407
Temperature T
Fig.
= Hc at T= 0K. It is convenient to introduce reduced co/
T/Tc and
,
h(t)
H (T)/H
C
2
ft l-/
The actual temperature variation of h

by a polynomial in which the
5-95
Lead
Mercury-a
718
4153
Mercury-/?
3-95
Molybdenum
Niobium
9-46
Osmium
0-7
Rhenium
1-70
0-49
in
terms of which
(I.2a)
is
more accurately represented
coefficient
of the
2
t
term
differs
from
unity by a few per cent.
The superconductivity of a wire or film carrying a current can be

quenched when this reaches a critical value. For specimens sufficiently
Technetium
Thallium
Thorium
Tin
Titanium
Tungsten
(gauss)
99
30
51
283
~20
~5
Lanthanum-/*
Ruthenium
Tantalum
109
014
Lanthanum-a
TC (K)
Aluminium
Iridium
ordinates
called Silsbee's
called the critical or threshold magnetic
in Figure
H *H [l-(lJ],
is
rule (Silsbee, 1916).
Table
where
1600
803
411
340
10
4-482
1944
65-82
201
66
830
11-2
2-39
1-37
171
162
306
100
3-722
0-40
~001
Uranium-a
Uranium-y
0-6
Vanadium
5-30
0-92
1310
53
0-75
47
Zinc
Zirconium
(cf.
~2000
1-80
Roberts (1963) for most references)
Superconductivity
Matthias, 1957; Roberts, 1961), a very large
number of
alloys
and
compounds which also become superconducting. Some of these

compounds consist of metals, only one of which by itself becomes
superconducting, some have constituents of which neither by itself is
superconducting, and some even are semiconductors. The possibility
of superconductivity in semiconductors and semimetals has been
discussed by M. L. Cohen (1964), and both GeTe (Hein et al., 1964)
and SrTi0 3 (Schooley et al., 1964) have been found to be superconducting at very low temperatures.
The Meissncr
effect, and the reversibility of the S.C. transition

conductor were placed in an external magnetic field, no
magnetic flux could penetrate the specimen. Induced surface currents
would maintain the internal flux, and would persist indefinitely. By
1.3.
If a perfect
same token, if a normal conductor were in an external field before

became perfectly conducting, the internal flux would be locked in
the
it
by induced persistent currents even if the external field were removed.
o o
A:He=0,
B%0.
C:0<H e<H o
B:H e=0
T>TC
T<TC
T<TC
T<TC
(b)
(a.)
(d)
(c)
Fig. 3
10
No. valence electrons/atom
Fio.2
The
C:0<Hp<H
e n c.
temperatures of superconductors range from very low

values up to 181K for Nb 3 Sn (Matthias et al., 1954). Matthias
(1957) has pointed out a number of regularities in the appearance of
critical
superconductivity and in the values of

the following
Tc
Superconductivity has been observed only for metallic substances for which the number of valence electrons
lies between
8.
(2) In all cases involving transition metals, the variation
H e =0,
T<TC
(d)
Fig. 4
Because of this, the transition of a merely perfectly conducting specimen from the normal to the superconducting state would not be
reversible,
and the
final state
of the specimen would depend on the
path of the transition.
of Tc with
number of valence electrons shows sharp maxima for Z = 3, 5,

and 7, as shown in Figure 2.
(3) For a given value of Z, certain crystal structures seem more
favourable than others, and in addition Tc increases with a high power
of the atomic volume and inversely as the atomic mass.
the
B:
the principal of which are
(1)
about 2 and
T<TC
As an example, Figures 3 and 4 show the flux configuration for a

perfectly conducting sphere taken from point A in Figure 1 to
point
by the different paths
ABC and ADC,
respectively.
distribution at C, as well as that at B, depends
The
final field
on whether one proceeded via Bov via D, and the irreversibility of the transition
is evident.
Careful measurements of the field distribution around
a spherical
Superconductivity
specimen by Meissner and Ochsenfeld (1933), however, indicated that
regardless of the path of transition the situation at point

is always
that shown in Figure 3c the magnetic flux is expelled from the interior
of the superconductor and the magnetic induction B vanishes. This is
:
called the Meissner effect,
tion
is
and shows that the superconducting transi-
connectivity of the body, so that
one has a superconductor with a

and only the hole may be
The magnetic properties of such a superif
hole, the Meissner effect occurs in the metal
threaded by magnetic
flux.
conducting ring are thus essentially determined by the relative size of

the diameter of the ring to the diameter of the hole.
reversible.
Figure 5 illustrates this by showing B vs. e curves both for a perfect

conductor and for a superconductor, taking the case of long cylindrical specimens with axes parallel to the applied field.
e is a uniform,
1.4.
The
The
specific heat
specific heat
of a superconductor consists,
metal, of the contribution of the electrons
(Cg). For a normal metal
>'
*^n
perfect conductor
/>
He
is
the
at
of a normal
like that
(Ce) and
that of the lattice
low temperatures
Wntt,gn = yT+A(T/0) 3
,
(1.3)
Sommerfeld constant, which is proportional to the density of

Fermi surface, is the Debye temperature, and
electronic states at the
cO
a numerical constant for
all metals. Experimentally the two contribe separated by plotting CJTvs. T 2 so that the
slope of the resulting curve is A/0 3 and the intercept is y.
In the superconducting phase
butions to
Cn can
superconductor
"a
C|
= Ces +Cgs
Cs (H=0) and C (H> c ) for tin as

measured by Corak and Satterthwaite (1954), displaying the characteristic features ofa sharp discontinuity in C,of the order
of 2y7c at Tc
and a rapid decrease of Cs to values below Cn varying about as T 3
It is customary to attribute the difference
between Cs and C entirely
to changes in C on the assumption that C is the same in
e
both phases.
g
This seems reasonable in view of the electronic nature of the superconducting phenomenon, and is supported by the absence of any
Figure 6 shows values of both
Applied Field He
Fro. 5
external
field.
In increasing
field
H =H
both specimens have
5=0
until
e
c , when they become normal and B =
e If the field is now
again decreased, the induction inside the perfect conductor is kept at
its threshold value B =
c by surface currents, and in zero field the
.
specimen is left with a net magnetic moment, as is illustrated in Figure

4d.
The superconductor, however, expels the flux at the transition and
returns reversibly to
its initial
state with
B=
for
< He < Hc
The vanishing of the magnetic induction, corresponding

pulsion of the magnetic flux,
is
to the ex-
the basic characteristic of all ideal
superconducting material with dimensions large compared to a basic

length which will be mentioned later. It is quite independent of the
observable change in the lattice parameters (Keesom and Kamerlingh

Onnes, 1924), and by the detection of only minimal changes in the
elastic properties (see, for instance, Alers
and Waldorf,
1961).
On this
assumption
^s
*-n
which allows one to determine

specific heat difference after
f-'es
Ces
ê
(1.4)
from measured values of the
Ce = y7"has been determined separately.
There has recently been some evidence that the lattice contributions
to the specific heat in the two
phases are not quite equal in the case of
Superconductivity
10
very low temperatures.

in
For
11
these elements possible small differences
Cg therefore do not much affect the validity of 1.4.

Ccs for tin calculated on the basis of 1.4 from the
Figure 7 displays
Figure
results in
6,
plotted logarithmically in units of l/yTc vs.
This shows that for l/t>2, one can represent
CJyTc =
A subsequent chapter
existence of a finite
in the
1//.
by the equation
aexp(-b/t).
will discuss that this is
gap
Ces
(1.5)
an indication of the
energy spectrum of the electrons
separating the ground state from the lowest excited state.
The number
of electrons thermally excited across this gap varies exponentially

it has become
apparent that such an energy gap determines the thermal properties
as well as the high frequency electromagnetic response of all super-
with the reciprocal of the temperature. In recent years
(deg.Kf)
Fig. 6
conductors, and that
it
must indeed be one of the principal features
of a microscopic explanation of superconductivity.

1.5.
Theoretical treatments
The macroscopic characteristics of a superconductor have been

subject of a number of phenomenological treatments of which
principal ones will be discussed in subsequent chapters. F.
the
the
and H.
London
(1935a, b) developed a model for the low frequency electromagnetic behaviour which is based on a point by point relation
between the current density and the vector potential associated with
a magnetic
electrons
field.
This implies wave functions of the superconducting

in the presence of such a field extend rigidly to
which even
the limits of the superconducting material
and then vanish abruptly.
A thermodynamic treatment and an associated two-fluid model based

1.0
1.5
2.0
2.5
3.0
3.5
on essentially equivalent simplifications were worked out by Gorter

and Casimir (1934a, b). These complementary theories provide highly
4.0
1/t
indium (Bryant and Keesom, 1960; O'Neal et al., 1964), so that 1.4
may not be exact for this element and possibly other superconductors
as well. Ferrell (1961) has suggested that this is due to a shift in the
phonon frequency spectrum. However, the superconducting elements for which reliable values of C exist are those with a relatively
high Debye temperature for which
Cg < Ce
and useful tools in the semi-quantitative analysis of many

problems involving superconductors. Their limitations become
apparent principally in situations in which size and surface effects are
successful
Fig. 7
in
both phases
down
to
important.
Pippard (1950, 1951) has shown that such effects become tractable
when one takes into account the finite coherence of the superconducting wave functions which is such as to allow them to vary only slowly
over a
finite distance.
This leads (Pippard, 1953) to a non-local
Superconductivity
12
and the vector

The equation has only
integral relation between the current density at a point
potential in a region surrounding the point.
been solved for a few special cases. In many instances, however, it

reduces to a modified version of the London equation, so that the
much simpler London formalism can then be used with the Pippard
CHAPTER
II
Phenomenological Thermodynamic Treatment
modifications (Tinkham, 1958).
Ginzburg and Landau (1950) have developed on a thermodynamic

basis
an
method of
alternate
treating the coherence of the super-
conducting wave functions. Their treatment
is
compatible with
Pippard's electromagnetic approach, and forms a highly useful com-
plement to
it.
A successful microscopic theory of superconductivity has recently

been developed by Bardeen, Cooper, and Schrieffer (1957). It is based
on the fact, established by Cooper (1956), that in the presence of an
attractive interaction the electrons in the neighbourhood of the
Fermi
surface condense into a state of lower energy in which each electron

is
paired with one of opposite momentum and spin. Bardeen, Cooper,
and
Schrieffer
(BCS) have been able to show that a finite energy gap
number of Cooper pairs

from the state with one pair less. This leads to the correct thermal
and electromagnetic properties to display superconductivity.
The attraction between electrons necessary to form Cooper pairs
can in principle be due to any suitable kind of interaction. The discovery (Maxwell, 1950; Reynolds et al., 1950) that for many superconducting elements the critical temperature depends on the isotopic
mass showed that for these substances the attractive interaction is one
between the electrons and the lattice. The BCS theory and its extensions have been worked out on this basis. However, the isotope effect
separates the state with the largest possible
is
The phase transition

Long before the determination of
2.1.
the reversibility of the superconducting transition by the discovery of the Meissner effect, attempts
had been made to apply thermodynamics to it by Keesom (1924), by

Rutgers (Ehrenfest, 1933), and in particular by Gorter (1933), who
virtually predicted the Meissner effect by pointing out that the success
of these early thermodynamic treatments strongly suggested the
reversibility
of the transition.
The discovery of the Meissner
effect finally enabled Gorter and

Casimir (1934a) to develop a full treatment of the superconducting
phase transition in a manner analogous to that of other phase transitions. They start with the fact that two phases are in equilibrium with
one another when their Gibbs free energies (G) are equal. The free
energy of a superconductor is most easily expressed by a diamagnetic
description developed in Chapter III, which attributes to the superconductor a magnetization
(H e) in the presence of an external
field
Then
V
G,(He ) = G/0)- j
For an
ellipsoid,
their
compounds
(see section 8.1).
Furthermore the
effect
pressure in transition metals does not correlate with the
temperatures as
it
) is
uniform, and
G s (H e ) = G s (0)- VJ M(He)dHe
of
(11.10
Debye
does in non-transition superconductors (Bucher
(H.l)
e.
He
apparently absent or considerably reduced in some transition metals
and
M(H
He
dvj M(He)dH
The last term
in this expression gives the
work done on
and Garland (1963a, b) have attributed these anomalies to the existence of overlapping bands in the
electronic energy spectrum at the Fermi surface. However, there is
by the magnetic
also a hypothesis that in transition metals the attractive interaction
parallel to the external field does the superconducting

into the normal one at a sharply defined value of
.
and Olsen,
1964).
Kondo
responsible for pairing
(1962)
may
be a magnetic one (Matthias, 1960).
field.
As
the magnetization
is
the specimen
diamagnetic, that
is,
negative, the field raises the energy of the superconducting specimen.

It will
be shown in Chapter III that only for a quasi-infinite cylinder
13
phase change
For
all
other
14
Phenomenological thermodynamic treatment
Superconductivity
is an intermediate state consisting of a mixture of normal

and superconducting regions. Even under these circumstances, however, any magnetic work is done solely on the superconducting portions, and for any shape of specimen this always equals, per unit
shapes, there
volume,
He
JM(H )dHe = -H 2 /Stt.
(II.2)
Thus one can
15
shows that the latent heat Q = T(Sn S s ) is zero

and is positive when c > 0. Thus there
isothermal superconducting-to-normal
absorption
of
heat
in
an
is an
transition, and a corresponding cooling of the specimen when this takes
place adiabatically. The resulting possibility of cooling by adiabatic
magnetization of a superconductor was suggested by Mendelssohn
(Mendelssohn and Moore, 1934) and has been used by Yaqub (1 960)
for low temperature specific heat measurements of tin.
Equation
II.5 also
at the transition in zero field,
write for any specimen
G,(/rc)
= (7,(0)+WJc2 /87r.
In the normal state the susceptibility
is
(H.3)
generally vanishingly small, so
that
G n (Hc) =
G(0).
Since the condition of equilibrium defining
H (T)
C
is
that
Gn (Hc) = G {H
S
C),
one has
01.4)
This is the basic equation of the thermodynamic treatment developed by Gorter and Casimir. As S = - (dG/dT) H differentiation
Pi
of 11.4 yields
,
Sn (0) - Sffl = - (VHJAtt) (dHJdT).

At T=
Tc
(II.5)
= 0, and Sn = Ss At any lower temperature, Hc > 0, and

shows that for < T< Tc dHJdT < 0. Hence
furthermore Figure
A further differentiation of II.4 yields,
the entropies of the two phases are equal at the critical temperature in
zero field; at any lower, finite temperature the entropy of the super-
conducting phase is lower than that of the normal one, indicating that
the former is the state of higher order. This ordering will later be
shown to follow from a condensation of electrons in momentum
space.
It
follows from Nernst's principle that
Sn = S s at T=
in this limit the slope of the threshold field curve
entropies of the two phases are also equal at
must pass through a maximum
at
0,
so that
must vanish. As the
T= Tc
their difference
some intermediate temperature.
Cs -Cn =
(VT/47r)[Hc (d
upon
H /dT
multiplication by T:
+ (dHJdT) 2).
(II.6)
Atr=ro ^ = 0,and
c
C,- Cn =
(*T/4tt)
{dHJdTfj^
Te
>
0,
(H.60
so that the thermodynamic treatment predicts the observed discontinuity in the specific heat. As the entropy difference between the
tvvo
Tc
phases passes through an extremum at
some temperature below
the specific heats of the two phases at that temperature
must be
16
Superconductivity
equal,
and
at even lower temperatures
course tend toward zero at
Cs is smaller than
C.
Both of
T= 0. The variation of Cs - C as a func-
tion of temperature, as well as that of Ss -S, are
shown
in Figure 8.
Thermodynamics of mechanical effects

The thermodynamic treatment developed thus far has ignored any
changes in the volume at the transition, as well as any dependence of
2.2.
17
There has been extensive experimental work on pressure effects on

by Swenson (1960) and sumrecently
Olsen
and
Rohrer
most
by
(1960). These latter
marized
the critical field. This has been reviewed
authors (1957) and, independently, also Cody (1958), have succeeded

in refining earlier work of Lazarev and Sudovstov (1949), and have
obtained for different superconducting elements empirical values of

the length
change of a long rod at the transition. (Andres et at., 1 962).
H on pressure as well as on temperature. In taking these into account
Differences in the behaviour of transition
one should begin by considering possible magnetostrictive field effects

on the volume in going from II. 1 to II. 1'. Ignoring this, however,
and noting (see Figure 1 1) that for the special case of a quasi-infinite
have been pointed out by Bucher and Olsen (1964).

The magnitudes of the several mechanical effects are exceedingly
8
9
small. Typical values for 8HJ8p are of the order of 10~ -10~
cylinder parallel to the external field the area under the magnetization
gauss/dyne-cm
curve up to any
field
value
H <H
c is
QABQ-Gjm =
equal to
one can write
j%tt,
(VJ*ir)Hl
01.7)
Differentiating this with respect top in order to obtain
V= (8GI8p) T H
and non-transition metals
-2
and the fractional length change of a long rod

-8
Using the above thermodynamic relations this
-7
yields a difference in the thermal expansion coefficient of about 10
per degree, and a fractional change in compressibility of one part
is
a few parts in 10
in 10
5
.
yields
V5 {He)- Vjm =
(H}l87r)(dVs !8p) T
(n.8)
Vn {Hc)-VM = *mv,EftT,p)l*n\
Vn {Hc)-Vs {0) = {H}l%ir)(dVJBp) T +{Vs HJAn)(dHcl*P)TComparing
II.9
with II.8 shows that the
side of the former
is
first
01.9)
superconductor
upon changing the field from zero to the critical value. It is the second
term which gives the actual volume change at the transition
V(HC )-VS (HC ) - (Vs Hc /47r)(dHc l8p) T
The
interrelation between magnetic
and thermal properties
magnetic and the thermal properties of a superconductor. Equation
term on the right-hand
just the magnetostriction of the
2.3.
One of the most remarkable features of the thermodynamic treatment

outlined in the preceding sections is the manner in which it links the
Similar differentiation of II.3 and II.4 leads to
(11.10)
This term exceeds the magnetostrictive one by more than an order of

magnitude. The derivatives of 11.10 with respect to T and to p yield
for example, indicates that quite independently of the detailed

shape of the magnetic threshold field curve, its negative slope indiII. 5,
cates that the superconducting
phase has a lower entropy than the

normal one. The quantitative verification of an equation such as II. 6',
called Rutgers' relation, provides the best available confirmation of
the basic reversibility of the superconducting transition. The following
taken from Mapother (1962), compares for a few particularly

favourable elements the specific heat discontinuity measured caloritable,
metrically, with
hold
its
field curves.
value calculated with II.6' from measured thres-
The agreement is seen
to be excellent:
expressions for the changes at the transition of the coefficient of
thermal expansion et=(l/V)(SV/dT) t and of the bulk modulus

K = - V{8pj8V). AtT= Tc,
= 0, this yields
c
-, = (U47T)(8Hc ldT)(dHc l8p\
(11.11)
Element
(millijoules/mole)
Indium
Tin
and
*- =
(K /47r)(dHc /8p)
2
.
(IU2)
Tantalum
9-75
10-6
41-5
9-62
10-56
41-6
18
Superconductivity
The relations between the thermal properties and the threshold field
curve of course also imply that
a specific temperature variation is

either assumed or empirically determined for one of the former, this
uniquely specifies the temperature variation of the latter. Kok (1 934),
for example, showed that if one substitutes into equation II.6 a parabolic variation of
c,
if
as given by equation
one obtains a cubic

It was mentioned in Chapter I that both
1.2,
temperature variation of Ccs

of these are only fair approximations to the actual temperature
dependence of these quantities, and that in fact the threshold field can
be represented more accurately by a polynomial which in reduced
.
co-ordinates has the form

h(t)
The
= 1-
a n t\
T=
(see
directly to
polynomial
to neglect
is
must vanish, as otherwise Ss S would not

equation II.5), and 2> = 1 to make //(l) = 0. If
in the lattice specific heat,
~^f=(MWHHT^-a
and one continues

follows that
it
...)x
argument: As shown by equation II.5, Sn > Ss and since S varies

linearly with T, Ss must approach zero with some power of T greater
than unity. Hence one can write
,
0,
Coc T l+X ,
so-called phenomenological two-fluid
tivity
have in
two-fluid
common two
The system
dependence of
Ces
is,
no matter what
CJT^Q
exhibiting superconductivity possesses an ordered
or condensed state, the total energy of which

order parameter. This parameter
is
T= Tc to unity at T= 0K, and can thus

which
is
characterized by an
generally taken to vary from zero
be taken to indicate that
finds itself in the superconducting
(2) The entire entropy of the system is due to the disorder of noncondensed individual excited particles, the behaviour of which is
taken to be similar to that of the equivalent particles in the normal
state.
In particular, two-fluid models
make
the conceptually useful
assumption that in the superconducting phase a fraction #" of the

conduction electrons are 'superconducting' electrons condensed into
an ordered state, while the remaining fraction 1 #" remain 'normal'.
artificiality
of this division cannot be overemphasized;
its
use-
fulness will presently appear.
the precise temperature
as T-+0.
Applying
to
The free energy per unit volume of the normal electrons continues
be the same as that of electrons in a normal metal, that is
where y
(l/27T)a 2 (Hl/Tl).
(11.15)
'
2
gn (T) = -\yT
this limit to
equation 11.14 thus yields
models of superconduc-
general assumptions:
'
It follows, therefore, that
(11.16)
model
The Gorter-Casimir
The
The
CJTozT*.
and
T-+0, dHc /dT-+0. One
state.
(11.14)
the two terms on the left-hand side, the second just equals the
Sommerfeld constant y. The first is subject to the following general
so that
recalling that as
2.4.
fraction of the total system
Of
T l+X ,x >
and
Both of these last equations are exact expressions which permit the
evaluation of the Sommerfeld constant from a detailed knowledge of
the threshold field curve. Mapother (1959, 1962) has carried out a
searching analysis of the extent to which magnetic and thermal data
can actually be correlated in practice without introducing excessive
errors due to extrapolation; Serin (1955) and Swenson (1962) have
also discussed the relation between the two types of data.
at
2
2t
x(2a2) + (-2<7 2 /-...)}.
o:
II.6,
2
y = -(l^Tr^Hl/Tîhd^rldr )^.
(1)
substituted into equation II.6,
any changes
equation
then obtains
this
equivalent expression results from applying the above argument
An
(11.13)
first coefficient a,
vanish at
19
is
(11.17)
the Sommerfeld constant. For the 'superconducting' elec-
trons g (T)
s
is
taken to be a condensation energy relative to the normal
CHRIST'S
COLLEGE
LIBRARY
20
Phenometwlogical thermodynamic treatment
Superconductivity
phase, and the considerations of the

this to
g s (T)
The
first
section of this chapter
show
be
#" of
-HllSrr.
The value of a must be chosen so as to give a reasonable fit to

mental data. With a = one obtains
experi-
QOT.n =
(11.270
(H.1J
volume of the superconducting phase

electrons and 1 of n electrons is
total free energy per unit
containing a fraction
iT(J)
s
a(\
- fT)gn {T) + b(iT)8s (T).
(11.19)
The simplest choice of a(l-iT) = 1-iT; b(iT)=ir, makes

G&if, T) a linear function of 1P, so that the equilibrium condition
(3C/air)r = can be satisfied for only one value of Tat which iT can
assume any value between and l This would mean that for any value
of
the normal and superconducting phases can be in equilibrium
at only that one temperature, which is not the case. Thus it is necessary
to choose a(l - iT) and b(iT) with more care. Gorter and Casimir
.
(1934b) chose
3yTc t\
SS(T) = yTc t\
'
therefore
G (ir, T) =
21
= l-/4
(11.260
(11.250
and
y = (WirKHlfT?).
Here again
which
is
is
(11.230
the cubic temperature variation of the specific heat
only an approximation. Clearly no value of a will change
equation 11.27 into an exponential expression.
comparison of
=
representation of h(t) to a
equation 11.23' with equation 11.15 also shows that the choice a
makes a 2 =\, and reduces the polynomial
parabolic form. This not only indicates once again the interrelation
between the magnetic and thermal properties, but also points up that
a(l
- #") =
- ir)\
(l
b{iT)
Hr,
(11.20)
the Gorter-Casimir
tively.
so that
G3 (ir,T) = -\{\-Hr)*yT 1 -inill%iT.
(11.21)
Within
model can be used
this limitation,
at best only semi-quantita-
however, the concept of the two inter-
penetrating 'fluids' of condensed
and uncondensed electrons
is
very
useful in obtaining a semi-quantitative understanding of many super-
Applying the equilibrium condition yields

a(l
- *0"~ m
'
conducting phenomena, and will be used repeatedly in subsequent
2
HllA-n yT
(IL22)
chapters.
There have been a number of attempts
which at
Tc
with
1T - 0,
p. 280) to improve
model so as to yield
more nearly the correct exponential variation of Ces and the corresponding non-parabolic dependence of h(t). These modifications have
either tried different functional forms for a(l - 1T) and b(iT) in
reduces to
2
y = (WttxHHIIT .).
Substituting 11.23 back into 11.22:
(\-1T)-
(TJT)
(11.24)
Oi.:
Putting this back into 11.21 and differentiating to obtain other

thermal quantities yields
s s (ir,T) = yT(\-iry = y rc r (1+0[)/(1 a)
Some of these
variations do yield considerably better equations for

and magnetic superconducting properties. However, the
principal virtue of a two-fluid model is to provide a conceptual tool
of primarily qualitative nature, and the various suggested improvements rarely add much to the basic physical picture of the two groups
the thermal
Hr = |_^/(i~0
f electrons.
,
and
[(l
[5],
equation TJ.19, or have introduced additional adjustable parameters.
r2
so that
Cs (iT,T) =
(see
the quantitative aspects of the Gorter-Casimir
+ a)/(l-a)]yrc / (l+a)/(, - a \
Static field description
CHAPTER
III
this
23
B = H+4ttM,
As
description
is
equivalent to attributing to the superconductor a
magnetization per unit volume
Static Field Description

3.1. Perfect
M/=
diamagnetism
susceptibility of
the magnetic induction at the interior of a superconductor is due to

induced surface currents.! In the presence of an external magnetic
3.2.
of an external
field
H e is, therefore, the following:
in the interior: B,
H,-
M,-
0,
where M,-
is
at the surface:
3S ^
0,
outside:
Be =
U +H
1/47T.
The influence of geometry and the intermediate state

The great convenience of the diamagnetic mode of description is
illustrated by considering an ellipsoidal superconducting specimen in
an external field e which is parallel to the major axis. The conventional proof, that inside a uniform ellipsoid B, H, and
are all constant and parallel to
e is independent of susceptibility and therefore
the magnetization
s,
where
s is
where
is
B,
=
=
Be =
0,
H,
0;
and
H +H
e
0,
M, ^
0;
s,
where now H,
is
which
is
cf. [1], p.
are, respectively, the
found to have the value of -e\2mc (Kikoin and Goobar,

50 and p. 193 [2], p. 83).
III.l
and
III.2 yields
M,= -H /47r(l-D)
e
(IU.3)
and
H,
In the
distorted
22
semi-major and semi-minor axes, and
- (1 -b 2 /a 2 ) 112 For an infinite cylinder with its axis parallel to He

D = 0; for an infinite cylinder transverse to the field, D = \, and for
a sphere, D-l/3.
e
the field due to the
t That electron currents and not, for example, spins are responsible for
the diamagnetism of a superconductor is demonstrated by its gyromagnetic
1940;
a and b
Combining
magnetization of the sample.
ratio
For an
given by
is
it
at the surface: 3 S
outside:
(IH.2)
-(HMS-'>
this description is
in the interior:
= B.-AirDMu
the demagnetization coefficient of the specimen.
of revolution this
It is this field which causes the distorted field distribution near a superconductor as shown in Figure 3c.
formally correct, it is much more conby an equivalent one which treats the superconductor in the presence of an external field as a magnetic body with an
interior field and magnetization such that
show that
unnecessary)
H,
the field due to the sur-
ellipsoid
Although
now
where 3 S is the surface current density; and

e
applies to the superconductor. Further standard treatments
(with vector notation
face currents.
venient to replace
per unit volume;
(HI.1)
which means that the superconductor has the ideal diamagnetic
Even in the absence of a microscopic explanation of the phenomenon

of superconductivity, it is reasonable to assume that the vanishing of
field, the magnitude and distribution of this current is just such as to

create an opposing interior field cancelling out the applied one.
formal description of a macroscopic superconductor in the presence
-(1/4tt)H,
= HJ{l-D).
(IH.4)
neighbourhood of the superconductor, the external field is

by the magnetization of the specimen. It follows from the
24
Superconductivity
continuity of the normal
component of B and of the
tangential
com-
He
ponent of //that for an ellipsoidal specimen the exterior field distribution is as shown in Figure 9. At the equator of the specimen
(a) transverse
cu nder
,
and
H sphere
\p)
H~ = H,= He l(l-D),
25
(III.5)
(aX
!i
(c) longitudinal
cylinder
at the pole
Hp =
Bi
(IH.6)
0.
For the longitudinal infinite cylinder with axis parallel to e ,D =

and eq = e The exterior field at the surface of the specimen is,
therefore, everywhere the same, and the cylinder remains entirely
superconducting until the applied field becomes equal to the critical
\\
Superconducting state
\\
Intermediate state
2H c /3
H c /2
Applied
He
Field
Fio. 10
Fig. 9
value
c.
The entire body then becomes normal. The magnetization

is shown in Figure 10, in which for con-
curve for such a specimen

venience
For
all
-A-nM is
plotted against
other ellipsoidal shapes,
e.
D ^ 0, and the non-uniformity of
the field distribution around the superconductor raises the question
of what happens when
Hcq = H > H
c
e.
To assume
that a portion of
shown in
would lead to a contradiction: the boundary between the
= C) but in the
superconducting and normal regions occurs where
now normal region the field would equal e
c There is, in fact,
no simple, large-scale division of such a specimen into normal and
superconducting regions, which allows a field distribution such that
< c in the latter, and
C in the former,
C at the
the specimen near the equator then becomes normal, as
Figure
Fig. 11
11,
H <H
H>H
boundaries.
H H
H H
\
H=H
Instead one must postulate, as was

b y F. London (1936), that once
>
first
(1
done by
- D)HC
Peierls (1936)
and
the entire specimen
is
subdivided into a small-scale arrangement of alternating normal

and superconducting regions, with B =
c in the normal regions, and
**
in the others.
The
distribution of these regions varies in such a
Superconductivity
26
way
that the total magnetization per unit
linearly
from
to
Mi = -HJ47r(l - D) = - BJ4*r
at
at
Hence, for
(1
H
H
c {\
- D),
c.
Bi
is
as the
when
the external field
is
reduced to zero, for as long
specimen remains superconducting.
(UI.8)
c,
trapped even
(III.7)
H -A-nDMi = H
H -(MD)(H -H
e
Thus if such a non-ideal specimen is placed in a

magnetic field sufficiently high to make it entirely normal, and the
field is then reduced, the anomalous regions will become superconducting before the bulk of the specimen. Should some of these regions
high critical fields.
be multiply-connected, then the flux threading them at the moment

of their transition into superconductivity can no longer escape, and
-D)Hc <He < Hc

M,= -(l/4irZ(/fc -fQ,
Hi
27
volume changes
(III.9)
e).
Magnetization curves for a transverse cylinder (D = I) and for a

sphere (D = 1/3) are also shown in Figure 10. Note that the area under
each of the curves
is
given by
j MidHe = -H?I8tt.
(111.10)
just the magnetic work done on the specimen in raising the

from zero to
as cited in equation II.2. In the region
c
in which the specimen is neither entirely
(1 D)
c =5
e ^
c
normal nor entirely superconducting, it is said to be in the intermediate
This
is
field
state.
VI
The
H H
detailed structure of this state will be discussed in
Chapter
Applied Field H e
at this time it is only necessary to emphasize that this intermediate
state exists, in
some
field interval, for
Fig. 12
any geometry other than that
of a quasi-infinite cylindrical sample parallel to the external
field.
Trapped flux
important to distinguish the reasons and conditions for the intermediate state from those giving rise to the phenomenon of trapped
flux or the incomplete Meissner effect. As mentioned earlier, the
3.3.
It is
magnetic flux threading a multiply connected superconductor is

trapped by an indefinitely persisting current, and cannot change
unless the superconductivity of the specimen
is
quenched.
similar
As a result, after it has once been normal in an external field, such

an imperfect specimen is less than perfectly diamagnetic in an external
field
H< H
shown
the same
c,
and
retains a paramagnetic
moment in
units as in Figure 10.
The
ratio of
This
to
-H
c is
called the
The perfect conductor

To emphasize once again the
3.4.
difference between a perfect conductor
a nd a superconductor,
superconductor. Strains,
ment of the former, as developed by Becker
fections can create inside a superconductor regions with anomalously
field.
fraction of trapped flux.
situation can arise in a simply-connected but
non-homogeneous
concentration gradients, and other imper-
zero
in Figure 12 for a long cylinder parallel to the field, using
it is
useful to outline an electromagnetic treat-
the discovery of the Meissner effect.
et al. (1933) just before
Superconductivity
In a perfect conductor, the equation of motion for an electron of

m and charge e in the presence of an electric field E does not
contain a retarding term and would simply be
add to Maxwell's equations the following two relations in order to

treat the electromagnetic properties of a superconductor:
28
mass
mv =
In terms of the current density J
of the electrons, one can write
where
eE.
form
in the
E=
(47rA /c ) J,
011.12)
A2
mc2/4wne2
(IE. 13)
length,
-6
(A)
(47rA
field
/c)curlJ+H
by a vector potential curl A
gauge such that div A
= 0,
(B)
0.
= H and
choosing a
(B) reduces to
4ttA
J+A
(BO
0.
for a density of
atom it has a value of
electrons corresponding to one electron per
order of 10
and
and
Replacing the
The parameter A has the dimensions of
E = (ÂVJ),
(IU.11)
= nes, where n is the number density
III.l
29
the
cm.
Note that (A)
is
and thus describes the property of

and III.4 is
identical to UI.2,
perfect conductivity, but that the difference between (B)
Using Maxwell's equation curlE

2
(4ttA /c) curl
= -H/c,
J+H
one finds that
the important
(UI. 14)
0,
and applying another Maxwell equation curlH
Solution of this for any geometry
V 2 H = H/A 2
decays exponentially
(111.15)
any specimen
which decreases exponentially as one
that the solution of III. 15 for
geometry yields a value of
For a
direction from the plane x =
enters the specimen.
V 2 H = H/A 2
OH. 17)
= 4tt3jc yields for the
perfect conductor the equation
Von Laue (1949) showed
one that application of Maxwell's equations now leads
to
now shows that H, and not only H,
upon penetrating
into a superconducting specimen. For the semi-infinite slab described above, the solution of III. 17
is
H(x)
H(0)exp(-x/A),
(IU. 18)
semi-infinite slab extending in the x0, the
appropriate solution
which shows that for x >
is
A,
H(x)
0, in accordance with the Meissner
effect.
H(x)
Clearly, for x
H(0) exp ( - x/X).
P A, H(x) 0. Thus equation III.
interior of a perfect
6 confirms that in the

cannot change in
had when the specimen became perfectly
conductor the magnetic
time from the value

conducting.
it
(UI. 1 6)
1
field
Clearly the London equations (A) and (B) do not, in fact, yield the
complete exclusion of a magnetic field from the interior of a superconductor. Instead, the*y predict the penetration of a field such that
it
decays to
the
London
/e
of its value at the surface in a distance
penetration length.
Its
A.
This
is
called
existence has been fully confirmed
experimentally, although empirical values are consistently higher

3.5.
The London equations
for a superconductor
The
incorrectness of IU.16 was demonstrated by the discovery of

Meissner and Ochsenfeld (1933) that regardless of the magnetic history of the specimen, the field inside a superconductor always
vanishes. F.
and H. London (1935a, b; see
[2])
therefore proposed to
than those predicted by the defining equation ni.13, as will be discussed in a later chapter. The existence of this slight penetration of an
exterior field
must be taken into consideration in the discussion of

superconducting thin films, wires, or colloidal particles, and in a
detailed treatment of the intermediate state.
Superconductivity
30
Applying curlE
= H/c to equation (B), one obtains

curl[E-(47rA
/c
J]
By defining a
particle density
0,
/i(R)
E (47rA
showing that
/c ) J
postulates.
particles of charge q described
by the wave
function
^/(r
the
mean
,r2 ,...,r N ),
current density at a point
H(r a )
magnetic
curlA(r a )
(III. 19)
given by
tnc
field,
.drN
A(ra)
The mean
is
0,
(111.24)
field
(H< i/c ).'
local value of the carriers
...dr N
Q,
and the current density
(^)[(4ttA /c)J + A].
same gauge as that leading to (BO, 111.25 for a simply connected

superconductor reduces to
(IH.21)
0.
W=
follows that
2
...J
^-c A(r )W*V8Ql.-r x )dr
(111.25)
In the
in the
= W v + (9/c)A,
p,
t
momentum
which can be rewritten as
W=W
therefore, one assumes that the wave function

is perfectly rigid
X
under the application of a magnetic field, that is, that
F() always,
-2J
A(R).
given by
If,
J(R)=
mc
brought into a magnetic
(111.20)
[ fl^tnvô-^VamscR-rjx
xdr
it
is
p
.
vanishes, so that
then
QSU8)
wave functions of the superconducting carriers. In F. London's own

words ([2], p. 150): '...superconductivity would result if the eigenfunctions of a fraction of the electrons were not disturbed at all when
- ^-AOrJ V * f U(R-r.
8(R- ra)</r,
But if the particle density n(R) is a sufficiently smooth function so that

one can replace it by a constant n, then in view of the defining equation
III. 13, 111.24 is seen to be identical to (BOThus the London equation (B) or (B') implies that the magnetic
presence of a field
N
s
...dr N
A possible explanation of this is contained in the London equations

1
>=
= -n(R)
J(R)
themselves.
equation 111.22 can be written as
the system
In the absence of a
properties of a superconductor are due to a complete rigidity of the
R in the presence of a
field
is
j ...j P*Y8(R.-ra)dr
<f>
In a system of
grad<,
where is a scalar. In the most general case of a multiply connected

superconductor or a superconducting portion of a current-carrying
circuit, one cannot prove that < vanishes. Hence (A) does not always
follow from (B) and the perfect conductivity implicit in (A) and the
perfect diamagnetism in (B) must be considered as independent
...drN . (111.22)
0.
(IIL26)
The London equation thus implies that superconductivity is due to a

condensation of a number of carriers into a lowest momentum state
P s = 0. By the uncertainty principle this requires the essentially unlimited spatial extension of the appropriate wave functions, and
makes it impossible for them to be affected by local field variations.
It also follows from 111.26 that
v*
= -(qlmc)A,
(IH.27)
'
32
Superconductivity
33
showing that in a simply connected superconductor the charge flow

is entirely determined by the externally applied field, and exists only
in
its
presence.
3.6. Quantized flux
London already observed ([2], p. 151] that the unlimited extension

of the wave function of the superconducting charge carriers has a very
fundamental consequence in a multiply connected superconductor.
F.
Consider, for example, a superconductor containing a hole. The wave

functions must then be single valued along any closed path enclosing
orbit
By analogy
wave functions in an atomic

one can then apply the Bohr-Sommerfeld quantization rules
the hole.
and require
to the electronic
that for the superconducting charge carriers
p-dl
nh,
(IU.28)
(J>
and the fluxoid
is
just equal to the total flux associated with the hole.
This flux is thus seen to be quantized.

The quantization of flux was verified experimentally by Doll and
Nabauer (1961) and by Deaver and Fairbank (1961). These

ments have shown that the quantum of flux is given by
A This shows that q
kC
= 2e,
2x10
that
is,
gauss-cm2
experi-
that the superconducting charge
of electrons. It has already been mentioned that

indeed this is the fundamental premise of the microscopic theory.
A number of authors (Byers and Yang, 1961; Onsager, 1961;
Bardeen, 1961b; Keller and Zumino, 1961; Brenig, 1961) have
carriers are pairs
extended the
London argument
for flux quantization in a rigorous
and Yang as well as Brenig have shown

explicitly that the quantization is due to a periodicity of the free
energy of the superconductor as a function of flux. The free energy of
the normal phase is essentially independent of flux, and there must
fashion. In particular Byers
along any path enclosing the hole. According to 111.25
means
jMttA 2
(b
Since
this
then
that
m
J-dl+&>A-dl =
he
n-
(m.29)
H = curlA, the contour integral of A equal to the surface

H over the area enclosed by the contour, and this in turn
is
integral of
Thus
H-c/S
he
J<fl+0 =
0.
(111.30)
(111.31)
London called the left-hand side of this equation

that according to 111.31 such a fluxoid
is
a.
fluxoid,
and we see
quantized in integral
multiples of
he
&Note that
compared
if
the contour
is
This flux periodicity of

(1961).
equals the magnetic flux <P threading the contour:
<J)A-rfl=
therefore occur a corresponding periodic variation of the critical

temperature at which the free energies of the two phases are equal.
(H1.32)
taken at a distance from the hole large
to the penetration depth A, the current density vanishes,
Tc
has been observed by Little and Parks
The Pippard non-local theory
35
As a consequence it is impossible to test the validity

penetration law, such as, for example, the London
particular
of any
small specimens.
CHAPTER
IV
relation III. 17,
The Pippard Non-local Theory

The penetration depth A
The London equations lead
4.1.
to an exponential penetration of an
externally applied magnetic field into a superconductor, so that the
penetration can be characterized by the depth A at which the

fallen to 1/e
of
its
field
has
value at the surface. Quite in general, and inde-
pendently of any particular set of electromagnetic equations for the

superconductor, one can define the penetration depth for an infinitely
thick specimen
by
H{x)dx.
(1V.1)
This would apply equally well to an exponentially decaying field as

to one, improbable though it may be, which remains constant to a
and then vanishes suddenly.

Shoenberg ([1], p. 140) has pointed out that in this way one can
treat problems involving either very thick specimens (thickness a > A)
certain depth
or very thin ones {a
<^ A)
independently of a detailed knowledge of
the appropriate electromagnetic equations. Using IV. 1 to calculate

the ratio of the magnetic susceptibility \ of a sample into which the
field has penetrated, to the susceptibility xo of an identical
applied
sample from which the field is entirely excluded, he finds equations

of which the following are applicable to a plate of thickness la in a
uniform field parallel to its surface
One can then deduce directly the variation

question, without having to make any
parameter
in
of A with the
assumptions about the true penetration law. The results of such
measurements can therefore help to choose between different electromagnetic theories if these predict different parametric dependences of
field,
x/xo
The
detailed
IV.2 and
all
form of the
=
=
- A/a
2
aa /A
field
for
>
(IV.2)
A,
The oldest method of measuring the penetration depth consists of

determining the magnetic susceptibility of samples with large surface
to volume ratios to make the penetration effects appreciable.
Shoenberg (1940) measured the temperature dependence of the susceptibility of a mercury colloid containing particles of diameter
between 100 and 1000 A. Desirant and Shoenberg (1948) used composite specimens consisting of about 100 thin mercury wires of
3
diameter about 10" cm, and Lock (1951) carried out extensive
measurements of the magnetic behaviour of thin films of tin, indium,

and lead. Casimir (1940) suggested a method using macroscopic
specimens in which the mutual inductance was measured between
two coils closely wound around a cylinder of superconducting
material. It was applied successfully by Laurmann and Shoenberg
(1947, 1949), by Shalnikov and Sharvin (1948), and most recently
with certain refinements by Schawlow and Devlin (1959), and by
McLean
for a
<
(IV.3)
A.
penetration does not enter at
all
into
does so only through the numerical parameter a
in the
equations for
(1960).
A superconductor has finite surface impedance at high frequency,

this
impedance
is
limited in the superconducting phase by the
penetration depth A, as in the normal phase
it is
limited by the skin
Pippard (1947a) was the first to use this as a means of

measuring A, and he and his collaborators have carried out a large
number of experiments at different frequencies and varying experimental conditions (see Pippard, 1960). Basically all these measurements involve observing the change in the resonant frequency of a
depth
other equations for large specimens of other shapes, and

34
impurity content, etc.
the penetration depth.
and
x/Xo
by measurements on large specimens; with very small
specimens this can only be done if one can determine absolute values
of a and of A, which is very difficult. On the other hand, one can
measure the variation of the susceptibility of large or of small specimens with any parameter affecting only A: temperature, external
S.
36
Superconductivity
cavity containing the specimen
when
the specimen passes
normal to the superconducting phase. At
T< Tc
from the
where \<8, these
changes are proportional to 8 - A. If 8 is independent of temperature,

as is the case for a metal in the residual resistivity range, then any
temperature variation of the observed changes must be due to the
temperature variation of
Dresselhaus et
A.
al.
(1964) use instead of a
cavity a rutile resonator to which the specimen
is
coupled, and also
observe changes in the resonant frequency.
measurements, however, shows a small deviation from IV.5 at

/
< 0-8, which becomes particularly pronounced at low temperatures.
This deviation
Schawlow (1958), Jaggi and Sommerhalder (1959, 1960), and most

al. (1960) have measured the penetration of a
field
through a thin cylindrical film of thickness
less
y(.t)
barely discernible in the normal plot of A(r) vs. y(t),

'2
1400p
than
1200 >
the penetration depth.
4.2.
is
= (1-f4) -1
but is displayed strikingly in Figure 13,

,
which shows for Schawlow's results (1958) the variation of the slope,
where
recently Erlbach et
magnetic
1000
The dependence of A on temperature and
field
According to the London theory, an external magnetic field penetrates into a superconductor to a depth characterized by (see equation HI. 13)
where n s
is
the
(mc
It is
400
be the only temperature-dependent factor

in fact the Gorter-Casimir two-fluid
200
number density of the superconducting electrons.
reasonable to expect
this to
and
in this defining equation,
BCS
THEORY
d y 600
2 112
l4irn se
model assumes that

n s (t)
where iît)
is
#xq*m
a1.0
av.4)
1
2.0
1.5
25
depth one obtains
3.5
4.0
4.5
5.0
A(0)
the penetration depth at
(IV.5)
(IV.6)
T= 0K. Very near T
IV.5 can be written
The solid line indicates the values of dX/dy calculated

by Miller (1960) on the basis of the BCS theory; the experimental
results appear to deviate less from IV.5 than is predicted by theory.
Furthermore it appears that in impure specimens no deviation from
IV.5 can be found at
as
*-Ww.
Fig. 13
dXjdy, with y(t).
= A(0)/(l-/4) ,/2
= (mc 2/47r/;/0)e 2) ,/2
A(/)
is
3.0
the order parameter.
The temperature dependence of

is given by 11.25', so that substituting this and IV.4 into the defining equation for the penetration
where
37
sented to a very high degree of approximation by IV.5. This is a

striking success of the phenomenological theories discussed in the
preceding chapters. Close inspection of the recent very precise
The slope of A(r)

(IV.7)
Daunt et al. (1948) were the first to point out that the empirical
temperature variation of the penetration depth can indeed be repre-
all (Waldram, 1961).

plotted as a function of y(t), as well as the inter-
cept, yield values for A(0) if one ignores the small deviations from
IV.5. Appropriate empirical values for pure bulk samples are shown
in
Table
II.
They exceed by a
expect from the
London
what one would

one makes rather
factor of about five
definition IV.6, unless
38
Superconductivity
unlikely assumptions of low densities of superconducting electrons

or of a large effective mass. Experiments on very small samples, and
measurements on impure metals, yield even higher values of A(0),

although none of the factors in IV.6 appear to depend on size or
purity. This failure of the
London theory
will
be discussed
in the
Table
II
Al
A(0)(A)
Sn
500
1300
380-450*
640
440
390
510
Tl
470-600*
920
Cd
Hg
In
Nb
Pb
is
quite considerable.
Pippard pointed out that to assume that the entire entropy change
takes place in the thin layer into which the field penetrates would,
therefore, result in an unreasonably high entropy density in this layer.
Yet this is just what one is led to believe by the London model, according to which the superconducting wave functions or, in two-fluid
language, the corresponding order parameter #", remains rigidly
following sections of this chapter.
lement
39
difference between the normal and superconducting phases, which
unchanged by the application of an external
Reference
field.
Any change in the
Faber and Pippard, 1955a

Khaikin, 1958
Laurmann and Shoenberg, 1949

Lock, 1951
McLean and
Maxfield (1964)
Lock, 1951
Pippard, 1947; Laurmann an
Shoenberg, 1949; Lock, 1951
Schawlow and Devlin, 1959
Zavaritskii, 1952
* Anisotropy.
Z0
Pippard ( 1 950) investigated the change of the penetration of a small,
r.f. field
e is
kMc/s) at a given temperature as an external d.c. field

from zero to the critical value. This change, divided by
the penetration depth in zero
field, is
plotted against temperature in
There are clearly two effects: one at low temperatures

(which Bardeen (1952, 1954) has shown to follow from an extension
14.
London equations to include non-linear terms), and one near

This latter involves a change in A with
in just that region in
which A varies appreciably with temperature. By a thermodynamic
derivation Pippard has shown that this temperature variation of A
leads to a dependence of the superconducting entropy on field. He
of the
Tc
3.0
35
TC
(9-4
raised
Figure
25
T(K)
finds that
S(He )-S(0) =
^^V/U
Fig. 14
thermodynamic functions with field must therefore be confined to the

thin layer into which the field penetrates.
Recent measurements of the field dependence of the penetration
depth at
and 3 kMc/s (Spicwak, 1959; Richards, 1960, 1962; Pip1
pard, 1960; Dresselhaus et
al.,
1964) have
certain unexpectedly complicated features.
of the change frequency dependent, but even
av>8)
for a superconductor of total surface A, assuming IV.5 to hold. Near

Tc this change contributes as much as one-fourth of the total entropy
is
sign can change under

an increase in the pene-
its
certain conditions. In particular there can be

tration depth when the applied field
~/4)]
shown that this effect has

Not only is the magnitude
parallel to the specimen surface,
and at the same frequency a decrease when the field is perpendicular.

Bardeen (1958) and Pippard (1960) have suggested that these complexities may be due to field induced deviations of the superconducting
and normal electron densities from their equilibrium values.
4
40
4.3.
Superconductivity
41
a broadened transition even for ideally homogeneous samples.

Goodman (1962c) has discussed this in some detail.
The range of coherence
The unreasonably high entropy
density in the surface layer led
Pippard (1950) to propose a basic modification of the London model,

according to which the order parameter changes gradually over a
which he calls the range of coherence of the superconducting wave functions. In terms of the microscopic theory this
certain length f ,
distance can be considered as the typical size of the
4.4.
The Pippard
non-local relations
In 1953 Pippard measured the penetration depth in a series of dilute

alloys of indium in tin, and found that the decrease in the normal
electronic
mean
free
path of the metal was accompanied by an
Cooper pairs. Any
change in the thermodynamic functions of course extends over as

wide a region as the change in the order parameter, and thus a value
> A would correspond to a more reasonably small value of the fieldinduced entropy density.
Pippard (1950) obtained an estimate of the range of coherence of
the order parameter by minimizing the Gibbs free energy of the superconductor in the presence of an external field. The resulting relation
between the fractional change of the penetration depth and the ratio
A(0)/ allows him to estimate from his experimental data on the field
-4
effect on A that M 20A(0) 10
cm. Such a distance is much larger
than the smallest colloidal specimen or the thinnest films in which
10-
is still known to exist, and it is therefore of great

importance to realize that, to quote Pippard (1950, p. 220) the range
of order must therefore not be regarded as a minimum range necessary
superconductivity
'
for the setting
up of an ordered
state,
10
20
)0
Strong support is given to the existence of this range of coherence

by the extreme sharpness of the superconducting transition under
suitable conditions.
De Haas and Voogd
of tin taking place within a range

of one millidegree, and a sharpness approaching this value has come
to be the criterion for the quality of a specimen of suitable shape and
orientation. Applying a simple statistical argument, Pippard shows
would create a broader
40
50
(cm)
Fig. 15
(1931) have observed
resistive transitions in single crystals
that fluctuations
.L
30.
but rather as the range to which
order will extend in the bulk material'.
transition unless the super-
appreciable rise in the value of A(0). This has been confirmed by
Chambers
(1956),
and by Waldram
(1961),
whose
results are
shown
Figure 15. Such a dependence of A(0) on the mean free path is quite
incompatible with the London model, for clearly none of the para-
in
meters in the defining equation IV.6 varies appreciably with the
mean free
conductivity of a bulk sample can be created or destroyed only over
electronic
an entire domain of diameter M 10A(0).

In the next section as well as in 6.5 it will be shown that the range of
~
coherence is much smaller than 10 4 cm in low mean free path alloys
as well as in certain pure metals. For such materials one would expect
This experimental result, added to the previous questions which had

been raised about the correctness of the London phenomenological
path.
treatment, led Pippard (1953) to develop a fundamental modification

of this model, based on the concept of the range of coherence of the
42
Superconductivity
will
it
be
remembered, lead to the relation

A(R),
(IV. 10)
4-nXl
A^,
= mc 2 /4ime 2
One way
They do not, however,
so that one can also write this as
J(R)
mean
free path
is
London value IV.6 by
According to Pippard this is because IV.P1 does

not correctly describe the relation between current density and the
vector potential in such a case. PI still implies, as does equation
III.B', the basic London idea of a wave function which is completely
factor of four to five.
A(R).
(IV.ll)
to introduce a dependence of the penetration depth
electronic
satisfactorily explain the finding that A(0) in
pure, bulk superconductors exceeds the
2
IW~
These equations satisfactorily explain the onset of a mean free path

on the penetration depth at a critical value of /, as found by
Pippard and others, as well as the very large penetration depth values
obtained from experiments where / is limited by boundary scattering.
effect
J(R)= where
43
superconducting phase. The basic London equations,
on the
to write
rigid
under the application of an external
field
momenta are ordered or correlated over an

(IV.P1)
distance over which
H and A vary
is
because the electronic
infinite distance.
Thus the
quite immaterial the same kind of

;
would hold if the field varied very slowly as if it varied very

But according to Pippard the range of momentum coherence
4
not infinite but only about 10~ cm, so that the electromagnetic
relation
where is a constant of the superconductor in question, and (/) a

parameter depending on the mean free path /. It is evident from the
analysis in Chapter
HI
that IV.P1 leads to an expression for the field
penetration into a semi-infinite slab which has the
H{x)
London form:
H exp(-x/X),
rapidly.
is
response of the superconductor should be affected profoundly

field varies
only
if
The
but where
now
As experimentally
that (/)
is
XL
(TV. 12)
found to increase with decreasing
must decrease as
is
(/)
(/)
->/as /->0. This
is
if
is
somewhat analogous
to the
problem of electrical
conductivity in a normal conductor, for which the relation
a(/)E(R)
(IV. 14)
decreases.
tends toward this value as

the case
if,
/-> a>,
the
could apply
clear
with the range of coherence of the pure superconductor,
and assumes that
A relation like PI
the field varied slowly over a distance of the order off.

situation
J(R)
/, it
As a first step toward a modification of the London model, Pippard

identifies
rapidly over this distance.
but that
for example,
is
valid only
if
E(R) varies slowly over a distance of the order
of/.
An
which
varies inversely as the square root of the frequency. At sufficiently low
applied alternating field penetrates only a finite distance,
temperatures and high frequencies, the electronic
mean
S,
free
path in
normal metal may be longer than this skin depth, so that electrons
may spend only part of the time between collisions in the field penetrated region. Pippard (1947a) showed how this makes the electrons
less effective as carriers of current and leads to a higher surface
resistance, as observed by H. London (1940) and Chambers (1952).
Under these conditions Ohm's law (IV. 14) can no longer be a valid
approximation; the current at a point must be determined by the
the
(IV. 13)
where a is a constant of order unity. (/) is thus an effective range of

coherence which has a size (w 10 " 4 cm) characteristic of the metal in
a pure superconductor, but which becomes limited by the normal
electronic
10- 4 cm.
mean
free path as the latter
becomes much smaller than
integrated effect of the field over distances of the order of the

free
mean
path (see Pippard, 1954). The details of this so-called anomalous
44
skin effect were
worked out by Reuter and Sondheimer
(1948),
who
derived that
JCR)_
3a CR(R-E)e- R "dT
4ir/J
(IV. 15)
is just the expression IV.9 for the range of coherence derived

from an uncertainty principle argument, with a = 018.
From P2, the penetration depth A as defined by IV. 1 can be
This
evaluated explicity in two limiting cases:
where a is the d.c. conductivity and / the mean free path. The form
of this equation ensures that in the case of a rapidly varying field the
current density at a point R is determined by the integral of the field
over a distance comparable to the mean free path /.
In a superconductor of range of coherence , the current density
at a point in the case of a rapidly varying field should also be deter-
mined by an integral of the field over a distance of the order of g, and

not, as is implicit in the London equation as well as in PI, by the field
variation over a quasi-infinite distance. Because of this analogy to the
anomalous conduction
in a
normal metal, and because some special

known, Pippard (1953)
solutions of equation IV. 15 were already
proposed as the basic relation for the electromagnetic response of a

pure superconductor the equation
3ne 2
J(R)= -
4n$
Somewhat misleadingly, as
London equation is a truly
R(R-A)e~ R ltdr
mS
this
(IV.P2)
R*
erroneously implies that the basic
local relation,
P2
is
called the Pippard
non-local relation.
Sommerhalder (1962) have observed this effect.

The validity of P2 is strongly supported by Bardeen's proof ([5],
pp. 303 ff.) that an energy gap in the single electron spectrum requires
a non-local relation between current density
BCS
and vector potential. In

theory leads to a relation entirely equivalent to P2 if one
for
5<
for
g> A, (Pippard limit).
A,
(London
feM
nv
/7re(0),
striking
BCS
value
g,
= 0l8hv
/k B Tc
(IV.17)
(IV. 1 8b)
agreement with the
chapter will mention
BCS value
of 0-18, as cited in IV.17.
how measurements
of the transmission of
strong support to this value.

Peter (1959) has solved the Pippard non-local relation
case of cylindrical superconducting films of thickness
radius
r.
He
finds that
film to a value
the energy gap at 0K. Substituting the

3-52k B Tc IV.16 becomes
(IV. 18a)
infrared radiation through thin superconducting films lends further
(IV. 16)
is
limit),
The second of these is the one applicable to the case of an infinite

mean free path, and correctly predicts a penetration depth into very
pure superconductors which is much larger than the London value.
IV. 18a is identical to IV. 12 obtained directly from PI. This is of
course a reflection of the fact that PI is the limiting form for <^ A of
the more general equation P2.
Equations IV. 18 show that the range of coherence of a superconductor can be calculated from absolute values of the penetration
depth. Faber and Pippard (1955a) have in this way obtained values
-5
of 2-1 x 10
cm for tin, and 12-3 x 10 -5 cm for aluminium. These
values differ very much, but when substituted into equation IV.9
together with known values of Tc and v (from anomalous skin effect
data [Chambers, 1952]), both correspond to a = 015. This is in
Hi such
an external
field
's
P2 for the
d < A and
penetrates through the
that
HJH^Vrd^faFitld).
&=
2e(0)
V(Zolt)*L
1/3
assumes
where 2e(0)
A.-
later
This relation leads to a reversal of the phase of the magnetic field

penetrating into a superconductor (Pippard, 1953). Drangeid and
fact the
45
Superconductivity
(IV. 19)
the range of coherence in a specimen of unlimited mean free path,
and can be calculated from IV.17; is the actual range of coherence

in the film, and A should be the London penetration depth as calculated from IV.5 and IV.6. Schawlow (1958), however, has shown that
46
good agreement with
Superconductivity
measurement on
(Gor'kov 1959b) that the mean free path dependence of this aspect of
the range of coherence is given by
can be found by
substituting for A the empirical value for bulk samples (510 A) and
considering as being determined by the size-limited mean free path
of the electrons in the films. A similar analysis has been used by
Sommerhalder
It is
his
tin films
(1960).
now generally accepted that whenever one applies the equation
of the Pippard theory (or those of the Ginzburg-Landau treatment

to be discussed presently) to the case of small or impure specimens,
oX-
1/2
47
(IV.21)
(0
a function of the mean free path shown graphically by Gor'kov

and approximated to within about 20 per cent by the simple expression
(Douglass and Falicov, 1964)
x(/) is
one obtains good agreement by using for the

in
a bulk sample, not the London value
A^.
ideal penetration depth

but rather the depth deter-
mined experimentally. For example, the results of Whitehead (1956)

on the magnetic properties of mercury colloids were shown by
Tinkham (1958) to be in excellent agreement with the prediction of
the London limit of the Pippard theory if one modifies equation
IV.18b and writes
where X b
is
now
\W
In the limit
<^
IV.21 thus reduces to
The
with
(IV.20)
relatively
mean
= V(to 0-
the empirical penetration depth for a bulk sample
(IV.23)
slow variation of this aspect of the coherence length

path is essentially due to the fact that not every
free
electronic collision destroys the superconducting coherence.
The other aspect of the range of coherence
and takes the place of the London value A L The mean free path / is
limited by boundary as well as by impurity scattering. Ittner (1960a)
(IV.22)
(s4
x(/)
is
that
it
determines the
distance over which the magnetic field or the vector potential at a
given point influences the current density. This
is
expressed by the
has similarly found that such a modification of the Pippard equations

adequately predicts the results of the observations by Blumberg (1 962)
Pippard equation IV.P2.

actual
mean
critical field of moderately thin films. In analysing the magnetic

behaviour of small (or very impure) specimens, for which * / <^ A, it
is
thus in general possible to obtain adequate precision without
attempting to solve the
difficult relation IV. P2. Instead one can use

IV.20 to calculate the penetration depth, and then substitute this value
of A into the London equation IV.10.
In discussing the mean free path dependence of the coherence
length one must
superconductor
remember
in
that
two subtly
tioned in Section 4.3,
is
it
is
related to the behaviour of a
different ways.
One of
these, as
men-
the distance over which the order parameter
of the superconducting phase varies. It is this aspect which, for

example, in Chapter VI will enter into the discussions of the width
of a boundary between the normal and superconducting phases.
It
follows from Gor'kov's analysis of the influence of impurities
is
important
in this application is the
distance between electron collision, so that
tion IV. 13 applies. This
of the
What
means
now
equa-
that
(IV.24)
/ <g
It is this mean free path dependence which enters, for
example, into equation IV.20.
for
The Ginzburg-Landau phenomenological theory
49
With these one then finds from V.3, remembering that the free energy
difference between the phases equals the magnetic energy, that
CHAPTER V
=
Ht2 _
The Ginzburg-Landau
47ra
47r(rc -r) 2/fl - x2

(V.5)
P
Near
Phenomenological Theory
Tc
indeed
is
\8T/ T=Te
Pc
known
to vary linearly with (Tc -T), so that
the correctness of equation V.5 justifies the assumptions V.4. All
In 1950 Ginzburg and Landau (G-L) introduced a phenomenological
further
thermodynamic manipulations are now
approach to superconductivity which, like that of Pippard, modifies

the absolute rigidity of the superconducting order parameter or wave
function which is implicit in the London model. Although the theory
and
other conclusions drawn using V.4 are restricted to tempera-
was
originally formulated so as to reduce always to the 'local'
London equations in zero field, Bardeen
(1954) has shown that it can

be modified so as to be compatible with a non-local equation of the
Pippard type. Furthermore, Gorkov (1959, 1960) has derived the G-L
equations, under certain conditions, from his formulation of the
BCS
G-L introduce an order parameter >p which they normalize so as to

2
= n s where n s is the density of the superconducting elec\*fi\
ip is thus a kind of 'effective' wave function of the superconducting electrons. According to the general Landau-Lifshitz theory
of phase transitions (1958), the free energy of the superconductor
trons,
depends only on
peratures near
tures very near
and can be expanded in series form for temIn the absence of an external field, the supercon-
\ifj\
Tc
ducting free energy (per unit volume, as are all equations

(7,(0)
= GB (O) + o#| 2 +(|8/2)|0| 4
Minimizing the free energy with respect to
2
\<p\
listed) is
then
(V.l)
Tc
Both Bardeen (1954) and Ginzburg (1956a) have
full superconducting range

by introducing different forms for a(T) and @{T), the former using
expressions based on the Gorter-Casimir two-fluid model.
The outstanding contribution of the G-L model in any temperature
range arises from its ability to treat the superconductor in an external
field
H H
now increased not only by the

e
c The free energy G s (He) is
volume term H*/9v, but also by an extra term connected with
.
the appearance of a gradient of
M>l
=-/A
i/j,
as
ifj
is
not completely rigid
in the
Such a gradient would contribute to the energy in

analogy to the kinetic energy density in quantum mechanics which
depends on the square of the gradient of the wave function. Introducing this extra energy is equivalent to requiring that not change
presence of
e.
*/>
too abruptly.
One is thus
led to a concept of gradual, extended varia-
tions of the superconducting order
parameter quite analogous to
Pippard's model of the range of coherence.

In order to preserve gauge-invariance,
term to be
yields the zero field
G-L assume the extra energy
J-L/^-âJ
equilibrium value
2
possible, but they
considered extensions of the model to the
usual
theory.
make
all
(V.6)
(V.2)
In the immediate vicinity of Tc one can assume that the coefficients a
where A is the vector potential of the applied field, and e* a charge

which, as stated in the original version of the theory, 'there is no
reason to consider as different from the electronic charge'. Modifica-
and
tions of this view will
from which
/?
(7,(0) - (7(0) =
-<x /20.
(V.3)
have the simple form

*(j)
jB(D
= p(Tc ) -
(rc -r)(sa/ar) r=re
t2
(V.4)
and
48
fie
be discussed presently.
G-L thus write
G s(He ) =
m~M
*
GM + fr+Â
Uc-W*~A
12
-
(V.7)
50
Superconductivity
One must now minimize

leads to the
with respect to both
this
tp
and to A, which
Note that with
geometry
this
two equilibrium equations:
H=
curlA
~
dz
2m\
(V.G-L1)
The meaning of
dtfj*
these equations
becomes
clearer
by introducing a
dimensionless parameter k defined by
V2 A =
-^J, =
c
t^'w^-W^
mc
2e*
KT
:=
h
Aire*"'
+
In a very
weak
stant (that
is,
A.
4>
A-ne*
0o>
lôl
iff
remains practically con-
and G-L2 reduces
mc'
Ag-
where
A=
Aire*
to
The
mc2
mentally,
C A.
(V.8)
and
be expressed.
G-L
c is
field, k,
and
are the three
theory which are to be determined experi-
in terms of
(V.12)
4ne* 2 ifa
again denotes zero
subscript
parameters of the
(V.ll)
<
(V.G-L2)
the function
V0 = 0,
V2 A
I0I
mc
HxO,
field,
rigid),
.,/ZcAq,
.-,
which various
the bulk critical
field.
field
is
weak
tion depth of a superconductor in the
and
size effects
can
the empirical penetrafield limit,
and
is
the
quantity which through equation V.12 determines the zero field
Here, as in V.2, the subscript
denotes the zero field value. This of

London's expression (B). Non-local versions of the G-L
treatment are obtained by substituting an integral expression for the
second term in V.6. In its present local form the G-L treatment is
course
is
just
restricted to temperatures near
Tc
for
two reasons:
in the first place
equilibrium value of the order parameter
i/jq. For a bulk sample conwas discussed in the previous

chapter, and this in turn affects both O and k.
k can be determined in a number of ways, two of which follow
directly from the defining equation V.
In the immediate vicinity of
Tct the experimental variation of A (/) can be expressed by IV.7:
taining impurities A
increases, as
1 1
because of the simple forms assumed for the functions a(T) and fi(T),
and secondly because only near Tc is A > and can the non-local
electromagnetic character of superconductivity be ignored.
The
set
G-Ll and G-L2 of coupled non-linear equations
in
ifj
and
A have been solved for essentially one-dimensional problems. Taking

the z-axis to be normal to the infinite superconducting boundary, the
field
H along the>--axis, and the current J
x-axis,
and potential
Also one can write
A along the
one obtains (using V.l)

2
</
dz
-tN**w^*-t^-*
^4
A
2
dHr
dT T=Te
so that
dH
8/jV dT T=T
mc 2
(V.10)
xAT,
Thus k
is
xT 2 xX 4 (0).
seen to be temperature independent, at least for
(V.l 3)
T& Tc
52
Superconductivity
One can
from the
also use the expression for the penetration depth derived
BCS theory to be,
very near
Tc
larly in
53
measurements used to evaluate A L (0), and in part, particuthe case of aluminium, due to the large value of because of
skin-effect
>
which non-local conditions set in very close to Tc The values of k

calculated from supercooling are probably the most reliable.
In terms of the parameters k, Aq, and
c , equation (V.9) reduces
.
-^
V2
(l
_-./!
_y?/ik-
J/2
V2 \ATj
so that
,*2
,2
4/i
2
,
dH
dT t=t
x7?xAf(0).
(V.14)
where now A L (0)
is
the
London penetration depth
111.13 using the actual free electron density n. This
from the value of the normal
state
calculated
from
resistance
to
Ginzburg (1955) pointed out already before the formulation of

theory that values as calculated from V.13 and V.14 could
be made to agree very well with those obtained from supercooling
data by taking e* = 2 or 3e. More recently Gor'kov (1958) has formution.
BCS
BCS microscopic theory in

terms of Green's functions, and was able to show (1959, 1960) that
the G-L equations G-Ll and G-L2 are identical to his expressions
lated the electromagnetic equation of the
Tc when ip is taken to be proportional to the energy gap, and

when one takes e* = 2e. This again is an indication that the current
carriers in superconductivity are the doubly charged Cooper pairs.
near
this value
of e*, V.13 and V.14 yield
*c= 108 xlO 7
and
= 216xl0
= 0, V.9' is satisfied in the absence of an external

{A = 0) by ip2 = ipl; difi/dz = 0. In other words, the presence of
the phase boundary as such has no influence on the function tp, which
the boundary, z
field
has the same value
tp
everywhere. In the presence of an external
field
however, this solution no longer applies, and one must integrate
V.9' and V.10 with the boundary condition

the condition
H = dA/dz = H
and
e,
difi/dz
tp
= ipl for z--co, and

= 0. This integra-
for z
cannot be carried out exactly. Neglecting higher order terms,

however, one finds equations for
and for A as functions of z. At
tion
i/j
= 0,
the value of
tp is
CV 13)
'
4(+V2)
ô
m 0- 1 , this equation predicts a decrease of ip by only

about 2-3 per cent when e = c It is not surprising, therefore, that
the change in penetration depth with field is also very small. This can
With values of k
dH
dT T=T
tMo),
(V.130
= ipl, and
dz
At
is
use results on supercooling, as will be discussed in a subsequent sec-
With
tp
can be calculated
anomalous skin
(Chambers, 1952).
Another method of calculating k for a given superconductor
the
Far from the phase boundary, for z-> o,
dHc
dT T=T
Tc X L (0).
(V.140
be calculated formally by using the defining equation IV. 1 from which

one finds that, with a weak measuring field normal to
For
tin,
the
first
of these yields k
= 0-158,
values which are in excellent agreement.
the second 0-149,
two
8(k+V2) 2 # 2
(
For indium, however, the
respective values are 01 12 and 0051 (Davies, 1960; Faber, 1961).

For aluminium, the equations yield 005 and 001 (Davies, 1960).
This lack of agreement may be in part due to errors in anomalous
An
For a measuring
field parallel to
(V.16)
e,
the effect
is
tripled.
54
Superconductivity
It is
ifj
evident that in the limit k-*0, the effect of the external field on
vanishes, so that one returns to a situation formally
and on A
CHAPTER
London picture. It must however be noted that even

deduced from the empirical value of A As a result
equivalent to the
for k
= 0,
one can
j/tq
is
in certain cases,
VI
such
as, for
example, the treatment of very
thin films, allow k to vanish without necessarily reducing the

treatment to the London one.
The Surface Energy
G-L
6.1.
The surface energy and
the range of coherence
wave
on a
boundary between the superconducting and normal phases. H.
London (1935) already pointed out that the total exclusion of an
Closely tied to the range of coherence of the superconducting

functions
is
the existence of an appreciable surface energy
external field does not lead to a state of lowest energy for a super-
conductor unless such a boundary energy exists. In the presence of

an excluded external field,
e the energy of a superconductor in-
creases by Hg/Sir per unit volume. It would, therefore, be energetically
more favourable
for a suitably shaped superconductor to divide up

number of alternately normal and superconducting
layers such that the width of the latter is less than A, and that of the
former very much smaller than that. The resulting penetration of the
into a very large
external magnetic field into the superconducting layers
much reduces
the magnetic energy of the sample, while the extreme narrowness of

the normal layers keeps negligible their contribution to the total free
energy. This situation
is
made energetically unfavourable by the

To make each superconducting layer
existence of a surface energy.
narrower than A, a slab of thickness c/must have d/X such layers. This
is avoided by an interphase surface energy cc, per unit surface whose
contribution exceeds the gain in magnetic energy, that
is:
Hid
2d
'
(VI.l)
8tt
where the energies have been calculated for a volume of slab of unit
surface area.
Hence
>
XH[
28tt
55
(WW)
Superconductivity
56
The surface energy
It is convenient and customary to express the surface energy in terms

of a parameter A ' of dimensions of length, such that
C is the configurational boundary such that if #" dropped

C after being constant up to that point, one would
sharply to zero at
(VI.2)
have the same superconducting free energy as the actual amount. The
free energy per unit volume of the superconductor is lower than that
(VI.3)
normal state by an amount Hc/Stt. A configuration boundary

shown on the inside of the magnetic boundary is essentially equivalent to a reduction of the superconducting volume and hence an
increase in the total free energy by an amount equal to HcI%t times
the distance C-M per unit area of interphase boundary. The intro-
8tt
Thus one
Similarly
57
in the
sees that
as
A'>
duction of the Pippard range of coherence thus leads to a configurational
boundary surface energy A
'
w . From this one must subtract
the decrease in energy due to the penetration of the

indicates that the distance
C-M
field.
Figure 16
corresponds to the resulting net
surface energy parameter
A m -A.
Position
Fio. 16
is
H H
the condition for the diamagnetic behaviour of superconductors.!
Empirical values of
'
for pure superconductors turn out to be an
is
of the externally applied
field
iV and
along a direction perpendicular to
One can
two effective boundaries, indicated by

and C.
is the magnetic boundary defined so
that if inside the superconductor B =
and then dropped
c up to
off sharply to zero, the total magnetic energy would equal the actual
value, given by the integral of BH/Stt over the entire superconductor.
the s-n interphase boundary.
define
t F.
London
detailed field
pp. 125-130) has shown that taking into account the

penetration leads to the condition A' > A.
([2],
field
equal to
H(z)-Hc
-MH = -
intimately related to the Pippard range of co-
herence. Figure 16 shows the variation of the order parameter
ducting phase the increase in the free energy in the region where
is changing is given by V.6; in addition there is a reduction of the
energy due to the penetration of the
order of magnitude larger than the penetration depth.
The surface energy
(VIA)
The condition for the Meissner effect is that f > A, i.e. that A > 0.
The Ginzburg-Landau theory was formulated so as to lead explicitly to the existence of a surface energy, which arises as in the
Pippard approach from the gradual variation of the order parameter
*p over a finite distance, from the zero value in the normal region to
its full equilibrium value in the superconducting domain. Again the
surface energy is that amount which is needed to equate the energies
= c In the superconof the two phases in equilibrium, with
e
(VI.5)
If,-
4tt
is the value of the penetrated field at any point inside the
superconducting region. Thus the surface energy is given by the
integral of the difference between the superconducting and normal
where H(z)
free energies
over the entire superconducting half-space

00
G s {H,z)-
H:
H(z)Hc H\
.
4tt
+-P-G
/I
(0)--^
(VI.6)
The surface energy
Superconductivity
58
tent,
which gives for A
59
and ultimately to become negative. This has indeed been inferred
by Pippard (1955) and by Doidge (1956) from their studies of flux

trapping and the superconducting transition in dilute solid solutions
of indium in
Direct measurements of J in such alloys by Davies
tin.
(1960) has demonstrated
CO
its
decrease with shortening
/,
and Wipf
work
(1961) has traced this decrease to actual negative values. All the
where A
ductor,
is
the empirical penetration depth into a bulk supercon-
and k the dimensionless parameter defined
in the previous
chapter. This equation requires numerical integration.
For k <^
A becomes negative at a critical concentration of

approximately 2-5 atomic per cent of indium in tin.
cited indicates that
Changes of A with decreasing mean
it
reduces to
A =
1-89-
(VI.8)
The
free path also follow
numerical integration of VI.7, which yields that
is thus, according to the G-L

10A for most pure elements. The
the G-L model and Pippard's range of
thickness of the transition layer
This prediction
is
>
A<
from the
for
(VI. 10)
1/V2.
in good agreement with the work on tin-indium

Chambers (1956) found that the addition of 2-5
theory, of the order of A /k
alloys just cited.
intimate relation between
atomic per cent of indium to tin about doubles the penetration depth
coherence
first
is
shown by Gorkov's
principles.
terms of the
He
finds
critical
velocity of the metal.
derivation of
G-Ll and G-L2 from
an expression for the
G-L parameter k in
momentum and
temperature and the Fermi
Using equations IV. 17 and 111.13,
compared
to pure tin, so that according to the defining equation k
should be increased by a factor of approximately four. This would
make k
0-6,
which
close to the theoretical value of 0-707.
The surface energy and the intermediate state

Chapter II mentioned that a superconducting specimen with a demag-
6.2.
A
0-96
?-
(VI.9)
50
G-L
theory are of comparable
size.
netization coefficient
magnetic
Comparing VI.8 and VI.9 shows that, as expected, the Pippard range
of coherence g and the surface energy parameter A as derived from
In short, both approaches
necessarily lead to a positive surface energy because both require that
field
e satisfies
stantiated the suggestion of
Landau
It therefore also follows from both theories that the surface energy
must decrease and may even become negative when the range of coherence decreases and the penetration depth increases. Equations
IV.12 and IV.21 show that this is just what happens to A and to when
one
would, therefore, expect A to decrease with increasing impurity con-
c.
All
(1937, 1943) of a laminar struc-
normal layers
approaches
B = Hc
c.
while
Landau
B=
Clearly the width of the laminae
is
further suggested that in
in the superconducting ones.
strongly influenced by the
nitude of the interphase surface energy A. Indeed
field.
free path of the superconductor decreases. In alloys
-D)HC <HC < H
normal and superconducting layers. The thickness

of the normal layer grows at the expense of the superconducting one
as the external field
mean
(1
ture of alternating
the
length comparable to the difference between this distance and the
the inequality
experiments on the detailed structure of this state have generally sub-
the characteristic superconducting order parameter vary over a finite
penetration depth of an external magnetic
D is in the intermediate state when the external
distance. Both, therefore, obtain a net surface energy parameter of
the
is
this simplifies
to
the
as
for an infinite plate of thickness

(>
1),
the
sum a
Landau
mag-
finds that
L oriented perpendicularly to the field
of the thickness of the superconducting layer, a s ,
and that of the normal one,
a, is given
by
LA
(VI.11)
60
The surface energy
Superconductivity
where
is
a complicated function of the ratio of the external to the
e jHc Numerical values for Y(HJH have been calcuby Lifshitz and Sharvin (1951). A typical result is a value a 1 -4
= 0-8. A similar equation has also been
for L = 1 cm and
C
derived by Kuper (1951), who predicts numerical values which are
smaller by a factor of two or three. Typical experimental results fall
in between these predictions.
These results have been obtained by a variety of methods, all
making use of the fact that in the intermediate state lines of flux pass
only through the normal laminae, and emerge from the specimen
wherever these laminae end on the surface. A number of authors
(Meshkovskii and Shalnikov, 1947; Shiffman, 1960, 1961) have
critical field
lated
mm
HJH
i\,\t\
e2&
&&
The
61
series
superconducting laminae. The gradual shrinking of these areas with
and the corresponding growth of the light, normal

The domains show a peculiar type of
corrugation, not predicted by the Landau model, and adding to the
surface to volume ratio of the laminae.
increasing field
regions
is
clearly visible.
Phase nucleation and propagation

H. London (1935) pointed out that the existence of a positive surface
energy at the interphase boundary must under suitable conditions
give rise to phenomena analogous to superheating and supercooling
6.3.
in the
i\i\i\i\
shows a
of photographs obtained by Faber

(1958) with superconducting tin powder on an aluminium plate,
taken with increasing external field oriented perpendicularly. The
dark areas are covered with powder and are therefore the ends of the
frontispiece
more familiar phase transitions. In
phase transition cannot exist at
all if
fact a stable nucleus for the
the surface energy
is
everywhere
Indeed there are many experimental observations that when

a specimen is placed in a greater than critical magnetic field which is
positive.
then reduced, the normal phase persists in
fields less
the superconducting equivalent of supercooling.

Fig. 17
tion curve illustrating this
'supercooling'
passed very fine bismuth wire probes across the surface of a specimen,
and observed the magnetoresistive fluctuations in the probe resistance
when passing from
and cluster on the ends of the superconducting laminae, as shown
schematically in Figure 17; the latter will be attracted by flux and
move onto
the ends of the normal laminae.
The
resulting
powder
patterns can be easily seen and photographed. Another optical
method
is
shown
c.
This
is
in Figure 18.
The degree of
characterized by the parameter Si
= H IHc
t
this
or by
the parameter
<j>,
m 1-af - {Hl-Hf)IHl
(VI.12)
the end of a normal lamina to that of a super-
conducting one. Others have spread on the surface of a flat specimen

fine powder, superconducting (Schawlow et al, 1954; Schawlow,
1956; Faber, 1958; Haenssler and Rinderer, 1960) or ferromagnetic
(Balashova and Sharvin, 1956; Sharvin, 1960). The former will shun
flux
is
than
A typical magnetiza-
consists of placing a thin sheet of magneto-optic glass (for
tin, 5/ is commonly of the order of 0-9; in aluminium the degree

of supercooling is usually much larger, and values of St as low as 002
For
have been observed.

Superheating is the name given to the persistence of the supercon.
normal phase, probably because of large local field values resulting

from demagnetization effects. Centre portions of long tin rods could
made to superheat to S = 1-17.

Much information on the nucleation
example, cerium phosphate glass) on the specimen surface, and

observing the reflection of polarized light (P. B. Alers, 1957, 1959;
be
De
and on
Sorbo, 1960, 1961).
fields above
This is very rarely observed.
c
Garfunkel and Serin (1952) have shown that this is so because the
ends of any conventional specimen cannot resist the initiation of the
ducting phase at
its
of the superconducting phase
relation to the surface energy has been obtained by
Faber
62
Superconductivity
The surface energy
on supercooling in tin
and aluminium. His technique consisted of winding on a long cylindrical specimen several small, spaced coils the field of which could be
made to add or to subtract from a field produced by a large solenoid
surrounding the entire sample. With the sample normal, the field of
the solenoid could be lowered to some value between H, and
c and
the field could then be lowered locally by a suitably directed current
through one of the smaller coils. The superconducting phase then
(1952, 1955, 1957) in a series of measurements
nucleated in the portion of the sample under the
coil,
and spread
63
some of which exist in even the purest specimens. This

supported by Faber's finding that any handling of the specimens
between measurements could change the location and effectiveness of
of local strain,
is
the nucleation centres. Strained regions probably contain a high
density of dislocations.
By correlating the size of the nucleating field t with the time it

took to be effective, Faber could deduce the depth of the nucleating
flaw below the sample surface, and found this always to be between
-4
-3
10
and 10
cm. Etching down the surface to this depth would
uncover further flaws extending to a similar depth. It is thus reason-4-10~ 3
cm as being the approximate size of the
nucleating flaws. At temperatures well below Tc this length is considerably bigger than the width of the interphase boundary, and one
able to take 10
can therefore imagine such a flaw to consist of a region of negative

surface energy surrounded by a shell across which the surface energy
increases to the
(1952) has
normal
shown
positive value of the bulk material.
that there
is
Faber
a potential barrier against the further
growth of this nucleus until one has reached a degree of supercooling

such that
,
<f>,
Hc
H,
Applied Field
He
Fig. 18
where A
is
flaw size,
tected by pick-up coils distributed along the specimen.
At a
given temperature the degree of supercooling varied confrom point to point in a given specimen but at a given point
siderably
frequently remained reproducible even when in between measurements the specimen was warmed to room temperature. This indicated
that nucleation must occur at particular spots, some of which promote nucleation more effectively than others. As the surface energy
can be lowered and may even become negative due to strain, it is
reasonable to assume that the spots favouring nucleation are regions
(VI. 13)
the surface energy parameter, r a length of the order of the
and
//
a small constant determined by the flaw's shape and
demagnetization factor.
perature variation of
rapidly throughout the sample. In this fashion supercooling could be

studied at different portions of the sample. The transition was de-
-+n,
</>,
The measurements in fact show that the temis very much like that of A, as determined
from other experiments.

Both Faber (see Faber and Pippard, 1955b) and Cochran et al.
(1958) found that supercooling was much enhanced after a specimen
had been placed temporarily in a field much higher than the bulk
critical value. This shows that certain superconducting nuclei can be
quenched only by such a high field and supports much other evidence
that in a non-ideal specimen there can exist small regions of high
strain which remain superconducting in very high fields.
By means of a series of pick-up coils along his specimens, Faber
(1954) was able to observe the propagation of the superconducting
phase once the transition had been initiated at some nucleus. From
CHRIST'S COLLEGE
IDDADV
I
Superconductivity
The surface energy
growth of the superconducting phase

The nucleus, which is always near
the surface, first expands to form an annular sheath around the specimen. This sheath then spreads along the entire length of the specimen
with a velocity of the order of 10 cm/sec, and finally the superconducting phase spreads inwards to fill the entire sample.
The growth of a superconducting region is limited principally by
the interphase surface energy on the one hand, and by eddy current
damping on the other. If there were no surface energy, the superconducting phase could propagate by means of very thin filaments
which displace no magnetic flux and therefore create no retarding
The second of these functions appears to give a good fit to various

results for tin over a rather wide range of temperature, but Faber's
induced currents. For a sheath of
equation IV. 17, as well as empirical values for A
64
his results he infers that the
occurs in a series of distinct stages.
finite thickness, on the other hand,

which propagates in the presence of an external field c eddy currents
are generated, and the magnetic energy gained in the phase transition
is balanced by the unfavourable surface energy as well as the eddy
current joule heating. Faber (1954, 1955) has shown that the resulting
velocity of propagation for very pure specimens under optimum conditions is given by
A(I/o)A- (lHc
aluminium data can be represented only by the first of these. There

seems to be a definite difference in the temperature dependence of the
surface energy for these two metals which is at present not understood.
The uncertainty
The
table
below
lists
for tin
and for
Element
way by Faber, as well as those

ways by Davies (1960), Sharvin (1960), and
Shiffman (1 960), can be fitted by a number of empirical functions of
temperature. According to the G-L theory, the surface energy should
have the same temperature variation as A at least very near Tc where
k is independent of temperature. Hence one would expect
different
= J(0)(l-/4 )- ,/2
(VI.15)
Aluminium
Indium
18
Tin
0-50
16
4-4
0-64
2-3
2-3
0-51
Supercooling in ideal specimens
Near
Tc A becomes
,
large,
and the flaws
nucleation centres. Measuring
some information on supercooling in

(1957) has found for aluminium, S,
al.
lose their effectiveness as
in this region can, therefore, give
unflawed material. Faber
ideal,
= 0036,
1.
(VI.150
for In 016,
and
for
Sn
(1958) for aluminium are in reasonable
agreement. These results can be compared with theoretical predictions arising from the G-L model. Equation V.9' has an interesting
consequence with regard to the normal phase. One would expect that
with
described by the equation would be
e S*
c , the half-space
= 0. This is indeed a solution, but the equation
entirely normal, with
H H
</<
is
also satisfied by a second solution with
this solution
#/>
<^ 1,
so that H(z)
ifj
# 0.
Assuming that
for
everywhere, and remem-
becomes
for/
(0).
3-4
bering that in the geometry chosen A(z)
which can also be written
j-o--w
number
10 5 Ao(0)
(cm)
10 5
(cm)
10 <d(0)
(cm)
0-23 values of Cochran et
values of A(T) obtained in this
A(t)
of course
the best available values of ^(0) for a
The
of metals, from a comparison of all available experimental data. Also

listed are values of > the range of coherence, as calculated from
6.4.
where / is the electronic mean free path in the normal phase, a the
normal electrical conductivity, and A is a constant of the specimen.
By measuring the temperature variation of v, Faber has used this
measured in
dependence of
(VI. 14)
equation to obtain the temperature variation of

aluminium.
in the temperature
introduces a degree of doubt about the extrapolated value at 0K.
-H ]/H y
e
65
7ES
= H(z)z,
the equation
Superconductivity
66
The surface energy
This has the form of a wave equation for a harmonic oscillator, which
known
is
(which
is
which vanish for z= co

the required boundary condition for the normal phase) if
to have periodic solutions
tp
V2^(/+i), =
67
For superconductors with a dimension small compared to X /k

the order parameter is essentially constant throughout and one can
solve the G-L equation with the simplifying assumption k a 0. The
,
critical fields
of supercooling are then given by
0,1,2,...
tic
In other words, for any value of
k,
conductor becomes unstable with regard to the formation of laminae

of superconducting material when
HJH =
C
K/(n +
of which the highest value, with n
J)
< B and
the field
IHc = V(2)k.
c2
is
c2 is
2V5^H
a
V8jHc
that of
and
(VI. 18)
1
/V2.
most pure superconductors,

field to which the
then the lowest
normal phase can persist in a metastable fashion.

c2 is thus the
lower limit to which an ideal superconductor can be supercooled,
and therefore in the region very near Tc one would expect the experimental value of S t to equal \/(2) k (Ginzburg, 1956, 1958a; Gor'kov,
1959b,
= 0, is
c2
= V6-/Z,
for a slab of thickness la,
(VI. 17)
V2,
A distinction must now be made as to whether k < / V2 or k>
C2
for a sphere of radius a,
c2
In the former case, which
the normal phase of the super-
c2
for a cylinder of radius r (Ginzburg, 1958a).
Hc2
For all
these geometries
decreases with increasing specimen size, approaching
tonically the value given
mono-
by VI. 18, which depends only on the value
of k characteristic of the material.
The compatibility of the G-L theory with the Pippard range of cosize, or mean free
herence under those circumstances of temperature,
c).
The values of k calculated in this fashion from Faber's measurements of St are: 01 64 for tin, 0112 for indium, and 0026 for aluminium. The first two of these agree very well with k values deduced
from experimental penetration depths. In aluminium the lack of
agreement is probably due to the appearance of non-local effects very
close to Tc Ginzburg (1958b) has noted that this is more likely to
path which eliminate the need for a non-local electromagnetic formulation is brought out once again by the similarity of VI. 18 with the
corresponding expression derived by Pippard (1955). He finds, also
by minimizing the free energy, that

2 3A o
Hc2 - V jn
n
c-
(VI. 19)
invalidate calculations involving the penetration depth than those
regarding the surface energy and supercooling. Non-local effects
become important
when
for the former
when >
for the latter only
This differs from VI. 18 only by a numerical factor of order unity

since
6.5.
Thus K-values calculated from supercooling data are probably

most reliable, except for the effect discussed in section 6.7.
the
/.
Superconductors of the second kind
According to equation VI. 10, the surface energy becomes negative

when k > l/\/2. A similar conclusion follows from the Pippard nonlocal model when A > $ (equation VI. 4: seeDoidge, 1956). The existence of a positive surface energy was shown to be necessary for much
The surface energy
Superconductivity
68
of the magnetic behaviour usually found in superconductors.

therefore, not surprising that superconductors in
which
this
It is,
energy
is
negative display quite different characteristics. They are accordingly

called superconductors of the second kind.
For a bulk specimen of such a superconductor the volume
free
energy in the superconducting phase remains lower than that of the
normal one in external fields up to the thermodynamic value

c
defined by equation II.4. The negative surface energy, however,
makes it energetically favourable for interphase boundaries to appear
at field lower than
c and for superconducting regions to persist to
In the limit k
1/V2, H =H
cl
= Hc2 Goodman
.
69
(1962a) has inter-
polated between the latter value and those given by VI.21 to get a
k A numerical solution has

cl /Hc for all
been obtained by Harden and Arp (1963).
The magnetization curve predicted by the Ginzburg-LandauAbrikosov (G-L- A) model can be compared with experiment, as it is
graphical representation of
possible to determine the value of k for a specimen by independent

measurement. Gor'kov (1959) has derived an expression for k valid
when
the electronic
mean free path
is
much smaller than
the intrinsic
H
H Goodman (1961) has shown that this can already
,
fields
higher than
be deduced from the London model by the single addition of a

negative surface energy term.
The details of the behaviour of superconductors of the second

kind can be deduced from the G-L theory, which is equally valid for
k > \/\/2 as for k <
section
still
/\/2. In particular, the analysis of the preceding
holds; that
is,
the
normal phase has a
stability limit at
H given by equation VI. 18, which shows that for k > 1/V2,
H > H Abrikosov (1957) has used the G-L equations to analyze
field
c2
c2
in
some
detail the
magnetic behaviour of superconductors of the

in the magnetization
second kind, and finds the features indicated
curve shown in Figure 19 for a cylindrical sample parallel to an
Hcl
There is a complete Meissner effect only up to

= ci < c at which point the magnetization changes with
e
infinite slope. For values of k not much larger than 1 /V2, Abrikosov
predicts in fact a discontinuity. At somewhat higher field, the magnetization approaches zero linearly, with a slope
external field
Hc
H c2
Applied Field H e
Fig. 19
coherence length This was shown by

the convenient form
.
-4tt^=
1-18/(2^-1),
(VI.20)
and vanishes
c2
= V(2)kHc
The magnetization curve should be
ko
(VI. 18)
Abrikosov canvalues of k; for
fully reversible.
not solve the equations determining

1
(1962a) to have
+7-5xloy /2 p.
(VT.22)
entirely at
BL =
k>
Goodman
cl
for all
is
the parameter for the pure substance,
heat constant, in erg
ohm-cm. For
V(2)kHc i/Hc =
In k+ 0-08
(VI.21)
deg
-2
,
y the Sommerfeld specific

and p the residual resistivity in
tin this predicts quite closely the resistivity at
which the
surface energy becomes negative (Chambers, 1956).
Using
he obtains
cm -3
model
this equation,
Goodman
satisfactorily explains the
(1962a) has shown that the G-L-A

magnetic behaviour of substances
70
Superconductivity
The surface energy
Ta-Nb alloys investigated by Calverley and Rose-Innes

and his own U-Mo alloys (Goodman et ai, 1960).
Further-
such as
(1960)
more, recent magnetization measurements on Pb-Tl single

crystals
(Bon Mardion et ai, 1962), indicate a considerable degree
of reverDetailed quantitative verification of the G-L-A

magnetization curves, as is possible only near T was
provided by Kinsel et al.
c
(1962), who used In-Bi specimens to compare values
of k calculated
from equations VI. 18, VI.20, VI.22, and from
Harden and Arp's
values of ci /Hc The different values of k for a given
specimen agree
to within a few per cent. Similar agreement can
also be deduced from
the results of Stout and Guttman (1952)
on In-Tl alloys. The G-L-A
model is thus well substantiated.
sibility.
The negative
surface energy need not be due to a short mean

free
it is possible for the coherence
length to be shorter
than the penetration depth, even in a pure superconductor;
this is
path. In principle,
most
likely in superconductors with a high

Tc (cf. equationIV.17).
Indeed, Stromberg and Swenson (1962) have found
that the magnetization curve of very highly purified niobium
is that of a superconductor of the second kind, with a value of
cl and
c2 corresponding
to k ~ 1 1 This conclusion is consistent also
with the results of Autler
(1962) as well as of Goedemoed et al. (1963).
Kinsel et al. (1963) have found with their
In-Bi alloys that the
effective value of k as defined by equation VI.
18 rises gradually as
the temperature decreases below T increasing
by about 25 per cent
c,
as T approaches 0K. This agrees with the
calculations of Gor'kov
(1960). The experiments further show that
at any temperature
nor the size
effects to
be discussed
in the
71
next chapter can increase the
of a superconductor without limit. Both Clogston (1962)

and Chandrasekhar (1962) have pointed out independently that in
sufficiently high fields it is no longer correct to assume that the free
energy of the normal phase is independent of field. With a finite
paramagnetic susceptibility Xp (which was ignored in deriving equa2
tion II.4), this free energy is, in fact, lowered by an amount \X.H
critical field
Thus, in sufficiently high
fields, this
alone could already bring about
from the superconducting to the normal phase. The limit

on the critical field imposed by this mechanism is estimated to be two
or three hundred K gauss, and this is consistent with the results of
Berlincourt and Hake (1962).
a transition
The mixed state or Shubnikov phase

The magnetization curve of type II superconductors clearly shows
that for
< e < cl the material is neither in the usual supercX
6.6.
H H
conducting nor
region the
in the
normal phase. Abrikosov (1957) has called this
mixed state, and De Gennes ([14]) has suggested naming it

honouring the scientist who first suggested the
the Shubnikov phase,
= 1/V2
continues to be the critical value for the

onset of superThus a specimen with k ~ 0-65 at its transition
temperature is there a superconductor of the first kind,
but becomes
conductivity.
one
of the second kind at that temperature at which k

reaches the
critical
value.
The temperature dependent increase in k leads to a

corresponding
decrease of the surface energy. Specimens for which
k goes through
the value 1/V2 at some temperature are those for
which at that temperature the surface energy changes from being
positive to being
negative, as has been observed for indium alloys
by Kinsel
et al.
There
is
964).
reason to believe that neither a negative surface

energy
fundamental nature of type
II
superconductivity (Shubnikov et
al.,
1937).
It is
evident from the importance of the negative surface energy that
mixed
specimen must contain as large an area of

is compatible with a minimum of normal
volume. This could be brought about by a division of the material
into a large number of very thin normal and superconducting sheets
in the
state the
interphase surfaces as
or laminae
G-L-A
(Goodman,
1961, 1964; Gorter, 1964). According to the
mixed state consists of a regular array

of normal filaments of negligible thickness which are arranged parallel
theory, however, the
and are surrounded by superconducting material.

At the normal filaments the superconducting order parameter
vanishes, and then rises from these linearly with distance. It reaches
to the external field
its
maximum
value as quickly as possible, that
the order of .
filaments,
means
and
falls off
over a distance of
at the
over a distance of the order of A
that the field decreases to zero only
at distances at least of the order of A. This

6
is
The magnetic field has a maximum value

if
>
normal
.
This
the filaments are spaced
mixed
state structure
can
72
Superconductivity
The surface energy
be shown to have a lower energy than any laminar arrangement

([14], p. 111.81).
One can
that the order parameter
thus think of the mixed state as
material were pierced by a
if
the superconducting
number of infinitesimally
thin filamentary
holes, regularly spaced parallel to the external field
containing magnetic
flux.
From the
and thus each
discussion in Chapter II
it
there-
fore follows that the total flux associated with each normal thread
quantized in units of
is
This flux does not penetrate far into the

superconducting material because of superconducting currents circu<f>
lating in planes perpendicular to the filament. This creates a vortex

line of superconducting pairs along each normal thread, in striking
analogy to the vortices existing in liquid Helium II (Rayfield and
Rcif, 1964).
The
and the currents associated with an isolated vortex line

extend over a distance of about A. The interaction between two
flux
vortex lines can thus be appreciable only at distances less than
A.
This means that when the formation of vortex lines becomes energeti= ci they can essentially immediately achieve
cally favourable at
H H
a density corresponding to a separation of about A without creating

much interaction energy ([14], pp. III. 74ff.). This causes the abrupt
decrease of the magnetization at
cl predicted by Abrikosov and
verified experimentally. It is not certain, however, whether the

magnetization actually decreases discontinuously at this field or
whether it merely drops with an infinite slope. The former would
correspond to a first order transition with a latent heat, the

only to an infinity in the specific heat.
With the external
field increasing
beyond
cX
latter
more and more
vortex lines are formed until their spacing approaches
Mh
finite
except along the
normal filaments of
negligible
volume. Thus the material can still be considered as entirely superconducting. Abrikosov (1957) showed in fact that in the mixed state
one can characterize the material by a mean square order parameter
and that near Hc2 this varied linearly with the magnetization.
The correctness of this and therefore the validity of the vortex
structure has been substantiated by measurements of the specific heat
(Morin, et al., 1962; Goodman, 1962b; Hake, 1964; Hake and
Brammer, 1964) and of the thermal conductivity (Dubeck et al.,
y*2 ,
1962, 1964).
De Gennes and his collaborators
(cf. [14],
Vol. II) have studied the
properties of an isolated vortex line, as well as the interaction between

lines. This leads to possible collective vibrational modes (De
Gennes and Matricon, 1 964), as well as to a surface barrier inhibiting
the motion of lines into or out of the superconducting material (Bean
and Livingston, 1963; [14], p. 111.85), De Gennes and Matricon
such
(1964) have also suggested the possibility of investigating the vortex
of the mixed state by slow neutron diffraction. Preliminary results have recently been reported (Cribier et al., 1 964).
line structure
In an ideal type
II
superconductor, homogeneous and devoid of
lattice imperfection, the
vortex lines would be pushed out of the
material by the Lorentz force
if
the specimen carried any current
In any actual material,

motion of the lines is inhibited by defects and inhomogeneities
which form potential barriers by which lines the are pinned. Anderson
at right angles to the field (Gorter, 1962a, b).
the
(1963).
c2
964) and Matricon (1 964) have shown that a triangular

somewhat lower energy throughout the mixed state. This
changes the coefficient in equation VI.20 from 118 to 116.
al. (1
everywhere
remain uniform, so that bundles of lines move together.

This vortex or flux creep has been further discussed by Friedel et al.
Kleiner et
is
lines tends to
array has a
centre of the vortices, which are
(1963) has investigated the thermally activated 'creep' of lines at low

current densities, and has shown that on a local scale the density of
(Abrikosov, 1 957). According to Abrikosov, the vortex

lines form a square array at all fields except very near
cU but
as //nears
73
A fundamental feature of the vortex structure of the mixed state is
With
increasing current densities to creep changes into a
viscous flow of the lines, giving rise to resistive
phenomena (Anderson
this has been done
and Kim, 1964). Extensive experimental work on

by Kim era/. (1963, 1964).
Tinkham
(1963, 1964) has
like that of the
mixed
shown that
a quantized vortex structure
state occurs even in
pure films
if
they are very
74
Superconductivity
and placed in a perpendicular external field. This is in agreement

with magnetization measurements on such films by Chang et al. ( 963)
and penetration depth and critical field data of Mercereau and Crane
(1963). Guyon et al (1963) have investigated the dependence of the
critical field on thickness. For thin films so narrow as to contain
only
a single row of vortices Parks and Mochel (1964) calculated that the
free energy should have a minimum at values of the perpendicular
external field at which the vortex diameter just equals the film width.
thin
At Tc
should result in a corresponding minimum of the film

resistance. They have observed such minima and take this as direct
evidence for the existence of quantized vortices.
6.7.
this
Surface Superconductivity
As mentioned in Chapter V,
the
boundary condition applicable to
G-L order parameter W is that its derivative vanish. Saint-James

and De Gennes (1963) have shown that in an external field parallel to
the
CHAPTER
The Low Frequency Magnetic

Behaviour of Small Specimens
7.1. Increase in critical field
When one of the dimensions of a superconducting specimen becomes

comparable to the penetration depth, its critical magnetic field becomes much higher than that of a bulk sample of the same material
at the same temperature. This follows already from the basic GorterCasimir thermodynamic description, according to which the free
energy difference per unit volume between the superconducting and
normal phases is
Hi
Gn (0)-GM =
the surface this leads to the persistence of an outer superconducting
sheath up to a
c3
1-695
c2
The thickness of this sheath is of the order of .
In
Its existence, explicitly
an external
netization
field
M(He
by many experiments (see, for example, Hempstead and Kim,

Tomasch and Joseph, 1963), explains what had often been
a puzzling discrepancy between magnetic and resistive transitions.

The surface sheath exists also in Type I superconductors, but can be
only
= 2-40kHc
if
c2
so that
>
c.
As
Hc3 > H
c2
for k
= \/2kHc
>
it
follows
that
Under this condition,

way of obtaining k for Type I
materials (Strongin et al. 1964; Rosenblum and Cardona, 1964).
The existence of the surface sheath in Type I superconductors means
c3
a measurement of
c3
/Hc
is in
0-42.
fact a
supercooling experiments are carried out on cylindrical

in a longitudinal field, as is usually the case, the ideal lower
limit for super cooling is
c2 rather than
c2 (cf. section 6.4). Thus the
that
if
samples
experimental value of S, should be set equal to 1-695V(2)k and the

values of k thus calculated are therefore correspondingly reduced.
a superconductor acquires an effective
mag-
and becomes normal when
verified
detected
(VII.l)
field
H
1963;
VII
lie
M{H )dHe = -*
e
The
(VII.2)
077
under the magnetization curve, and it was

that for any ellipsoidal specimens VU.2
=
was satisfied when
Actually this is true only when one
e
c
neglects the penetration of the external field into the sample, which
lowers the effective magnetization and the susceptibility of the
sample, as shown by equations IV.2 and IV.3. The susceptibility
determines the initial slope of the magnetization curve; a lower x
means that the curve has to go to a higher critical field to satisfy
equation VTI.2. Clearly, assuming this curve to remain linear with
slope x right up to a critical field
s
integral is the area
pointed out in Chapter
ni
"I
Hi
Xo
(VII.3)
X
75
76
Low frequency magnetic behaviour of small specimens
Superconductivity
and
CVII.4)
11
Hauser and Helfand, 1962), and have been used by Lutes (1957) in the
interpretation of his measurements of the critical field enhancement
in tin whiskers.
v^3
=
7T
using the
for a <^ Aq,
It is possible to relate
(VII.5)
the thin film critical field to the basic super-
London equation to evaluate a =
IV.3 (Ginzburg, 1 945

[11 p. 172). Similar expressions can be derived for spherical and
cylindrical samples. The resulting equations agree well with the fre$ in
of the bulk material. The penetration

conducting parameters anti
depth appearing in VII.8 should be given by 1V.20, in which (/) is
determined by IV. 13 with the film thickness taken as the effective
mean
free
path (Tinkham, 1958). In the limit a
quently observed enhancement of the
critical field in small specimens

uses for the penetration depth A the appropriate Pippard
value as calculated from IV.20. This is a good example of how ex-
<
this yields
(Alloy*
(VII.8 ')
when one
pressions derived from the

fied value
The
London model can be used with
the modi-
of A (Tinkham, 1958).
field
enhancement calculated from the Ginzburg-Landau
theory leads to nearly identical results. The essential difference is that

because of the additional terms V.6 in the G-L free energy of the
superconductor, the penetration depth increases in the presence of an
external field (see equation V.16), so that the critical field for small
samples becomes even higher. For thin films of thickness 2a the

critical field is
(Douglass and Blumberg, 1962). The use of the thin film susceptibility
as derived by Schrieffer (1957) with non-local electrodynamics leads
to
20-40 per cent higher values of the numerical constant (Ferrell and
Glick, 1962;Toxen, 1962).
7.2.
High
The
size effect
field
threads and superconducting magnets
on the critical field is particularly striking in experiments using extremely thin evaporated films. In their experiment on
the Knight shift in tin, Androes and Knight (1961) used films of thickGinsberg and Tinkham
ness a 100 A and found
c (0) 25 kgauss.
(1960) saw no effect on the superconducting properties of their
10-20 A lead film in a field of 8 kgauss.
The equivalent of small superconducting specimens can exist also
in bulk material. In an inhomogeneous specimen there will be local
variation of the surface energy due to varying strain or to varying
sir
(VII.6)
la
where /(*) is the same function of k which appears

and is very small for small values of k.
For very thin films, a < A G-L find that
in
equation V. 1 6,
electronic
mean
free path. If locally the surface energy
lower than the value elsewhere,

this
which for very small k reduces
ti c
field
to
even when the surrounding material has become normal

1 955). Under these conditions one can thus have a situation
(Pippard,
quite analogous to that of small specimens: small superconducting
(VII.8)
the same expression which for thicker films gives the supercooling field
c2 Expressions similar to VII.6 and VII.8 have also
been derived for spheres and wires (Silin, 1951; Ginzburg, 1958a;
is
is sufficiently
may be energetically favourable for
region to remain superconducting in the presence of an external
regions exist in a matrix of normal material (Gorter, 1935; Mendels-
sohn, 1935;
This
it
Shaw and Mapother,
1960). If their dimensions are
small compared to the penetration depth, the critical

regions will be correspondingly raised, and
it is
field
of these
known (Faber and
Pippard, 1955b; Cochran et al, 1958) that such regions can persist in
78
Low frequency magnetic behaviour of small specimens
Superconductivity
high
fields.
many
In
instances these regions are threads which can
form continuous superconducting paths from one end of the
men
to the other, resulting in a resistive transition
speci-
much broader and
extending to much higher fields than the magnetic one (Doidge, 1 956).
are, of course, likely to touch each other in many places,
The threads
what Mendelssohn (1935)
resulting in
called a superconducting
sponge. The multiple connectivity of such a structure generally leads

to highly irreversible magnetic transition with almost total flux trapping. Bean (1962) has used a simplified model with which to calculate
the magnetization curve of such a sponge. He has confirmed some
features of this
model with an
artificial
79
which has been verified by Zavaritskii (1951, 1952). Note that as the
penetration depth is inversely proportional to 0, A(//) for thin films
even in fairly small fields (Douglass, 1961c).
is much larger than A
Douglass (1961a) has pointed out that because of the proportionality
of the energy gap to
/r,
by Gorkov (1959, 1960),

field dependence of the
Thus one can write
as derived
equations VII.9 and VII. 10 represent the
energy gap
in sufficiently thin films.
e\Hs)
for 2a
< V(5)A
(VII. 11)
filamentary superconductor
made by forcing mercury into the pores of Vycor glass (Bean et a/.,
1962). The possible relevance of this to superconducting magnet wire
will be discussed in
7.3. Variation
Chapter XIII.
of the order parameter and the energy gap with magnetic
field
From equations V.G-L1 and V.G-L2 one can also calculate the variation of the order parameter
*fi inside the thin films. For thicknesses 2a

very small compared to the width of the transition layer Xq/k, or in
the equivalent Pippard terms for 2a < g if; can be considered con,
stant,
and one can take k
H
"6
For very thin
K 0.
This leads to (Ginzburg, 1958a)
\"c/ OA 6J/ L
30 \H
3oUc7\V
X o/)
A
(VII.9)
films VII.8 applies, so that
For thicker
films, VII.9
G-L2 must be
<l<i
For such films, therefore, i/j(Hs ) = 0, which means that the transition
into the normal state is of second order, without a latent heat and with
a discontinuity only in the specific heat, and not in the entropy. There
can be no supercooling, and therefore, no hysteresis. For thicker films
and bulk samples the transition in an external field, as discussed in
Chapter II, is always of first order. The critical thickness below which
there
is
a second order transition
2a
is
V(5)A
energy gap at
H =H
e
do not apply, and G-Ll and

The resulting variation of the
VII. 10
asa function of film thickness has been
calcu-
Douglass (1961a). It is displayed by the curve in Figure 20.

The points are gap values which Douglass (1961b) obtained from tunnelling experiments (see Section 10.6). Similar results have been found
lated by
by Giaever and Megerle (1961), also by means of the tunnel effect, as

and Tinkham (1961) with thermal conductivity
measurements. With e s the empirical variation of the energy
well as by Morris
H H
gap with
,
and
solved numerically.
field closely
Ginzburg-Landau-Gorkov prebelow Tc In such high fields the
agrees with the
dictions even at temperatures well
80
Superconductivity
order parameter
then small enough to
is
make tenable
the basic
G-L
assumptions as well as Gorkov's identification of the energy gap with

W, Tinkham (1962) has proposed ways in which the G-L equations
can be extended to give agreement also with low field results over a
wide range of temperature. The limitations of these equations in this
region have been discussed by Meservey and Douglass (1964).
Bardeen (1962) has calculated the critical field and critical current
for thin films
on the
basis of the
BCS theory. At higher temperatures
CHAPTER
The Isotope
8.1.
VIII
Effect
Discovery and theoretical considerations
The various phenomenological treatments based on
the empirical
his results generally confirm the predictions of the
Ginzburg-Landau
theory, including the vanishing of the energy gap and a resulting
characteristics of a superconductor provide an astonishingly complete macroscopic description of the superconducting phase. How-
second-order transition at the critical field in sufficiently thin films.

At much lower temperatures, however, below about TJ3, Bardeen
ever, they do not give any clear indications as to the microscopic nature
any thickness the energy gap remains finite and the

transition a first-order one. However, Maki (1963) as well as Nambu
One of the first such clues arose through the simultaneous and independent discovery, in 1950, by Maxwell, and by Reynolds et al., that
the critical temperature of mercury isotopes depends on the isotopic
finds that for
and Tuan (1963) predict

second order at
verify this
down
all
to
that the phase transition should be of the

temperatures. Merservey and Douglass (1964)
= 0- 14.
of the phenomenon.
mass by the relation
Tc M a =
Ave. mass no.:
199.5
r-
constant,
(vm.i)
200.7 (nat)
202.0
203.3
J
4.20
4.00
Fig. 21
81
82
Superconductivity
The isotope
where Mis the isotopic mass and a m . This is illustrated in Figure

21,
showing the variation of threshold field near T for different isotopes.
c
The
effect has since also
been established in a number of other elements. The following table contains the most reliable experimental
values of the exponent a, together with quoted probable errors.
Element
Cd
0-51
Hg
0-504
Mo
0-33
Os
Pb
Rh
Ru
0-461 0.025
0-501
0-4
001
Zn
was recog-
8.2. Precise threshold field
Shaw
Hake
The
measurements
variation of critical temperature with isotopic
lished
by measuring the critical
field
mass was estab-
as a function of temperature,
etal., 1961
et al.,
1958
Gcballee/o/., 1961
Finnemoreand Mapother, 1962
0-505 0019
0-46 002
0-462 001
0-50 005
0-62 01
Tl
subtle nature of the pertinent electron-lattice interaction
Maxwell and Strongin, 1964
<01
<005
Sn
independently suggested just such a mechanism without knowing of

the experimental work. However, it took several more years until the
Olsen, 1963
Reynolds et al., 1951

Matthias et al., 1963
Hein and Gibson, 1964
0-21
clearly pointed out the direction in which a microscopic explanation

of the phenomenon had to be sought. In fact, Frohlich (1950) had
nized and a valid microscopic theory began to be developed.
Reference
010
83
effect
0-5
Maxwell, 1952a
al., 1952
Serin et
Lock
et al.,
1951
Maxwell, 1952b
Alekseevskii, 1953
Geballeand Matthias, 1964
In all the non-transition metals, with the exception of molybdenum,

the results are consistent with a = 1/2. However, small mass
differences and the possibility of impurity and strain effects limit the
experi-
mental
reliability,
as
is
made evident by the variations between differ-
ent measurements
on the same element. Thus one cannot rule out

deviations from the ideal value of a = which may be as high as
20
per cent in some cases. In view of recent theoretical work to
be discussed in Chapter XI,
it is
significant that the trend of the published
= \ is toward lower values. The situation in the

ruthenium and osmium, however, appears to be
different. This will be further discussed in Section
1 1.5.
The inference to be drawn from the dependence of T on the isotopic
c
mass is startling. A relation between the onset of superconductivity,
which is quite certainly an electronic process, and the isotopic
mass,
which affects only the phonon spectrum of the lattice, must mean that
deviations from a
transition metals
superconductivity
the electrons
is
very largely due to a strong interaction between

lattice. Thus the discovery of the isotope effect
and the
and then extrapolating
this to
zero
field.
Magnetic measurements of
course make use of the perfect diamagnetism of a superconductor, and
can be made in one of two ways either the change in flux through the
sample at the transition induces an e.m.f. in a pick-up coil which is
connected to a suitable galvanometer, or the changing susceptibility
of the sample is reflected in the change of the mutual inductance of
coaxial coils of which the sample forms part of the core. Either of
:
methods can be applied with great accuracy in spite of simple

and has the further advantage of measuring a bulk
property virtually unaffected by the possible presence of small regions
with different superconducting characteristics. By providing a
these
apparatus,
84
Superconductivity
The isotope
misleading short-circuiting path, such minor flaws can lead to very

when Tc is measured by observing the variation of
A polynomial which fits the data for all tin isotopes as found by
erratic results
et al. (1951) to within one-half
electrical resistance.
The
careful determination of critical field curves which arose as

almost a by-product of the work on the isotope effect established a
//
85
effect
of a per cent
Lock
is
= l-10720/ 2 -0-0944/ 4 + 0-3325/ 6 -01660/ 8
(VIII.3)
All measurements to date have indicated that to within the available

precision all isotopes of a given element follow the
polynomial.
One
also finds that
same
critical field
has the same mass dependence
4-LEAD
Tc This means that the superconducting condensation energy

Hq/Btt varies proportionally to the isotopic mass, and also that, as
shown by equations 11.15 or 11.16, the value of y is independent of
as
Fig. 23
number of interesting
of the reduced
isotopic mass.
characteristics. Figure
critical field
22 shows the variation

as function of t 2 m T 2 /T 2 for a
C
m Hc /H
number of tin isotopes measured by Serin et al. (1952). It is evident,

as was indicated earlier, that equation I.2a is only an
approximation]
and that a
better representation for
is
a polynomial
W) = - S of,
i
n=2
(vni.2)
It
has also been found that in going from one element to another,
show small but definite variations.
the reduced threshold field curves
For
all
elements there are deviations from a
strictly
parabolic varia-
by a similar small amount in one direction, but in the

case of lead and mercury by an amount in the opposite direction.
Figure 23 shows these deviations as a function of reduced temperature. It is important to emphasize the smallness of these deviations.
tion, generally
86
Superconductivity
so as not to allow them to obscure the basic

similarity of the superconducting behaviour of all elements in terms
of reduced co-ordinates.
This not only sanctions the continuing
discussion of superconductivity in general terms with only
occasional references to specific
elements, but also allows one to look for a
microscopic explanation
of superconductivity, which in first approximation
need not concern
itself with the distinctive characteristics
of individual elements, but
only takes account of general and common
features. The deviations
of the measured threshold fields from a simple
parabolic variation
must be, according to the thermodynamic
treatment developed in
Chapter n, correlated with the empirical deviations

of the specific
heat from the corresponding change as the
cube of the temperature
Serin (1955) showed this strikingly by plotting
both these deviations
on the same graph, using the best available data for tin.
This is shown
in Figure 24. Mapother (1959) has
since established the correlation
between the experimental non-parabolic
threshold fields and the
exponential variation of the specific heat.
CHAPTER
IX
Thermal Conductivity
9.1.
Low
temperature thermal conductivity
normal metals, heat

and by the quantized
In
is
carried both by the conduction electrons
lattice vibrations, the
thermal conductivity consists of the

Km
phonons. The
sum of these two
k en -r k
total
contributions
(IX.1)
where e and g denote the electrons and the lattice, respectively. The
is limited by two scattering mechanisms the
phonons and the lattice imperfections, and one can write at T< :
electronic conductivity
\\k cn
The
first
= aT 2 + Po /LT.
(1X.2)
of the terms on the right gives the
due
resistivity
and predominates
electron scattering by phonons,
to the
at higher tem-
peratures; the second that due to scattering by imperfections, which
becomes important below the temperature at which k en has a
maximum:
TL* =
(IX.3)
Po/2aL.
In these equations p is the residual electrical resistivity, L the Lorentz

-8
(2-44 xlO
watt-ohm/deg2 ) and a is a constant of the
number
material which
is
inversely proportional to
@2
Note that for a given
material the addition of impurities increases p and thus raises Tmax

In pure metals and dilute alloys, k en
k g ; it is only in metals con.
>
taining as
much
as several per cent impurities that the
two contri-
butions are of the same order of magnitude.
The
two-fluid
model allows one
to predict qualitatively
what hap-
pens to the thermal conductivity of a metal when it becomes superconducting (see Mendelssohn, 1955; Klemens, 1956). The condensed
'superconducting' electrons cannot carry thermal energy nor can
With decreasing temperature their number

and that of the 'normal' electrons correspondingly
they scatter phonons.

increases,
7
87
88
Superconductivity
decreases, which will result in a rapid decrease of the electronic heat

conduction. At the same time the conduction by phonons will be
enhanced, as these are no longer scattered as much by electrons.

In pure specimens, the decrease in k will usually exceed any gain
es
in
kgs and
the total conductivity in the superconducting phase will

then be much smaller than in the normal phase. This is illustrated,
,
for example, by the results of
Hulm
(1950)
on pure
Hg shown
in
Thermal conductivity
89
For moderately impure specimens the superconducting conductivity will then not be very different from the
corresponding normal one. This is shown, for example, by the results
of Hulm (1950) on a Hg-In alloy, also displayed in Figure 25. The
results of Lindenfeld (1 96 ) on lead alloys shown in Figure 26 indicates
what happens with increasing inpurity content: as the phonon contribution to the normal conductivity becomes more appreciable, the
the thermal circuit.
0.30
K (watt/cm-deg)
Pb + 6%Bi
Pb+3*h
-Pb+6%ln
0.20-
0.10-
Fig. 25
Figure 25. There
exist, however, pure materials in which the normal

not very high but which are very free of grain boundaries and other lattice defects. In the superconducting phase of such
substances at very low reduced temperatures the phonons are then
conductivity
is
hardly scattered by anything except the specimen boundaries, resulting in a large value of kgs This has been observed, for example,
by
gain in
k^ increasingly outweighs
tivity in the
in the
the decrease in
superconducting phase becomes
k es and the conduc-
much
larger than that
normal one.
9.2. Electronic
conduction
Calverley et
al. (1961) in tantalum and niobium.

Suppressing the electronic conduction in the normal phase by
adding impurities decreases the effect of condensing electrons out of
on thermal conductivity by the superconducting transition

indeed due to the disappearance of electrons from the conduction
If the effect
is
process, then
one should be able to write IX.2 for a superconductor as

!/*
x(ir)aT 2 +y(^)p Q ILT,
(IX.4)
90
Superconductivity
where x(if) and y(ir) are functions only of the order parameter or
which indicates the fraction of condensed electrons. Equation 11.25
shows that IT is a function only of / = T/Tc so that one can write
,
instead
written in this
form
(IX.4)
to agree with the
nomen-
clature introduced by Hulm (1950).
He pointed out that if one chooses

a sample in which the electronic heat conduction is predominantly
limited by one or the other of the two scattering mechanisms, the
measured
ratio
k e Jk en then equals the appropriate ratio function g(t)
or /(r). To a first approximation, at least, these functions should be

universal functions for all superconductors and be related to the
microscopic nature of the phenomenon.

For a specimen for which Tmax < Tc as
,
pure
tion
is
BCS
theory.
The gradual change from a phononsame
scattered to an impurity-scattered electronic conduction in the
material of increasing impurity
is
recent results of Guenault (1960)
Uk = aT 2 /g(t) + PoLT/f(t).
The equation has been
the basis of the
the case for reasonably
Hg and Pb, and for extremely pure Sn and In, the heat conducjust below Tc is by electrons limited by phonon scattering. For
91
particularly well illustrated
on a
series
by the
of monocrystalline tin
specimens.
When thermal conductivity measurements on superconductors are

extended to small values of t, as was first done by Heer and Daunt
(1949) and later by Goodman (1953), /(/) is found to decrease very
rapidly.
Goodman
pointed out that this could be represented by an
equation of the form
At)
= aexp(-*/0,
(IX.7)
and suggested that this implied the existence of an energy gap between
the ground state and the lowest excited state available to the assembly
of superconducting electrons.
This conclusion can be inferred from thermal conductivity results
in the following manner. Simple transport theory shows that
such samples
KJKn *
All pertinent measurements
show
the
same
qualitative features: g(t)
breaks away sharply from unity with a discontinuous slope,

and decreases as a power of / which is about 2 for Sn and In (Jones
and Toxen, 1960: Guenault, 1960), and 4 to 5 for Pb and Hg (Watson
at
and Graham, 1963; see also Klemens, 1956). Calculations by Kadanoff and Martin (1961), by Kresin (1959) and by Tewordt (1962,
1963a) appear to explain the experimental results for Sn and In,
but not for Hg and Pb.
For specimens for which Tmax ^ Tc , the electronic conduction in
the superconducting phase
is
at all temperatures limited
by impurity
*/*,
Ce
(IX.8)
/ is
the
mean
free path,
specific heat of the electrons.
free paths (which may differ in magnitude) vary only slowly

with temperature, then the temperature variation of k e Jk e must be
due entirely to that of the specific heats. In other words
mean
f(t)
Cen
is
known
* kjk M
CJC
(IX.9)
to vary linearly with temperature, so that IX.7 implies
a'Tc texpi-b/t).
(IX.10)
(IX.6)
shown
/(0 approaches unity smoothly with a continuous

decreases
(1/3) lv
v tne average velocity, and Cc the

Assuming that v the Fermi velocity in
the normal metal, remains the same for the uncondensed 'normal'
electrons in the superconducting phase, and that in both phases the
where
Ces =
* /CO.
Several investigations (see Klemens, 1956) have
it
that
scattering, so that for these
lower temperatures
ke
(IX.5)
sit).
that at
slope,
more slowly than
git).
and
The
/=
that at
results
are in reasonable agreement with expressions for /(/) derived

Bardeen etal. (BRT, 1959) and by Geilikman and Kresin (1959)
by
on
That such a temperature variation of the specific heat corresponds to

an energy gap in the electronic spectrum can be shown as follows: If
a gap of width 2e lies below the lowest available excited state, the
number of thermally
excited electrons will be proportional
expi-2e/2k B T), where k B
is
the Boltzmann constant,
to
and the factor
2 arises because every excitation creates two independent particles,
92
Superconductivity
an electron and a
hole.
Thus the
energy of the superconducting

phase is equal to the condensation energy per particle
multiplied by
the exponential factor, which remains unchanged,
through two differentiations with respect to temperature, to
appear in the
specific
heat.
The parameter b
1.0
in IX. 10
is
93
free
thus seen to equal 2e/2k T

B c
.6
Figure 27, together with a theoretical curve calculated with a gap
equal to 3-50 k B Tc
The agreement is somewhat deceptive, since there

good evidence that the gap width for aluminium is only 3 40 k B Tc
From an observed anisotropy in the temperature dependence of k
at very low temperatures Zavaritskii (1959, 1960a, b) has been able
to infer a corresponding anisotropy in the width of the energy gap in
the spectrum of the superconducting electrons in the case of cadmium,
tin, gallium, and zinc. To the last he could apply theoretical expressions due to Khalatnikov (1959), from which he deduced a gap anisotropy of about 30 per cent. A similar result holds for cadmium. The
measurements of Zavaritskii also show that the gap anisotropy can
have different forms in the case of gallium the value of the gap can
be approximated by an ellipsoid compressed along the axis of rotation; for zinc and cadmium this ellipsoid is stretched out along the
.
is
Aluminium
K en
.4-
(.Zavaritskii)
axis of rotation.
{Aluminium(Satterthwaite)
ITheory (BRT)
.4
.6
.8
1.0
9.3. Lattice conduction
Fig. 27
According to the microscopic theory to be discussed in Chapter

XI,
the energy gap is a function of temperature.
The parameter b can
therefore be written as
<T)
kB
where
(0)
Tc
*(0)
kB Tc
"
x
e(D
(0)
the gap value at 0K.
The detailed dependence of

on b has been calculated by BRT, and the function
e(DMO),
calculated from the BCS theory, has been tabulated
by Miihlschlegei
(1959). Measurements oikJk can thus be used
to infer the value of
e
<0)lkB Tc
is
In cases where the energy gap is a function of the magnetic field,

measurements of k c Jk cn can be used to infer this field dependence.
This technique has been used by Morris and Tinkham (1961) for thin
films (see Section 7.3), and by Dubeck et al. (1962, 1964) for type II
superconductors in the mixed state (see Section 6.6).
kjk en
The appropriate temperature dependence of kjk

en has been
observed in a number of metals. The results
for aluminium by
Satterthwaite (1960) and by Zavaritskii
(1958a) are shown in
Far below Tc the fraction of 'normal' electrons becomes so small as

to make k cs <^ k gs At the very lowest temperatures, the phonons are
primarily scattered by crystal boundaries in a manner which is the
same in the superconducting as in the normal phase. The charac3
teristic T dependence in this limit (Casimir, 1938) has been well
established experimentally (Mendelssohn and Renton, 955 Graham,
.
1958).
In the normal state there occurs at these temperatures
still
appre-
ciable heat conduction by electrons, limited only by impurity scattering
Thus
and varying
linearly with temperature (see equation IX.2).
in this range
kjk s = aT-\
where a
is
(IX.11)
a constant of the material which can have values as high
as several hundred.
For example, a
suitable lead wire can have
94
k n /k s
Superconductivity
10 at 0-1 K.
A number of authors (see Mendelssohn,
1955)
suggested using such wires in ultra-low temperature experiments
as
thermal switches which would be 'open', i.e. non-conducting, in
the
CHAPTER X
superconducting phase, and 'closed' when the superconductivity

is
quenched by means of a suitable magnetic field. Such heat switches
are now widely used (see, for instance, Reese and Steyert, 1962).
The Energy Gap
At somewhat higher temperatures,
at which the phonons begin to

be scattered by the 'normal' electrons even in the superconducting
phase, there is necessarily a concurrent rise of the electronic
conduction. Experimentally it is very difficult to separate the
conduction
mechanisms. Where this has been possible (Conolly and Mendels-
sohn, 1962; Lindenfeld and Rohrer, 1963) the results have

been
consistent with the pertinent calculations by BRT and
by Geilikman
and Kresin (1958, 1959).
10.1. Introduction
Ever since the initial discovery of superconductivity it had been known

but barely noted that the striking electromagnetic behaviour of a
superconductor at low frequencies is not accompanied by any corresponding changes in its optical properties: there is no visible change
at
Tc
to
its
although the
reflectivity of a
metal at any frequency
conductivity at that frequency.
Thus
frequencies the resistance of a superconductor
The thermal conductivity in the intermediate state

A number of experiments, in particular those of Mendelssohn and co-
9.4.
workers (Mendelssohn and Pontius, 1937; Mendelssohn and Olsen,

1950; Mendelssohn and Shiftman, 1 959), have shown that the thermal
conductivity of a superconductor in the intermediate state generally
does not change linearly from its value in the one phase to its
value
when at a given temperature the external field is varied.

Instead there appears an extra thermal resistance, which in some
cases
in the other
can be very large, and which is attributed to the scattering of

the
predominant heat carriers (electrons or phonons) at the boundaries
between the superconducting and normal laminae which make up the
intermediate state. For materials in which
nates this has been analyzed by Cornish
phonon conduction domiand Olsen (1953) and by

and Wyder (1963) have devel-
Laredo and Pippard (1955). Strassler

oped a treatment for very pure specimens
in which the conduction is

mostly by electrons. Experiments on the thermal conductivity in the
intermediate state thus yield strong confirmation that the laminar
structure, observed by various techniques at the surface of
a specimen,
actually persists throughout a bulk sample.
is
related
at the very high optical

is
a constant, inde-
pendent of temperature, and equal to that of the normal metal. At

about the time of the discovery of the isotope effect steadily improving high frequency techniques had shown that atOK the normal
resistance persisted
down to frequencies of the order of 10 13 c/sec, but

10
remained zero up to frequencies of the order 10 c/sec. In 1952

already Shoenberg ([1], p. 202) concluded from this that at some frequency between these two limits '.. quantum processes set in which
could raise electrons from the condensed to the uncondensed state
that
it
and thus cause energy absorption'.

As shown in the previous chapter, Goodman (1953) very shortly
after this inferred from his thermal conductivity results the existence
of an energy gap in the single electron energy spectrum. A similar
conclusion had been deduced a few years earlier by Daunt and
Mendelssohn (1946) from the absence of any Thomson heat in the
superconducting state. This indicated to them that the superconducting electrons remain effectively at 0K up to T= Tc by being in
low-lying energy states separated from all excited states by an energy
gap of the order of k B Tc
In the years which followed, the existence of such a gap was firmly
established by a large number of experiments, and this, together with
the electron-phonon interaction indicated by the isotope effect, pro.
vided the keystones of a microscopic theory. This chapter will

95
96
The energy gap
Superconductivity
describe a few experiments which indicate the

energy gap most clearly
directly. The subject has been reviewed
by Biondi et al. (1958)
recently by Douglass and Falicov
(1964).
and
and
electron excitations
97
would be expected to occur across the narrower

would be reflected in an upward curva-
portions of the gap, and this

ture of
Ces when
plotted semi-logarithmically against
compares a number of measurements which show

10.2. The specific heat
After the resurgence of interest in specific
heat measurements as a
result of the suggestive results of precise
threshold field measurements,
of Goodman's thermal conductivity results,
and of the first clear
experimental verification of a deviation from a 3
T law by Brown et al
(1953) on niobium, there have been in recent
years a number of
measurements which clearly indicate the exponential

variation of
corresponding to an energy gap. The first of these
were the
this
BCS
1/r.
Figure 28
curvature with
3CWT)3
results of
Corak
et al. (1954) on vanadium and by

Corak and Satterthwaite
on tin and since then the exponential variation of C
es has been
established in a number of elements. The
appropriate column in
(1 954)
Table III lists the energy gap values of these elements

deduced from
the specific heat measurements. Note that in
units of k B Tc these gaps
are of very similar size for widely varying
superconductors. This again
bears out the basic similarity of all
superconductors in terms of reduced co-ordinates.
It is
perhaps useful to consider
briefly the difficulty
of obtaining
good values for Ces What is measured, of course, in

both the superconducting and in the normal phase, is the total
specific heat. It
.
is then
necessary to separate the electronic from the
lattice contribution in
the normal phase in order to be able to
subtract the latter from the
total specific heat in the superconducting
phase. Unfortunately,
at
low temperatures,
with large Debye
Cga
even
small compared to C only for metals

temperatures. These are just the hard, high-melting
is
point metals which are difficult to obtain with

high purity, without
which superconducting measurements are misleading.
The softer and
lower melting point metals, on the other hand,
have a very unfavourable ratio of electronic to lattice specific heat.
Measurements by Goodman (1957, 1958), Zavaritskii
(1958b), and
Phillips (1959) on aluminium have shown
at very low temperatures
(/ < 0-2) a deviation of C
es from a simple exponential law (Boorse,
1959). Cooper (1959) has pointed out that this
can be a consequence
of anisotropy in the energy gap. At the
lowest temperatures most
Fig. 28
the exponential law expected
theory of Anderson
(1
from the
BCS
theory. According to a
959) (see Section 12.2) the gap anisotropy of an
element diminishes with the addition of impurities. Indeed Geiser and

Goodman (1963) have found in aluminium specimens of different
purity that the deviation of
with increasing impurity.
Ccs from
an exponential form decreases
98
Superconductivity
The energy gap
10.3. Electromagnetic absorption in the far infrared
The magnitude of the energy gap 2e(0) can be characterized by
a fre-
i/
? such that hv ? = 2e(0). It is at this frequency that one would
expect the change from the characteristically superconducting re-
quency
sponse to low frequency radiation, to the normal resistance main-
99
The measurements of the transmission of such radiation through

superconducting films will be discussed in a later section. Richards
and Tinkham (1960), Richards (1 961), and Ginsberg and Leslie (1962)
have observed directly the absorption edge at the gap frequency in
bulk superconductors. Radiation from a quartz mercury arc infrared
Table
III
Energy gap (2<Q)lk B Tc)
Element
Aluminium
316
2-9
3-37 b , 3-43 c
3-3 d
3-5
...
...
3-3
...
...
3-5
3-9
3-63 a , 3-45 b
3-5
Cadmium
Gallium
Indium
4-1
Lanthanum
2-85
Lead
414
...
3-9
3-7
...
4-0
4-33 a , 4-26 b
...
3-9
418 d
4-6
2-8
Mercury
Niobium
...
...
...
4-4
3-7
...
3-84 e ,3-6*,
3-7
3-59 8
Rhenium
Ruthenium
Tantalum
3-3
...
31
< 30
3-6
3-6
3-60, 3-5',
3-65 u
2-8
3-2
Thallium
Thorium
3-5
...
3-6
Tin
3-3
3-5
3-6
3-46 a , 3-47 b
3-6
3-65 d
J-VL
10
15
Vanadium
20 25 30 35 40 45 50
FREQUENCY (cm -1 )
Fig. 29
tained at high frequencies. Unfortunately, the frequencies corresponding to gap widths inferred from the specific heat measurements
are 10 u -10 12 c-sec~ \ which is an experimentally awkward range
at
the upper limit of klystron-excited frequencies, yet very
low for
mercury arc ones. Only recently have Tinkham and collaborators
developed the techniques needed to detect the very low radiation
intensities available in this far infrared region.
Zinc
3-4
...
...
...
...
3-6
3-4'
3-6
2-5
...
3-4
A from infrared absorption (lead: Ginsberg and Leslie,
1962;
lanthanum: Leslie et al., 1964; all others Richards and Tinkham, 1960).
B from infrared transmission (Ginsberg and Tinkham, 1960).
C from microwave absorption (aluminium: Biondi and
Garfunkel, 1959; tin: Biondi et ai., 1957).
heat data to exponential (Goodman, 959).

Dby
E from tunneling ("Giaevcr and Megerle, 1961; Zavaritskii,
fitting specific
1961;
d
Douglass and Merservey, 1964;
Sutton. 1962; 'Giaever, 1962; "Sherrill and
Douglass, 1962;
Townsend and
Edwards, 1962; "Dietrich, 1962).
Fcalculated from XI.32 (Goodman,
1959).
100
The energy gap
Superconductivity
monochromator was fed by means of a light pipe into a cavity made

of the superconducting material under investigation. The cavity contained a carbon resistance bolometer, and was shaped so that the
incident radiation
would make many
reflections before striking this
For frequencies lower than v the superconducting walls of

g
do not absorb, and much radiation reaches the bolometer.
absorption by the walls sets in, and the signal from the bolo-
detector.
the cavity
At
g,
meter decreases sharply. Figure 29 shows normalized curves of the

fractional change in the power absorbed by the bolometer,
in arbitrary units, plotted against frequency for all the metals investigated
by Tinkham and Richards. The gap values obtained are listed in

Table III. The absorption edges for Pb and Hg show a certain struc-
which has also been found in the same elements in infrared

transmission measurements (Ginsberg et al., 1959). Ginsberg and
ture,
Leslie (1962) have
shown
that this structure persists even in a lead

alloy containing 10 atomic per cent of thallium, so that it is
probably
not due to gap anisotropy. The effect may be due to states of collective
excitations lying in the gap (Tsuneto, 1960)
into account in the
BCS
theory.
which have not been taken
However, calculations of Maki and
Tsuneto (1962) lead one to expect that the energy of collective excitations should be drastically shifted by impurity scattering.
Richards (1961) has reported measurements on single crystals of
pure tin and of tin containing 01 atomic per cent indium. His results
show
that the position of the absorption edge varies with

crystal
orientation, which clearly indicates the anisotropy of the gap.
Furtheranisotropy decreases with increasing impurity, which

strongly supports Anderson's suggestion (1959) that the anisotropy
more
this
becomes smoothed out in impure samples. The absorption edges

observed by Richards have a structure which, unlike that seen in
Pb
and in Hg, occurs for frequencies greater than v These postcursor
g
peaks do not seem to change with impurity, and have not yet found
101
from a simple two-fluid picture, according to which at any finite

temperature a fraction of the electrons remains ' normal'. H. London
pointed out that in the presence of an alternating electric field these
this
electrons absorb energy as they
would
in a
normal metal, and that
needed to sustain an alternating current even in a superconductor because of the inertia of the superconducting electrons.
Into a normal metal an alternating field penetrates to a skin depth
such a
field is
which leads to anomalous results if the mean free path l> 8, as is

the case at high frequencies and low temperatures (see p. 42). In the
8,
superconducting phase, the theory of the anomalous skin effect still

applies in principle, but has to be modified both because for high frequencies the superconducting penetration depth A is much smaller
than the skin depth 8 (except very near Tc ) and decreases very rapidly
with decreasing temperature, and because the number of 'normal'
Tc Both of these lead to a reduc-
electrons also drops sharply below
tion of the resistance in the superconducting phase as
that in the normal one
below
Tc
compared
to
the ratio of the resistances decreases rapidly
changes more gradually at lower temperatures where both
A and the order parameter are
0K where
there are
and
fairly constant,
no more 'normal'
finally vanishes at
electrons.
Unpublished calculations of the variation of RJR with temperaand with frequency have been made by Serber and by Holstein
on the basis of the Reuter-Sondheimer equations, the London theory,
ture
and the two-fluid model. Typical results are the solid curve labelled
rc and the dashed one labelled 2-37 k B Tc in Figure 30. With
10
c/sec there is general experimental agreefrequencies up to 8 x 10
calculations,
as shown, for example, by the recent
ment with these
results of Khaikin (1958) on cadmium and of Kaplan et al. (1959) on
tin. Their temperature dependence for a given frequency can be
represented by an empirical function, suggested by Pippard (1948):
0-65Ar B
an explanation.
#0 =
even at lower frequencies (H. London, 1940). One can understand
(l-/2 )0-/4
4/3
2
.
(X.1)
is as v
at low frequencies, tending toward a constant value at higher frequencies.
However, surface impedance measurements at frequencies con10
siderably higher than 8 x 10 c/sec show appreciable deviations from
the predictions of the simple two-fluid model. Figure 30 shows the
The frequency dependence

10.4. Microwave absorption
Although the resistivity of a superconductor vanishes at 0K for frequencies up to v there is a finite resistance at higher
temperatures
g
4
/
102
ratio
Superconductivity
RJR n
measured
The energy gap
as a function of reduced temperature

for
at three microwave frequencies
by
aluminium as
Biondie/A/ (1957) The
of kB TJh. For 0-65, the results
agree
frequences are given in units

well with the temperature variation
calculated without regard to an
energy gap. For 2-37, however, such
calorimetrically the
103
amount of energy absorbed by an aluminium
wave guide, over a range of frequencies ranging from 0-65k B Tc

10
10
(1-5 x 10
c/sec) to 3-91^7^ (10 x 10
c/sec) at temperatures down
calculations would give the

evident that for / > 0-7, the measured
ratio
considerably exceeds the predicted
one. The same is true for
hv - 304k B T except that in this
c
case the deviation already begins
at
dashed curve, and
it is
O.^r^k
0.6
07
'
'
'
0.8
'
0.9
1.0
Fio. 30
Clearly an additional absorption

quencies,
and of course
mechanism occurs
sufficient to bridge the
c,
are not
gap at / = 0, but become effective at that temperature at which the gap has shrunk
to a width of 2-37
B T A series
of measurements of the resistance ratio
as a function
both of frequency
and of temperature thus serves to map out

the temperature variation
aP f 3ny g,Ven ^Perconductor. Biondi and
no?
(1959)
1.0
for these fre-
due to the boosting of condensed electrons across the energy gap. If this
gap had a constant width at all
t< 1 the appearance of this extra absorption
would depend only on
the frequency. Its temperature
dependence, however, clearly shows
that the energy gap varies with
temperature, tending toward zero as
/-M. As a result, photons of energy 2-37k T
for example,
Garfunkel
u
have
obtained values of the resistance
ratio by measuring
1.5
Energy
this is
2.0
(in
2.5
units of
3.0
3.5
4.0
kTc )
Fig. 31
The accuracy of the measurements was such that the absorption of 10 " 9 watt could be detected. Their results give a temperato 0-35K.
ture variation of the

tions of the
gap which
is
in close
agreement with the predic-
BCS theory.
Mattis and Bardeen (1958) and Abrikosov et ul. (1958) have developed a theory of the anomalous skin effect in superconductors on
the basis of the BCS theory. Miller (1960) used the work of the former
to calculate the surface impedance for many different frequencies
temperatures.
8
The
close agreement between his results
and
and the
104
105
Superconductivity
The energy gap
measurements of Biondi and Garfunkel is shown in Figure 31, in

which points calculated by Miller are superimposed on smooth
of the energy gap. In particular, a detailed analysis by Hebel (1959)

has shown that the empirical results are compatible with the manner
of piling up predicted by the microscopic theory. Hebel's results and
some empirical values are given in Figure 32, in which the ratio of the
curves representing the empirical values. The theoretical treatments

are equally successful in the lower frequency range in which there are
no gap
relaxation rate in the superconducting phase to that in the normal one

variation of what can
is plotted against temperature. The temperature
effects.
Nuclear spin relaxation
10.5.
When
the nuclear spins of a substance are aligned by the application

of an external field, they again relax to their equilibrium distribution
be considered as the attenuation of the nuclear alignment is markedly

different from the corresponding change in the attenuation of an
predominantly by interaction with the conduction electrons. In this

interaction, a nucleus flips its spin one way as the electron spin flips
way so as to conserve the total spin. The electron can do this

is available an empty final state of correct energy and
spin direction, and the nuclear relaxation rate in a normal metal
depends therefore both on the number of conduction electrons (itself
proportional to the product of the density of states and the energy
derivative of the Fermi function) and on the density of states in the
the other
only
if
vicinity
To
there
of the Fermi surface.
predict the temperature variation of this relaxation process in
the superconducting phase one
is tempted to use again a simple twomodel, according to which the number of 'normal' electrons
available decreases rapidly below T To this should, therefore, correc
spond a decrease in the relaxation rate as compared to that in the
fluid
'0
normal phase. But the energy gap severely modifies the density of
gap there are, by
definition, no available states at all, and the missing states are 'piled
up on either side. The presence of the energy derivative of the Fermi
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
states available to the interacting electrons. In the
Fig. 32
'
function in the relaxation rate expression makes this rate essentially

proportional to the square of the density of states evaluated over a
range k B T on either side of the Fermi energy. At temperatures near
ultrasonic elastic
< k B T, so that the pile-up of

an appreciable increase of the rate over
that in the normal phase. At lower temperatures, the gap becomes
wider than k B T, and the relaxation rate rapidly diminishes, approach-
ductors
7;.,
the gap
states
is still
on either side
very narrow and

results in
ing zero as T-*-0.
The measurements of Hebel and Slichter (1959), of Redfield (1959)..

and of Masuda and Redfield (1960a) fully confirm this consequence
wave in a superconductor. As this difference is one

of the most striking consequences of the BCS theory, its discussion
and the general description of ultrasonic attenuation in superconis postponed until a later chapter.
In his calculations, Hebel avoids singularities on either side of the
gap by introducing a parameter r which represents a smearing of the
density of states over an energy interval small compared to the width
of the gap. It is possible to interpret this in terms of an anisotropy of
the gap, since the relaxation process samples the gap over all directions simultaneously. With this interpretation, the data on aluminium
106
of
Superconductivity
The energy gap
Masuda and
Redfield (1960a, 1962) indicate an anisotropy of the

order of 1/10 of the gap width, and recent measurement
by the same
authors (Masuda and Redfield, 1960b; Masuda,

1962b) indicate that
this anisotropy decreases in impure
aluminium. Anisotropy of magnitude similar to that in aluminium has been found
by Masuda
(1962a) in cadmium.
10.6. The tunnel effect
The most recent and the most direct measurement of the
energy gap
has been provided by the work of Giaever
(1960a), who essentially
metal,
all
107
at 0K. In the last of these, electrons
fill
all
available states
up to the Fermi level EF in the superconductor, there is a gap of halfwidth e(0), and states up to EF e(0) are filled. With such conditions
there can be no tunneling either way, as on neither side of the barrier
are there any available states.
A potential difference applied between the two metals will shift the
energy levels of one with respect to the other. It is evident from
Figure 33 that tunneling will abruptly become possible when the
;
applied voltage equals e(0).
The subsequent
variation of tunneling
on the details of the

on either side of the gap.
of current with voltage due to the
current with applied voltage of course depends

density of states curve of the superconductor
At
first,
there
is
a very rapid
rise
(0)
Voltage
Fig. 34
large density of piled-up stages; for voltages
much exceeding e(0), the
tunnelling samples the density of states well beyond the gap,
superconductor
normal metal
variation of I vs.
insulator
tion of
Fig. 33
and the
V approaches the purely ohmic character of a junc-
two normal metals. This
is
summarized
in
Figure 34, which
gives with the solid line the current- voltage characteristic of the
superconducting-normal junction at 0K. The dotted line indicates
measured the width of the gap with a voltmeter. He

accomplished this
by observing the tunneling of electrons between
a superconducting
film and a normal one across a thin insulating
barrier.
Quantum-
mechanically, an electron on one side of such a

barrier has a finite
probability of tunneling through it if there is
an allowed state of equal
or smaller energy available for it on the other
side. Figure 33 shows
the density of states function in energy
space for a sandwich consisting,
from left to right, of a superconductor, an insulator,

and a normal
<
T< T
the modification being due to the fact

c
on both sides of the junction some electrons
are excited across the gap or the Fermi level, respectively. The dashed
line shows the behaviour at T > Tc i.e. for a junction of normal metals.
Nicol et al. (1960) and Giaever (1960b) have extended such experiments to cases where both metals of the junction are superconductors,
but with very different critical temperatures, such as Al (Tc = 1-2K)
and Pb (Tc = 7-2K). The gaps of the two will be correspondingly
the behaviour at
that at finite temperatures
'08
different,
is
shown
The energy gap
Superconductivity
and
for such a junction the density of states function at
in Figure 35.
A tunneling current will
begin to flow
the potential difference between the

this case,
0K
when
two metals is (0) Pb +e(0) AI In

however, the modification due to finite temperature is more
.
than with an s-n junction. Imagining the density of states

curve of Figure 35 with a few excited electrons beyond both gaps, and
a few available states remaining below both, one recognizes that now
significant
superconductor
tion of the energy gap with magnetic field was discussed in Chapter
VI I. Recent tunneling studies have verified other aspects of the energy
gap, in particular its relationship to the phonon spectrum of the
lattice. This will be summarized in Chapter XI.
Simultaneous tunneling of two electrons has been observed by
Taylor and Burstein (1962), in agreement with the calculations of
superconducting
superconductor
109
compared to the penetration depths, and because of their size their

critical fields are very high. This and its use in investigating the varia-
6,-e 2 e,+e2
insulator
Voltage
Fig. 35
Fig. 36
the current / at
first increases with increasing potential V, then

decreases for e(0) Pb -e(0)
A1 < K<(0) Pb + (0) A1 and then increases
again. Figure 36 shows the current-voltage characteristics
in this
case; the limits of the negative resistance region are very sharp.
Thus
,
the current-potential characteristics yield the energy gap values at

a
given temperature for both metals.
Schrieffer and Wilkins (1962). This is not to be confused with the

tunneling of Cooper pairs, as predicted by Josephson (1962), which
will be discussed in Section 1 1.7. The results of Taylor and Burstein
also indicate the possibility of tunneling assisted by the simultaneous

absorption of a phonon. Theoretical aspects of this have been dis-
The energy gap values obtained by this method for several superconductors are listed in Table III, and can probably be considered
as
cussed by Kleinman (1963) and Fibich (1964).
the most reliable of all experimental determinations.

Measurements
as a function of temperature closely support the thermal variation
of the energy gap predicted by the BSC theory. The films used
are thin
10.7.
Far infrared transmission through thin films
Tinkham, Glover, and Ginsberg (Glover

and Tinkham, 1957; Ginsberg and Tinkham, 1960) have measured
In a series of experiments,
110
Superconductivity
The energy gap
the transmission through thin superconducting films

of electromagnetic radiation in the far-infrared range of
wavelengths between 0-1
and 6 mm. Their results lend themselves to an ingenious

analysis
leading to a number of very fundamental conclusions
about the inter-
independent of frequency
in the
1 1
range under investigation. The super-
conducting conductivity can be written as the complex quantity

(X.2)
relation of the energy gap, the response to high

frequency radiation,
It
then follows from general electromagnetic theory that
= T^Hi-rt^)
+[( I
-^> ,/2 ^]~}~
(X- 3 >
Microwave work on bulk superconductors, such as the measurements

of Biondi and Garfunkel (1959), have shown that at T< Tc and
ho < k B Tc
the surface resistance vanishes. It follows
from
this that
the real, lossy part of the conductivity must also vanish in this range,
0, so that the low frequency measurements of Ts /T can be

used to evaluate the corresponding values of a2 /a. For a number of
or a,
samples of tin and lead with widely varying normal conductivity, all
the data of Glover and Tinkham fit a universal curve represented by
il n
As a n
is
(\la)(kB TJtiw),
0-27.
(X.4)
independent of frequency, X.4 implies that
a2
This
is just
cc
(X.5)
1/cu.
the frequency dependence which follows from the
London
equation
curlJ + -_-2
Fig. 37
and the existence of perfect conductivity and of the Meissner

effect in
the limit of zero frequency (see Tinkham
[10], pp. 168-176).
In Figure 37, the curve labelled TJT is one which can
be drawn
n
through the empirical values of the ratio of the transmissivity
in the
superconducting phase, Ts , to the normal value, T,
all suitably
normalized for film resistance and substrate refraction, and
conductivity.
The
transmissivity of a substance
is
related to
curlE
real
number, an , which to a good approximation
= -H
c
leads to
a2
c2
4ttA
(X.7)
2
,
its
One can approximate the conductivity of the film in the
normal state by a
(X.6)
0,
since this with Maxwell's equation
plotted
against frequency.
H=
is
An
imaginary conductivity which
is
inversely proportional to the
frequency thus corresponds to the consequences of X.6 the Meissner

:
CHRIST'S
I
COLLEGE
mm nw
112
Superconductivity
The energy gap
and a finite penetration depth A. However, the magnitude of A

from the experimental transmission results with the aid
of X.7 exceeds the London value \ L = mc 2 jATT 2ne 2 by at least a factor
Substituting X.7 into the first of these two relations shows that the
imaginary conductivity o 2 must be accompanied by a real conduc-
effect
calculated
often. Furthermore, there is nothing in the
why a2 /cr
tivity
which takes the form of a delta-function
London theory to explain
equation like X.4.
On the other hand the

as
l< A,
A2
Pippard treatment predicts
that (see equation IV. 18a)
(c /8A ) 8(co
Similarly, in terms of the empirical value
at the origin:
- 0).
(X.9)
X.4 for o 2 /o one would
have
TT\
k B Tr
o~
2a
a, (to)
for different superconductors should satisfy a universal
for these films, in which
1 1
(lo/OAl,
where (equation IV.9)
S(o)-O).
(X.10)
Such an infinite real conductivity at zero frequency of course does not
afiv /k B
Tc
introduce losses.
Hence
ne2
CT
On
XI X X
to
For a normal metal
mvQ
6
and hence the Pippard theory
leads to
10
12
8
-h<y/k BTc
Fig. 38
kB T
On
htxi
Turning now to the high frequency far infra-red transmissivity data,

and subsequent decrease of Ts /T indicates that at a frequency roughly corresponding to the peak, a real, lossy component
ct, of the superconducting conductivity must appear. In the absence
of such a component Ts /T would continue to rise. The appearance of
the peak
for all superconductors. This
is
strikingly verified
by the
results of
Glover and Tinkham.
The real and imaginary parts of any linear response function, such
as the electrical conductivity, are related by a pair of integral transforms known as the Kramers-Kronig (K-K) relations. In terms of the
conductivity these take the form:
Tinkham et al. do not determine the gap quite unambiguously (see Forrester, 1958). However, accepting the existence of
+ 00
a 2 (co
i<)
t0
)dco\
(0 2
o 2 (to)
is,
of course, highly suggestive of an energy gap. Taken by themselves,

the data of
+ 00
co x
a real component of conductivity at or near some critical frequency
-.
co
to
(X.8)
a gap from other experiments allows a fully consistent interpretation

of the transmission results from which the magnitude of the gap as
well as other interesting quantities can be derived.
Superconductivity
14
The energy gap
The calculations of Miller (1960) of the variation of a

shown in Figure 37, the ordinate being scaled in units of
\a n are
it
A removed from under the o-,(o>) curve by

must reappear somewhere else, and it can do so only
the form of a delta function of strength A. This being
follows that any area
the energy gap

at the origin in
2e(0)
1 1
the case, one can then again apply the
K-K
relations to
show
that
associated with such a delta function

is the width of the gap at 0K. An energy gap implies
a normal metal, the imaginary part of the conductivity
vanishes for frequencies beyond the gap. Using X.3 one can then
where 2c(0)
a,(oi)
A8(oj-0)
(X.12)
that, as for
cr,/<x from the measured values of TJT to a first approxin

mation, and then apply an iterative procedure using the K-K relations
must be a contribution to the imaginary conductivity of magnitude
calculate
as well as the
sum
rule about to be
mentioned to obtain final values

of ajcr,,. Figure 38 gives the result thus obtained by Ginsberg and
Tinkham for lead, showing the precursor peak also found for mercury. One ignores this in deriving energy gap values from the limit
>
<y
i/CT/.- 0- The resulting gap widths are listed in Table III.
10.8. The Ferrell-Glover sum rule
The intimate connection between the experimentally verified decrease
of aj/a near
co
g , corresponding to the existence of a gap,
frequency London-type imaginary conductivity a \
and the low
<x 1/eo,
the real part of the conductivity vanishes.
The appropriate K-K relaa is an even

t
function,
a 2 (o>)
TTOi
9f(a>i)dh>|.
CX.11)
must lead to the appearance of a
ff2 ccl/o,
which was
seen to correspond to the Meissner effect and infinite conductivity.

One sees further that in terms of the parameter a of X.4, one can
write
A\on
(7Tl2)(k B
Tclh)(Ma).
(X.14)
Determining A/a from their transmission data and using this relation, Ginsberg and Tinkham obtain values for a of 0-23 for lead, 0-26
for tin,
and 0- 19 for thallium. These, as well as Glover and Tinkham's
value of 0-27 for both tin and lead, are in remarkable agreement both
with the Faber-Pippard data (0-15 for tin and indium) and with the
BCS
prediction for
all
metals (0-18).
The agreement
is
particularly
one considers the simplifications of the theory on the

one hand, and the wide variety and considerable difficulty of the
experiments on the other.
From X.13 and X.7 it is evident that
convincing
if
At these very high frequencies all electrons are free in both the normal
and the superconducting phases, and one would thus expect cr 2 (co)
and, therefore, the integral in X.l to have the same value in both
phases. In other words, there exists the sum rule that this integral
Thus the Ferrell-Glover sum-rule
remains unchanged under the superconducting transition.
by Gor'kov.
From this
delta function X.12. In turn this
leads to a London-type imaginary conductivity
A2
(X.13)
IA/tho.
The argument has now come through a full circle. An energy gap
corresponds to a disappearance of a^w) in the superconducting
phase over some frequency range in which this conductivity is finite
in the normal metal. This, according to the Ferrel-Glover sum rule,
corre-
sponding to infinite conductivity and the Meissner effect at zero

frequency, was first pointed out by Ferrell and Glover (1958) and
further elaborated by Tinkham and Ferrell (1959). The first of these
papers pointed out that at extremely high frequencies, such that hut
far exceeds any of the binding energies of an electron in the metal,
tion for the imaginary conductivity then becomes, since
aiiai)
c I8A.
(X.15)
leads to an inverse proportionality

between the square of the penetration depth and the energy gap. Such
a relation is implicit in the Pippard model and the Bardeen theory,
and appears explicitly in the Ginzburg-Landau treatment as extended
Microscopic theory of superconductivity
117
under suitable conditions. The absence of statistical fluctushows that the superconducting state is a highly correlated one
involving a very large number of electrons. Thus it is necessary to find
inherent in the basic properties common to all metals an interaction
transition
ations
CHAPTER
XI
Microscopic Theory of Superconductivity

11.1. Introduction
empirical description of superconductivity, perhaps the most striking

feature to be noticed
is
how much
quantitative information can be
given about superconductivity in general without speaking about the
of any one of the
indicates that the explanation for superconductivity should be in-
herent in a general, idealized model of a metal which ignores the complicated features characterizing any individual metallic element. It
should, therefore, be possible to find in the simple model of the ideal
metal the possibility of an interaction mechanism leading to the superstate,
in such a
way that the energy
and to derive from
this at least qualitatively the
properties of an ideal superconductor.
One would judge from
this that an explanation for superconducshould be fairly easy, until he realizes the extreme smallness of
the energy involved. A superconductor can be made normal by the
tivity
which at absolute zero is of the

order of a few hundred gauss. The energy difference between the
superconducting and the normal phase at absolute zero, which is
given by Hq/Stt, thus is of the order of 10~ 8 e.v. per atom. How
very small this is can best be judged by remembering that the Fermi
energy of the conduction electrons in a normal metal is of the order
of 10-20 e.v. The simple model of Bloch and Sommerfeld gives a
reasonably accurate description of the basic characteristics of a metal
although it completely ignores, among other things, the correlation
energy of the conduction electrons due to their Coulomb interaction.
This energy is of the order of 1 e.v.
As a further difficulty in arriving at a microscopic theory of superapplication of a magnetic field
conductivity one must add the extreme sharpness of the phase

116
conducting elements clearly indicated that in these the interaction in

question must be one between the electrons and the vibrating crystal
lattice,
and indeed Frohlich (1950) had suggested such a mechanism
independently of the simultaneous experimental results.
many superconducting elements.
The astonishing degree of similarity in the superconducting behaviour

of metals with widely varying crystallographic and atomic properties
conducting
number of electrons
of the system relative to the normal metal is lowered by a very small

amount. The discovery of the isotope effect in a number of super-
In reviewing the contents of the preceding chapters, which give an
specific properties
correlating a large
11.2.
The
electron -phonon interaction
Frohlich and, a little later, Bardeen (1 950) pointed out that an electron
moving through a crystal lattice has a self energy by being 'clothed'
with virtual phonons.
through the
means is that an electron moving

and the lattice in turn acts on
of the electrostatic forces between them. The
What
this
lattice distorts the lattice,
the electron by virtue
is quantized in terms of phonons,

and so one can think of the interaction between lattice and electron
as the constant emission and reabsorption of phonons by the latter.
These are called 'virtual' phonons because as a consequence of the
oscillatory distortion of the lattice
uncertainty principle their very short lifetime renders
it
unnecessary
Thus one can think of the electron

being accompanied or 'clothed', even
to conserve energy in the process.
moving through the
lattice as
by a cloud of virtual phonons. This contributes to the electron

an amount of self-energy which, as was pointed out by Frohlich and
by Bardeen, is proportional to the square of the average phonon
at 0K,
energy. In turn this
is
inversely proportional to the lattice mass, so
would have the

mass dependence indicated by the isotope effect. Unfortuhowever, the size turns out to be three to four orders of
that a condensation energy equal to this self-energy

correct
nately,
magnitude too large.

It was only seven years later that Bardeen, Cooper, and Schrieffer
(BCS, 1957) succeeded in showing that the basic interaction responsible for superconductivity appears to be that of a pair of electrons
by means of an interchange of virtual phonons. In the simple terms
118
Superconductivity
used above
this
means
that the lattice
is
distorted
by a moving
elec-
19
between a pair of electrons just above the Fermi surface, these elecform a bound state. The electrons for which this can occur
as a result of the phonon interaction lie in a thin shell of width ^ hu) q
where hco q is of the order of the average phonon energy of the metal.
If one looks at the matrix elements for all possible interactions which
phonon. A second electron some

when it is reached by the propagating
fluctuation in the lattice charge distribution. In other words, as shown
in Figure 39, an electron of wave vector k emits a virtual phonon q
trons can
k'. This scatters k into k q and

The process being a virtual one, energy need not be
conserved, and in fact the nature of the resulting electron-electron
interaction depends on the relative magnitudes of the electronic
energy change and the phonon energy ficoq If this latter exceeds the
take a pair of electrons from any two k values in this shell to any two
others, he finds that because of the Fermi statistics of the electron
these matrix elements alternate in sign and, being all of roughly equal
tron, this distortion giving rise to a
distance away
which
is
is
in turn affected
absorbed by an electron
k' into k' + q.
magnitude, give a negligible total interaction energy, that is, a

vanishingly small total lowering of the energy relative to the normal
situation of unpaired electrons. One can, however, restrict oneself to
matrix elements of a single sign by associating all possible k values in
pairs, kj and k 2 , and requiring that either both or neither member of
a pair be occupied. As the lowest energy is obtained by having the
largest number of possible transitions, each represented by a matrix
all of the same sign, one wants to choose these pairs in such
a way that from any one set of values (kj, k^, transitions are possible
into all other pairs (k|", k. As momentum must be conserved, this
element
means that one must require that
k + k2
1
that
is,
that
all
bound
k,'
pairs should
+ k^ = K
(XI.1)
have the same total
momentum K.
(See, for example, Cooper, 1960.)
Fig. 39
To
the
former, the interaction

lattice
is
is
the charge fluctuation of the
attractive
then such as to surround one of the electrons by a positive
screening charge greater than the electronic one, so that the second
and is attracted by a net positive charge.

The fundamental postulate of the BCS theory is that superconductivity occurs when such an attractive interaction between two
electrons by means of phonon exchange dominates the usual repulsive
screened Coulomb interaction.
electron sees
11.3.
The Cooper
pairs
Shortly before the formulation of the
been able to show that
if
there
is
BCS theory, Cooper (1956) had
a net attraction, however weak,
find the possible value of kj
same time
lie in
a narrow
and k 2 which
1 and at
Fermi surface k F
satisfy XI.
shell straddling the
one can construct the d iagram shown in Figure 40, d rawing concentric
of radii k F - 8 and k F + 8 from two points separated by K. It is
clear that all possible values of k, and k 2 satisfying XI. 1 are restricted
to the two shaded regions. This shows that the volume of phase space
circles
what has become known as Cooper pairs has a very

for K = 0. Thus the largest number of possible
yielding the most appreciable lowering of energy is
available for
sharp
maximum
transitions
obtained by pairing all possible states such that their total momentum
vanishes. It is also possible to show that exchange terms tend to reduce
the interaction energy for pairs of parallel spin, so that it is energetically most favourable to restrict the pairs to those of opposite
spin.
One can, therefore, summarize the
basic hypothesis of the
BCS
120
Superconductivity
theory as follows: At
0K
correlated one in which in

in
thin shell near the
the superconducting ground state
momentum space
Fermi surface are
the
is
a highly
normal electron states
to the fullest extent possible
occupied by pairs of opposite spin and momentum. The most direct

verification of the existence of these pairs arises from the flux quantization measurements mentioned in Chapter III.
The energy of this state is lower than that of the normal metal by a
finite amount which is the condensation energy of the superconducting
0K must equal Hi/Sir per unit volume. Furtherhas the all-important property that it takes a finite
quantity of energy to excite even a single normal ', unpaired electron.
state
and which
more,
at
this state
'
For not only does this require the very small amount of energy needed
121
mentioned earlier, namely that the correlation energy in question is so

very much smaller than almost any other contribution to the total
electronic energy. BCS therefore take the bold step of assuming that
all
interactions except the crucial
one are the same
for the supercon-
ducting as for the normal ground state at 0K. Taking as the zero of
energy the normal ground state energy and including in this all
normal state correlations and even the self energy of the electrons due
to virtual phonon emission and reabsorption, BCS proceed to calculate the superconducting ground state energy as being due uniquely
to the correlation between Cooper pairs of electrons of opposite spin
and momentum by phonon and screened Coulomb interaction.
The interaction leading to the transition of a pair of electrons from
the state (k t -k | ) to (k' t -k' I ) is characterized by a matrix
,
element,
-]^
fc/
= 2(-k'i,k'tl#int|-k!M),
(XI.2)
all terms comremoved.

have
been
superconducting
phases
and
mon
Vkk is the difference between one term describing the interaction
between the two electrons by means of a phonon, and a second one
giving their screened Coulomb interaction. The basic similarity of the
where i/ int
is
the truncated Hamiltonian from which
to the normal
Fig. 40
up a bound pair, but more importantly the occupation of a

k state by an unpaired electron removes from the system a large
number of pairs which could have interacted so as to occupy k and
k. Hence the total energy difference between having all paired
electrons and having a single excited electron is finite and equal to a
to break
single
large multiple of the single pair correlation energy. In terms of the
theBCS theory correctly yields an

has already been shown that such an energy gap not
only leads to the observed variation of the specific heat, the thermal
single electron spectrum, therefore,
energy gap.
It
conductivity,
teristic
BCS
of individual substances.
Vkk
therefore
make
the further
and constant for all

electrons in a narrow shell, straddling the Fermi surface, of thickness
(in units of energy) less than the average energy of the lattice, and
that Vkk vanishes elsewhere. Measuring electron energy from the
Fermi surface, and calling e k the energy of an electron in state k, one
simplifying assumption that
is
isotropic
can state
this formally
by the equations:
and the absorption of high frequency electromagnetic
radiation, but also that
it is
Vkk .= V forhfcl.M &
correlated with the existence of perfect
diamagnetism and perfect conductivity in the low frequency

11.4. The ground state energy
The recognition of the basic electron
sible
superconducting characteristics of widely different metals implies that

the responsible interaction cannot crucially depend on details charac-
(XI.4)
limit.
mechanism responfor superconductivity does not remove the major difficulty

interaction
Vkk =
and
The
basic
BCS
elsewhere.
criterion for superconductivity
condition
V<
0.
is
equivalent to the
Superconductivity
122
It is well to
note clearly at this point that this simplification of the
interaction parameter
F necessarily leads to what can be called a law
of corresponding states for

identical predictions for the
all
superconductors, that
exist,
and
to see whether this
respect to h k
virtually
is,
in terms of reduced co-ordinates. Any empirical deviation from such

complete similarity is, therefore, no invalidation of the basic premise
of the BCS theory, but merely an indication of the oversimplification
inherent in XI.4. (See footnote, page
30.)
Let h k be the probability that states k and k are occupied by a

pair of electrons, and (\h k ) the corresponding probability that the
possible XI.5' can be minimized with
This leads to
[h k (l-h k)}
magnitudes of all characteristic quantities
is
123
'
= vw
(XI.6)
2e k
l-2h.
By defining
KStMl-Ml
e(0)=
1/2
(XI.7)
kf
equation XI.6 simplifies to
h,==*-!)
(XI.8)
states are empty. W(Q), the ground state energy of the superconducting
state at
0K
as
compared
to the energy of the
normal metal,
is
then
where
Ek = [4+e 2 (0)]
given by
1/2
(XI.9)
relation
Substituting XI.8 back into XI.7 one obtains a non-linear
^(0)=
SÂrSW^l-MMl-^}"
k
2
.
(XI.5)
for(0):
Ky
kk"
e{0)
g(0)
"2Z[ I + eW
The summation is over all those k-values
for
which
Vkk
9* 0
k hk
- v2
{h k (i
kK
-MMi -h)) m
(Xi.50
to an
This can be treated most readily by changing the summation
k
to e.
integration
from
integration and transforming the variable of
surface
Fermi
the
of
either
side
states
on
Assuming symmetry of
=
introducing the density of single electron states of one
(c
0),
and
spin in the normal state at e
The first term gives the difference of kinetic energy between the superconducting and normal phases at 0K. The factor 2 arises because for
every electron in state k of energy e k there is with an isotropic Fermi
surface another electron of the same energy in k. This first term can
be either positive or negative, and is smaller than the second term
The limit of integration is
which
to XI.4,
from a
For such a transition to be
gives the correlation energy for all possible transitions
pair state (k,
k)
to another (k',
k').
(XI. 10)
so that
using XI.4 one can simplify to
wm - Sk 2e
'
k must initially be occupied and k' empty. The simultaneous

probability of this is given by h k {\ h k >). The final state must have k
empty and k' occupied, and this has probability h k -{\ h k). The
square root of the product of these probabilities multiplied by the
matrix element for the transition and summed over all possible values
of k and k' gives the total correlation energy.
W(0) must of course be negative for the superconducting phase to
= 0: M0), XI. 10 becomes

JlCOq
M0)
The
[e
the
+ 2 (0)] ,/2
phonon energy above which, according
V=0.
solution of XI. 11
possible,
e(0)
is
= /mysinMl/MO) V\.
(XI.12)
one finds
Putting this back into XI.9 and XI.7 and finally into XI.5',
given by
is
state
superconducting
of
the
that the ground state energy
W(0)
= -
2MQ)(W 2
exp[2/M0)F]-l
(XI. 13)
124
Superconductivity
from any theory which postulates an interaction between electrons

and phonons and allows this interaction to be cut off at some average
phonon energy hw q k B 6, beyond which the interaction becomes

repulsive. A term like this had been contained in the earlier
attempts
of Frohlich and of Bardeen, and, as mentioned before, is much too
large. The success of the BCS theory lies in the appearance
of the
exponential denominator which reduces W(0) by many orders of
magnitude. Although a precise calculation of the average interaction
parameter V for a specific metal continues to be among the most
important questions still to be solved, various estimates (Pines, 1958
Morel, 1959; Morel and Anderson, 1962) indicate that the values
Vx 0-3, derived from a knowledge of
are reasonable.
of N(0)
Q,
Thus the denominator has a value of about e 7

The isotope effect follows from the numerator of XI. 1 3, as it would
from any theory involving electron-phonon interaction with a cut.
off frequency related to the
6 and hence to the isotopic mass.
Debye
Equation XI. 13 shows that
H
~=
2
discussed by Ehashberg(1961),Bardeen[9],Schrieffer(1961),Betbeder-
Matibet and Nozieres (1961), and Bardasis and Schrieffer (1961).

quasi-particles is found to be very small even up
The damping of the

to energies well
the
beyond the Fermi energy. This
BCS assumption embodied
off of the
in
XI .4,
is in
contradiction to
as the justification of the cut-
Coulomb interaction at hu) q is essentially that quasi-particles

damped as not to be available for pair
of larger energy are so strongly
It is thus necessary to modify the BCS cut-off by taking into

account the existence of the repulsive interaction for e k > hwq This
does not appreciably affect the gap at the Fermi surface (e k = 0), but
will result in its variation with e k , as will be further discussed in
formation.
Section 11.7.
With a compound tunnelling arrangement in which electrons are

and then have the possibility of tunnelling through a second junction into normal metal,
Ginsberg (1962) was recently able to place an upper limit on the lifeinjected into a layer of superconducting lead
time of the quasi-particles in a superconductor. According to his pre7

liminary result this upper bound is 2-2 x 10~ sec, which is only about
times as large as the average time calculated by Schrieffer and
Ginsberg (1962) for quasi-particle recombination into pairs by means
of phonon emission. This has also been calculated by Rothwarf and
five
^(0)
cc {hu>
q)
For a group of isotopes, one
finds
(k D Q)
Tc
cc
Tc Mr* 12
cc
Mfol
(XI. 14)
Cohen
so that
(XI.15)
Any
appreciable deviation of the isotope effect exponent from the

value 0-5 could indicate that the simplifying BCS assumption of
a cut-
Coulomb and phonon interaction at hw has to be modiq

(Tolmachev, 1958; Swihart, 1959, 1962). Bardeen (1959) has
pointed out that the cut-off may be determined by the lifetime of the
'normal' electrons which can be excited across the gap. These elecoff for both
fied
trons are not the bare, non-interacting electrons of the simple BlochSommerfeld model. Instead they are so-called quasi-particles
'clothed' by their interactions with each other and with the lattice
\1], pp. 184-95). As a result the wave functions describing them
are not eigenfunctions of the system, so that the particles
have a finite
lifetime. The effect of this on the pair interaction
has been further
(see
125
The numerator of this quantity follows from dimensional reasoning
(1963).
Swihart (1962) as well as Morel and Anderson (1962) have studied

the isotope effect for different forms of the energy dependence of the
They find that the exponent of the isoXI.

5
less than the ideal value of one half by
equation
is
mass
in
topic
amounts of 10-30 per cent which increase with decreasing TJ6.
However, the isotope effects in ruthenium (Geballe et ol., 1961,
Finnemore and Mapother, 1962), osmium (Hein and Gibson, 1964)
and perhaps also in molybdenum (Matthias et a I., 1963) appear to be
electron-electron interaction.
1
too small to be explained by these calculations.

This raises questions about the origin of the attractive interaction
responsible for the formation of
Cooper
pairs in these as well as
perhaps in other metals. Matthias (see for example, 1960) has repeatedly suggested that in all transition metals there exists an attractive
magnetic interaction responsible for superconductivity. However,
both Kondo (1963) and Garland (1963a) have tried to explain the
126
Comparing XI.16 with XI.7 one
on
Rondo assumes a
the other hand, believes that the electrons of high effective
mass
As
1/N(0)
11.6.
added to the usual
As
attractive interaction
by exchange of
virtual
phonons.
Garland (1962b) calculated the magnitude of the isotope effect for

superconducting elements and obtains results which agree closely
available experimental results, including in particular the
all
reduced
2c(0)
d-band tend not to follow the motion of the s-electrons. This

results in 'anti-shielding' the interactions between ^-electrons, leading
to an attractive screened Coulomb interaction between them being
with
gap has the
2^^/sinh [1 /N(0)
(XI. 1 7)
V\.
larger interband interaction; Garland,
V& 3-4, this can be approximated by
in the
all
sees that this energy
value 2e(0), which according to XI. 12 equals
and d bands of the electronic spectrum, and not because of a magnetic

interaction.
127
Superconductivity
apparently anomalous superconducting behaviour of the transition

metals as a consequence of the overlap at the Fermi energy of the .v
effect in transition metals.
This also
results, at least quali-
from Rondo's calculations. Garland was also able to explain

the anomalous pressure effect in transition metals (Bucher and Olsen,
2 (0)
The superconductor
4Aco9 exp [-
(XI. 1 8)
/tf(0) V\.
at finite temperatures
the temperature of the superconductor is raised above 0R, an

increasing number of electrons find themselves thermally excited into
These excitations behave like those of a

normal metal; they are readily scattered and can gain or lose further
energy in arbitrarily small quantities. In what follows they are simply
single quasi-particle states.
called
normal electrons. At the same time there continues to exist the

all electrons still correlated into Cooper pairs, and
tatively,
configuration of
1964).
displaying superconducting properties, being very difficult to scatter

or to excite. One is thus led again to a two-fluid point of view.
As at 0R, one can write down an analytic expression for the ground
The energy gap at 0K
From XI.5' one can see that the contribution of a
state energy
11.5.
(k,
-k)
to this total condensation energy
single pair state
is
Letting
Wk =
2* k h k -2Vj:
W{J) containing a kinetic energy term and an interaction
term. In both, the presence of the normal electrons must be accounted

for, which is done by introducing a suitable probability factor fk
{0-MM
,/2
.
fk =
probability of occupation of
(XI.16)
1
-2fk =
first
term represents the kinetic energy of both electrons in the

and the second term the total interaction energy due to all
pair state k,
Wn] K E
.
the lowest excited state of the superconductor
must correspond to breaking up a single pair by transferring an electron from a

state k to another, leaving an unpaired electron in - k. The condensation energy is then reduced by
k The first term of this can be made
arbitrarily small, and is analogous to the excitation energy in a normal
metal, for which there is a quasi-continuous energy spectrum above
the ground state. The second term of
k however, is finite for all
values of k, which is why in the superconducting phase the lowest
excited state is separated from the ground state by an energy gap.
-k
k nor
occupied by a
2 M[fk + V-2fk)h k
k
(XI. 19)
electron.
This leads to a kinetic energy term
possible transitions into or out of the state.
At 0R
by a single
is
probability that neither
normal
The
-k
k or of
normal electron, then
],
where the summation is over the same range as at 0R, and h k retains
the same definition, though no longer the same value. The second
term
(k,
in the brackets clearly gives the probability that the pair state
k) not be occupied by normal electrons but by a correlated pair.
The
correlation energy at a finite temperature
is
kk'
x(l-2/*)(l-2/*0.
(XI.20)
128
Superconductivity
The last two terms ensure
that the correlated pair states not be occu-
pied by normal electrons.
It is
obvious that the presence of these
terms decreases the pairing energy.

The thermal properties of the superconductors can
where
Wm-TS =
the magnitude of the energy gap one must
expression for
fk
with respect to
fk
which one obtains by minimizing the
[W(T)\ K B MW(Tj\ C0 -TS,

.
(XI.21)
fk =
to the
Wv
The critical temperature Tc is reached when

up so that e(Tc) = 0. Hence
W
1
free
this
Ml-hM* = V S[Mi-M]"
l-2h
As long
(i-2A0
(XI.24)
and again obtains
One
now
(XI.28)
k B Tc
= M4/Kêxp[-
1/W(0) V\.
(XI.29)
tion with pressure in aluminium.
11.7.
hi
is
The exponential dependence of the transition temperature has been

verified by Olsen et at, (1964) by means of measurements of its varia-
<T)= F[M1-/'a<)] ,/2 (1-2/,0,
Ek
pair states are broken
f de tan .
all
<XL27)
k B Tc < hw q the solution of this can be written as
(XI.23)
This time one defines
where
as
2e 4
(XI.26)
7^^(-^H'
(XI.22)
and XI.22 into XI.21, and minim ising

energy with respect to h k one now obtains
J [e2+
Substituting XI. 19, XI.20
C xp(Ek /k B T)+])-
Jiuia
state of highest possible order
TS = -2k B T-Z {A.lnA. + (l-/*)m(l-A)}.
an
free energy
XI.26, XI. 18, and XI.24 yield for e(T) sl non-linear relation which,
changing as before from a summation over k to an integration over
e, becomes
J is the temperature and S the entropy. This last is due entirely
normal electrons; the electrons which are still paired are in a

and do not contribute at all. Thus the
entropy is given by the usual expression for particles obeying FermiDirac statistics
129
find
first
This yields
now
be found
quite readily by writing down the free energy of the system and
requiring this to be at a minimum. The free energy is
G=
To evaluate
defined as
-Hi
Ek m [e k + e 2 (!T)] ,/2
(XI.25)
energy gap at
XL 18
and XI.29
yields for the width of the
0K
2e(0)
3-52 kB Tc .
(XI.30)
sees that, as at 0K, 2e(T) represents the contribution
of a
and that to break up
one such pair at any finite temperature removes from the superconducting energy at least this amount. In other words, the superconducting state continues to contain an energy gap 2e(T) separating the
lowest energy configuration at any given temperature from that with
one less correlated pair.
single pair state to the total correlation energy,
Experimental verification of predicted thermal properties
Combining equations
This
is in remarkable quantitative agreement with empirical values

obtained from the wide variety of measurements mentioned in Chap-
ter
X. Table HI shows that for the most widely different elements
the energy gap does not appear to deviate from this idealized value
by more than about 20 per cent. The theoretical temperature variation

of the gap width is displayed in Figure41
firmed by a
number of experiments.
this
has also been well con-
Superconductivity
130
Muhlschlegel (1959) has tabulated values of the energy gap, the

entropy, the critical magnetic field, the penetration depth, and the
specific heat, all in reduced coordinates, as functions of the reduced
temperature. All these are in close agreement with experimental
results.
These agreements clearly vindicate the basic BCS approach accord,
ing to which the similarities between superconductors outweigh their

differences, so that an
approximate law of corresponding states should
1.0
the dependence of the interaction parameter
Fon k and k',
131
so as to
be able to calculate directional effects. Even more challenging are the

previously mentioned attempts to relax, even in an isotropic model,
the assumption XT.4 that Fis strictly constant for e k < hojq and is then
cut off abruptly. A better knowledge of the variation of Fwith e k in
would allow the more precise calculation of the corresponding

dependence of the energy gap on e k The actual form of this variation
undoubtedly more nearly resembles the solid line in Figure 42 rather
than the dotted line which corresponds to the simple BCS assumption.
Usually one is interested in excitation energies of the order of k B Tc
and the BCS assumption is then fully applicable as long as k B Tc < hu) q
turn
OB
em
o.6
02
0.2
0.6
0.4
0.8
t.O
Fig. 41
is called the weak coupling limit. As hw q &k B , where

Debye temperature, this requires that
which
hold.f This similarity principle had of course emerged from
much pre-
vious experimental evidence. However, differences between metals

and anisotropics in a given metal do exist, and the experimental evi-
dence for gap variations from one metal to another, as well as for gap
anisotropics, clearly indicates the need to refine the details of the BCS
calculations. For one thing it is of course desirable to take into account
t Deviations from such a law can occur even with the BCS assumption
of constant Kif in solving equations XI.27 and XI.28 one takes into account
higher order terms in k B Te lhwq (Muhlschlegel, 1959). The resulting correction factors appearing in equations XI. 30, XI.35, and XI.36 are, however,
too small to explain the empirical deviations from similarity discussed in
this section. Thouless (I960) has shown that in the BCS formulation the
energy gap at 0K is only 4-0 k B Tc even in the non-physical limit
the
Tc <
is
e.
For a number of superconducting elements, in particular for Pb and

Hg, this condition does not hold.
Swihart (1962, 1963) as well as Morel and Anderson (1962) have
investigated the consequences of an energy dependence of the interaction Kmore realistic than that assumed by BCS. In particular they
take into account that, as was mentioned earlier, lifetime effects are
too small to justify cutting off the Coulomb repulsion at hm q Therefore these authors include in the interaction a repulsive part (V> 0)
The resulting variation of the energy gap at
for energies e > hw
.
0K
as a function of e k has been
shown by Morel and Anderson
have the form represented schematically
in
to
Figure 42. Swihart found
Superconductivity
132
that a rise of this gap function
on moving from
leads to the correct specific heat
jump
the Fermi surface
for lead at
Tc The
.
relation
between calorimetric and magnetic properties indicates that such a

gap variation is also consistent with the observed critical field curve
and probably also with that for mercury.

For even higher quasi particle energies the energy gap continues
to change sign periodically at multiples offiw This is consistent with
q
the observations of Rowell et al. (1962), who found maxima in the
tunneling conductance with that periodicity. Excitation of high
energy quasi particles involve multi-phonon interactions.
for lead
A precise calculation of the energy

content
itself
gap variation with
ek
in
which the energy gap
is
of the tunnel are superconducting. This current can be considered
/sla
.
n
SaTh V S+
3.6
kT c
calculation
V^g
Al|
26(0)
1 InRe
3.2
Ru
IS, -
fTl
Zr
(1964).
2.4
In considering an energy gap which changes sign as a function of

it
Pb
4.0 _
was carried
out for lead by Culler et al. (1962), using an on-line computer facility.
The relation between the phonon spectrum and the tunneling
characteristics has been fully discussed by Scalapino and Anderson
ek ,
et al.
The tunneling discussed thus far in this section and in Section 10.6
more quasi-particles. Josephson
(1962) has predicted an additional tunneling current when both sides
necessary to recognize the different frequency distributions for the
and transverse phonons. Such a
Rowell
involves the passage of one or
it
longitudinal
ments with lead, tin, and aluminium. Indications of this structure

had been seen earlier by Giaever et al. (1962) in lead and by Adler
and Rogers (1963) in indium.
must take into account the details of the phonon spectrum,

as determined, for example, by neutron diffraction. In particular it
Instead
taken to vary with
133
(1963) have closely verified the expected structure by tunneling experi-
cannot
with assigning to the phonons an average energy hcu
e(0) is
ek
must be remembered that
in
10r4
an experiment involving thermal
Ek
denned by XI. 9. This involves only the

However, the
details of the variation of the variation of the gap with e k can be
verified by tunneling experiments, in which the conductance dl/dV is
is
the energy
square of the gap, and
(Bardeen, 1961a,
962a; Cohen et al.
however pointed out that
Fig. 43
therefore always positive.
is
directly proportional to the density of states in the superconductor

1
10"
Tc /)
or electromagnetic absorption across the gap, the quantity actually
observed
10' 2
10' 3
have
one cannot use the standard
1962).Schrieffer<?/a/. (1963)
for tunneling
as being due to the direct passage of coherent

side of the insulating barrier to the other.
Cooper
pairs
from one
As has been elaborated by
Anderson (1963) and by Josephson (1964), the
relative
phase of the
superconducting wave functions on either side of the barrier has

physical meaning because it is a quantity conjugate to the number of
not quasi-particle eigenstates of the

individual metals making up the tunnel. Instead the appropriate
and because this number is not

As a result the energy of the
system depends on this phase difference, and in turn this gives rise
to a flow of pairs across the barrier in the absence of an applied
density of states to use
potential difference.
expression for the quasi-particle density of states. This
when an
electron tunnels
the initial
and
from one
is
m)
because
side of the barrier to the other,
final states are
is
Ek
Hvv^}
electrons
on each of
constant, that
is,
the
two
sides
not fully determined.
The Josephson current is very difficult to detect because it is quenched by a magnetic field of a few tenths of a gauss. It was first observed
Superconductivity
by Anderson and Rowell (1963) and by Shapiro (1963). The temperature dependence has been studied by Fiske (1964), following calculations by Ambegeokar and BaratofF (1963). Ferrell and Prange
(1963) have discussed the self-limitation of the Josephson current by
the magnetic field it generates itself, and De Gennes (1963) has derived
an expression for the current from the Ginzburg-Landau-Gor'kov
except for the upward deviation at the lowest temperature which was
34
mentioned
earlier (see Figure 28).
Further numerical predictions of the
=
yTc
equations.
A more
realistic cut-off
can also yield theoretical justification for
The following
table
TJ@. Such a correlation was

whose plot of energy gap values
against TJ0 for 17 different superconductors is shown in Figure 43.
Goodman used gap values deduced from empirical values of y, H
and Tc by combining XI. 1 3, XT. 8, and XI.20, and remembering that
is
taken from
BCS theory
Goodman
[7] (p.
= ffl^jAftO). This yields

(XI.32)
11.8.
The
One can
Element
yTc
Lead
Mercury
Niobium
Tin
Aluminium
Tantalum
3-65
listed in
Table
215
most experimental values agree with
obtain the electronic specific heat in the superconducting
phase by twice differentiating with respect to temperature the free

energy expression XI.21. At sufficiently low reduced temperatures,
for which 2e(7")
2-60
2-60
2-58
2-57
2-25
Zinc
Thallium
III.
specific heat
> k D Tc
this yields
closely
318
307
Vanadium
V3
Appropriate values of 2e(0)/( B rc ) are
how
CJTJ
k B Tc
(XI.35)
212) and shows
(1958),
include
2 43.
the apparent correlation of e(0) with
suggested by
135
Hi
this.
The theory
also yields that
0170,
(XI.36)
(see equation 11.15) that the predicted

polynomial expansion of the threshold field is
from which one can calculate

coefficient
of
2
t
in the
yTc
a2
107.
(XI.37)
where K and Kj, are first and third order modified Bessel functions of
the second kind. This simplifies in the temperature regions indicated
This agrees exactly with the experimental value for tin (VIII.3) and
closely with that for several other elements. In terms of the deviation
to the following exponential expressions:
of the threshold
yT
8-5 exp(-l -44TJT),
2-5
< TJT <
field curve from a strictly parabolic variation as displayed in Figure 23, any value of a 2 greater than unity corresponds
to a curve below the abscissa; only mercury and lead are seen to have
6,
(XT.34)
26 exp (- -62TJT),
< TJT <
1 1
deviations corresponding to values of a 2 smaller than unity.
The BCS calculations are based on an isotropic model, in which the

Kdoes not depend on the direction of A: and k
Pokrovskii (1961) and Pokrovskii and Ryvkin (1962) have investigated the effects of anisotropy on thermal and magnetic properties.
interaction parameter
Experimental data at
this
regions where they are in
time exist only in the
first
of these two
good agreement with the BCS
values,
10
'
Superconductivity
136
find that in anisotropic superconductors the specific heat ratio
They
137
transitions interfere either constructively or destructively depending
in Xl.35 should be smaller than 2-43, the quantity in XI. 36 larger than
on the type of scattering phenomenon
therefore the coefficient a 2 larger than 107. In the second

of the papers cited these results are compared with extensive experi-
interference in the case of electromagnetic interaction, such as the
mental data.
action which determines the nuclear relaxation rate.
The thermal conductivity in superconductors has been calculated

on the basis of the BCS theory for several of the pertinent mechanisms.
Bardeen et al. (BRT, 1959) and Geilikman (1958) have derived the
mental results expected
01 70, and
ratio of the electronic conductivity in the superconducting phase to
by impurity
have been well confirmed
experimentally, as was discussed in Chapter IX. The derivation of
BRTforthecaseofelectronicconductionlimitedbyphononscattering
(equation IX.5) does not, however, lead to the empirical behaviour.
Calculations by Kadanoff and Martin (1961) and by Kresin (1959)
are in better agreement, but further theoretical work is needed for this
that in the normal one
when
this is primarily limited
scattering (equation IX.6). Their results
involved. There
is
constructive
absorption of electromagnetic radiation, and the hyperfine inter-
The
experi-
two cases are therefore qualitatively

those which follow from a two-fluid model consideration of the total
number of electrons available as well as from the density of available
states. It has already been mentioned how this explains the observed
rise in the nuclear relaxation rate just below the critical temperature
in these
(Figure 32).
On
the other hand, the contributions of the
two
fere destructively in the case of the absorption of
transitions inter-
phonons, such as
occurs in the attenuation of ultrasonic waves. This destructive interference so decreases the probability of absorption that the effect of
the increase in density of states on either side of the gap
is
completely
conduction mechanism, in which quasi-particle life times may again

be important (see [7], pp. 272 ff.). According to calculations of
Tewordt (1962, 1963), however, these appear to have little effect on
wiped out, and the absorption just below Tc drops very sharply. For
low frequency phonons, ha> <^ 2e(0), the ratio of attenuation coeffi-
conduction mechanism.
BRT as well as Geilikman and Kresin (1958, 1959) have derived
the lattice conductivity limited by electron scattering. Experimentally
with an
this
cient in the superconducting

infinite slope,
-?
a
very difficult to separate out this part of the heat transport.

Where this has been possible (Connolly and Mendelssohn, 1962;
it is
Lindenfeld and Rohrer, 1963) the results have been in general

agreement with the theoretical predictions.
This function
is
and
shown
is
and normal phase
o.J<x
2/{l+exp[2e(T)lk B T]}.
in
Tc
drops below
given by
(XI.38)
Figure 44, which includes experimental
points on both tin and indium by
Morse and Bohm
(1957). It should
be contrasted with the theoretical prediction for nuclear relaxation

11.9.
One
Coherence properties and ultrasonic attenuation

BCS theory arises as a
of the most striking predictions of the
consequence of the pairing concept, and experimental verification of this point is thus of particular importance. In a normal metal
the scattering of an electron from state k t to state k' t is entirely
independent from the scattering of an electron from - k | to -k'
or of any other transition. The coherence of the paired electrons in
the kf and -k j states in the superconducting phase, however,
direct
makes
(see
two transitions interdependent. The details of the theory

pp. 212-24) show that the contribution of the two possible
these
[7],
rate,
shown
in
Figure 32.
Measurements of the ultrasonic attenuation

in different crystal directions
in single crystals of tin
has yielded very convincing demonstra-
When an electron absorbs a

momentum can both be conserved only if the
tion of the anisotropy of the energy gap.
phonon, energy and
component of the electronic velocity parallel to the direction of sound

propagation is equal to the phonon velocity, which is the velocity of
sound S. Since, however, the Fermi velocity of the electrons, v is
,
several orders of magnitude larger than S, this
electrons which
is
possible only for
move almost at right angles to the direction of sound
138
Superconductivity
propagation. Thus a measurement of the attenuation of sound propagated in a particular crystalline direction involves only those electrons
To
whose velocity
state in the presence of an external field,
a thin disk at right angles to this direction. The value of the energy gap appearing in equation XI. 38 i > thus
one averaged over this particular disk. Such measurements have been
1.0
directions
lie in
11.10. Electromagnetic properties
describe the many-particle
interaction as a perturbation,
wave function of the superconducting
BCS treat the electromagnetic
and obtain an expansion
in terms of the
spectrum of excited states in the absence of the field. This wave function is then substituted into an equation of the form III. 20 to calculate
the current density. Mattis and Bardeen (1958) and also Abrikosov
et al. (1958) have expanded this to treat fields of arbitrary frequency.
The
result of the former has been used by Miller (1960) to calculate

values of cri/o n and of a 2 lan over a wide range of temperatures and
TIN
0.8
139
x INDIUM
frequencies. His calculations are in excellent agreement with all the
experimental results using weak
0.6
in
Chapter X,
to
its
if the
energy gap
is
fields at
high frequencies, described
taken as a parameter to be adjusted
empirical value.
The treatment of a magnetic field as a perturbation in the BCS

formulation makes it very difficult to extend it to high field values
(H m c). This can be done more readily from a representation of the
0C n
BCS
0.4
ideas in terms of Green's functions which has been developed
by Gor'kov (1958). A simplified version of this method has been presented by Anderson (1960). The electromagnetic equations occurring
in this formulation were shown by Gorkov (1959, 1960) to be equivalent to the Ginzburg-Landau expressions in the region near Tc and
under circumstances where A > . As was pointed out in Chapters V
and VII, Gor'kov showed that the energy gap is proportional to the
G-L order parameter, so that the dependence of the latter on temperature, magnetic field, and co-ordinates, also applies to the former.
02
The successful application of these ideas to a number of experimental

results
has been mentioned
in
Chapter VII.
An apparent shortcoming of the original BCS
performed on variously oriented tin single crystals both by Morse et al.

(1959) and by Bezuglyi et al. (1959). Their results are in good agreement and are summarized in the following table:
Wave
vector q
2e(0)/k B Tc
parallel to [001]
3-2 01
parallel to
4-3
[1 10]
perpendicular to [001] and 18 from [100]
0-2
3-5
01
treatment is its lack

of gauge invariance. It was suggested by Bardeen (1957) and worked
out by various authors that this can be remedied by taking into
account the existence of collective excitations. A discussion of this
with full references is given in [7] (pp. 252 ff.).
There exists as yet no fully satisfactory explanation that the Knight

superconductors does not vanish in any of the elements in
which is has thus far been studied mercury (Reif, 1 957), tin (Androes
and Knight, 1961), vanadium (Noer and Knight, 1964) and aluminium
shift in
'40
Superconductivity
(Hammond and
The Knight shift is defined as the fractional difference in the magnetic resonance frequency of a
nucleus
in a free ion and the same nucleus in a metallic medium. It is
due to
the field at the nucleus created by the free electrons, and is usually
Kelly, 1964).
CHAPTER
XII
taken to be proportional to the electronic spin susceptibility. A literal

interpretation of the Cooper pairs of opposite spin would lead
one
to expect that in a superconductor this susceptibility and hence
the
12.1. Introduction
should vanish at 0K. A number of authors (see

[7],
pp. 261-263; Anderson, 1960; Suhl, 1962; Cooper, 1962) have
suggested why this may actually not be the case, and although none
of these explanations appears fully adequate, they have shown that
Ever since the discovery of superconductivity there have been many

searches for new superconducting materials. Roberts (1961) has
recently listed more than 450 alloys and compounds with critical
temperatures ranging from 016 up to 18-2K. In the appearance of
Knight
shift
the
Knight shift
the
BCS
offers
no fundamental disagreement with the idea of
theory.
(1962, 1964) deduce
from the temperature variation of the Knight

that in the superconducting state the dominant
to the d-electron spin does vanish, as the simple
vanadium
contribution due
superconductivity
among
Compounds
these substances there exist certain regu-
which were discovered by Matthias (1957) and to which

reference was made in Chapter I. One might consider as an ultimate
goal of any complete microscopic theory the ability to derive these
Matthias rules from first principles. This would be equivalent to being
larities
It is, furthermore, possible that the Knight shift in

some of these
elements is not primarily due to spin paramagnetism. Clogston et al.
shift in
Superconducting Alloys and
theory would predict. This, however, leaves a
finite Knight shift

due to orbital paramagnetism which involves electrons too far from
the Fermi surface to be involved in pairing. Thus this contribution
to the Knight shift in vanadium
not affected by the superconducting

transition, and perhaps the orbital part is the dominant one
in tin
and mercury.
is
some precision the actual critical temperature

of any superconductor. At the moment our understanding of superconducting and of normal metals is still very far from such
able to calculate with
achievements.
One of
the
many ways
of increasing this understanding
is
sys-
tematic study of superconducting alloy systems in which solvent or

solute are used as controlled parameters. This has been done in a
number of experiments.
12.2. Dilute solid solutions with
Serin, Lynton,
non-magnetic impurities
and collaborators (Lynton
et
al.,
1957; Chanin et
al.,
1959) have investigated the superconducting properties of dilute

alloys of various solutes into tin, indium, and aluminium, up to the
limit of solid solubility. For low impurity concentrations, of the order
of a few tenths of an atomic per cent,

reciprocal electronic
mean
Tc decreases linearly
with the
free path, independently of the nature of
When plotted against the reduced co-ordinate //, where

the coherence length of the pure solvent, the fractional change
the solute.
is
in
Tc is the same for elements as different as Sn and Al (Serin,
1960).
shown in the initial portions of both curves in Figure 45. The

existence and the magnitude of this seemingly general effect lend
This
is
141
Superconductivity
Superconducting alloys and compounds
strong support to Anderson's model of impure superconductors
anisotropic energy gap indeed leads to a lowering of Tc of the observed

magnitude. Hohenberg (1963) has calculated the dependence of Tc
142
(Anderson, 1959). He suggested that the energy gap anisotropy is

smoothed out by impurity scattering and disappears when the electronic mean free path is comparable to
fiv
so-
MO)
the energy gap,
and the density of
on the concentration of
states
impurities.
This general mean free path effect on Tc has also been found in
tantalum by Budnick (1960). It has been verified by using a number
of different ways of scattering the electrons by mechanical deforma-
143
and cold work in aluminium (Joiner and Serin, 1961), by size

effects in indium (Lynton and McLachlan, 1962), by quenching
(De Sorbo, 1959), electron irradiation (Compton, 1959), neutron
bombardment (Blanc et al., 1960), and by using isoelectronic ternary
compounds (Wipf and Coles, 1959) in tin.
Figure 45 shows that for P /l > 1 the effect on Tc deviates from the
initial linear decrease in a way which depends on whether the solute
tion
+.02
ELECTRONEGATIVE
+.01
Aoll
is
-.01
electropositive (valence smaller than that of solvent) or electro-
al. (1961) have extended such

measurements to higher concentrations. They found that for both
types of impurities Tc ultimately rises to values above that of the
negative (valence larger). Chiou et
-02
and were able to repissent the variation of Tc with impurity

all cases by an empirical relation containing two
solvent,
-04
combination.
-05-
parameters an average phonon frequency m q (which is proportional

to the Debye temperature ), the density of normal electron states at
concentration in
parameters adjusted according to the particular solvent-solute
According to the BCS theory (equation XI.29),
Fig. 45
This should then result in a lowering of
Tc
by an amount approxi-
resonance in aluminium (Masuda and Redfield, 1960a, 1962) and ultrasonic and infrared absorption in tin (Morse et al., 1959; Bezuglyi,e/ al.,
1959; Richards, 1961) have
shown
by about 10 per cent from
be lowered by about
confirm
this very well.
Kadanoff
per cent
its
that the
gap
in these elements
average value, so that Tc should

P The measurements of Tc
when /
Recently Caroli et
al.
(1962),
Markowitz and
and Tsuneto (1962) have shown in terms of the

microscopic theory that Anderson's idea of the smoothing of an
(1963),
is proportional to the Sommerfeld y),

and the BCS interaction parameter V. Specific heat measurements on
tin alloys have recently enabled Gayley et al. (1962) to find the effects
of the addition of indium, bismuth, and indium antimonide on the
values of y and of for tin. One can use equation XT.29 to calculate
the corresponding change in Tc This seems to account for most of
the difference in the behaviour of electropositive and electronegative
solutes, at least in the case of indium and bismuth, but not for the
the Fermi surface, N(0) (which
mately equal to the square of the fractional anisotropy. Nuclear
varies
Tc depends on three
increase in
increase
is
Tc at high solute concentrations. One concludes that this

mainly due to
effects
of alloying on the interaction
energy V.
Any attempt to calculate Kin the presence of impurities has to take
144
Superconductivity
wave vectors k are no longer

good quantum numbers. Hence the question arises of the criterion
for pairing of the electrons. Abrahams and Weiss (1959) and
Anderson (1959) have pointed out that in impure superconductors
Cooper pairs are formed of two electrons the wave functions of which
are identical except for the reversal of the time co-ordinate, and which
have the same energy. The former authors have used this to deduce
into account that with scattering the
145
Also the absorption edge of infrared radiation at the

gap frequency can be very sharp (Ginsberg and Leslie, 1962).
Detailed magnetization curves (Lynton and Serin, 1958) however,
et al., 1956).
show
that the transitions for such alloys are nevertheless not fully
46 for 311 per cent In-Sn cylinders

In decreasing field the magnetic
moment does not attain its full diamagnetic value until vanishes.
This indicates that flux is initially trapped, but then leaks out as
reversible, as
shown
in Figure
transverse to an external
field.
suggested by Faber and Pippard (1955b).

12.3. Compounds with magnetic impurities
Matthias and collaborators have traced the occurrence of superconductivity in a large number of compounds containing paramagnetic and ferromagnetic impurities (Matthias, 1960). Their
can be summarized as follows:

Ferromagnetic transition elements with 3d electrons (Cr, Mn, Fe,
Co, and Ni) put into fourth column superconductors (Ti, Zr) raise
results
Tc more than
Ad
do corresponding amounts of transition elements with
electrons (Re, Rh, Ru, etc.) (Matthias and Corenzwit, 1955;
Matthias et al., 1959b). At the same time magnetic measurements on

Ti-Fe and Ti-Co alloys indicated the absence of localized moments.
The effect of the 4d electrons can be attributed to the increase in
Applied Field
He
the
number of valence
electrons per
atom toward
The
particularly favourable for superconductivity.
Fig. 46
3d electrons
is
is
difficult to esti-
mate. Anderson (1959, 1960) has discussed the general implications

of the use of time-reversed wave-functions. Detailed microscopic
calculations of the impurity effects on the superconducting parameters
have been attempted by Caroli

Kadanoff(1963).
et al.
(1962) and by
Markowitz and
annealed solid
conductors according to several
criteria.
Transitions occur within a
few millidegrees, and very little flux remains in suitably oriented

cylindrical samples after an external field has been removed (Budnick
same reason adding Fe
(3d electrons) to a Ti 6 V 4 compound lowers Tc less than does an

equal amount of Ru (4d electrons): in both cases Tc is decreased
.
because the number of valence electrons per atom rises beyond five,
but with Fe the apparent magnetic interaction counteracts this in
part. It must be pointed out, however, that ferromagnetic transition
fifth column superconductors (Nb,
V) lower Tc in approximate agreement with the expected effect due to
the change in valence electrons per atom (MUller, 1959). There does
not appear to be any added effect due to the magnetic nature of the
impurities. Why such effects should appear with fourth column
metals but not with fifth column ones is far from clear, as in neither
elements with 3d electrons put into
to note that the work
on carefully homogenized and

solutions has shown these to be 'well-behaved' super-
It is interesting
a number
extra rise with
attributed to a magnetic electron-electron inter-
action favouring superconductivity. For the

several impurity effects, the magnitude of which
five,
146
Superconductivity
958b, 1959a).
case are there any localized magnetic moments associated with the 3d
solute atom.
et al.,
Quite recently Cape (1963) has measured the electrical and magnetic properties of very carefully prepared alloys of Ti containing
effective
0.2 to 4 at
Mn. Depending on
the
method of preparation
these
moments
is
147
decrease, for each per cent
is correlated with the spin rather than with the

magnetic moment of the solute. This is shown in Figure 47
in which - ATC for each per cent, the spin, and the effective moment
of rare earth impurity,
/x
eff are
plotted for the different rare earths.
Tc
A higher effective moment,
hep phase, which however is not
consistent with the usual suppression of
centage of neodynium, which has the same spin but a smaller moment.
exist only in the
superconducting. This
The magnitude of this
perhaps for the same reason as in

the case of the 3d impurities in fourth column metals erbium, with
spin 3/2 and large moment lowers Te less than does an equal per-
specimens are either in a single hexagonal close packed (hep) phase,

or contain an admixture of a second, body centred cubic (bec) phase.
Localized
in fact, appears to tend to raise
superconductivity by impurities retaining localized
moments (see
The non-magnetic bec phase, on the other hand, has a transition temperature which is raised above that for pure Ti by an amount
commensurate with the increase in the number of valence electrons.
Hake et al. (1962) had earlier deduced from their measurements of
transport properties that the hep phase of Ti-Cr, Ti-Fe, and Ti-Co
also carried localized magnetic moments. In addition there is calorimetric evidence (Cape and Hake, 1963) that in Ti-Fe samples only a
small fraction of the volume is superconducting. These results throw
considerable doubt on Matthias' speculation that iron-group impurities which do not carry a localized magnetic moment enhance
superconductivity by means of a magnetic interaction between
below).
electrons.
While 3d impurities in fifth column metals (for example Nb) do not

show any evidence for a localized moment, they do when put into
sixth column metals (for example, Mo), and in fact Matthias et al.
(1960) found that the change in behaviour occurs in
Nb-Mo solutions
Mo. One would therefore

some special effects on Tc to appear in 3d compounds with
sixth column metals. Until the recent discovery of the superconductivity of Mo, no such metal was known to be superconducting. For
that reason, this effect was studied on superconducting Mo
8 Re 2
and indeed small amounts of 3d impurities lower Tc far more than one
would expect from valence effects. It is in fact this which made the disat a concentration of about 60 per cent
expect
Fig. 47
All these compounds containing 4/electrons show ferromagnetic

behaviour at somewhat higher concentrations of the rare earth
solutes, with the Curie temperature rising with increasing number of
4/ electrons. Such dilute ferromagnetism has not been observed for
compounds with 3d electrons which

interaction
is
indicates that the s-f magnetic
rather long range, while the d-d one
is
a short-range
covery of the superconductivity of Mo so difficult: a few parts per

million of iron are enough to depress Tc below the measurable range
(Geballe et al, 1962). A less abrupt decrease in T is obtained when
c
rare earth elements with 4/electrons are put into lanthanum (Matthias
inter-action effective only through nearest neighbours,
which
is
impossible in dilute solutions (Matthias, 1960).

Interesting analogies in the variation of the Curie temperature and
the superconducting critical temperature are found by investigating
the magnetic characteristics of so-called Laves compounds AB2
,
where B is germanium or a noble metal (Ru, Os,
Ir,
Pt)
and A is either
148
Superconductivity
a rare earth with 4/ electrons (A') or one of the group Y, Sc, Lu, or
La {A"), none of which contain 4/ electrons (Suhl et al., 1959). A'B2
is
always ferromagnetic,
A"B 2 always
superconducting. Comparing
149
an amount proportional to the

between the initial and final electron
electron-spin scattering interaction by
reciprocal energy difference

state.
In the normal state this difference can be arbitrarily small, in
the Curie temperatures of the former with the critical temperatures of
the superconducting case this difference cannot be smaller than the
on spin and on the number
energy gap. As a result the free energy of the normal phase is lowered
more than that of the superconducting one, and the onset of super-
the latter one finds a similar dependence
of valence electrons per atom. This
but one of a number of interesting correspondences which Matthias has found between superconis
conductivity therefore occurs at a lower temperature. Suhl and
and ferromagnetism. There are, for example, several groups

of isomorphous compounds which are either superconducting or
ferromagnetic (see, for example, Matthias et al., 1 958a Compton and
Matthias ignore the small changes
Matthias, 1959; Matthias et al., 1962). Also, the appearance of locali-
(1960)
ductivity
zed
moments when
a ferromagnetic impurity
netic transition element
electrons in a
manner
is
put into a non-mag-
seems to depend on the number of valence
similar to the criterion for the appearance of
superconductivity (Matthias, 1962). Matthias hasfrequentlysuggested
may
that an electron configuration favourable to superconductivity

also be favourable to ferromagnetism.
The possible coexistence of superconductivity and ferromagnetism

in the
same substance has been investigated in lanthanum-rare earth

compounds (Matthias et al., 1958b) and in Laves compound
binary
mixtures (A'i^ x A%)B
(Matthias et
al.,
1958c; Suhl et a/.,1959).
Both magnetic (Bozorth et al., 1960) and calorimetric measurements

(Phillips and Matthias, 1960) have shown that ferromagnetism and
superconductivity occur in the same sample, but the evidence
entirely conclusive in ruling out the possibility that these
is
not
two phe-
nomena merely exist side by side in different portions of the specimen.

Anderson and Suhl (1959) have shown that the actual coexistence of
ferromagnetism and superconductivity on a microscopic scale is
energetically possible if the ferromagnetic alignment occurs in the
form of extremely small domains probably of the order of 50 A. They
V,
in the interaction
and as a result their prediction (dTJdc -* 0)
impurity concentrations
show
is
matrix element
for very small magnetic
probably wrong. Abrikosov and Gor'kov
that magnetic impurity effects
linearly with impurity concentrations.
on
V initially
lowers
Tc
Atmuch higher concentrations
Suhl and Matthias find that S7y3c->co, which is supported by

experiment (Hein et al., 1959). Similar calculations have been carried
out by Baltensperger (1959). Suhl (1962) has recently reviewed this
and
similar work.
Abrikosov and Gor'kov (1960) as well as De Gennes and Sarma
(1963) show that magnetic impurities will lower the energy gap more
rapidly than the transition temperature. There should thus be a
range of concentration for which the alloy has a finite critical tem-
perature at which
its
DC resistance disappears without the existence
of an energy gap. Indeed Reif and Woolf ( 1 962) have found this para-
They measured the electrical resistance as

number of lead and indium
film containing magnetic impurities. The gap decreased twice as
rapidly as the transition temperature, and an indium film containing
1 at
Fe, for example, had no resistance below 3K but a perfectly
ohmic tunneling conductance.
doxical behaviour to exist.
well as the tunneling characteristics of a
Phillips (1963) has pointed out that such gapless superconductivity
Suhl and Matthias (1959) have treated the general problem of the
lowering of Tc due to the presence of magnetic impurities by extending
an argument of Herring (1958), according to which the polarization
does not violate any fundamental principle. The spin-flipping scattering of the conduction electrons by the magnetic ions gives the former
a very short lifetime. This broadens the electron states, particularly
those nearest the gap, so much as to spread the states into the gap.
At a certain impurity concentration states will have spread throughout
due to the coupling of the conduction electrons with the spins of the
paramagnetic impurity ions lowers the free energy in both the normal
and in the superconducting phases. The free energy is lowered by each
making it disappear. The density of states,

however, will still have maxima at what used to be the edge of the gap,
and as long as this exists the material will have zero DC resistance.
call this 'cryptoferromagnetic' alignment.
the width of the gap,
Superconductivity
have been worked out by Skalski et al. (1963). In

terms of the Ferrell-Glover rule and the frequency dependence of the
conductivities shown in Figure 37, the situation can be described by
saying that at some concentration there is a finite real conductivity a
of the gradient of h k which, however, have yet to be justified from

more fundamental considerations. From these he concludes that a
normal layer sandwiched between two superconductors will itself be
-5
supreconducting if it is no thicker than about 10
cm. A superconducting layer between two normal metals will remain normal up to
50
The
details of this
For some further range of impurity concentration,

however, o-j will still be less than aN for cu/wg < 1 resulting in a reduced
delta function at the origin. At even higher concentrations, ct, x aN
for all frequencies. The sum rule is now satisfied without an infinite
DC conductivity, so that the metal is normal in every respect.
at all frequencies.
some similar critical thickness.

Cooper (196 ) has given a more intuitive argument for the possibil1
ity that the
may be
He emphasized
superconducting properties of thin metallic films
strongly affected by direct contact with other metals.

that in the BSC theory
12.4.
Superimposed metals
A recent series of experiments by Meissner (see Meissner,
1960 for full
one must clearly distinguish between the range

of the attractive interaction between electrons, and the distance over
which as a result of this interaction the electrons are correlated into
Cooper pairs. The range of the interaction is very short (10~ 8 cm) ; the
of the wave packets of the pairs, on the other hand,
references) has revived interest in the question whether thin layers of
'size'
superconducting material deposited on a normal metal would themselves become normal, and whether conversely sufficiently thin layers
order of the coherence length, that is, 10
of normally non-superconducting metal would become superconducting when in contact with a superconductor. Such superimposed metals
differ
from the sandwiches used
in the tunnelling
experiments by the
absence of an insulating layer.
Parmenter (1960a) has constructed a theory for such direct metallic

contacts in which he attempts to introduce directly into the
BCS
extend a considerable distance into a region in which the interaction

between electrons is not attractive. Thus when a thin layer of superconducting material is in contact with a layer of normal metal, the
zero-momentum
pairs
formed because of the attractive interaction in

As a result the ground
the superconductor extend into both layers.
a spatial variation of the parameter h k appearing
state energy of this thin bimetallic layer
of h k 12 and of
-h k ) 112
, broadly analogous to the extra energy term

V.6 in the Ginzburg-Landau theory. Near the boundary of a superconductor this leads to a significant variation of the energy gap over
-6
distances which are of the order of 10
cm, that is, two orders of
(1
magnitude smaller than the coherence length The configurational

surface energy resulting from this gap variation turns out in this
-5
theory to be about 10
cm (Parmenter, 1960b) which is an order of
magnitude smaller than the generally accepted value.
To investigate the behaviour of superimposed metallic layers under
this theory, Parmenter postulates a set of plausible boundary conditions involving the continuity of h k and of the normal component
.
of the
cm. This, as Cooper points

out, is analogous to the difference between the range of the nuclear
interaction and the much larger size of the resulting deuteron wave
packet. Because of this long coherence length the Cooper pairs can
formulation a dependence of the energy gap on position by postulating

in equation XI.5.
This adds to the kinetic energy portion of the ground state energy (the
first term in equation XI.5) terms involving the square of the gradient
is
-4
is characterized by some average over both metals of the parameter N(0) V, which in turn determines the energy gap of the layer and its transition temperature,
according to equations XI. 8 and XI.29. The form of this average of

course depends on the nature of the boundary between the two metals
1
the better the contact, the more effective is a superimposed layer in

changing the properties of the substrate. Regardless of how one
accounts for this, one would expect the average to depend also in some
manner on the
normal
energy gap width and the transition

the values they
would have
Similarly a combination of
to
have a
11
The thicker the

and the more the
temperature are decreased from
relative thickness of the
two
layers.
layer, the smaller the average interaction,
Te
if
only the superconductor were present.
two superconductors would be expected

somewhere between the Tc values of the two materials,
Superconductivity
52
varying from one extreme to another as the relative thickness of the
two layers is varied.

These qualitative conclusions presuppose that both layers of the
CHAPTER XIII
bimetallic film are sufficiently thin so that the coherent electron pairs
extend over the entire volume. One expects the critical thickness for
this to be of the order of the coherence length, although it is not clear
whether this should be the ideal value or the mean free path limited
value (f). If one of the two superimposed metals is much thicker than
whatever critical length is appropriate, then presumably the average
Superconducting Devices
interaction
is
determined by the ratio of the smaller thickness to the
critical length.
The experiments of Smith et al.

on or between
silver films
(1
96 1 ) with lead films of about 500 A
varying from 100 to 7000
A indicate
a de-
crease of the transition temperature of the lead with increasing silver
Wilhelm ( 935) and

of Meissner (1960). Similar results have been obtained by Hilsch and
Hilsch (1961 ) with combinations of copper and lead films. These agree
with the calculations of De Gennes and Guyon (1962) and the
more extensive treatment of Werthamer (1964). However, the work
of Rose-lnnes and Serin (1961) has shown that results can be strongly
influenced by varying evaporation procedures, even under conditions which quite preclude ordinary bulk intermetallic diffusion.
Interpenetration of metals seems to occur quite readily with superimposed layers, possibly by the mechanisms of surface and defect
diffusion. Because of this the experimental situation is at this time far
from clear.
thickness, supporting earlier work of Misener and
13.1.
The
Research devices
characteristics of superconductors
have for a long time already

been put to use in many low temperature experiments. It is very common to use niobium wires, for example, in electrical connections to
samples which one wishes to isolate thermally as well as possible. Such
wires are superconducting with a high critical field throughout the
entire liquid
helium temperature range, and combine low thermal
transport with perfect electrical conductivity.
heat switches at temperatures below
0TK
The use of lead wires as

has been mentioned in
Chapter DC.
More
specialized research devices using superconducting
com-
ponents of varying complexity have been suggested or used frequently,
and it is possible in this cursory survey to mention only a few of these.

A number of such devices have been developed to detect very small
potential differences, as occur, for instance, in studies of thermo-
powers. Pippard and Pullan (1952) improved earlier designs

by Grayson Smith and co-workers (Grayson Smith and Tarr, 1935;
Grayson Smith et al., 1936) by using a single turn of superconducting
electric
wire to construct a galvanometer capable of detecting e.m.f.s of
10" ,2 V. With a resistance as low as 10~ 7 ohm this required a current

5
sensitivity of only 10~ amp the time constant L/R was kept short by
;
the single turn design which reduced the effective inductance.
conducting magnetic shield made possible controlling
001
A super-
fields as
low as
gauss.
A different approach to the measurement of very small potentials

was suggested by Templeton (1955b) and by De Vroomen (De
Vroomen, 1955; De Vroomen and Van Baarle, 1957). These authors
designed 'chopper' amplifiers in which the small
d.c. signal is
con-
verted into an alternating one by passing through a superconducting
wire which
is
modulated into and out of the normal

153
state
by being
Superconductivity
Supei conducting devices
placed in an alternating magnetic field. The resulting oscillating

potential across the wire is then amplified in a conventional manner.
10~ ' ' V.
These devices can operate stably with a noise level at about
have been observed for many

and for strained or impure samples of the superconducting
elements. For niobium published values of the critical field at 0K
vary from about 1950 to 8200 gauss. Quite recently Kunzler et al.
(1 961 b) discovered Nb s Sn to have a critical field of about 200 kgauss,
and similar critical fields have since been found in other substances.
These seem to be either intermetallic compounds of the /3-wolfram
structure, or body centered cubic alloys. When suitably prepared
154
Templeton (1955a) has also designed a superconducting reversing

switch to suppress undesirable thermal voltages in measurements of
6
potential differences of the order of about 10~ V.
temperature experiments as well as superconducting
magnets require rather high direct currents at very low voltages.
To avoid the use of thick electrical leads which would bring too
Many low
heat into the helium dewar, Olsen (1958) has designed a

superconducting rectifier and amplifier which, together with a low
much
temperature transformer, allows one to feed in a low alternating

current through thin leads. The rectification occurs as the current
flows through a superconducting wire placed in an external, nearly
critical field, such that the field due to the current in one direction
is sufficient
to
make
the wire normal during about one-half of each
tively large values of the critical field
alloys
these materials remain superconducting while carrying current densities
as high as 5 x 10
amp/cm2
in fields
almost up to the
critical
value.
The
critical fields
thermodynamic
of these materials are
critical fields
much
too high to be the
as defined by equation
II.4.
How-
have discussed two reasons why superconductivity can persist in a given specimen to fields higher than
c One
possibility is that the material is sufficiently inhomogeneous, so as to
ever, earlier chapters
display the characteristics of a 'Mendelssohn sponge', as discussed
cycle.
D. H. Andrews
et al. (1946)
made use of the change
in resistivity
at the superconducting transition in designing a bolometer.
A different
superconducting radiation detector has been suggested by Burstein

et al. (1961) who pointed out that a tunnelling device (Chapter X)
suitably biased would respond to absorption of electromagnetic
radiation in the microwave and submillimetre range.
RF
detection
with a tunneling device has been achieved by Shapiro and Janus

(1964). For work at high frequencies superconducting metals may
also be used to construct resonant cavities of extremely high Q. This
has been discussed by Maxwell (1960), and preliminary experiments

have been reported by Fairbank et al. (1964) as well as by Ruefenacht
and Rinderer (1964). Thought is also being given to the use of
superconducting cavities in high energy proton linear accelerators
(Parkinson, 1962; Fairbank et al., 1964). Many of the devices listed
in this section as well as others
have recently been discussed by
in Section 7.2.
In such a specimen superconductivity persists in a
filamentary structure, the dimensions of which are
than the penetration depth.

conducting to a
1931,
H >H
s
c,
much
smaller
a result, the filaments remain superas given by equation VII.8.
On
the
mechanism for high field superconductivity was discussed in Chapter VI, where it was shown that superconductors of the second kind remain in a superconducting mixed
other hand, a quite different
up to U c2 > c (Abrikosov, 1957). Superconductors of the

second kind are materials which may be quite homogeneous and
which have a negative surface energy, generally because of their very
state
Goodman
(1961) was the first to

mechanism to explain the high
critical field, found by Kunzler and others, and there is convincing
evidence that this is indeed the case (see for example, Berlincourt and
Hake, 1963). The specific heat results of Morin et al. (1962) on V3 Ga
short electronic
mean
free path.
suggest the possible relevance of this
the second kind

13.2. Superconducting
field
As
are consistent with the behaviour expected for superconductors of
Parkinson (1964).
As early as
155
De Haas and Voogd found critical fields as high as
15 kgauss in some lead-bismuth alloy wire. Other instances of
(Goodman,
observed by Berlincourt and
magnets
rela-
limit for
1963b), and so are the critical fields

(1962, 1963) in the low current
Hake
a number of high field alloys and compounds. Hauser

Swartz (1962) have further shown that the
(1962) as well as
Superconductivity
Superconducting devices
magnetization curves of suitably prepared specimens of various

compounds are consistent with the identification of these materials
of 4-3 kgauss, and since then the interest in the subject has grown
156
as superconductors of the second kind.

role of defects
systematic study of the
on the magnetization curve has been
carried out by
Livingston (1963, 1964).
However, Gorter (1962a, b) has pointed out that a homogeneous

superconductor with uniform negative surface energy cannot in the
presence of a transverse magnetic field carry the high current densities
which are actually observed in most of the compounds and alloys
under discussion. This can best be understood in terms of the vortex
structure of the mixed state which is created by the external field (see
Section 6.6). When a current passes through the specimen at right
angles to the vortices, it interacts with the latter so as to push them
out of the specimen. This, as was mentioned in Section 6.6, can be
prevented only if the vortices are pinned down by local variation of
the surface energy, as would be present if the specimen were inhomogeneous. Indeed, there
capacity
is
is
157
much scientific and technical activity in a large

number of laboratories. Kunzler?/ al. (196 la) and others used Mo 3 Re
to wind solenoids producing up to 5 kgauss; much higher fields were
achieved soon thereafter as a result of work with Nb 3 Sn (Kunzler
et al. 1961b), Nb2 Zr (Kunzler, 1961; Berlincourt et al., 1961) and
NbTi (Coffey et. al., 1964). Solenoids wound of these materials
have produced fields up to 100 kgauss, and both suitable
explosively, with
superconducting wire as well as entire solenoid assemblies have
become commercially available. At the moment, the size of these

measured in inches, but large-scale superconducting coils
producing fields well in excess of 100 kgauss seem quite feasible.
Kropschot and Arp(1961) have recently reviewed the subject of superconducting magnets, and have discussed the considerable technical
and economic advantages of such devices. Much information can also
be found in [11] as well as in Berlincourt (1963).
is still
much evidence that the high current carrying
associated with the presence of dislocation in cold-worked
specimens (Hauser and Buehler, 1962). Annealed samples
may
still
13.3. Superconducting
Much
computer elements
research and development
work
is
currently being devoted to
have a very high critical field while carrying a low current density,
but turn normal when the latter is increased. Rose-Innes and Heaton
(1963) have used Ta-Nb wire to show very strikingly how sample
treatment can change the current carrying capacity without changing
attempts to use superconductors both as switching devices and as

memory storage elements in electronic computers. The basic idea for
the critical
further able to carry high current densities in high

through cold work they are made to contain a high density
of dislocations which pin down the current carrying regions. A nearly
uniform distribution of these dislocations explains why the critical
niobium wire wound on to a thicker (0009 in.) tantalum wire. A

sufficiently large current through the former, called the control
winding, can quench the superconductivity of the latter, called the
gate. The two materials are chosen because the convenient operating
temperature of 4-2K is only a little below the critical temperature
of Ta, but much lower than that of Nb, so that a control current
sufficient to 'open the gate' is still much less than the critical cur-
current increases as the cross-sectional area of the specimen (Lock,
rent of the control.
1961a; Hauser and Buehler, 1962).
large so as to
Thus
field.
the present picture of high field superconductors
basically they are materials characterized
energy.
is
that
by a negative surface
They are
fields if
The ability of some superconductors to carry high current

in
high
fields,
Yntema
densities
of course, suggests their use in the winding of magnets.
(1955) described a superconducting solenoid
wound with
niobium wire and producing up to 7 kgauss, but this received little

attention. In 1960 Autler wound a niobium solenoid creating a field
a superconducting switching element originated with Buck (1 956) who

invented the cryotron. This consists of a layer of thin (0003
The diameter of the gate
is
in.)
furthermore kept
maximize the amount of gate current, Ig which can be

,
controlled by the control current, Ic Calling

.
the critical field of
the tantalum gate at the operating temperature, and
D its diameter,
then
(/,)m
H ttD,
c
(xni.i)
Superconductivity
158
flows only
and
open,
*c
(XIII.2)
= number of turns/unit length
of control winding. Thus
(XIII.3)
This
is
the 'gain' of the cryotron, which must be kept at a value
(a)
59
cryotron A or B is open, (b) cryotrons A and B are

A nor B are open. More complicated logical circuits
Buck (1956) as well as in review

by Haynes (1960), and by Lock (1961b).
are discussed by
(1959),
where n
if:
(c) neither
articles
by Young
Basically all these cryotron circuits consist of a number of parallel

superconducting paths between which the current can be switched by
the insertion of a resistance into the non-desired branches. Under
steady-state conditions the power dissipation is zero as long as there
is
always at least one path which remains superconducting. The speed
greater than unity in order that the gate current of one cryotron can
be used to control another.

.+
INPUT
"ONE"
INPUT
"ZERO"
37
;-!
READ
"ZERO"
READ
"ONE"
Fig. 48
Fig. 49
A great variety of logical circuits can

this reciprocal control
cuits contain the basic
be built up by making use of

number of cryotrons. Most of these cirflip-flop or bistable element, shown in Figure
of a
through this element can flow in either one or the other

branch and, once established in one, will flow in it indefinitely since
it makes the other one resistive. The choice of branch can be dictated
48. Current
by placing a further cryotron gate in series with each branch, and conan outside signal, which can 'open the gate', making
the corresponding branch resistive and forcing the current into the
other path. This is shown in Figure 49, which also indicates that if
each branch also controls the gate of a read-out cryotron, the position
of the bi-stable element can be read. Figure 50 shows other basic
logical circuits using cryotrons; the current through the heavy line
trolling this by
with which the resistance can be inserted, that is, the speed with which
a given gate can be made normal, depends on the basic phase transition time
and is small enough
( as
10~
10
sec) not to be a limiting factor
at this time (see, for instance, Nethercot, 1961
Feucht and Woodford,
On the other hand, the switching time from one current path
to another is determined by the ratio L/R, where L is the inductance
1961).
of the superconducting loop
made up
of the current paths, and
R the
resistance introduced by an opened gate. The usefulness of wirewound cryotrons is severely limited by the fact that this time is no less
than 10~ 5 sec, even if the gate consists of a tantalum film evaporated
on
to an insulating cylinder. Because of this
development
effort
is
directed toward
all
making
current research
and
thin film cryotrons
Superconductivity
160
161
however, no need for a

is not in turn used
to drive another unit. One therefore often calls the memory elements
low gain cryotrons.
The Crowe cell basically consists of a thin film of superconducting
consisting of crossed or parallel gate
and control films separated by

and placed between additional superconducting
shielding films called ground planes. The resistance of the thin film
gates is comparable to that of a wire gate, but the ground planes confine magnetic flux to a very small region and thus result in L/R values
8
10
of the order of 10" -10~ sec. Cryogenic loops with a time constant
-9
superconductivity in another. There
insulating layers,
greater-than-unity gain, as the controlled current
of 2x 10
sec have been operated (Ittner, 1960b). An account of
many of the design considerations governing such thin film cryotrons
material (for example, lead) with a small hole, a few millimetres in

diameter, which has a narrow cross-bar running across it. This is
drive 'wire' in the form of a
shown schematically in Figure 51.
can be found
second narrow
in several
papers in
is,
above the cross-bar, separated only by

a thin insulating layer. As long as the entire configuration remains
superconducting, the magnetic flux threading the hole must retain its
[9].
strip lies just
INPUTS
a\or
IB
xr5=-fo
_<ztXp
SENSE
B
-^^Zpr*^
(neither
c\
t
nor B
WIRE.
cnto
QXlo
Fio. 51
Fig. 50
original value,
is
Suggestions for superconducting
memory
devices were advanced
which we
shall take to
passed through the drive wire,
and the remainder of the
film.
be zero. Therefore
from penetrating, and

which shows a
The cross-bar is very thin and
keep the
lating current will be such as to
fact that a current induced in a superconducting ring will persist in-
schematic cross section of the cell.

narrow and therefore has a low critical current.
possibility of a two-state
can circulate either way one has the
memory storing one bit of information with
no dissipation of power other than that required to maintain the low

temperature. Of the three suggestions it is that of Crowe on which in
recent years most attention has been concentrated and which will be
briefly described here. Before doing so it might be noted that persistent current memory devices have in common with switching
cryotrons that a current in one superconducting circuit quenches the
a current
will
simultaneously by Buckingham (1958), Crittenden (1958), and Crowe

(1958). Their devices are basically quite similar and make use of the
definitely. Since the current
if
induce currents in the cross-bar

The direction of this induced circu-
it
flux
results in a flux distribution indicated in Figure 52a,
When
the induced
current exceeds this critical value, the cross-bar becomes normal. The
flux now changes to the configuration shown in Figure 52b, as the
remainder of the film remains superconducting. If finally the drive

current is again removed, the superconductivity of the cross-bar is
restored, and now the flux threading the hole is trapped, as long as the
cross-bar remains superconducting, by a persistent current which
in the opposite direction
of the originally induced flow. Even
is
when
the drive wire current
is
now removed,
the flux distribution remains
that of Figure 52c.
The
163
Superconductivity
162
rendered more complicated than
The operation of the Crowe cell is

indicated in the preceding simplified account because the cross-bar
heats up through joule heat when it becomes normal, and the thermal
is
Crowe cell (Garwin, 1957) is indicated

which shows on equal time scales, but arbitrary vertical
scales, the drive current Id and the cross-bar current /c Pulse 1 is
too small to induce a critical value of Ic Pulse 2 results in Ic > Icril
the cross-bar becomes momentarily normal, and after the drive pulse
idealized operation of a
in Figure 53,
may be appreciable. Crowe (1957), Rhoderick (1959),

Von Ballmoos (1961), and several papers in [9] discuss the resulting
recovery time
complications.
STORE
"0"
Id
READ STORE
READ
"1"
_
V
v--
STORED STORED
"0"
"0
-
is
removed a
persistent current l
v
stored. Pulse 3
is
it
is
now
4,
READY
a 'readFig. 53
induces a current in a direction
opposite to that of the persistent current. With pulse
"I"
IV
K READO"
out' pulse which has no effect since
STORED
however, the
state
Crowe cells can be arranged into a two-dimensional matrix of

memory elements with the drive wire forming part both of an x- and
read-out.
a y-circuit, as indicated in Figure 51 Driving pulses Ix Iy are then so

chosen that either alone is not sufficient to activate the device, but
persistent current
is
reversed, storing the other possi bility of the two-
memory, and now read-out pulse 5 succeeds in driving the

cross-bar well beyond the critical value. Note that this is a destructive
The memory
very close to
duced
it
is
sensed by means of a wire below the cross-bar, also
but electrically insulated.
in the sense
wire because of
linking the cross-bar changes, that
is,
A current pulse will
be in-
proximity whenever the flux

whenever the cross-bar becomes
its
normal. Thus we note on Figure 53 that the sense wire response Is to

pulse 3 is nothing, which can be taken as ' Read 0', while its response
to 5
is
a pulse which can be taken as 'Read
'.
The reader is again referred to [9] for a number

memories built up of such matrices.
superconducting
papers
on
of
Rose-Innes (1959) has estimated the consumption of liquid helium
required to keep a memory like that cold, and finds this to be of the
order of two litres per hour for an array of one million cells. This is
that both together do.
as
well within the capacity of closed cycle helium refrigerators such
the one described by McMahon and Gifford (1960).
Bibliography
General References
University Press,
[I] shoenberg, d., Superconductivity, Cambridge
1952.
[2]
London,
f.,
[3]
Progress
in
Superfluids, Vol.
Low
I,
New York,
Temperature Physics, Vol.
Wiley, 1950.
C. J. Goiter, ed.
I,
New York, Interscience,
1955.
Superconductivity: Experimental Part, Handbuch der
Physik, Vol. XV, S. Fliigge, ed.; Berlin, Springer, 1956.
ibid.
[5] bardeen, J., Theory of Superconductivity,
Graham and A. C.
M.
Phys.,
G.
Low
Temp.
VII
Int.
Conf
Proc.
[6]
Hollis-Hallett, eds. ; Toronto, University Press, 1960.
[4] serin, b.,
[7]
bardeen,
j.,
and schrieffer,
Superconductivity, Progress in
Ill,
[8]
C.
J.
j.
r.,
Recent Developments
Low Temperature
in
Physics, Vol.
New York, Interscience, 1961.

Review of the Present Status of the Theory of Super-
Goiter, ed.;
bardeen,
j.,
conductivity, IBM Journal 6, 3 (1962).

Proc. Symp. Super cond. Techniques, Washington, May, 1960;
Solid State Elect r. 1, 255^08 (1960).
Physics, C. de
[10] tinkham, m., Superconductivity, Low Temperature
Witt, B. Dreyfus, and P. G. De Gennes, eds. London, Gordon
[9]
[II]
[12]
and Breach, 1962.

High Magnetic Fields, H. Kolm, B. Lax, F. Bitter, and R. Mills,
eds.; New York, Wiley, 1962.
Proc. VIII Int. Conf. Low Temp. Phys., R. Davics, ed.; London,
Butterworth, 1964.
Conf on the Science of Superconductivity, Colgate,
1963; published in Rev. Mod. Physics, 36, 1-331 (1964).
Lecture
[14] Metaux et Alliages Supraconducteurs, P. G. De Gennes,
Notes, Paris 1962-63.
[13] Proc. Int.
Individual References
e., and weiss, p. R. (1959), Cambridge Conference on
Superconductivity (unpublished).
abrtkosov, a. a. (1957), J.E.T.P. USSR 32, 1442; Soviet Phys.
J.E.T.P. 5, 1 174; /. Phys. Chem. Solids 2, 199.
abrikosov, a. a., and gorkov, l. p. (1960), J.E.T.P. USSR 39, 1781
Abrahams,
Soviet Phys. J.E.T.P. 12, 1243 (1961).

165
ABRIKOSOV,
J.E.T.P.
A. A.,
GORKOV,
USSR 35, 265
L. P.,
and KHALATNIKOV,
Soviet Phys. J.E.T.P. 8,
82
(1
I.
M. (1958),
959) see also

;
khalatnikov, i. m., and abrikosov, a. a. (1959), Advances

Physics, N. F. Mott, ed., London, Taylor and Francis Ltd.
in
adkins, c. J. (1963), Phil. Mag. 8, 1051 ; [13], p. 21 1.

adler, J. g., and Rogers, J. s. (1963), Phys. Rev. Lett. 10, 217.
alekseevskii, n. e. (1953), J.E.T.P. USSR 24, 240.
alers, g. a., and waldorf, d. l. (1961), Phys. Rev. Lett.
Journal 6, 89 (1962).
6,
677;
108, 1175.
rickayzen,
j.,
g.,
and tewordt,
l.
(1959), Phys. Rev. 113,
982.
IBM
p. b. (1957), Phys. Rev. 105, 104.

alers, p. b. (1959), Phys. Rev. 116, 1483.
ambegaokar,
v., and baratoff, a. (1963), Phys. Rev. Lett. 10, 486;

Erratum: ibid., 11, 104.
Anderson, p. w. (1959), /. Phys. Chem. Solids 11, 26.
ANDERSON, P. w. (I960), [6], p. 298.
Anderson, p. w. (1962), Phys. Rev. Lett. 9, 309.
Anderson, p. w. (1963), Ravello Lectures (unpublished).
Anderson, p. w., and KIM, y. b. (1964), [13], p. 39.
Anderson, p. w., and rowell, J. m. (1963), Phys. Rev. Lett. 10, 230.
Anderson, p. w., and suhl, h. (1959), Phys. Rev. 116, 898.
andres, k., olsen, j. l., and rohrer, h. (1962), IBM Journal 6, 84.
ANDREWS, D. H., MILTON, R. M., and DE SORBO, W. (1946), J. Opt. Soc.
36, 518.
androes, g. m., and knight, w. d. (1961), Phys. Rev. 121, 779.

autler, s. h. (1960), Rev. Sci. Inst. 31, 369.
autler, s. h., rosenblum, e. s., and GOOEN, K. h. (1962), Phys. Rev.
Lett. 9, 489; see also [13], p. 77.
bean, c.
bean, c.
9,93.
bean, c.
becker,
261 (1951).
(1962), Phys. Rev. Lett. 8, 250.
p.
DOYLE, m.
p.,
P.,
r.,
v..
and pincus,
a. u. (1962),
Phys. Rev. Lett.
and Livingston, J. d. (1964). Phys. Rev. Lett. 12, 14.

heller, c, and SAUTER, F. (1933), Z. Phys. 85, 772.
berlincourt, t. G. (1963), Brit. J. Appl. Phys. 14, 749.

berlincourt, t. o., and hake, r. r. (1962), Phys. Rev. Lett. 9, 293.
berlincourt, t. g., and hake, r. r. (1963), Phys. Rev. 131, 140.
berlincourt, t. g., hake, r. r., and Leslie, d. h. (1961), Phys. Rev.
Lett. 6, 671.
betbeder-matibet,
o.,
and nozieres,
p.
(1961), C. R. Acad. Sci. 252,
3943.
BEZUGLYl,
P. O.,
USSR 36,
BIONDI, M.
GALK1N,
1951
A.,
A. A.,
and KAROLYUK,
A. P. (1959), J.E.T.P.
Soviet Phys. J.E.T.P. 9, 1388.
FORRESTER, A. T., GARFUNKEL, M.

Mod. Phys. 30, 1 109.
P.,
and SATTERTHWAITE,
C.B. (1958), Rev.
biondi, m.
A.,
BIONDI, M.
A.,
and garfunkel, m. p. (1959), Phys. Rev. 116, 853, 862.

GARFUNKEL, M. P., and MCCOUBREY, A. O. (1957), Phys.
Rev. 108, 495.
BLANC,
J.,
(1960),
balashova, b. m., and sharvin, vu. v. (1941), J.E.T.P. USSR 17, 851
ballmoos, f. von (1961), Thesis, E.T.H., Zurich.
baltensperger, k. (1959), Helv. Phys. Acta 32, 197.
bardasis, a., and schrieffer, j. r. (1961), Phys. Rev. Lett. 7, 79.
bardeen, j. (1950), Phys. Rev. 80, 567; see also Rev. Mod. Phys. 23,
GOODMAN,
[6],
B.
B.,
KUHN,
G.,
LYNTON,
E. A.,
and WEIL,
L.
p. 393.
blumberg, R. H. (1962), J. Appl. Phys. 33, 1822.

BON-MARDION, O., GOODMAN, B. B., and LACAZE,
2,321.
boorse, h. a. (1959), Phys. Rev. Lett. 2, 391.
bozorth, r. m., davis, d. o., and Williams, a.
A. (1962), Phys. Lett.
j.
(I960), Phys. Rev.
119, 1570.
brenig, w. (1961), Phys. Rev. Lett. 7, 337.

a., zemansky, m. w., and boorse, h.
j.
(1952), Phys. Rev. 87, 192.
j.
(1954), Phys. Rev. 94, 554.
j.
(1957),
j.
(1958), Phys. Rev. Lett. 1, 399.
j.
(1959),
Nuovo CimentoS,
brown,
1766.
Cambridge Conference on Superconductivity (un-
published).
bardeen,
bardeen,
bardeen, j. (1962a), Phys. Rev. Lett. 9, 147.

BARDEEN, j. (1962b), Rev. Mod. Phys. 34, 667.
bardeen, j., cooper, l. n., and schrieefer, j. R. (.1957), Phys. Rev.
bardeen,
alers,
bardeen,
bardeen,
bardeen,
bardeen,
bardeen,
167
Bibliography
Superconductivity
166
J.
(1961a), Phys. Rev. Lett. 6, 57.
j.
(1961b), Phys. Rev. Lett. 7, 162.
a. (1953),
Phys. Rev. 92,
52.
bryant, c. a., and keesom, p. H. (I960), Phys. Rev. Lett. 4, 460; Phys.
Rev. 123,491 (1961).
bucher, e., gross, d., and olsen, j. l. (1961), Helv. Phys. Acta 34, 775.
bucher, e., and olsen, j. l. (1964), [12], p. 139.
buck, d. a. (1956), Proc. I.R.E. 44, 482.
12
Super conduc tivity
68
Buckingham,
M.
J.
(1958), Proc.
V Int.
Conf.
Bibliography
Low Temp.
Madi-
Phys.,
son, J. R. Dillinger, ed.: Madison, U. of Wisconsin Press, p. 229.

budnick, J. I. (1960), Phys. Rev. 119, 1578.
budnick, J. I., lynton, e. a., and SERIN, b. (1956), Phys. Rev. 103, 286.
BURSTEIN, E., LANGENBERCi, D. N., and TAYLOR, B. N. (1961), Phys. Rev.
Lett. 6, 92.
byers, n., and yang, c. n. (1961), Phys. Rev. Lett. 7, 46.

calverley, a., Mendelssohn, K., and rowell, p. M. ( 96 ), Cryogenics
1
2,26.
69
Phys. Lett. 9, 106.
calverley, a., and rose-innes, a. c. (1960), Proc. Roy. Soc. A255, 267.
cape, j. a. (1963), Phys. Rev. 132, 1486.
caroli, c, de gennes, p. g., and matricon,
j.
(1962). J. Phys. Rod.
23, 707.
chandrasekhar, b. s. (1962), Phys. Lett. 1, 7.

chang, g.k., jones, r. f.., and toxen, a.m. (1962), IBM Journals, 12.
chang, g. k., kinsel, t., and SERIN, b. (1963), Phys. Lett. 5,
chanin, g., lynton, e. a., and serin, b. (1959), Phys. Rev. 114, 719.
chiou, c, quinn, d., and seraphim, d. (1961), Bull. Am. Phys. Soc. 6,
122; seraphim, D.,cmou,c, and quinn, d., Acta Met. 9, 861 (1961).
I
clogston,
CLOGSTON,
a.
m. (1962), Phys. Rev. Lett. 9, 266.
A. M.,
GOSSARD,
A.
C, JACCARINO,
V.,
and YAFET,
Y. (1962),
Phys. Rev. Lett. 9, 262; see also [13], p. 170.
COCHRAN,
J. F.,
MAPOTHER,
D. E.,
and MOULD,
R.
E.
(1958), Phys. Rev.
103, 1657.
cody, G. d. (1958), Phys. Rev. Ill, 1078.

COFFEY, H. T., FOX, D. K., HULM, J. K., SPAN,
R. E.,
and REYNOLDS, W.
T.
Am.
Phys. Soc. 9, 454.

COHEN, M. H., FALICOV, L. M., and PHILLIPS, j. c. (1962), Phys. Rev. Lett.
8, 316; see also [12], p. 178.
cohen, m. l. (1964), [13]. p. 240; Phys. Rev. 134, A51 1.
collins, s. c. (1959) (unpublished). I am grateful to Prof. Collins for
a detailed description of this experiment.
(1964), Bull.
compton, v. b., and Matthias, b. t. (1959), Acta Cryst. 12, 651.

compton, w. dale (1959), private communication to B. Serin.
conolly, a., and Mendelssohn, k. (1962), Proc. Roy. Soc. A266, 429.
l. n. (1956),
l. n.
Phys. Rev. 104, 1189.
(1959), Phys. Rev. Lett. 3, 17.
Crittenden, jr., e. c. (1 958) Proc. Vint. Conf. Low Temp. Phys., Madison, J. R. Dillinger, ed.; Madison, U. of Wisconsin Press, p. 232.
crowe,
crowe,
j.
w.
w.
(1957),
IBM Journal 1,
295.
Conf. Low Temp. Phys., Madison,

J. R. Dillinger, ed.; Madison, U. of Wisconsin Press, p. 238.
CULLER, G. J., FRIED, B. D., HUFF, R. W., and SCHRrEFFER, J. R. (1962),
Phys. Rev. Lett. 8, 399.
casimir, h. b. g. (1938), Physiea 5, 595.

casimir, h. b. g. (1940), Physiea 7, 887.
chambers, r. g. (1952), Proc. Roy. Soc. A215, 481.
chambers, r. g. (1956), Proc. Canib. Phil. Soc. 52, 363.
cooper,
cooper,
COOPER, L. N. (1960), Am. J. Phys. 28, 91.

cooper, L. N. (1961), Phys. Rev. Lett. 6. 689: IBM Journals, 75 (1962).
cooper, l. n. (1962), Phys. Rev. Lett. 8, 367 see also [12], p. 126.
CORAK, W. S., GOODMAN, B. B., SATTKRTHWAITE, C. B., and WEXLER, A.
(1954), Phys. Rev. 96, 1442; see also Phys, Rev. 102, 656 (1956).
corak, w. s., and satterthvvaite, c. b. (1954), Phys. Rev. 99, 1660.
cornish, f. h. j., and olsen. j. l. (1953), Helv. Phys. Acta 26, 369.
CRIBIER, D., JACROT, B., MADHOV RAO, L., and FARNOUX, B. (1964),
daunt,
DAUNT,
j.
(1958), Proc.
Int.
and Mendelssohn,
j.
g.,
J.
G., MILLER, A. R.,
k. (1946), Proc. Roy. Soc.
PIPPARD, A.
B.,
A185, 225.
and SHOENBERG,
D. (1948),
Phys. Rev. 74, 842.

da vies, E. A. (1960), Proc. Roy. Soc. A255, 407.
deaver, jr., b. s., and fairbank, w. m. (1961), Phys. Rev. Lett. 7, 43.
de gennes, p. g. (1963), Phys. Lett. 5, 22.
de gennes, p. g., and guyon, e. (1962), Phys. Lett. 3, 168.
de gennes,
de gennes,
and matricon, j. (1964), [13], p. 45.

and sarma, g. (1963), /. Appl. Phys. 34,
and shoenberg, d. (1948), Proc. Phys. Soc.
p. g.,
p. g.,
1380.
desirant, m.,
60, 413.
de sorbo, w. (1959), J. Phys. Client. Solids 15, 7.
de sorbo, w. (I960), Phys. Rev. Lett. 4, 406; 6, 369.
de sorbo, w. (1961), IBM Conf. on Superconductivity (unpublished).
DIETRICH, I. (1964), [12], p. 173.
doidge, p. r. (1956), Phil. Trans. Roy. Soc. A248, 553.
doll, r., and nabauer, m. (1961), Phys. Rev. Lett. 7, 51.
Douglass, jr., d. h. (1961a), Phys. Rev. Lett. 6, 346.

Douglass, jr., d. h. (1961b), Phys. Rev. Lett. 7, 14.
Douglass, jr., d. h. (1961c), Phys. Rev. 124, 735.
Douglass, jr., d. h. (1962a), Bull. Am. Phys. Soc. 7, 197.
Douglass, jr., d. h. (1962b), Phys. Rev. Lett. 9, 155.
Douglass, jr., d. h., and blumberg, r. h. (\962). Phys. Rev. 127, 2038.
douglass, jr., d. h., and falicov, l. m. (1 964), Progress in Low Temp.
Phys., Vol. IV, C. J. Gorter, ed.; New York, Interscience.
douglass, jr.. d. H.. and meservey, r. b. (1964a), [12], p. 180.
1
.
Bibliography
Superconductivity
170
Douglass, jr., d. h., and meservey, r. ii. (1964b), Phys. Rev. 135, A 19.
drangeid, k. e., and sommerhalder, r. ( 962), Phys. Rev. Lett. 8, 467.
DRESSELHAUS, M. S., DOUGLASS, JR., D. H., and KYHL, R. L. (1964), [12],
1
L1NDENFELD,
L.,
P.,
LYNTON,
E. A.,
and ROHRER,
H. (1963),
P.,
LYNTON,
E. A.,
and ROHRER,
H. (1964),
DUBECK,
LINDENFELD,
L.,
[13], p. 110.
ehrenfest,
p.
BUASHBERO,
(1933),
Comm.
Leiden Suppl. 75b.

USSR 38, 996; Soviet Phvs. J. E.T.P.
Q. M. (1960), J. E. T. P.
11, 696.
ERLBACH, E., GARWIN,

Journal*, 107.
faber, t.
faber, T.
faber, t.
faber,
FABER,
faber,
R.
L.,
and SARACIIIK.
e.
(1952), Proc. Roy. Soc.
E.
(1954), Proc. Roy. Soc. A223, 174.
e.
(1955), Proc. Roy. Soc. A23I, 353.
t. e. (1957), Proc.
T. t. (1958), Proc.
M.
P.
(1960), l.B.M.
A214, 392.
Roy. Soc. A241, 531.

Roy. Soc. A248, 460.
communication.
and pippard, a. b. (1955a), Proc. Roy. Soc. A231, 336.
e., and pippard, a. b. (1955b), [3], Chapter IX.
iairbank, w., pierce, J. m., and WILSON, p. b. (1964), [12], p. 324.
t. E. (1961), private
faber, T.
faber, t.
ferrell,
ferrell,
ferrell,
ferrell,
T. H.,
and Matthias,
and MATTHIAS,
T. H.,
MATTHIAS,
t. h.,
E.,
r. a. (1961),
and glick, a. J. (1962), Dull. Am. Phys. Soc. 7, 63.

r. a., and GLOVER III, R. e. (1948), Phys. Rev. 109, 1398.
r. a., and PRANGE, R. e. (1963), Phys. Rev. Lett. 10, 479.
feucht, d. l., and WOODFORD, JR., J. B. (1961 j, J. Appl. Phys. 32, 1882.
r. a.,
mini, m. (1964), Bull. Am. Phys. Soc. 9, 454.

HNNtMOKF., D. K., and mapoi hik, D. E. (1962), Phvs. Rev.
B. T. (1964), [12], p. 159.
B. T.,
HULL,
W., and CORENZWIT,
JR., G.
E.
giaever, i. (1964), [12], p. 171.

GIAEVER, L, HART, JR., H. R.,andMGERLE, K. (1962),/%.?. Rev. 126,941
giaever, i., and megf.rle, k. (1961), Phys. Rev. 122, 1 101.
Ginsberg, D. M. (1962), Phys. Rev. Lett. 8, 204.
Ginsberg, d. m., and LESLIE, j. d. (1962), IBM Journal 6, 55.
GINSBERG, D. M., RICHARDS, P. L., and TINKHAM, M. (1959), Ph)'S. Rev.
Lett. 3, 337.
Ginsberg, d. m., and tinkham, m. (1960), Phys. Rev. 118, 990.
ginzburg,
ginzburg,
v. l. (1945), /.
v. l. (1955),
Lett. 9, 288.
FORRESTER,
A. T. (1958),
j.,
de gennes,
p. g.,
and MATRICON,
J.
(1963), Appl. Phvs.
irohlich,
305.
USSR29,
748; Soviet Phys. J.E.T.P.
3,
621
v. l. (\956a),J.E.T.P. USSR 30, 593; Soviet Phys. J.E.T.P.

Dokl. Akad. nauk USSR 110, 368; Soviet Phvs. Dokladv 1.
541.
v. l.
(1956b),7..r.P.
USSR 31,
541
Soviet Phys. J.E.T.P.
4, 594.
7,78.
ciiNZBURG,
l.
(l958a),J.E.T.P.
v. l. (1958b),
USSR 34,
Soviet Phvs. J.E.T.P.
Physica 24, S42.
ginzburg, v. l., and landau, l. d. (1950), J.E.T.P. USSR 20, 1064;

sec also ginzburg, v. l., Nuovo Cimento 2, 1234 (1955).
glover in, R. e., and tinkham, m. (1957), Phys. Rev. 108, 243.
GOEDEMOED, S. H., VAN DER GIESSEN, A., DE KLERK, D., and GORTER,
Lett. 2, 119.
H. (1950), Phys. Rev. 79, 845.
garfunkel, m. p., and serin, b. (1952), Phys. Rev. 85, 834.

OAKLAND, JR.. J. w. (1963a), Phys. Rev. Lett. 11, 111.
garland, jr., J. w. (1963b), Phys. Rev. Lett. 11, 114.
garland, jr., j. w.( 1964). [12], p. 143.
garwin, R. l. (1957). I.B.M. Journal 1, 304.
C.AYLEY, R. !., LYNTON, E. A., and SERIN, B. (1962), Phvs. Rev.
USSR 9.
ginzburg,
ginzburg. v.
Phys. Rev. 110, 776.
Phys.
J.E.T.P.
2,589(1956).
ginzburg,
FISKE, m. d. (1964), [13], p. 221.
43.
IBM Journal 6, 256.
(1962),
geilikman, b. t. (1958), J. E.T.P. USSR 34, 1042; Soviet Phys.

J.E.T.P.1,12\.
geilikman, b. t., and kresin, v. z. (1958), Dokl. Akad. nauk USSR
123, 259; Soviet Phys. Doklady 3, 1 161.
geilikman, b. t., and kresin, v. z. (1959), J. E.T.P. USSR 36, 959;
Soviet Phys. J.E.T.P. 9, 677.
geiser, r., and goodman, b. b. (1963), Phys. Lett. 5, 30.
giaever, i. (1960a), Phys. Rev. Lett. 5, 147.
giaever, i. (1960b), Phys. Rev. Lett. 5, 464.
friedf.l,
b. t.
(1961), Phys. Rev. Lett. 6, 275.
p. 328.
DUBECK,
geballe,
GEBALLE,
GEBALLE,
c.
j.
(1963), Phys. Lett. 3, 250.
goodman, b. b. (1953), Proc. Phys. Soc. A66, 217.

goodman, b. b. (1957), C. R. Acad. Sci. 224, 2899; see also
126,
Sci. 246. 3031 (1958).
goodman,
u. b.
(1958), C. R. Acad. Sci. 246. 3031
C. R. Acad.
Bibliography
Superconductivity
172
goodman,
(1961), Phys. Rev. Lett. 6, 597;
b. b.
IBM
Journal
6,
63.
goodman,
goodman,
goodman,
GOODMAN,
GOODMAN,
IBM Journal 6,
62.
B. B.
(1962a),
b. b.
(1962b), Phys. Lett. 1, 215.

(1962c), J. Phys. Rod. 23, 704.
b. b.
HILLAIRET,
J.,
VEYSS1E,
J. J.,
and WEIL,
L.
(1960),
[6],
p. 350.
gorkov,
L. P.
(\958), J.E.T.P.
l. p.
(1959), J.E.T.P.
USSR 34,
7,
505.
2,
hebel, l. c. (1959), Phys. Rev. 116, 79.

hebel, L. c, and slichter, c. p. (1959), Phys. Rev. 1 13, 1504.
heer, c. v., and daunt, j. g. (1949), Phys. Rev. 76, 854.
HEIN, R. A., FALGE JR., R. L., MATTHIAS, B. T., and CORENZW1T, E.
(1959),
hein, r. a., and gibson, j. w. (1963), Phys. Rev. 131, 105.
HEIN, R. A., GIBSON, J. W., MATTHIAS, B. T., GEBALLE, T. H., and CORENzwit, E. (1962), Phys. Rev. Lett. 8, 313.
HEIN, R. A., GIBSON, J. W., MAZELSKY, R., MILLER, R. C, and HULM,
K.
1
gorkov,
USSR 36,
1918; 37, 833, 1407; Soviet
Phys. J.E.T.P. 9, 1364; 10, 593, 998 (1960).

l. p. (1960), [6], p. 315.
gorkov,
gorter,
gorter,
gorter,
gorter,
GORTER,
gorter,
gorter,
Mus. Teyler
.1.
(1964), Phys. Rev. Lett. 12, 320.

HEIN, R. A., GIBSON, J. W., PABLO, M. R.,
c.
J.
(1933), Arch.
c.
J.
(1935), Physica 2, 449.
c.
j.
(1962a), Phys. Lett. 1, 69.
c.
j.
(1962b), Phys. Lett. 2, 26.
c.
j.
(1964), [13], p. 27.
Hempstead, c. f., and KIM, y. b. (1963), Phvs. Rev.

herring, c (1958), Physica 24, SI 84.
c.
J.,
c.
j.,
and casimir, h. b. g. (1934a), Physica 1, 306.

and casimir, h. b. g. (1934b), Phys. Z. 35, 963 Z.
hilsch, p., and hilsch, r. (1961), Naturwiss. 48, 549.

HIRSHFELD, A. T., LEUPOLD, H. A., and BOORSE, II. A. (1962), Phys. Rev.
7, 378.
grayson smith,
ii.,
mann,
Roy. Soc. Can. 30,
grayson smith,
h.,
K.
techn.
c, and wilhelm,
j.
o. (1936), Trans.
g. a. (1935), Trans. Roy. Soc. Can. 29.
guenault, a. m. (1960), [6], p. 409; Proc. Roy. Soc. A262, 420 (1961).
guyon, e., caroli, C, and martinet, a. (1964), J. Physique 25, 661.
haas, w. j. de, and voogd, j. (1931), Comm. Leiden 214c.
haenssler, f., and rinderer, l. (1960), [6], p. 375.
hake, r. R., and bremmer, w. g. (1964), Phys. Rev. 133, A 179; sec
r., [13], p.
R. R., LESLIE, D. H.,
124.
and BERLINCOURT,
T. G. (1962), Ph)'S.
Rev.
127, 170.
HAKE, R.
R.,
MAPOTHER,
D. E.,
and DECKER,
D. L. (1958), P/lVS. Rev.
1522.
HAMMOND,
harden,
hauser,
hauser,
and KELLY, G. M. (1964), [13], p.

and arp, v. (1963), Cryogenics 4,
R. H.,
j. l.,
j. J.
j. J.,
185.
105.
(1962), Phys. Rev. Lett. 9, 423.
and buehler,
e.
(1963),
Lett. 12, 145.
p.
(1963), J.E.T.P.
USSR 45,
1208; Soviet Phvs. J.E.T.P.
18,834(1964).
23.
also hake, r.
R. D.
127, 1501.
hohenberg,
13.
andTARR, F.
and BLAUGHER,
Phys. Rev. 129, 136.
Phys. 15, 539.

graham, g. m. (1958), Proc. Roy. Soc. A248, 522.
grassmann, p. (1936), Phys. Z. 37, 569.
HAKE,
73
196.
B. B. (1964), [13], p. 12.

B. B.,
HAUSER, J. J., and iiiu and, e. (1962), Phys. Rev. 127, 386.
HAYNES, M. K. (1960), [9], p. 399.
heaton, j. w., and rose-innes, a. c. (1963), Appl. Phys. Lett.
(1961), Phys. Rev. 125. 142.
1 18,
hulm,
j.
ittner m, w.
ittner in, w.
A204, 98.
(1960a), Phys. Rev. 119, 1591.
b. (1960b), Solid State Jr., July/Aug.
b.
and sommerhalder, r. (1959), Helv. Phys. Acta 32, 313.

and sommerhalder, r. (I960), Helv. Phys. Acta 33, 1.
joiner, w., and serin, b. (1961), private communication; see also
jaggi,
r.,
jXggi,
r.,
serin (1960).
jones, R. e., and toxen, a. m. (1960), Phys. Rev. 120,
josephson, b. d. (1962), Phys. Lett. 1, 251.
josephson,
b. d.
kadanoff,
l. p.,
167.
(1964), [13], p. 216.
and martin, p. c. (1961), Phys. Rev. 124, 670.

kamerlingh onnes, h. (191 1), Leiden Comm. 122b, 124c.
kamerlingh onnes, h. (1913), Leiden Comm. Suppl. 34.
kamerlingh onnes, h., and tuyn, w. (1924), Leiden Comm. Suppl.
50a; see also tuyn, w., Leiden
KAPLAN,
R.,
NETHERCOT,
A. H.,
Comm.
198 (1929).
and BOORSE,
H. A. (1959), P/lVS.
116, 270.
keesom, w. h. (1924), 4C Congr. Phys. Solvay,
p. 288.
Rev
Bibliography
Superconductivity
174
keesom, w.
and kamerlingh onnes,
ii.,
h. (1924),
Comm.
l.chlcn
174b.
keller, J. b., and zumino, b. (1961), Phys. Rev. Lett. 7, 164.

khaikin, M.S. (1958), J.E.T.P. USSR34, 1389; Soviet Phys. J.E.T.P.
York
6,
(1952).
lazarev,
and sudovstov,
b. g.,
a.
i.
(1949), Dokl.
Adak. nauk
USSR
69, 345.
735.
khalatnikov,
I.
m. (1959), J.E.T.P.
USSR
36, 1818; Soviet Phys.
kikoin,
i.
k.,
and goobar,
also broer, l.
j. f..
s.
v. (1940), J. Phys. U.S.S.R. 3, 333; see
Physica 13, 473 (1947).
t.,
131, 2486.
HEMPSTEAD,
kleiner, w. h., roth,
B.,
and STRNAD, A. R. (1964), [13], p. 43.

m., and AUTi.ER, s. h. (1964), Phys. Rev.
m.,
e.
133,
A 1226.
kleinman, l. (1963), Phys. Rev. 132, 2484.
klemens, P. g. (1956), Chapter IV, Vol. XIV, Hanclbuch der Physik,
lindenfeld,
little,
w.
Flugge, ed.; Springer Vcrlag, Berlin.

kok, J. a. (1934), Physica 1, 11 03.
kondo, j. (1963), Prog. Theor. Phys. 29, 1.
kresin, v. z. (1959), J.E.T.P. USSR 36, 1947; Soviet Phys. J.E.T.P.
parks, r.
Livingston,
9,
1385.
1
(1961a), J. Appi. Phys. 32, 325.
KUNZLER,
J.
E.,
E.,
F. S. L.,
and WERNICK,
J. E.
(1961b),

kuper, C. g. (1951), Phil. Mag. 42, 961.
landau, l. d. (1937), J.E.T.P. USSR 7, 371 ; Phys. Z. Sowjet. 11, 129.
landau, l. d. (1943), J.E.T.P. USSR 13, 377.
landau, l. d., and lifshitz, e. m. (1958), Statistical Physics, pp.
434 ff. ; London, Pergamon Press.

laredo, s. j., and pcppard, a. b. (1955), Proc. Cambridge
Phil. Soc.
51, 369.
laurmann,
e.,
and shoenberg,
d. (1949), Proc.
Roy. Soc. A198,
560.
laurmann,
e.,
and shoenberg,
d. (1947),
K.,
Nature 160, 747.
p. (1961),
and parks, r. d. (1962), Phys. Rev. Lett. 9, 9; see also

d., and little, w. a., Phys. Rev. 133, A97 (1964).
J.
b. (1963),
Phys. Rev. 129, 1943; see also/. Appl. Phys.
LIVINGSTON,
lock,
lock,
lock,
lock,
j.
J. b. (1964), [13], p. 54.

m. (1951), Proc. Roy. Soc. A208, 391.
m. (1961a), Cryogenics 1, 243.
j.
m. (1961b), Cryogenics 2, 65.
J.
j.
m.,
Phil. Soc.
kropshot, R. h., and arp, v. d. (1961), Cryogenics 2,

kunzler, j. e. (1961a), Rev. Mod. Phys. 33, 501.
kunzler, j. e. (1961b), Conf. High Magn. Fields, Cambridge, Moss.
(to be published).
KUNZLER, J. E., BUEHLER, E., HSU, F. S. L., MATTHIAS, B. T., and WAHL, C.
HSU,
GINSBERG, D. M., FDMNEMORE, D.
a.,
S.
BUEHLER,
L.,
and beaudry, b. j. (1964), Phys. Rev. 134, A309.

and sharvin, yu. v. (1951), Dokl. Akad. nauk USSR
h.,
f.
34, 3028.
C. F.,
l.
lifshitz,
CAPELLETTI, R.
D.,
J.
79, 783.
lynton, e. A., and serin, b. (1962), Phys. Lett. 3, 30.

KINSEL, T., LYNTON, E. A., and SERIN, B. (1964), [13], p. 105.
KIM, Y. B., HEMPSTEAD, C. F., and STRNAD, A. R. (1963), Phys. Rev.
kinsel,
LESLIE,
spedding,
J.E.T.P. 9, 1296.
KIM, Y.
175
laue, m. von (1949), Theorie der Supraleitung, 2nd ed., Berlin,

Springer Verlag; Eng. transl. by L. Meyer and W. Band, New
London,
London,
London,
London,
London,
f.
f.,
f.,
pippard, a. b., and shoenberg, d. (1951), Proc. Camb.

47,811.
(1936), Physica 3, 450.
and London,
and London,
h. (1935a), Proc. Roy. Soc. A149, 71.

h. (1935b), Physica 2, 341.
H. (1935), Proc. Roy. Soc. A152, 650.

h. (1940), Proc. Roy. Soc. A176, 522.
lutes, o. s. (1957), Phys. Rev. 105, 1451.
lynton,
lynton,
lynton,
and mclachlan, d. (1962), Phys. Rev. 126, 40.

and serin, b. (1958), Phys. Rev. 112, 70.
a., serin, b., and zucker, m. (1959), /. Phys. Chem.
e. a.,
e. a.,
e.
Solids 3, 165.
MCLEAN, w. l. (1960), [6], p. 330.

mclean, w. l., and maxfield, b. w. (1 964), Bull. Am. Phys. Soc. 9, 454.
mcmahon, h. o., and gifford, w. e. (1960), [9], p. 273.
maki, k. (1963), Prog. Theor. Phys. 29, 603.
maki, k., and tsuneto, t. (1962), Prog. Theor. Phys. 28, 163.
mapother, d. e. (1959), Conf. on Superconductivity, Cambridge (unpublished).
mapother,
d.
e.
(1962),
IBM Journal 6,
77; see also Phys. Rev. 126,
2021.
markowitz, d., and kadanoff, l. p. (1963), Phys. Rev.

masuda, y. (1962a), IBM Journal 6, 24.
13
131, 563.
Superconductivity
176
masuda,
masuda,
Bibliography
Phys. Rev. 126, 127.

y., and redfield, a. g. (1960a), Bull. Am. Phys. Soc. 5, 176;
Phys. Rev. 125, 159(1962).
masuda, y., and redfield, a. g. (1960b), [6], p. 412; see also masuda,
y., Phys. Rev. 126, 1271 (1962).
matricon, J. (1964), Phys. Lett. 9, 289.
Matthias, b. t. (1957), Chapter V, Progress Low Temperature Physics,
Vol. II, C. J. Gorter, ed.; New York, Interscience.
Matthias, b. (1960), J. Appl. Phys. 31, 23S.
Matthias, b. t. (1961), Rev. Mod. Phys. 33, 499.
Matthias, B. t. (1962), IBM Journal 6, 250.
Matthias, B. t., and CORENZWIT, E. (1955), Phys. Rev. 100, 626.
MATTHIAS, B. T., CORENZWIT, E., and ZACHARIASEN, W. H. (1958a),
Phys. Rev. 112, 89.
MATTHIAS, B. T., COMPTON, V. B., SUHL, H., and CORENZWIT, E. (1959b),
Phys. Rev. 115, 1597.
MATTHIAS, B. T., GEBALLE, T. H., GELLER, S., and CORENZWIT, E. (1954),
Phys. Rev. 95, 1435.
MATTHIAS, B. T., GEBALLE, T. H., COMPTON, V. B., CORENZWIT, E., and
hull, JR., G. w. (1962), Phys. Rev. 128, 588.
y. (1962b),
MATTHIAS, B. T., GEBALLE, T. H., CORENZWIT, E., and HULL, JR., G. W.

(1963), Phys. Rev. 129, 1025.
MATTHIAS, B. T., PETER, M., WILLIAMS, H. J., CLOGSTON, A. M., CORENZWIT, E., and sherwood, r. c. (1960), Phys. Rev. Lett. 5, 542; clogston, a. m., et al., Phys. Rev. 125, 541 (1962).
Matthias, b. t., suhl, h., and corenzwit, e. (1958b), Phys. Rev.
Lett. 1, 92.
Matthias,
1,449.
Matthias,
suhl,
h.,
b. t.,
suhl,
h.,
and corenzwit,
and corenzwit,
e.
e.
(1958c), Phys. Rev. Lett.
(1959a), /. Phys.
Chem.
mattis, d. c, and bardeen, j. (1958), Phys. Rev. Ill, 412.

maxwell, e. (1950), Phys. Rev. 78, 477.
e.
e.
e.
k. (1962),
IBM Journal 6, 27.
and moore, J. r. (1934), Nature 133, 413.

k. and olsen, j. l. (1950), Proc. Phys. Soc. A63, 2.
k., and pontius, r. b. (1937), Phil. Mag. 24, 777.
k., and renton, c. a. (1955), Proc. Roy. Soc. A230,
k.,
157.
mendelssohn,
k.,
and shiffman,
c. a. (1959), Proc.
Roy. Soc. A255,
199.
and crane, l. t. (1963), Phys. Rev. Lett. 11, 107.

and Douglass, jr., d. h. (1964), Phys. Rev. 135, A24.
meshkovsky, a., and shalnikov, a. (1947), J.E.T.P. USSR 17, 851
mercereau,
j. e.,
meservey,
r.,
J. Phys.
miller, p.
b.
USSR
11,1.
(1960), Phys. Rev. 118, 928.
misener, a. d., and wilhelm, j. o. (1935), Trans. Roy. Soc. Can.

29,5.
morel, P. (1959), /. Phys. Chem. Solids 10, 277.
morel, p., and Anderson, p. w. (1962), Phys. Rev. 125, 1263.
MORIN, F. J., MAITA, J. P., WILLIAMS, H. J., SHERWOOD, R., WERNICK, J. H.,
and kunzler, j. e. (1962), Phys. Rev. Lett. 8, 275.
morris, d. e., and tinkham, m. (1961), Phys. Rev. Lett. 6, 600; see also
Phys. Rev. 134, Al 154 (1964).
morse, r. w., and bohm, h. v. (1957), Phys. Rev. 108, 1094.
morse, r. w., olsen, t., and gavenda, j. d. (1959), Phys. Rev. Lett.
15; 4, 193; see also morse, r. w., IBM Journal 6, 58 (1962).
muhlschlegel, b. (1959), Z. Phys. 155, 313.
muller, j. (1959), Helv. Phys. Acta 32, 141.
3,
nambu,
b. t.,
Solids 13, 156.
maxwell,
maxwell,
maxwell,
maxwell,
Mendelssohn,
Mendelssohn,
mendelssohn,
mendelssohn,
mendelssohn,
177
(1952a), Phys. Rev. 86, 235.

(1952b), Phys. Today 5, No. 12, p. 14.
(1960), Adv. Cryo. Eng. 6, 154.
e., and strongin, m. (1964), Rev. Mod. Phys. 36, 144.

meissner, h. (1960), Phys. Rev. 117, 672.
meissner, w., and ochsenfeld, r. (1933), Naturwiss. 21, 787.
Mendelssohn,
Mendelssohn,

k. (1955),
[3],
Chapter X.
A152, 34.
y., and tuan, s. f. (1963), Phys. Rev. Lett. 11, 1 19; see also
Phys. Rev. 133, Al ( 1964).
NETHERCOT, a. h. (1961), Phys. Rev. Lett. 7, 226.
nicol, j., shapiro, s., and smith, p. h. (1960), Phys. Rev. Lett. 5,
461.
and knight, w. d. (1964), [13], p. 177.

(1958), Rev. Sci. Inst. 29, 537; see also purcell,
payne, e. g. (1960), Adv. Cryo. Eng. 6, 149.
noer, r.
olsen, j.
j.,
l.
j.
r.,
and
olsen, j. l. (1963), Cryogenics 2, 356.

OLSEN, J. L., BUCHER, E., LEVY, M., MULLER, J., CORENZWIT, E., and
GEBALLE, T. (1964), [13], p. 168.
olsen, j. l., and rohrer, h. (1957), Helv. Phys. Acta 30, 49.
olsen, j. l., and rohrer, h. (1960), Helv. Phys. Acta 33, 872; see also
andres,
k.,
olsen,
O'NEAL, H.
R.,
SENOZAN, N.
j. l.,
and rohrer, h., IBM Journal 6, 84

M., and PHILLIPS, N. E. (1964), [12],
(1962).
p. 403.
Bibliography
Superconductivity
178
onsager, l. (1961), Phys. Rev. Lett. 7, 50.

Parkinson, d. h. (1962), Brit. J. Appl. Phys. 13, 49.
Parkinson, d. h. (1964), Brit. J. Appl. Phys. 41, 68.
parks, r. d., and mochel, j. m. (1963), Phys. Rev. Lett. 11, 354; see
also [13], p. 284.
r. h. (1960a), Phys. Rev. 118, 1174.
parmenter,
PARMENTER,
R. H. (1960b), [6], p. 317.
peierls, r. (1936), Proc. Roy. Soc. A155, 613.
peter, m. (1958), Phys. Rev. 109, 1857.

Phillips, J. c. (1963), Phys. Rev. Lett. 10, 96.
Phillips, n. e. (1958), Phys. Rev. Lett. 1, 363.
Phillips, n.
e.
Phillips, n.
e.,
(1959), Phys. Rev. 114, 676.
and Matthias, b. t. (1960), Phys. Rev. 121, 105.

l., and jekula, s. t., Phys. Rev. Lett. 9, 254.
PICKLESIMER, m.
A. B. (1947a), Proc.
a. b. (1947b), Proc.
a. B. (1948),
Roy. Soc. A191, 385.

Roy. Soc. A191, 399.
Nature 162, 68.

Roy. Soc. A203, 210.
a. b. (1950), Proc.
a. b. (1951), Proc.
Camb.
Phil. Soc. 47, 617.
Roy. Soc. A216, 547.

A. b. (1 954), Chapter I, Advances in Electronics and Electron
Physics, L. Marton, ed. New York, Academic Press.
pippard, a. b. (1955), Phil. Trans. Roy. Soc. A248, 97.
pippard, a. b. (1960), [6], p. 320.
pippard, A. B.,andPULLAN,G.T. (1952), Proc. Camb. Phil. Soc. 48, 188.
a. B. (1953), Proc.
POKROVSKH,
v. l.
1961 ),J.E. T.P.
USSR40, 641
13, 447.
pokrovskii, v. l., and ryvkin, m. s. (1962), J.E.T.P. USSR 43, 92;

Soviet Phys. J.E.T.P. 16, 67 (1963).
quinn in, d. j., and ittner m, w. b. (1962), J. Appl. Phys. 33, 748.
rayfield, g. s., and reif, f. (1963), Phys. Rev. Lett. 11, 305.
redfield, a. g. (1959), Phys. Rev. Lett. 3, 85; see also redfield, a. g.,
and anderson, a. g. (1959), Phys. Rev. 116, 583.
reese, w., and steyert, jr., w. a. (1962), Rev. Sci. Inst. 33, 43.
reif, f. (1957), Phys. Rev. 106, 208.
reif, f., and woolf, m. a. (1962), Phys. Rev. Lett. 9, 31 5.
reuter, g. e. h., and sondheimer, e. h. (1948), Proc. Roy. Soc. A195,
336.
Reynolds,
691.
c. a., serin, b.,
and nesbitt,
C. A., SERIN, B.,
WRIGHT, W.
II.,
179
and NESBITT,
L. B.
(1950),
Phys. Rev. 78, 487.
rhoderick, e. h. (1959), Brit. J. Appl. Phys. 10, 193.

Richards, p. l. (1960), [6], p. 333; see also Phys. Rev. 126,912(1962).
Richards, p. l. (1961), Phys. Rev. Lett. 7, 412.
Richards, p. L., and TTNKHAM, m. (1960), Phys. Rev. 119, 575.
Roberts, B. w. (1963), Superconducting Materials and Some of Their
Properties, General Electric Report, No. 63-RL-3252M.
rose-innes, a. c. (1959), Brit. J. Appl. Phys. 10, 452.
rose-innes, a. c, and serin, b. (1961), Phys. Rev. Lett. 7, 278.
rosenblum, b., and cardona, m. (1964), Phys. Lett. 9, 220.
rothwarf, a., and cohen, m. (1963), Phys. Rev. 130, 1401.
rowell, j. m. (1963), Phys. Rev. Lett. 11, 200.
rowell,
j.
m.,
anderson,
p.
w., and thomas, d.
e.
(1963), Phys. Rev.
Lett. 10, 334.
pines, d. (1958), Phys. Rev. 109, 280.
pippard,
pippard,
pippard,
pippard,
pippard,
pippard,
pippard,
REYNOLDS,
l. b.,
(1951), Phys. Rev. 84,
rowell,
j.
m.,
chynoweth, a. g., and phillips, t.
c. (1962),
Phys. Rev.
Lett. 9, 59.
ruefenacht, j., and rinderer, l. (1964), [12], p. 326.

saint james, d., and de gennes, p. g. (1963), Phys. Lett. 7, 306.
satterthwaite,
b. (1960), [6], p. 405; Phys. Rev. 125, 873
(1962).
scalapino, d.
and anderson,
p. w. (1964), Phys. Rev. 133, A921.

Phys. Rev. 101, 573.
a. l. (1958), Phys. Rev. 109, 1856.
a. l., and devlin, g. e. (1959), Phys. Rev. 113, 120.
A. L., MATTHIAS, B. T., LEWIS, H. W., and DEVUN, G. E.
(1954), Phys. Rev. 95, 1344.
schooley, j. f., hosler, w. r., and cohen, m. l. (1964), Phys. Rev. Lett.
schawlow,
schawlow,
schawlow,
SCHAWLOW,
j.,
a. l. (1956),
12, 474.
schrieffer,
j. r. (1957), Phys. Rev. 106, 47.

schrieffer, j. r. (1961), IBM Conf. on Superconductivity (unpublished).
schrieffer, j. r., and Ginsberg, d. m. (1962), Phys. Rev. Lett. 8,
207.
schrieffer,
j. r., scalapino, d. j., and wilkins, j. w. (1963), Phys.

Rev. Lett. 10, 336.
schrieffer, j. r., and wilkins, j. w. (1963), Phys. Rev. Lett. 10, 17.
serin, b. (1955),
serin, b. (1960),
serin,
162.
b.,
[3],
Chapter VII.
[6], p.
Reynolds,
391.
c. a.,
and lohman,
c. (1952), Phys. Rev. 86,
Superconductivity
180
shalnikov,
a.
I.,
and SHarvin, yu.
Bibliography
v. (1948), Izv.
Akad. nauk
USSR
12, 195.
shapiro,
shapiro,
(1963), Phys. Rev. Lett. 11, 80; see also [13], p. 223.
s.
s.,
shapoval,
and janus,
e. A.
a. r. (1964), [12], p. 321.
(1961), J.E.T.P.
14, 628 (1962).

sharvin, yu. v. (1 960), J.E.T.P.
USSR 41,
USSR 38, 298
11, 216.
shaw,
shaw,
r. w.,
r. w.,
and mapother, d. e. (1960), Phys. Rev. 118, 1474.

mapother, d. e., and hopkins, d. c. (1961), Phys. Rev.
121, 86.
sherrill, m. d., and Edwards, H. h. (1961), Phys. Rev. Lett. 6, 460.

SHIFFMAN, C. A. (1960), [6], p. 373.
shiffman, c. A. (1961), IBM Conf. on Superconductivity (unpublished).
shoenberg, d. (1940), Proc. Roy. Soc. A175, 49.
SHUBNIKOV, L. W., KOTKEVICH, W. I., SHEPELEV, J. D., and RIABININ,
J. N. (1937), J.E.T.P. USSR 7, 221.
silin, v. p. (1951), J.E.T.P. USSR 21, 1330.
Wash. Acad. Sci. 6, 597.

simmons, w. a., and douglass, jr., d.h.( 1962), Phys. Rev. Lett. 9, 153.
skalski, s., betbeder-matibet, o., and Weiss, p. r. (1964), Bull. Am.
silsbee,
f.
b. (1916), /.
Phys. Soc. 9, 30.

smith, p. h., shapiro,
s.,
miles,
J. l.,
and nicol,
J.
(1961), Phys. Rev.
Lett. 6, 686.
SPIEWAK, m. (1959), Phys. Rev. 113, 1479.

stout, j. w., and guttman, l. (1952), Phys. Rev. 88, 703.
strassler, s., and wyder, p. (1963), Phys. Rev. Lett. 10, 225.
stromberg, t. f., and swenson, c. a. (1962), Phys. Rev. Lett. 9, 370.
STRONGIN, M., PASKIN, A., SCHWEITZER, D. G., KAMMERER, O. F., and
craig, p. P. (1964), Phys. Rev. Lett. 12, 442.
suhl, h. (1962), Low Temperature Physics, C. De Witt, B. Dreyfus,
and P. G. De Gennes, eds. London, Gordon and Breach.
suhl, h., and Matthias, b. t. (1959), Phys. Rev. 114, 977.
suhl, h., Matthias, b. t., and corenzwit, e. (1959), /. Phys. Chem.
;
Solids 11, 347.
swartz, P. s. (1962), Phys. Rev. Lett. 9, 448.

swenson, c. a. (1960), Solid State Physics, Vol. 1 1, p. 41, F. Seitz and
D. Tumbull, eds.; New York, Academic Press.
swenson, c. a. ( 1 962), IBMJournal 6, 82 see also hinrichs, c. h., and
swenson, c. a. (1961), Phys. Rev. 123, 1 106; and schirber, j. e., and
swenson, c. a. (1961), Phys. Rev. 123, 1115.
;
181
swihart, j. c. (1959), Phys. Rev. 116, 45.

swthart, J. c. (1962), IBM Journal 6, 14.
swihart, j. c. (1963), Phys. Rev. 131, 73.
taylor, b. n., and burstein, e. (1963), Phys, Rev.
templeton, i. m. (1955a),/. Sci. Inst. 32, 172.
templeton, i. m. (1955b),/. Sci. Inst. 32, 314.
tewordt,
tewordt,
l.
(1962), Phys. Rev. 128, 12.
l.
(1963), Phys. Rev. 132, 595.
thouless, d.
j.
Lett. 10, 14.
(1960), Phys. Rev. 117, 1256.
tinkham, M. h. (1958), Phys. Rev. 110, 26.

ttnkham, m. h. (1962), IBM Journal 6, 49.
tinkham, m. h. (1963), Phys. Rev. 129, 2413.
tinkham, M. h. (1964), [13], p. 268.
tinkham, m. h., and ferrell, r. a. (1959), Phys. Rev. Lett. 2, 331.
tolmachev, v. v. (1958): see bogoliubov, n. n., tolmachev, v. v.,
and shirkov, d. v., A new Method inthe Theory ofSuperconductivity,
USSR Press, Moscow; Translation: ConNew York, 959) see also tolmachev, v. v.,
USSR 140, 563 (1961); Soviet Phys. Doklady 6,
Section 6.3 (Acad. Sci.

sultants Bureau, Inc.,
Dokl. Akad. nauk
800 (1962).
tomash, w. J., and Joseph, a. s. (1963), Phys. Rev. Lett. 12, 148.
townsend, p., and sutton, j. (1962), Phys. Rev. 128, 591.
toxen, a. m. (1962), Phys. Rev. 127, 382.
toxen, a. m., chang, G. K., and JONES, r. e. (1962), Phys. Rev. 126,
919.
tsuneto,
tsuneto,
Phys. Rev. 118, 1029.

Progr. Theor. Phys. 28, 857.
vroomen, a. r. de (1955), Conf. Phys. Basses Temp., Paris, p.580.
vroomen, a. r. de, and baarle, c. van (1 957), Physica 23, 785.
waldram, j. (1961), thesis, Cambridge University, private comt. (1960),
t. (1962),
munication.
watson, J. h. p., and graham, g. m. (1963), Can. J. Phys. 41, 1738.

werthamer, n. r. (1963a), Phys. Rev. 132, 663.
werthamer, n. r. (1963b), Phys. Rev. 132, 2440.
whitehead, c. s. (1956), Proc. Roy. Soc. A238, 175.
wipf, s. (1961), thesis, University of London; see also coles, b. r.,
IBM Journal 6, 6$ (1962).

wipf, s., and coles, b. r. (1959), Cambridge Superconductivity Conference (unpublished); see also coles, b. r., IBM Journal 6, 68
(1962).
yaqub, m. (1960), Cryogenics
1, 101, 166.
82
Superconductivity
yntema, g. b. (1955), Phys. Rev. 98, 1 197.

young, d. r. (\959), Progr. Cryogenics, Vol. I, p. 1, K. Mendelssohn,
ed.; London, Heywood & Co.
zavaritskii, n. v. (1951), Dokl. Akad. nauk USSR 78, 665.
zavaritskh, n. v. (1952), Dokl. Akad. nauk USSR 85, 749.
zavaritskii, n. v. (1958a), J.E.T.P.
J.E.T.P. 6, 837.
zavaritskii, n. v. (1958b), J.E.T.P.
J.E.T.P. 7, 773.
USSR
USSR
zavaritskii, n. v. (1959), J.E.T.P.

J.E.T.P. 10, 1069.
USSR
37,
1506; Soviet Phvs.
J.E.T.P.
USSR
J.E.T.P. 12, 831 (1961).

zavaritskii, n. v. (1960b), J.E.T.P.
J.E.T.P. 12, 1093 (1961).
USSR
USSR
zavaritskh, n.
v. (1960a),
zavaritskii, n. v. (1961), J.E.T.P.

J.E.T.P. 14, 470 (1962).
Index
Adiabatic Magnetization, 15
Anisotropy of energy gap
Bardeen-Cooper-Schrieffer (BCS)
theory - cont.
high frequency conductivity, 103,
114
Knight shift, 139^10
nuclear relaxation rate, 104-6, 137
penetration depth, 37, 52, 130
range of coherence, 48, 115
similarity principle, 122, 130
specific heat, 97, 130, 134-6
thermal conductivity, 91, 92, 136
thermal properties, 127-36
weak coupling limit, 131
BCS theory, 131

decrease with impurity, 97, 100,
and
106, 142
deduction from
infrared absorption, 100
nuclear spin relaxation, 106
96
thermal conductivity, 92
ultrasonic attenuation (table),
138
specific heat,
Anomalous skin effect, 44,

Anomaly in lattice specific
Atomic mass,
effect
101
103
heat, 9
Bulk modulus, 16
Tc 6
on
{See also isotope effect)
Atomic volume,
effect
on
Tc
Coefficient of thermal expansion, 17
Coherence see range of coherence

Coherence effects, 136-8
Cold work, 143
:
Bardeen-Cooper-Schrieffer (BCS)
theory, 12, 117-40, 150
(See also energy gap, interaction parameter
V,
quasi
Condensation energy,
particles)
and G-L theory,
52, 139
effect,
Condensation of electrons
mentum
103
films,
mo-
pairs, 12, 32, 52, 118-21,

125, 140, 144, 151
Critical current, 4, 80, 155, 161
Critical magnetic field, 4
effects,
current and field in thin
80
in
130
critical temperature, 129, 143
electromagnetic properties, 103,
critical field,
in
BCS theory, 130

G-L theory, 51
of lead and mercury, 132

of small specimens, 46, 58, 75-8,
80, 109, 155
of
superconducting
elements
114, 139-40
electron -phonon
in
space, 12, 14, 19, 21, 31,
Cooper
136-8
collective excitations, 100
critical
85, 91,
41
basic hypothesis, 120
coherence
19,
117, 126
Pippard non-local relations,

44
anomalous skin
Collective excitations, 100

Colloidal particles, 29, 35, 46
Compressibility, 17
interaction,
118-20, 125
ground state energy, 120-6
(table), 5
of thin
183
films, 46, 76-7, 80, 109
Index
184
magnetic field - cont.

precise measurements, 83-5
pressure effects, 1617
relation of thin film value to A6
Critical
and
lo,
relation
to
thermal
properties,
135
temperature dependence, 4, 18,
84-6, 130, 135
very high values, 27, 70-1, 109,
4, 85,
155
Critical field for supercooling, 66,
74,76
for surface superconductivity, 74
Critical temperature, 3
{See also isotope effect)
dependence on
atomic mass, 6
atomic volume, 6
discontinuity of specific heat,
specific heat, 143
thermal conductivity, 87-8, 90

variation of surface energy, 59, 70
9,
15, 17, 132, 135
of magnetic impurities,
145-50
effect of non-magnetic impurities,
141-4
in BCS theory, 129-43
Matthias' rules,
6, 141,
superconducting
Effective charge, 49, 52

Elastic properties, 9
Electron irradiation, 143

Electron-electron interaction,
82-3, 95, 117-25
Energy
148
elements
(table), 5
161-3
Cryotron, 157-63
Cylindrical specimens, 13, 16, 24
{See also thin wires)
cell,
10, 87, 124-5,
131, 134, 143
Demagnetization coefficient, 23
Density of electron states, 104-8,
123, 127, 129, 134, 143
Diffusion, 152
Dilute alloys
critical temperature, 141-4
magnetization curve, 144-5
11,91,96-7
thermal conductivity, 92, 95

tunnelling, 79, 106-9
ultrasonic attenuation, 137-8
dependence on
field, 79-80, 92, 109, 139
phonon spectrum, 132
position, 150-2
quasi-particle energy, 131-3
size, 79, 139
temperature, 90, 103, 108, 129,
139
in BCS theory, 120, 126-34, 139
in thin films, 79-80
elements
of superconducting
(table), 99
order parameter, 52, 79,
139
Meissner effect and perfect
conductivity, 110, 114-15,
120
penetration depth, 1 1
range of coherence, 44
Thomson
14,
150
Ferromagnetism, 145-8
Flux creep, 73
Flux quantization, 32-3, 72, 120
Free energy, 13-4, 19-20, 47-8,
57, 75, 93, 128, 148-9
heat, 95
18,38,78,128
185
G-L
parameter k - cont.
value for negative surface
energy, 59, 66, 67, 70
critical
deduction from
penetration depth, 51-3
supercooling, 51-3, 66
in thin films, 54, 78
normal
Gapless superconductivity, 149
Gauge
Gap
Entropy,
114-15,
relation to
{See also anisotropy of energy

gap)
correlation with TJ9, 134
deduction from
infrared absorption, 98-100
infrared transmission, 113-14
microwave absorption, 100-4
nuclear spin relaxation, 104-6
G-L
rule,
12,
relation to
Debye temperature,
sum
Ferrell-Glover
cont.
specific heat,
effect
Crowe
Dilute alloys
77
13-19,21,86, 132, 135

similarity of reduced field curves,
of
Index
in
in
and
conductivity
specific heat constant,
invariance
69
surface energy, 58
BCS theory, 139

G-L theory, 49
Geometry, influence of, 23-6

Ginzburg-Landau (G-L) theory,
12,
48-54, 150
basic equations, 50, 139
critical field of small specimens,
75-7
extension to lower temperatures,
49,80
temperature dependence, 70
Gorter-Casimir thermodynamic
treatment, 11, 13-19
Gorter-Casimir two-fluid model,
11, 19-21
{See also two-fluid model;
two-fluid order parameter)
application to G-L theory, 49
relation to penetration depth, 36
Gyromagnetic
ratio,
22
free energy, 48-9, 57, 75
limitations, 49, 52-3, 66, 80
non-local modifications, 48, 50

relation to
BCS
theory, 48, 52, 139

London equations, 50, 54
small specimens, 76-80
to
energy gap,
relation to penetration depth, 49,
53^, 78
-,
see
mean
free
path
Infrared absorption, 98-100

Infrared transmission, 45, 99, 109114, 115
Interaction parameter V, 121
BCS
cut-off, 121, 124-5, 131
of
non- magnetic impurities, 1 43-4
magnetic impurities, 149
effect
influence
on
isotope
effect,
124-6
quasi-particle
lifetime
124-5, 131
variation
with
energy, 131
Intermediate state,
effects,
quasi-particle
14,
23-6,
29,
59-61,94
52, 79, 139
G-L parameter
effects
effects
anisotropy, 131
superconductors of second kind.

67-72
supercooling, 65-7
surface energy, 57-9
G-L order parameter, 48
and free energy, 48-50, 57
effect of magnetic field, 53, 78,
139
gradual spatial variation, 49-50,
57-8, 73
proportionality
Impurity
5 1 -3, 58, 66,
and range of coherence, 58
68-70
Isotope effect, 12, 81-3, 95, 117,

124-6
absence in transition metals, 12,
82, 125
Index
186
Isotope effect - cont.
Index
Magnetic impurities, 145-50
of quasi-particle
124-6
in the BCS theory, 124
table of values, 82
effect
life
time,
16, 26, 75
effect, 109,
ideal
Knight shift, 77, 139^K)

Kramers-Kronig relations, 112, 114
Latent heat, 1 5, 78
Lattice parameters, 10
Laves compounds, 147-8
1 ,
depth, 29, 37-8, 43

microscopic implications, 11, 31,
43
non-linear extension, 38
prediction of penetration depth,
29,36
Low
frequency behaviour
diamagnetic description, 22-6
influence of geometry, 23-6
relation to high frequency response and energy gap, 1 14-15
small specimens, 75-80
field
distribution,
field
13-14,
small specimens, 75
superconductors of second kind,

68-9, 156
free path effects on

anisotropy of energy gap, 97, 100
106, 142
critical temperature, 141-4
G-L parameter k, 69
infrared absorption, 100
nuclear relaxation rate, 106
penetration depth, 35, 38, 41-3,
45-6,58, 112
range of coherence, 42-3, 45-7,
152
surface energy, 58-9, 70, 77
Mechanical effects, 16-17, 143
Mendelssohn 'sponge', 78, 155

Microwave absorption, 100-4
Mixed state, 71-74
Neutron bombardment, 143

Nuclear spin relaxation, 104-6
7-8,
field dependence of
energy gap, 79-80
entropy, 37
free energy, 13-14, 49
G-L order parameter, 53, 78
penetration depth, 35, 38-9, 53, 76
Magnetic
superconductors,
24-6,68
Mean
basic equations, 29, 42, 44,46, 1 1

incorrect values of penetration
penetration:
see
Nuclcation of superconducting
phase, 61-3
susceptibility,
34-5, 75, 77, 83
53
Quenching, 143
mean
field, 35,
38-9, 53, 76
free path, 35, 38, 41-3,
range of coherence, 43, 46, 112

79
temperature, 35-8, 51-3, 130
in BCS theory, 37, 52, 130
in Pippard theory, 45-6, 112
incorrectness of London values,
29,37-8,43, 112
methods of measurement, 35-6
superconducting
the
phase, 14, 19
Order parameter, see G-L order
parameter; two-fluid order para-
Order
in
meter
23,
Penetration depth, 29, 58

defining equations, 28, 34, 36
42, 45-7, 152

in
in
energy gap, 115

entropy, 38
frequency variation of conductivity, 111-2
G-L order parameter, 51, 78
susceptibility, 34-5
thin film critical field, 77
values in superconducting elements (tables), 38, 65
Perfect conductivity of superconductors, 4, 29-30, 114-15
Perfect conductor, 4, 6-8, 27-8
Persistent current, 3, 6, 26, 158-60
Phase propagation, 63-5
Phonon spectrum, 132
Pippard non-local theory, 12, 41-6
(See also range of coherence)
basic equations, 42, 44, 45
field
penetration
46
through thin
films,
45
penetration depth, 42-3, 45-6

reduction to local form (London
limit) 12,
45-6
of thin
58
energy gap, 44
field dependence of penetration depth,
mean
40
free path effect
on
Tc
and
BCS
Relation between magnetic and

thermal properties, 13-21, 86,
96, 132, 135
Rutgers' relation, 15, 17
Semiconductors, superconducting,
6
Silsbee's rule, 5
Similarity, 85-6, 96, 116, 121-2, 130
Size effect
on
76-7, 155
supercooling field, 67
critical temperature, 143
energy gap, 79-80
critical field, 46,
critical
magnetic
susceptibility,
34
penetration depth, 38, 46, 79

Skin depth, 35-6, 43
critical field, 46,
films,
77
75-8
G-L
theory, 46, 54, 67, 75-80

in Pippard theory, 46
in
Pressure effects, 12, 16-17
142
penetration depth, 40, 44-6
sharpness of transition 40-1
surface energy, 57
uncertainty principle 40, 45
values for Al, In, Sn (table), 65
Small specimens
relation to energy gap

susceptibility
BCS theory, 44
G-L theory, 49,
relation to
relation to
theory, 44-5
14,
Range of coherence, 1
and superimposed metals, 150-1
dependence on mean free path,
size, 38, 46,
critical field in thin films,
penetration depth
Magnetic
flux, 32-3, 72, 120

Quasi-particles, 124-5, 132
45-6,58,112
Magnetostriction, 16
Matthias' rules, 6, 141, 148
Lifetime effects, 124-6, 131

Localized magnetic moment, 145-6
London theory, 1 28-32, 36, 41-2
Magnetic
22-4
Magnetic
magnetic
superconductors,
78
133-4
Quantized
cont.
dependence on
field direction, 39,
187
frequency, 39
dilute alloys, 144
filamentary
Josephson
Penetration
Magnetization
area under magnetization curve,
depth -
low frequency behaviour, 75-80
Small specimens -
cont.
penetration depth, 35-8, 43,

45-6, 79
range of coherence, 45-6
Sommerfeld specific heat constant, 9
in dilute alloys, 143
independence of isotopicmass,85
relation to
G-L parameter
Specific heat of the electrons
comparison
of
17,
and
19-21,
dependence on temperature, 9,
11,18,20-1, 86,91,96-7,134
Tc
9, 15, 17, 78,
132, 135
BCS
theory, 130, 135
relation to
21,86, 96
energy gap, 11, 90, 96-7, 132
Rutgers' relation, 15, 17
Specific heat of the lattice, 9-10, 18
Spherical specimens
critical field of small spheres, 76
magnetization, 8, 26
penetration
depth
of small
spheres, 29, 35, 46
supercooling in small spheres, 67
critical field, 15, 17,
Spin, effect on Tc , 147

Strain, 26-7, 62, 77, 155
Superconducting alloys and compounds, 5-6

dilute alloys, 58-9, 87-90, 141-5
ferromagnetism, 145-8
high critical fields, 154-6
Laves compounds, 147-8
magnetic impurities, 145-50
Matthias' rules,
intermediate state, 59
phase nucleation and propa-
gation, 61-6
range of coherence, 56-8
154
reversing switches, 154
Superconducting elements
(table),
6,
141
non-magnetic impurities, 141-5

rare earth and transition metal
solutes, 145-9
thermal conductivity, 88-9
Superconducting filaments, 78, 155

Superconducting ring, 3, 8, 26, 30,
32
Superconducting transition
contrast with perfect conductor,
6-8
discontinuity of
specific
heat, 9,
15,
17,
78,
134
entropy, 14
free energy, 13-14,48
in dilute alloys, 144
in thin films, 78-81
length
and
volume
changes,
16-17
reversibility, 7, 13, 17,
144
speed, 159
Superconductors of second kind,

67-73, 155-6
52-3,
values for AI, In, Sn (table), 65

Surface impedance, 35-6, 52-3, 95,
101-4, 111, 139
critical fields
61-3,
65-7,
74
and temperatures,
surface energies, 65
Temperature dependence of
4,
18,
84-6,
130,
135
energy gap, 90, 103, 108, 130
G-L parameter k, 70
penetration depth,
35-8,
51-2,
130
specific heat, 9, 11, 18, 20-1, 86,
91,96-7, 130, 134
Superheating, 61
Superimposed metals, 150-2
Surface currents, 22
Surface energy, 55-74, 150, 156
dependence on temperature, 64-5
effect of strain, 62, 77, 156
in G-L theory, 57-8
in inhomogeneous specimens, 77,
156
energy gap, 91-3, 95

gap anisotropy, 92
specific heat, 91
Thermal expansion coefficient, 17

Thermodynamics of superconductors
BCS theory, 128

G-L theory, 48-9
Gorter-Casimir treatment, 11,
13-19
relation between magnetic and
thermal properties, 13-21, 86,
96, 132, 135
surface energy, 64-5, 70

surface impedance, 101-3, 139
thermal conductivity, 87-94, 136
two-fluid order parameter, 19-21,
36
Thermal conductivity, 87-94

in
BCS
of thin
films
(See also superimposed metals)

critical current, 80
critical field, 47,
energy gap values, 99

energy gap anisotropy, 138
isotope effect exponents, 82
penetration depth values, 38, 65
ranges of coherence, 65
specific heat discontinuities, 17,
135
superconducting elements, 5
theory, 92, 136

films, 79,
93
cont.
relation to
Thin
Table of
critical field,
order, 72, 78-81
Supercooling,
Pippard theory, 56-7

free path effect, 58-9, 67,
77
relation to
86, 134, 135
discontinuity at
devices,
189
Thermal conductivity -
cont.
negative values, 58-9, 62, 67, 69,

70, 157
heat switches, 94, 1 53

leads, 153
magnets, 78, 154-7
rectifiers,
magnetic
calorimetric data,
in
mean
60-4
radiation detectors, 154
69
*,
Surface energy
cavities, 154
computer elements, 157-64
d.c. amplifiers, 153-4
galvanometers, 153
memory
19-21,135
critical field,
in
Index
Index
188
75-80
critical thickness for second
order
transition, 78
cryotrons, 157-63
energy gap, 79, 93

infrared transmission, 46, 109-15
in G-L theory, 54, 75-80
in perpendicular field,
magnetic
75-80
behaviour,
73
33,
73-4,
penetration depth, 29, 35-6, 46,

79
relation of critical field to X
b
and
&77
second order transition, 78
supercooling, 67
susceptibility, 34-5, 76, 77
total field penetration, 36, 45
variation of G-L order parameter, 78
Thin wires, 29, 35, 67, 76
Thomson heat, 95
Threshold magnetic field: see critical magnetic field
Time-reversed
wave
functions,
144
Index
190
Transition metals
absence of isotope effect, 12, 82,
125-6
effect
on
Trapped
Tc
145-50
flux, 3,
26-7, 32, 120, 144,
161
Tunnelling, 106-9, 132-4
Two-fluid model
(See also Gorter-Casimir twofluid
and
model)
BCS
theory, 127
extension of G-L theory, 49
Two-fluid order parameter, 19-21,

36
gradual spatial variation, 40,
56-7
relation to
penetration depth, 36
rigidity in London theory, 39
Ultrasonic attenuation, 105, 136-8
Uncertainty principle, 31, 40, 45
relation to
nuclear spin relaxation, 104

penetration depth, 36
Valence elections,
143, 145
Vortex
lines,
72-4
effect
on
Tc
6,
s>
Monographs on Physical Subjects
continued
IONIZATION AND BREAKDOWN IN GASBS

F. Llewellyn Jones
LOW TEMPERATURE PHYSICS
L. C. JaCKSOl
magnetic amplifiers George M. EtringC

magnetic materials F. Brailsford
MASERS AND LASERS G. J. F. TrOUp
THE MEASUREMENT OF RADIO ISOTOPBS
LIVERPOOL
Taylor
MBCHANICAL AND ELECTRICAL VIBRATION

J.
turn this
book
to th
2 the last date
si
R. Barker
mercury arcs F. J. Teago

THE METHOD OF DIMENSIONS Alfred W. P
MICROWAVE LBNSBS J. Brown
microwavb spectroscopy M. W. P. Stran
MOLECULAR BEAMS K. F. Smith
NUCLEAR RADIATION DBTBCTORS J. Sharp
the nuclear reactor Alan Salmon
optical masers O. S. Heavens
ORDER-DISORDER PHENOMENA E. W. ElCQ
PHOTONS AND ELECTRONS K. H. Spring
PHYSICAL CONSTANTS W. H. J. Childs
physical formulae T. S. E. Thomas
THE PHYSICAL PRINCIPLES OF WIRBLBSS
J.
A. Ratcliffe
PRINCIPLES OF APPLIED GEOPHYSICS

D. Parasnis
relativity physics W. H. McCrea
sbismology K. E. Bullen
SBMI-CONDUCTORS D.A.Wright
SHOCK TUBES J. K. Wright
THB SPECIAL THBORY OF RELATIVITY
M<
Dingle
superconductivity Ernest A. Lyman

THE THBORY OF GAMBS AND LINEAR
gramming
S. Vajda
THERMIONIC VACUUM TUBBS

Sir
W. H. Aldoi
Edward Appleton
thermodynamics Alfred W. Porter

wave filtbrs L. C. Jackson
wave guides H. R. L. Lamont
WAVB MBCHANICS
H. T.
Flint
x-ray crystallography R. W. James

x-ray optics A. J. C. Wilson
Printed in Great Britain
Monographs on Physical Subjects

ALTERNATING CURRENT MEASUREMENTS David Owen
APPLICATIONS OF INTERFEROMETRY W. Ewait Williams
APPLICATIONS OF THERMOELECTRICITY H. J. Goldsmid
atmospheric electricity B. F. J. Schonland
ATMOSPHERIC TURBULENCE O. G. Sutton
atomic spectra R. C. Johnson
cartesian tensors George Temple
classical mechanics J. W. Leech
THB CONDUCTION OF ELBCTRICITY THROUGH GASES K. G.
Emeteus
the cosmic radiation
J.
E.
Hooper and M. Scharff
dielectric aerials D. G. Kiely

dipole moments R. J. W. le Fevre
the earth's magnetism Sydney Chapman
ELASTICITY, FRACTURE AND
FLOW
J.
,4
H.
J.
C^
^3
^_{
^t
Josephs
high energy nuclear physics W. Owen Lock

HI-GH FREQUENCY TRANSMISSION LINES Willis Jackson
INTEGRAL TRANSFORMS IN MATHEMATICAL PHYSICS C.
J.
Tranter
AN INTRODUCTION TO ELECTRONIC ANALOGUE COMPUTERS

M. G. Hartley
AN INTRODUCTION TO ELECTRON OPTICS L. Jacob
AN INTRODUCTION TO FOURIER ANALYSIS R. D. Stuart
AN INTRODUCTION TO THE LAPLACE TRANSFORMATION
C. Jaegar
AN INTRODUCTION TO SERVOMECHANISMS A. Porter

AN INTRODUCTION TO VECTOR ANALYSIS B. Hague
AN INTRODUCTION TO TENSOR CALCULUS AND RBLATIVITY
Derek F. Lawden
AN INTRODUCTION TO PHASE-INTEGRAL METHODS
J.
G. O. Jones
heaviside's electric circuit theory
J.
^3
^J
C. Jaegar
THB electric arc J. M. Somerville

elements OF pulse circuits F. J. M. Farley
BLBMENTS OF TENSOR CALCULUS H. Lichnerowicz
fluid dynamics G. H. A. Cole
frequbncy modulation L. B. Arguimbau and R. D. Stuart
FRICTION AND lubrication F. P. Bowden and D. Tabor
FUNDAMENTAL OF DISCHARGE TUBE CIRCUITS V. J. Francis
gbnbral circuit theory Gordon Newstead
THE GENERAL PRINCIPLES OF QUANTUM THEORY G. Temple
glass
CQ
^J
Heading
[continued on back flap]

Lynton Superconductivity

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Lynton Superconductivity

Hochgeladen von

Copyright:

Verfügbare Formate

GO

Although the fascinating phenomenon of

ence on the present state of the subject of

contains a description of the

principal characteristics of a superconductor,

together with a detailed discussion of the most

been applied to superconductors. The second

monograph describes the fundamental microscopic properties in terms of the

LONDON: METHUEN & CO LTD

First published in 1962

Second edition 1964

1962 and 1964 by E. A. Lynton

Catalogue No. Methuen 12/4081/66

hosts, Professors Neel

and pleasant year.

should like once again to thank

and Weil and Dr Goodman, for a stimulating

am very grateful to a large number of people who

Olsen, Pippard, Schrieffer, Shapiro,

Swihart, Tinkham, Toxen, and

McLean, and Weiss provided much helpful discussion. Above all my

and the critical magnetic field

Superconducting elements and compounds

The Meissner effect

Phenomcnological Thermodynamic Treatment

the time to read the entire

and suggested many improvements, not

Preface to the Second Edition

The perfect conductor

Nozieres, for his valuable

lation, edited with

Russian transilluminating footnotes by Dr. Gor'kov,

late for these

in the present edition.

and the intermediate

The Pippard Non-local Theory

Static Field Description

porated in the excellent French translation of Mme Nozieres, which

Many of these were also

ber of other changes have been made.

The phase transition

draft of the manuscript

have profited for

The penetration depth, A

The Ginzburg-Landau Phenomcnological Theory

The Surface Energy

Microscopic Theory of Superconductivity

and the range of coherence

Supercooling in ideal specimens

Superconductors of the second kind

Experimental verification of predicted thermal

11.10 Electromagnetic properties

vn Low Frequency Magnetic Behaviour of Small Specimens

Increase in the critical field

threads and superconducting magnets

Variation of the order parameter and the energy

Dilute solid solutions with non-magnetic im-

Thermal conductivity in the intermediate

temperature thermal conductivity

Superconducting computer elements

Electromagnetic absorption in the far infrared

Nuclear spin relaxation

Far infrared transmission through thin

The Ferrell-Glover sum