Frank J. Owens, Charles P. Poole Jr. Electromagnetic Absorption in The Copper Oxide Superconductors 1999

Electromagnetic Absorption in the
Copper Oxide Superconductors

SELECTED TOPICS IN SUPERCONDUCTIVITY
Series Editor: Stuart Wolf
Naval Research Laboratory
Washington, D.C.
CASE STUDIES IN SUPERCONDUCTING MAGNETS

Design and Operational Issues
Yukikazu Iwasa
ELECTOMAGNETIC ABSORPTION IN THE COPPER OXIDE
SUPERCONDUCTORS
Frank J. Owens and Charles P. Poole, Jr.
INTRODUCTION TO HIGH-TEMPERATURE SUPERCONDUCTIVITY
Thomas P. Sheahen
THE NEW SUPERCONDUCTORS
QUANTUM STATISTICAL THEORY OF SUPERCONDUCTIVITY
Shigeji Fujita and Salvador Godoy
STABILITY OF SUPERCONDUCTORS
Lawrence Dresner
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Copper Oxide Superconductors
Frank J. Owens
Army Armament Research Engineering and Development Center
Picatinny, New Jersey and
Hunter College of the City University of New York
New York, New York
and
Charles P. Poole, Jr.

Institute of Superconductivity
University of South Carolina
Columbia, South Carolina
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Preface to the Series
Since its discovery in 1911, superconductivity has been one of the most
interesting topics in physics. Superconductivity baffled some of the best minds
of the 20th century and was finally understood in a microscopic way in 1957 with
the landmark Nobel Prize-winning contribution from John Bardeen, Leon
Cooper, and Robert Schrieffer. Since the early 1960s there have been many
applications of superconductivity including large magnets for medical imaging
and high-energy physics, radio-frequency cavities and components for a variety
of applications and quantum interference devices for sensitive magnetometers
and digital circuits. These last devices are based on the Nobel Prize-winning
(Brian) Josephson effect. In 1987, a dream of many scientists was realized with
the discovery of superconducting compounds containing copper --oxygen layers
that are superconducting above the boiling point of liquid nitrogen. The
revolutionary discovery of superconductivity in this class of compounds (the
cuprates) won Georg Bednorz and Alex Mueller the Nobel Prize.
This series on Selected Topics in Superconductivity will draw on the rich
history of both the science and technology of this field. In the next few years we
will try to chronicle the development of both the more traditional metallic
superconductors as well as the scientific and technological emergence of the
cuprate superconductors. The series will contain broad overviews of
fundamental topics as well as some very highly focused treatises designed for a
specialized audience.
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Preface
In 1987 a major breakthrough occurred in materials science. A new family of

materials was discovered that became superconducting above the temperature at
which nitrogen gas liquifies, namely, 77 K or –196°C. Within months of the
discovery, a wide variety of experimental techniques were brought to bear in order
to measure the properties of these materials and to gain an understanding of why
they superconduct at such high temperatures. Among the techniques used were
electromagnetic absorption in both the normal and the superconducting states. The
measurements enabled the determination of a wide variety of properties, and in
some instances led to the observation of new effects not seen by other measure-
ments, such as the existence of weak-link microwave absorption at low dc magnetic
fields.
The number of different properties and the degree of detail that can be obtained
from magnetic field- and temperature-dependent studies of electromagnetic absorp-
tion are not widely appreciated. For example, these measurements can provide
information on the band gap, critical fields, the H–T irreversibility line, the amount
of trapped flux, and even information about the symmetry of the wave function of
the Cooper pairs. It is possible to use low dc magnetic field-induced absorption of
microwaves with derivative detection to verify the presence of superconductivity
in a matter of minutes, and the measurements are often more straightforward than
others. For example, they do not require the physical contact with the sample that
is necessary when using four-probe resistivity to detect superconductivity. Also,
there is no limit on the form of the samples required for electromagnetic absorption
studies since sintered and granular materials, crystals, and thin films are all equally
acceptable.
The purpose of this volume is to provide an introduction to electromagnetic
absorption measurements in superconductors, with an emphasis on the new super-
conducting materials, showing the variety of basic properties that can be delineated
by such measurements. The volume is not intended to be a detailed review of all
vii
viii PREFACE
the work done in the area, but rather an introduction to the field supplemented by
an outline of the theory and discussions of relevant experimental results. The focus
is on qualitative aspects and experimental measurements rather than on detailed
theoretical considerations so that the reader can obtain a basic understanding and
appreciation of the wealth of information provided by electromagnetic absorption
measurements, as well as insights into the mechanisms of absorption. Thus the
references cited are not meant to be comprehensive lists of work in the field but
collections of representative articles. The level of presentation is such that the
volume can be used as a supplementary text for a graduate course in solid state
physics, materials science, or superconductivity.
The book is intended to be self-contained in that it starts with an elementary
introduction to superconductivity, with an emphasis on those properties that are
germane to understanding electromagnetic absorption of the superconducting state.
Then we provide an overview of the properties of the copper oxide and fullerene
superconductors, followed by a chapter on experimental techniques and another on
electromagnetic absorption in the normal state. Our attention then turns to micro-
wave absorption in a zero magnetic field and in low magnetic fields; this is followed
by an explication of the role played by vortex motion. Absorption in the infrared
and optical regions is then treated, and the book ends with a discussion of
applications.
Acknowledgment
One of us (CPP) would like to thank his son Michael for drawing several of
the more difficult figures.

Contents
Chapter 1. The Superconducting State

1.1. Zero Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1. The Superconducting Gap . . . . . . . . . . . . . . . . . . . . 2
1.1.2. Cooper Pairs . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . 4
1.2. The Meissner Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.1. Magnetic Field Exclusion . . . . . . . . . . . . . . . . . . . . 7
1.2.2. Temperature Dependencies . . . . . . . . . . . . . . . . . . . . 12
1.2.3. Applied and Internal Fields . . . . . . . . . . . . . . . . . . . 14
1.2.4. Type I and Type II Superconductors . . . . . . . . . . . . . . . 17
1.2.5. Quantization of Flux . . . . . . . . . . . . . . . . . . . . . . . 23
1.2.6. Vortex Configurations . . . . . . . . . . . . . . . . . . . . . . 24
1.2.7. Flux Creep and Flux Flow . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Chapter 2. The New Superconductors

2.1. The Copper Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.1.1. Lanthanum and Neodymium Superconductors . . . . . . . . . 31
2.1.2. The Yttrium Superconductor . . . . . . . . . . . . . . . . . . . 34
2.1.3. Bismuth and Thallium Superconductors . . . . . . . . . . . . . 36
2.1.4. Mercury Superconductors . . . . . . . . . . . . . . . . . . . . 38
2.1.5. Infinite-Layer Phases . . . . . . . . . . . . . . . . . . . . . . . 39
2.1.6. Ladder Phases . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2. General Properties of Copper Oxide Superconductors . . . . . . . . . . 42
2.2.1. Commonalities of the Cuprates . . . . . . . . . . . . . . . . . 44
2.2.2. Energy Bands . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.2.3. Cooper Pair Binding . . . . . . . . . . . . . . . . . . . . . . . 49
2.3. Perovskite Superconductors . . . . . . . . . . . . . . . . . . . . . . . 50
2.4. Carbon-60 Superconductors . . . . . . . . . . . . . . . . . . . . . . . 51
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
ix
X CONTENTS
Chapter 3 . Experimental Methods and Complementary Techniques

3.1. Radio Frequency Measurements Using LC Resonant Circuits . . . . . . 55
3.2. Microwave Measurements Using Cavity Resonators . . . . . . . . . . 59
3.3. Electron Paramagnetic Resonance . . . . . . . . . . . . . . . . . . . . 62
3.4. Paramagnetic Probes . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.5. Stripline and Parallel Plate Microwave Resonators . . . . . . . . . . . . 66
3.6. Nuclear Magnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . 68
3.7. Nuclear Quadrupole Resonance . . . . . . . . . . . . . . . . . . . . . 69
3.8. Muon Spin Relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.9. Positron Annihilation . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.10. Mössbauer Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.11. Photoemission and X-Ray Absorption . . . . . . . . . . . . . . . . . . 71
Chapter 4 . Electromagnetic Absorption in the Normal State

4.1. Metallic State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.1.1. Electrical Conductivity .. . . . . . . . . . . . . . . . . . . . . 75
4.1.2. Surface Resistance . . . . . . . . . . . . . . . . . . . . . . . . 78
4.1.3. Power Dissipation . . . . . . . . . . . . . . . . . . . . . . . . 79
4.1.4. Temperature Dependencies . . . . . . . . . . . . . . . . . . . . 81
4.2. Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.3. Metal-Insulator Transition . . . . . . . . . . . . . . . . . . . . . . . . 83
4.4. Antiferromagnetic Transition . . . . . . . . . . . . . . . . . . . . . . . 83
4.5. Ferromagnetic Transition . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.6. Magnetoresistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Chapter 5 . Zero Magnetic Field Microwave Absorption

5.1. Electromagnetic Absorption and the Two-Fluid Model . . . . . . . . . . 95
5.2. Surface Impedance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.3. Electromagnetic Absorption in the BCS Theory . . . . . . . . . . . . . 99
5.4. Copper Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.4.1. Penetration Depth Measurements . . . . . . . . . . . . . . . . 102
5.4.2. Surface Resistance Measurements . . . . . . . . . . . . . . . . 105
5.4.3. Penetration Depth Measurements as a Probe of
s- and d-Wave Symmetry . . . . . . . . . . . . . . . . . . . . . 107
5.4.4. Electromagnetic Absorption Due to Fluctuations . . . . . . . . 107
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Chapter 6. Low Magnetic Field-Induced Microwave Absorption

6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
6.2. Properties of Low Magnetic Field Absorption Derivative . . . . . . . . 114
CONTENTS xi
6.3. Properties of Low-Field Direct Microwave Absorption . . . . . . . . . 120

6.4. Origin of Low Magnetic Field Derivative Signal . . . . . . . . . . . . 125
6.4.1. Loops and Josephson Junctions . . . . . . . . . . . . . . . . . 125
6.4.2. Absorption Mechanism . . . . . . . . . . . . . . . . . . . . . . 128
6.5. Magnetic Field Absorptionin Alternating Applied Fields . . . . . . . . 132
6.6. Low Magnetic Field Derivative Signal as a Detector of
Superconductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Chapter 7 . Electromagnetic Absorption Due to Vortex Motion

7.1. Theory of Electromagnetic Absorption Due to Vortex Dissipation . . . . . . 139
7.1.1. Penetrating Fields . . . . . . . . . . . . . . . . . . . . . . . . 139
7.1.2. Flux Creep, Flux Flow, and Irreversibility . . . . . . . . . . . . 140
7.1.3. Coffey–Clem Model . . . . . . . . . . . . . . . . . . . . . . . 142
7.2. Experimental Results . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
7.2.1. RF Penetration Depth Measurements . . . . . . . . . . . . . . 145
7.2.2. Microwave Bridge Measurements . . . . . . . . . . . . . . . . 148
7.2.3. Strip Line Resonator Measurements . . . . . . . . . . . . . . . 153
7.3. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
References .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
Chapter 8. Infrared and Optical Absorption

8.1. Absorption in the Infrared . . . . . . . . . . . . . . . . . . . . . . . . 159
8.2. Detecting Molecular and Crystal Vibrations . . . . . . . . . . . . . . . 160
8.3. Soft Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
8.4. Dielectric Constant and Conductivity . . . . . . . . . . . . . . . . . . 164
8.5. Reflectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
8.6. Kramers–Kronig Analysis . . . . . . . . . . . . . . . . . . . . . . . . 166
8.7. Drude Expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
8.8. Plasma Oscillations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
8.9. Energy Gap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
8.10. Absorption at Visible and Ultraviolet Frequencies . . . . . . . . . . . . 172
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
Chapter 9 . Applications
9.1. Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
9.2. Delay Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
9.3. Stripline Resonators . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
9.4. Cavity Resonators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
9.5. Transmission Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
9.6. Superconducting Antennae . . . . . . . . . . . . . . . . . . . . . . . . 186
9.7. Infrared and Optical Sensors . . . . . . . . . . . . . . . . . . . . . . . 188
xii CONTENTS
9.8. Magnetometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
1
The Superconducting State
This chapter presents a brief overview of the properties of the superconducting state,
with an emphasis on those characteristics that are germane to the absorption of
electromagnetic energy in this state.
1.1. ZERO RESISTANCE

Let us consider conductivity before we consider superconductivity. In a metal,
the valence electrons are relatively weakly bound to the atoms of the lattice, so they
detach themselves from these atoms, become delocalized in an energy state called
the conduction band, and wander around the lattice. The application of a sufficiently
strong electric field E will cause the conduction electrons at the top of the
conduction band, a region called the Fermi surface, to move through the lattice.
The electric field exerts a force F = –eE on the electrons, where e is the electronic
charge, and in the absence of any resistance, the electron velocity should increase
continuously. However, this does not happen because the electrons collide with the
vibrating atoms as well as with impurity atoms and defects in the lattice, and are
scattered out of the path of flow. The result is that the electrons acquire a limiting
velocity v, producing a current density J = nev, where n is the volume density of
electrons. The metal acquires a resistance R as a result of this scattering of the
electrons. Because the atoms are vibrating about their equilibrium positions in the
lattice, and at higher temperatures the vibrating atoms have larger amplitudes of
oscillation, the probability for electrons to scatter from them increases, and hence
the resistance increases with the temperature, as shown in Fig. 1.1 for sodium.
The resistance of a metal does not become zero as the temperature is lowered
to absolute zero, even though the lattice vibrations freeze out, but instead R
approaches a limiting value. This constant resistance at low temperature is called
the residual resistance, and is a result of scattering from imperfections and defects
in the lattice. In a superconductor, however, there is a transition temperature Tc at
1
2 CHAPTER 1
Figure 1.1. Temperature dependence of the resistance of sodium normalized to its value at 290 K.
which the resistance to direct current flow and low-frequency ac current flow
becomes zero. Figure 1.2 is a plot of the dc resistance normalized to its room
temperature value versus temperature for the superconductor
Hg0.8Pb0.2Ba2Ca2Cu3O8+x, which reaches zero resistance at 130 K, the highest
temperature of any superconductor at ambient pressure (1).
1.1.1. The Superconducting Gap
Prior to the development of the theory of superconductivity, experiments had
shown that the carriers of current in the superconducting state have a charge 2e,
which is twice the electron charge. This means that the electrons at the Fermi surface
of the metal, which carry the current, are bound in pairs called Cooper pairs (2).
The existence of these bound pairs in the superconducting state alters the energy
band structure by introducing a gap in energy, with the normal conduction electrons
above the gap and the Cooper pairs below. In a metal, the top occupied band is not
full, and the Fermi level demarcates the energy of the uppermost filIed state in the
band. In the superconducting state, the presence of bound electron pairs implies
that the energy gap D is located at the Fermi level. The magnitude of this supercon-
ducting gap corresponds to the binding energy of the electron pairs. It is the energy
THE SUPERCONDUCTING STATE 3
Figure 1.2. Temperature dependence of the resistance of the Hg-Pb-Ba-Ca-Cu-O superconductor

normalized to its value at 295 K. (After Iqbal et al., Ref. 1.)
difference between the normal electrons and the bound electron pairs at the Fermi
level.
As we will see later, this gap plays an important role in the absorption of
electromagnetic radiation in the superconducting state. If the incident electromag-
netic radiation has a photon energy less than the gap, there will be no absorption at
0 K. In fact, studies of the reflection of microwave and infrared (IR) radiation
provide evidence for the existence of this energy gap in the superconducting state.
A measurement of the frequency dependence of the reflection of infrared light from
a superconductor below Tc allows a determination of the energy gap. Figure 1.3
shows a plot of the fraction of light reflected from the elemental superconductor
indium at 3.39 K in the superconducting state relative to its normal state reflection
(3). The reduction of the reflection of infrared photons at 10 cm–1 starts where the
radiation begins to induce excitations across the superconducting gap; in effect,
each absorbed IR photon breaks a Cooper pair.
The Bardeen–Cooper–Schrieffer (BCS) theory in the weak coupling limit
predicts that the band gap Eg (0) = 2D (0) at absolute zero is related to the transition
temperature Tc by the expression (4)
Eg(0)=2D (0) = 3.52kBTc (1.1)

4 CHAPTER 1
Figure 1.3. Fraction of electromagnetic energy reflected from indium in the superconducting state as
a function of the frequency of the radiation. (After Richards and Tinkham, Ref. 3.)
As the temperature is raised above absolute zero, the superconducting gap decreases
in magnitude in the manner illustrated in Fig. 1.4, which presents a plot of
Eg(T)/Eg(0) versus reduced temperature T/T c for the element tantalum (5). The
temperature dependence of the gap follows an approximate (Tc – T)½ relation,
which is the well-known mean field result for the order parameter in a second-order
phase transition. This suggests that the superconducting transition is second order.
1.1.2. Cooper Pairs

One of the major problems in the development of an understanding of super-
conductivity is explaining how two negatively charged electrons can be bound into
pairs despite the repulsive electrostatic Coulomb force between them. In 1956, a
year before the discovery of the BCS theory, L. N. Cooper showed how lattice
phonons could produce a binding of two electrons near the Fermi level (2). The
effect of isotopic labeling on the transition temperature provided aclue to the nature
of the mechanism. Measurements of the transition temperatures of several isotopes
of the element mercury had demonstrated that the transition temperature shifts to
lower values as the mass of the Hg nucleus increases. More specifically, the
experiment showed that the shift of Tc is proportional to (m)–½ where m is the mass
of the mercury isotope (6). Since the spring constant k of a vibrating mass is given
by k = mw2, the vibrational frequency w = (k/m)½ measured by IR spectroscopy
is also inversely proportional to the square root of the atom’s mass. This result
provided a critical piece of evidence supporting the role of lattice phonons in
Figure 1.4. Temperature dependence of the reduced energy gap Eg(T)/Eg(0) versus reduced tempera-
ture T/T c for superconducting tantalum. (After Townsend and Sutton, Ref. 5).
superconductivity. The BCS theory, which appeared in 1957, proposed that the
Cooper pair binding arises from a phonon coupling mechanism.
A classical (i.e., nonquantum mechanical) description can be used to to obtain
some insight into how lattice phonons can cause binding of the electrons into pairs.
Because the valence electrons have detached themselves from atoms to move freely
through the lattice, the atoms of the metal have acquired a positive charge. When
the conduction electrons move past these positively charged atoms, the atoms are
attracted to the electrons and there is a slight shift in the positions of the atoms
toward the passing electrons. This situation is illustrated in Fig. 1.5. This distorted
region is slightly more positively charged than the rest of the lattice and it follows
the electron as it moves through the lattice. This more positive region may attract
a distant electron and cause it to follow the distortion as it moves through the lattice,
in effect forming a bound electron pair.
An alternative way to view the process is as an exchange of phonons between
two electrons, with one electron emitting a phonon which is then absorbed by
another electron. We say that the interaction between the electrons is transmitted
by the phonon. The process is represented diagrammatically in Fig. 1.6. The binding
energy of the two electrons is on the order of 10–4 eV, and the separation of the
electrons is about 10 3 Å, which is about 300 lattice spaces. Thus the quantum
mechanical wavelength of the Cooper pairs is much longer than the diameters and
6 CHAPTER 1
Figure 1.5. Illustration of how a conduction electron moving through a lattice distorts the lattice along
its path.
spacings of the atoms of the solid. As a result, the Cooper pairs do not “see” the
atoms of the lattice and are not scattered by them. The spins of the electrons of
the pair are oppositely aligned, so a bound Cooper pair has zero spin and is a
boson. This means that at absolute zero all Cooper pairs will be in the ground
state and have the same energy and therefore the same wavelength. Thus not
only is the wavelength of the pairs very long, but all the pairs have the same
wavelength. Further, it turns out that the phase of the wave of every pair is the same
as that of any other pair. Thus the Copper pairs have a phase coherence analogous
Figure 1.6. Illustration of the phonon exchange process between two electrons which binds them into
a Cooper pair.
THESUPERCONDUCTINGSTATE 7
to the waves of light produced by a laser. In other words, the motion of the pairs in
the lattice is correlated. It is this remarkable property of the quantum mechanical
wave describing the Copper pairs that accounts for their movement through the
lattice without scattering and the resulting zero resistance of the superconducting
state. The BCS theory explains how these circumstances reduce the energy of the
super electrons below the energy gap.
1.2. THE MElSSNER EFFECT

1.2.1. Magnetic Field Exclusion
The second major characteristic of the superconducting state, in addition to
that of zero resistance, is called the Meissner effect. If a superconducting material
is cooled below its transition temperature in an applied magnetic field B0
B0 = µ 0H0 (1.2)
where µ0 is the permeability of free space and H0 is the magnetic intensity; the
magnetic flux density Bin within the bulk of the material will be expelled below the
transition temperature Tc (7). This behavior is most commonly observed by meas-
uring the temperature dependence of either the magnetization M or the dimension-
less susceptibility χ
χ = M/H in (1.3)
of the sample. These various quantities have the following relationships inside the
superconductor
(1.4)
(1.5)
where the meter-kilogram-second (mks) system of units is used [in the centimeter-
gram-second (cgs) system µ 0 = 1 and x is replaced by 4pχ]. For a perfect supercon-
ductor, the internal field Bin = 0 and the dimensionless susceptibility χ = -1.This
means that we have for the magnetization or magnetic moment per unit volume
M = –Hin. The material, in effect, behaves like a perfect diamagnet. Figure 1.7
shows the results of a measurement of the temperature dependence of the magneti-
zation for a single crystal of Y-Ba-Cu-O. The effect occurs because the applied
magnetic field B0 causes the surface current density J shown in Fig. 1.8 to flow in
the proper direction to produce a dc magnetic field that cancels the internal field
and makes Bin = 0 inside the bulk of the superconducting sphere.
8 CHAPTER 1
Figure 1.7. Temperature dependence of the magnetization M of a single crystal of a Y-Ba-Cu-O

superconductor.
Although magnetic flux is excluded from the bulk, it can penetrate the surface
layers of the superconductor. Fritz London (8) used the two-fluid model of super-
conductivity and Maxwell’s equations to explain the Meissner effect and flux
penetration into surface layers. The two-fluid model envisions the superconducting
state as having a mixture of normal electrons and superconducting electrons, with
Figure 1.8. Shielding current flowing around the surface of a superconducting sphere in an applied dc
magnetic field.
the latter fraction increasing as the temperature is lowered in the range below Tc. In
order to describe the Meissner effect, London postulated that for a superconductor,
(1.6)
where m is the effective mass of the electron, ns is the volume density of Cooper
pairs, and e is the electron charge. Since curl J = 0 inside a superconductor, this
relation (1.6) ensures that there will be no magnetic field inside the bulk of the
material. If we make use of the inhomogeneous Maxwell curl equation with the
electric field term ∂D/∂ t set equal to zero
curl B = µ 0J (1.7)
we can take the curl of this expression and use it to eliminate curl J from Eqs. (1.6)
and (1.7) to obtain the Helmholtz differential equation
∇2 B = B/l2 (1.8)
where B denotes the internal field Bin and l, called the London penetration depth,
(1.9)
is a measure of the extent of the penetration of the magnetic field B into the material.
The values of l for the elemental superconductors are typically in the range of 10–6
cm (9). We can also take the curl of Eq. (1.6) and eliminate curl B from Eqs. (1.6)
and (1.7) to obtain the Helmholtz equation for the current density
(1.10)
The one-dimensional solutions of these two equations for a direction x perpen-

dicular to the surface
(1.11)
(1.12)
show that that the magnetic field B and the current density J are confined to a thin
surface layer of thickness λ. Figure 1.9a shows how an external field B0 enters the
superconductor at the surface and then decays exponentially through the surface
layer to zero far inside. For this geometry Eq. (1.11) becomes
(1.13)
10 CHAPTER 1
Figure 1.9. (a) Experimental decay of a dc magnetic field inside a Type I superconductor for the case
l << a, and (b) the current density inside a superconductor for the same case. The figure is drawn for
the thick sample case l < a.
where l << a. The presence of this field B induces a current density J through the
Maxwell curl relation (1.7). The applied field B0 and the internal field B(x) are both
in the z direction, so from Eq. (1.7) we find that J(x) flows in the y direction with
the value
(1.14)
which depends on the slope dB/dx of the internal magnetic field. The equation for
J (x) analogous to Eq. (1.13) is
(1.15)
and this current density also decays to zero in the surface layer, as shown in Fig.
1.9b. Note how the current density reverses direction on the two sides of the
material. This occurs because the derivative dB/dx of Eq. (1 .14) reverses sign.
To provide a physical picture for the relationship between B (x) and J(x) in
Eqs. (1.13) and (1.15) consider a superconducting slab of length L, width L, and
thickness 2a placed in a uniform magnetic field B0 with the orientation shown in
Fig. 1 .10. The applied field B0 and the internal field B(x) are both in the z direction,
and Figs. 1.9a and 1.9b are slices through the slab in the z-x plane at the position
y = 0. We see from the figure that the current density encircles the figure in planes
perpendicular to the applied field direction. The current density flows in opposite
directions on opposite sides of the slab.
We have been discussing the usual case in which the sample thickness a is
large with respect to the penetration depth l. Films of superconductors are often
made thin enough so that the thickness is less than l, with the result that external
fields penetrate even for a Type I superconductor. Figure 1.11 shows the current
density Jy(x) inside a thin film for which a << l.
Figure 1.10. Flat superconducting slab with thickness 2a much less than the penetration depth l.
12 CHAPTER 1
Figure 1.11.Current density Jy (x) inside a superconductor for a << l L. Note that for this case the
magnitude of Jy (x) decreases linearly with x.
1.2.2. Temperature Dependencies

The density of superconducting electrons ns has the temperature dependence
sketched in Fig. 1.12
(1.16)
and inserting this expression into Eq. (1.9) provides the temperature dependence
for the penetration depth l shown in Fig. 1.1 3
(1.17)
where l0 = l(0) is the penetration depth at absolute zero given by Eq. (1.9) with
ns = ns(T).
Besides l there is another important length parameter called the coherence
length x, which is a characteristic of the superconducting state. The boundary
between a superconductor in contact with a normal metal is not sharp because the
density of superconducting pairs increases in a gradual manner from the surface
into the bulk of the superconductor. The coherence length x is a measure of the
distance over which this density of the Cooper pairs changes to its final value. We
will see in the next section that the relative magnitudes of x and l determine the
behavior of a superconductor in a magnetic field.
Figure 1.12. Temperature dependence of the density ns (T) of superconducting electrons in the
superconducting state below Tc.
Figure 1.13.Temperature dependence of the penetration depth l(T) below Tc.

14 CHAPTER 1
1.2.3. Applied and Internal Fields

Equation (1.5) shows how the internal fields Bin and Hin in a material are related
to each other through the magnetization M and the susceptibility x of the material.
The question arises as to how these fields are related to the applied field
B0 =µ 0H0 for a negative susceptibility in the range -1< x < 0. We will examine this
for the case of a sample in the shape of an ellipsoid with an applied magnetic field
oriented either along its symmetry axis or perpendicular to this axis. In both cases
the internal fields in the ellipsoid given by Eq. (1.5) are parallel to the applied field.
For a general sample shape, or for an ellipsoid in an applied field with an arbitrary
orientation, the internal fields can have different directions than the applied field,
and they can also vary in strength from place to place in the sample. It is instructive
to treat ellipsoids because a long cylindrical sample can be approximated by an
elongated prolate ellipsoid, and a thin film of circular cross section can be approxi-
mated by a flat oblate ellipsoid.
In the ellipsoid under discussion, the internal magnetic fields Bin and Hin are
related to the applied fields B0 =µ 0H0 through a demagnetization factor N in
accordance with the two expressions
(1.18a)
(1.18b)
where N is a dimensionless geometrical coefficient with the range of values 0 £ N

£ 1. This factor determines the extent to which the magnetization of the sample
contributes to the internal magnetic fields Bin and Hin. The parameter N is a
geometrical coefficient because it depends on the ratio c/a of the ellipsoid's
semimajor axis c along the symmetry direction to its semimajor axis a perpendicular
to this direction. The demagnetization factors N|| and N^ for the applied field B0
aligned, respectively, along directions parallel and perpendicular to the symmetry
axis satisfy the normalization condition
(1.19)
Figure 1.14 shows the dependence of the demagnetization factors on this

c/a ratio, where c > a for a prolate ellipsoid, and c < a for an oblate ellipsoid. A
general ellipsoid has three principal directions and three demagnetization factors
with the condition nx + ny + nz = 1.
Eliminating the magnetization M between Eqs. (1.18a) and (1.18b) gives the
expression
(1.20)
Figure 1.14. Dependence of demagnetization factors parallel (N ||) and perpendicular (N ^) to the
symmetry axis on c/a ratio for a prolate (c > a) and an oblate (c < a) ellipsoid.
where N can be either the parallel or the perpendicular demagnetization factor. With
the aid of Eqs. (1.3) to (1 .5) we can write the internal fields in terms of the applied
field (1.2), the susceptibility and the demagnetization factor
(1.21a)
(1.21b)
(1.21c)
where we recall that B0 = µ 0H0 for the applied field. The B field has the property of
having lines that are continuous during the passage from one medium to the next,
whereas the H field lines can be discontinuous. We see from Fig. 1.15 that these B
lines are continuous. The prolate, oblate, and spherical shapes all expel some flux,
but for the applied field along the symmetry axis c, the prolate one does so to a
greater extent and the oblate one to a lesser extent than the sphere for which N =
1/3.
It is clear from Fig. 1.15 that the B field far from the ellipsoid is uniform with
the value B0 and inside the ellipsoid is also uniform with the value given by Eq.
16 CHAPTER 1
Figure 1.15.Magnetic flux through a prolate ellipsoid, a sphere, and an oblate ellipsoid in a uniform
magnetic field.
(1.21a). For the special case of a sphere for which N = 1/3, this inside field has the
value
(1.22)
The field outside the sphere B out is the vector superposition of the applied field B0
and a dipole field Bdipole arising from the magnetic moment µ = MV of the sphere
(1.23)
The radial Br and azimuthal Bθ components of this outside field depend on the
angle q and fall off with distance as 1 /r 3 in the following manner (10)
(1.24a)
(1.24b)
where q is the angle with respect to the applied field direction.

1.2.4. Type I and Type II Superconductors
We have been discussing “perfect” superconductors for which χ = -1. More
generally there are two types of superconductors characterized by the Ginsburg-
Landau parameter
k = l/x (1.25)
–– ––
with k < 1/√ 2 forType I andk > 1/√ 2 for Type II superconductors. The two types
are also differentiated by their behavior in a dc magnetic field. In Type I, as the
external magnetic flux density Bapp is increased, it does not penetrate the bulk of the
material in the superconducting state until a field is reached called the criticalfield
Bc , above which the superconducting state no longer exists. The situation is
illustrated in Fig. 1.16. In a Type II superconductor there is no magnetic field Bin
inside the material until a field Bc1 is reached, referred to as the lower critical field.
At Bc1 flux density begins to penetrate the sample but does not remove all of the
superconducting state. As the field is further increased to a value Bc2 referred to as
the upper criticalfield, more flux density continues to penetrate the sample. At
Bc 2 the superconducting state is totally removed. The copper oxide superconductors,
which can be superconducting as high as 133 K, are Type II superconductors. For
a Type II superconductor Bc2 can be quite large. Upper critical fields of several
hundred tesla (T) have been reported for high-temperature superconductors (see,
e.g., Ref. 11). In addition to the lower and upper critical fields, a Type II supercon-
ductor has what is called a thermodynamic critical field Bc given by
(1.26)
where k is defined by Eq. (1.25).

The upper critical magnetic field Bc2 is temperature dependent and often has a
dependence that can be described by:
(1.27)
where B0 is the critical magnetic field at absolute zero. This temperature dependence
is sketched in Fig. 1.17. The slope of the line at Tc has the typical value
18 CHAPTER 1
TYPE I SUPERCONDUCTOR
TYPE II SUPERCONDUCTOR
Figure 1. 16. Plot of magnetic field Bin inside a Type I and a Type II superconductor as a function of
external applied magnetic field.
(1.28a)
as indicated by the dashed line in the figure. If we equate Bc2 to the Pauli limiting
–– defined by equating the magnetic energy to the
field, i.e., the magnetic field BPauli
superconducting gap energy (2√2µ BBPauli = Eg) and make use of the BCS gap ratio
Eg = 3.53 kBTc, we obtain the slope of -1.83T/K given by Eq. (1.28a), a value close
to that observed with many cuprates. In practice this critical field slope is aniso-
tropic, with typical cuprate single crystals exhibiting slopes less than -1.83T/K for
the applied field aligned along the c direction and greater than this value for B0
aligned in the ab plane. A typical cuprate value for the lower critical field slope at
Tc is
(1.28b)
and this can also exhibit anisotropies. Type I superconductors have critical field
slopes dBc/dT of between –15 and –50 mT/K, which is near the geometric mean
Figure 1.17.Temperature dependence of critical magnetic field Bc(T) relative to its value Bc(0) at 0
K.
of the slopes ofEqs. (1.28a) and (1.28b). For the elemental superconductor lead we
have, for example, dBc /dT = –22.3 mT/K.
The existence of a critical magnetic field that removes the superconducting
state implies that there is an upper limit to the current density that can be carried
by the superconductor. This is a direct consequence of the fact that a current
produces a magnetic field. The critical current density Jc and the thermodynamic
critical field Bc are related by
(1.29)
where µ 0 is the permeability. This result for Jc is close to the depairing current
density
(1.30)
which is the current density that causes Cooper pairs to break up. The temperature
dependence of the critical current density is obtained from Eq. (1.29) with the aid
of Eqs. (1.17) and (1.27)
(1.31)
20 CHAPTER 1
and this is plotted in Fig. 1.18.

If a magnetic field Bapp having a magnitude between Bc1 and Bc2 is applied to
a Type II material in the superconducting state and then reduced to zero, some
magnetic flux remains trapped inside the superconductor. The dashed line in Fig.
1.16b intersects the ordinate axis Bin at the value of this trapped field. In effect the
superconductor remembers it was exposed to a magnetic field and if held below
Tc behaves like a magnet. For applied fields below Bc1, a Type II superconductor
totally excludes magnetic flux and is said to be in the Meissner state, while for fields
between Bc1 and Bc2 there is partial flux penetration and it is said to be in the mixed
state. In the mixed state there are thin tube like normal regions in which the magnetic
flux is present. A somewhat overly simplified picture of these thin threads of flux,
called vortices, is illustrated in Fig. 1.19. This figure is drawn for the special case
of a thin film in which the film thickness is comparable to the vortex diameter. With
a bulk superconductor, the vortex length far exceeds its diameter.
It is instructive to consider some characteristics of the region near the surface
of a Type II superconductor. The density of superconducting electrons or Cooper
pairs ns(x) is zero at the surface (x = 0) and gradually increases as one moves inward
until it reaches the bulk value ns (∞) far inside, as shown in Fig. 1.20a. The distance
inward from the surface where ns(x) becomes appreciable in magnitude is called
the coherence length x, and this fundamental length parameter is indicated in the
Figure 1.18. Temperature dependence of the critical current density Jc (T) relative to its value J c (0) at
0 K.
Figure 1.19. Illustration of the passage of magnetic field lines B through vortices in the mixed state of
a Type II superconducting thin film.
figure. If there is a magnetic field B0 in the region outside the superconductor, then
the field inside B (x) decreases with distance until it becomes zero far inside. The
fundamental length parameter l for the decay of B(x) inside from the surface is
called the penetration depth, and it is also indicated in Fig. 1.20a. This figure is
drawn for a Type I superconductor
–– for which the Ginzburg–Landau parameter ––
k = l/x has the value k < 1/√ 2 The case for a Type II superconductor k > 1 / √ 2
is sketched in Fig. 1.20b, and for the cuprates we have k ≈ 100.
In order to understand why some superconductors are Type II and some are
Type I, let us consider the free energy at the interface between a normal metal and
a superconductor. In a zero dc magnetic field, the Gibbs free energy per unit volume
of a material in the superconducting state Gs(T,0) is lower than that of the normal
state Gn(T,0) because of the ordering of the electrons into Cooper pairs, When a
magnetic field B0 is applied, the free energy per unit volume is increased by an
amount B20/2µ0 because the magnetization of the superconductor is opposite to the
direction of the applied dc magnetic field. However, at the interface between a
superconductor and a normal metal, the system must be in equilibrium, and the free
energies per unit area G* must be equal on both sides of the interface, i.e.,
G*n = G*s. The surface energy per unit area due to the ordering of the electrons into
pairs can be approximated as B2cx/2µ0 and the corresponding magnetic surface
22 CHAPTER 1
NORMAL SUPERCONDUCTING
a)
Figure 1.20. (a) Dependence of the magnetic field B and the density of superconducting electrons n s
on the distance x inside a Type II superconductor at a normal metal/superconductor interface, and (b)
change in the magnetic and electron ordering contributions to the Gibbs free energy G at the same
interface.
energy per unit area is approximately B2cl/2µ0, to give for the net free energy per
unit area at the surface
(1.32)
The relative magnitudes of x and l will determine whether the surface energy is
positive or negative. In a Type I superconductor, x is greater than l and the surface
energy is positive. The formation of normal regions in the bulk of the superconduc-
tor would increase the normal superconducting surface and hence further increase
the free energy, which would not be energetically favorable. When l is greater than
x, the surface energy is negative, and the appearance of normal regions in the bulk
of the superconductor would reduce the free energy, making it energetically
favorable to form the tubular normal regions (vortices) through which magnetic
flux can thread.
1.2.5. Quantization of Flux

In the mixed state, the flux penetrating the material in each vortex has the value
F0 given by h/2e = 2.07 × 10–15 weber, where a weber is a tesla (meter)2. In other
words, the flux in the mixed state is quantized. Increasing the applied magnetic field
increases the number of vortices in the superconductor, and this causes the flux
density Bin to increase in discrete increments determined by the value of F0.
The quantization of flux is a direct result of the coherence of the wave functions
describing the Cooper pairs. To obtain the expression for F0 mentioned above,
consider a small superconducting ring of radius R cooled to the superconducting
state and carrying a supercurrent of density J. Since the wave function of every
Cooper pair is in phase with that of every other pair, an exact integral multiple N
of the wavelength l of the pair is required to fit around the circumference 2pR of
the ring; otherwise the waves would not be coherent. In effect, the current in the
ring is quantized with the quantization condition
(1.33)
Since l = h/P where P is the momentum of a Cooper pair, we have in effect a Bohr
like momentum quantization condition for the current in the ring.
(1.34)
The energy of a current flowing in a loop can be written in terms of the current I
and the flux F through the loop,
(1.35)
Since the current I for n electrons moving around the loop with velocity v is
nve/2pR, where e is the electron charge, Eq. (1.35) becomes
(1.36)
The energy of n electrons moving around the ring can also be written
(1.37)
where m is mass of the electron, P = 2mv is the momentum of a Cooper pair which
contains two electrons. Comparing Eqs. (1.36) and (1.37) gives the momentum P
(1.38)
Substituting this into Eq. (1.34) and using the flux quantization condition
F = NF0 provides the expression for the unit quantum of flux.
24 CHAPTER 1
(1.39)
which has the numerical value given at the beginning of this section.
1.2.6. Vortex Configurations

A vortex has a core of normal material of radius x where the magnetic field is
the strongest; outside this core the magnetic field decreases with distance r from
the core. This surrounding field is appreciable in magnitude for r < l, and drops to
a very small value for r>> l, in accordance with Fig. 1.21. We see from Fig. 9.13
of Ref. 12 that for the cuprates, which have k >> 1 and hence l >> x, almost all of
the magnetic flux lies outside the core. As a result the penetration depth l may be
looked upon as the effective radius of a vortex. More quantitatively, the magnetic
field strength outside the core falls off with distance in accordance with the
expression
(1.40)
where K0(r/l) is the zero-order modified Bessel function. At large distances,

r >> l; the function K0(x) has the asymptotic behavior e-x/(2x/p)1/2; and this gives
for the magnetic field far outside the vortex core
(1.41)
Figure 1.21. Distance dependence of the magnetic field B(r) around an individual vortex, showing
how the core has the radius x and the flux distribution has the radius l.
This expression clarifies our assertion that for l >> x the penetration depth l is the
effective radius of the vortex. This distance dependence of B(r) is sketched in Fig.
1.21.
The factor F0/2pl2 in Eq. (1.41) is related to the lower critical field through
the expression
(1.42)
where k = l/x. The upper critical field has a similar expression, with the coherence
length replacing the penetration depth
(1.43)
At the lower critical field, the vortices are separated by the approximate distance
d @ l, and at the upper critical field, the density of vortices is so high that the cores,
which have the radius x, are almost touching.
1.2.7. Flux Creep and Flux Flow

In a mixed state below a certain value of the temperature and applied magnetic
field, the vortices are symmetrically arranged in a hexagonal pattern called an
Abrikosov lattice (13). The intersection points of the vortices with a plane perpen-
dicular to the applied field display this hexagonal lattice, as illustrated in Fig. 1.22a.
For a given magnetic field there will be some temperature at which this regular
arrangement becomes disordered as portrayed in Fig. 1.22b. The vortex lattice is
said to have melted and the vortices can move around in a random fashion that
resembles the motion of the molecules of a two-dimensional liquid. This phase is
called the vortex liquid phase. The temperature at which the vortex lattice melts
depends on the magnetic field strength. It is found that the dc magnetic field B and
the temperature Tat which the melting occurs are related by the expression (14)
(1.44)
The exponent q is usually close to 213, and measurements carried out on various
cuprates have provided values in the range from 112 to 3/4. The B-Tline described
by this equation is called the irreversibility line because below it magnetic proper-
ties such as magnetization as a function of dc magnetic field display hysteresis. The
magnetization is not reversible in the sense that when the dc field is decreasing, at
a certain point the value of the magnetization is different from what it is when the
dc field is increasing at that same point. Above the B-T irreversibility line, the
26 CHAPTER 1
Figure 1.22.Arrangement of vortices, viewed from the top, in the superconducting state of a Type II
superconductor: (a) for the ordered vortex lattice state and (b) for the melted fluid vortex state.
magnetic properties are reversible. Figure 1.23 shows a determination of the

irreversibility line in YBa2Cu3O7-x (1 1).
If a current density J is sent through a superconductor at some angle relative
to the applied dc magnetic field, there will be a force per unit length F acting on
each vortex given by
F = J × F0 (1.45)
where the fluxon vector F0 is aligned in the vortex direction and represents the
quantized flux present there. If this force is strong enough, the vortices may move.
This movement of vortices introduces an effective resistance to the current flow in
the superconducting state. The force [Eq. (1.45)] on each vortex does not change
when the applied field increases because the quantum of flux F0 confined by each
vortex remains the same. It is the density of vortices that increases with the applied
field, which means that the total force arising from all the vortices increases, and
as a result the resistance to current flow increases with increasing strength of the
applied dc magnetic field. The increase in resistance will also depend on whether
Figure 1 .23. Plot of the irreversibility line for a single crystal of YBa2Cu3O7-x. The magnetic properties
are reversible in the flux liquid phase above this line; they exhibit hysteresis in the flux solid phase of
pinned vortices below this line. (After Worthington et al., Ref. 11 .)
the vortices are in the lattice or the liquid phase. Vortex motion occurs more easily
in a liquid, so the resistance is higher for this phase.
The melted vortex fluid phase can be modeled as a two-dimensional liquid in
which a moving vortex experiences a frictional retarding force per unit length
Fdrag = hvv proportional to its velocity vv and a viscous drag coefficient h. In
equilibrium Fdrag equals the driving force (1.45), and for J perpendicular to F0 we
have
(1.46)
A regular array of vortices in a superconductor produces an average magnetic field

B in the material, and when this array moves, it generates an average electric field
E given by
E = vv × B (1.47)
Since the resisitivity r is defined by
r = E/J (1.48)
28 CHAPTER 1
the velocity vv can be eliminated between Eqs. (1.46) and (1.47) to provide an
expression for the resistivity induced by the moving vortices for the case in which
B and J are perpendicular to each other (15).
ρ=BΦ0/η (1.49)
This simple model predicts that at constant temperature below Tc the resistivity will
increase linearly with the strength of the applied dc field in the fluid vortex phase.
In the vortex lattice state, the vortices are more strongly bound at their lattice
sites and cannot move as easily as in the fluid state. They are considered to be
trapped in potential wells and movement can only occur by a thermally activated
hopping of bundles of vortices. Thus their velocity can be described by (16)
(1.50)
where U0 is the height of the energy barrier that has to be overcome in order for
flux bundles to hop. In the vortex lattice phase, a larger force is required to induce
changes in the resistance of the superconductor. The change in resistivity is obtained
by combining Eqs. (1.47), (1.48), and (1.50) to give for the vortex lattice state
(1.51)
which is also linear in the applied field. Figure 1.24 shows a measurement of
resistance versus temperature in zero magnetic field and a field of 10 tesla for the
Figure 1.24.Measurement of resistance normalized relative to the room temperature resistance Rn

plotted against temperature in a zero applied field and in a magnetic field of 10 T for the n = 3
Hg-Ba-Ca-Cu-O superconductor (T. Datta, unpublished).
HgBa2Ca2Cu3O10 (17) superconductor. As we will see later, the movement of flux

in a Type II superconductor has a pronounced effect on the electromagnetic
absorbing properties of the superconductor below Tc.
References
1. Z. Iqbal, T. Datta, D. Kirven, A, Lungu, J. C. Barry, E J. Owens, A. G. Rinzler, D. Yang, and F.
Reidinger, Phys. Rev. B49,12331 (1994).
2. M. L. Cooper, Phys. Rev. 104, 11289 (1956).
3. P. L. Richards and M. Tinkham, Phys. Rev. 119,575 (1960).
4. J. Bardeen, M. L. Cooper, and J. Schrieffer, Phys. Rev. 108, 1175 (1957).
5. P. Townsend and J. Sutton, Phys. Rev. 128, 591 (1962).
6. C. A. Reynolds, B. Serin, W. H. Wright, and L. B. Nesbitt, Phys. Rev. 78 ,487 (1950).
7. W. Meissner and R. Ochsenfeld, Naturwiss. 21,787 (1933).
8. E London and H. London, Proc. Roy. Soc. (London) A149 72 (1935).
9. A. L. Schawlow and G. E. Devlin, Phys. Rev. 113, 120 (1959).
10. C. P. Poole, Jr., H. A. Farach, and R. J. Creswick,Superconductivity, Academic Press, San Diego
(1995).
11. T. K. Worthington, W. J. Gallagher, andT. R. Dinger, Phys. Rev. Lett. 59, 1160 (1987).
12. C. P. Poole, Jr., H. A. Farach, and R. J. Creswick, Superconductivity, Academic Press, San Diego
(1995).
13. A. A. Abrikosov,J. Phys. Chem. Solids 2 199 (1957).
14. K. A. Müller, M. Takashige, and J. G. Bednorz, Phys. Rev. Lett. 58, 1143 (1987).
15. J. Bardeen and M. J. Stephen, Phys. Rev. 140A, 1197 (1965).
16. P. W. Anderson,Phys. Rev. Lett. 9,309 (1962).
17. T. Datta, Z. Iqbal, and D. Kirven (unpublished).
2
The New Superconductors
2.1. THE COPPER OXIDES

2.1.1 Lanthanum and Neodymium Superconductors
Prior to 1986, the highest transition temperature to the superconducting state
was 23.2 K in the niobium-germanium alloy compound Nb3Ge. In late 1986 Alex
..
Müller and George Bednorz of the IBM laboratory in Zurich, Switzerland, reported
evidence of superconductivity at 30 Kin a new class of materials, lanthanum copper
oxides (1). The observation was reported for the compound La2CuO4 doped with
small amounts of barium, with the formula La2–xBax CuO4. The optimum x for
superconductivity was about 0.2. Substitution of strontium for barium having the
composition La1.85Sr0.15CuO4 increased the transition temperature to about 40 K (2).
Since then, a number of materials in the copper oxide or cuprate family have been
discovered that superconduct at temperatures as high as 133 K at atmospheric
pressure; Table 2.1 gives some examples of these.
Figure 2.1 shows the tetragonal unit cell of the La-Sr-Cu-O superconductor.
An important feature of the structure is that the Cu2+ and O2– ions form a CuO2plane
in the unit cell, with each Cu2+ ion bonded to four oxygens and each O2– ion bonded
to two coppers in the plane. This particular planar arrangement of coppers and
oxygens, sketched in Fig. 2.2, is a common feature of all the superconducting
cuprates. The La-Sr-Cu-O compound has one plane per formula unit, and it is
perfectly flat. This material is a poor metal in the normal state, with a resistivity
three orders of magnitude greater than that of copper. It conducts electricity by the
hopping of holes in the CuO2 planes. Below Tc, the supercurrent flows in these
planes and is carried by Cooper pairs formed from mobile holes. The fact that the
conduction process is largely confined to the CuO2 planes means that many of the
properties of this material, such as resistivity, critical current, critical magnetic
fields, and penetration depth are anisotropic.
31
32 CHAPTER 2
Table 2.1.Progress in Raisingthe Transition Temperatures ofCuprate

Superconductors atAmbient Pressure
Material Tc (K) Year Reference
La2–xBaxCuO4 30 1986 1
YBa2CU3O7–x 90 1987 4
Bi2Sr2–xPbxCa2Cu3O10 113 1988 5
TI2Ba2Ca2Cu3O10 125 1988 6
HgBa2Ca2Cu3O8 133 1994 7
The concentration of holes in the copper oxide planes of La2CuO4 is increased

by replacing some of the La3+ by Sr2+ or Ba2+. For example, in La1.8Sr0.2CuO4, the
average charge on the copper in the planes is +2.2, which means that 20% of the
coppers are in the 3+ valence state. The Cu2+ ion has 9 electrons in its outer 3d
orbital, one electron short of a full shell. The absence of this one electron needed
to fill the shell constitutes a hole. The Cu3+ ion has 8 electrons in the 3d orbital, 2
electrons short of a filled shell, thereby providing two holes that can contribute to
the conduction process. Thus increasing the Sr2+ content in La2–xSrxCuO4 i ncreases
the hole concentration in the copper oxide planes and hence the conductivity. The
undoped La2CuO4 compound is an antiferromagnetic insulator with a Neél tem-
perature for the onset of antiferromagnetism of 341 K. As the Sr content is
increased, the Neél temperature decreases. In the region of Sr concentration where
the material is antiferromagnetic, it is not a superconductor, but it becomes one at
Figure 2.1. Unit cell of La-Sr-Cu-O showing the conducting layers and binding layers.
THE NEW SUPERCONDUCTORS 33
Figure 2.2. Arrangement of coppers and oxygens in the CuO2 plane of a cuprate superconductor.
Sr concentrations where the antiferromagnetic phase no longer exists. However,

there is evidence that short-range antiferromagnetic order persists even in the super-
conducting phase, and in this phase the superconducting transition temperature depends
on the Sr concentration. These features have been summarized in the so-called universal
phase diagram for copper oxide superconductors presented in Fig. 2.3. This diagram
shows how the Néel temperature and the superconducting transition temperature
depend on the strontium concentration and thus on the hole content.
Figure 2.3. Universal phase diagram of La-Sr-Cu-O showing the dependence of the transition to the
antiferromagnetic state and to the superconducting state on the concentration of Sr.
34 CHAPTER 2
The majority of the copper oxide superconductors carry current by means of

holes, but there are some in which the current is carried by electrons (3). When
neodymium copper oxide, Nd2CuO4, which has a structure that is similar to but not
identical with that of La2CuO4, is doped with cerium Ce4+ in the Nd3+ sites, it adds
one electron to the copper oxide planes. The resulting compound becomes super-
conducting at 30 K with the Cooper pairs formed from electrons.
2.1.2. The Yttrium Superconductor

The discovery that generated the extensive news coverage in 1987 was the
observation of superconductivity in YBa2Cu3O7–x at 90 K, 13 degrees above the
temperature at which liquid nitrogen boils (4). The unit cell shown in Fig. 2.4 is
orthorhombic, with the b axis slightly longer than the a axis, and it contains two
Figure 2.4. Orthorhombic unit cell of YBa2Cu3O7–x .

copper oxide planes lying adjacent to each other perpendicular to the c axis.
However, there are also present chains of Cu-O parallel to the b axis formed by
sharing an oxygen at a common corner. Doping of the copper oxide planes with
holes is achieved by reducing the oxygen content from the stochiometric value of
7.00. The material with lower oxygen levels has oxygen vacancies in the chains at
the common corner. In other words, as the oxygen content is decreased, some
connections between adjacent copper ions in the chains are removed. The oxygen
content of the planes is unaffected. As the oxygen is removed, the chains become
more positive and this in turn induces an increase in the hole concentration in the
copper oxide planes. This reduced oxygen content has a strong influence on the
properties of the material. For x greater than about 0.7, the unit cell is tetragonal
and the material is antiferromagnetic, with the Néel temperature decreasing as the
oxygen is further reduced. For x less than about 0.7, the unit cell is orthorhombic
and the material is no longer antiferromagnetic, but it becomes superconducting,
with the superconducting transition temperature increasing to slightly above 90 K
as x is reduced toward the optimum value of approximately 0.1. These properties
are summarized in Fig. 2.5.
Figure 2.5. Dependence of the antiferromagnetic and the superconducting transition temperatures on
the oxygen content in YBa2Cu3O7–x.
36 CHAPTER 2
The replacement of copper in the planes by a transition ion such as Ni or by

Zn reduces the transition temperature, and with high enough doping the supercon-
ductivity disappears. The deterioration of the superconductivity is greater with the
addition of Zn than with Ni, hinting at the possible importance of the magnetic
nature of the copper ion in the mechanism of superconductivity. Most rare earth
elements such as Nd or Gd can be totally substituted for Y without any effect on
the superconductivity. For example, the Gd3+ ion has a net magnetic moment
µ = 9.2 µ B and the Gd sublattice undergoes a transition to an antiferromagnetic
phase at 2.2 K. Substituting other magnetic rare earth ions such as Dy, Er, Ho, and
Nd for Y has the same effect as in the Gd case, representing an unusual situation
where the same material can be an antiferromagnet and a superconductor at the
same time.
2.1.3. Bismuth and Thallium Superconductors
In January 1988, H. Maeda and his co-workers (5) discovered a new family of
copper oxide superconductors having the general formula Bi2Sr2Can–1CunO2n+4,
where n refers to the number of copper oxide planes per formula unit. Figure 2.6
shows the bismuth structure of the n = 2 and n = 3 phases. Growth of the n = 3 phase
was facilitated by partial substitution of Pb for Bi, giving a transition temperature
of 113 K. Not long after the discovery of the bismuth superconductors, A. Hermann
and Z. Sheng (6) synthesized a family of superconductors containing thallium with
Bi,Pb 2223 Bi,Pb 2212
Figure 2.6. Crystal structures of two Bi-Pb-Ba-Ca-Cu-O superconductors.

the formula Tl2Ba2Can–1CunO2n+4. This series of compounds is isomorphic with the

bismuth series, with T1 substituting for Bi, and Ba replacing Sr; the structure of this
family drawn from a different perspective is shown in Fig. 2.7. The alternating
binding layers and conducting layers with their copper oxide planes are indicated,
and these will be discussed later. We see from Table 2.1 and Fig. 2.8 that the
transition temperature increased to 125 K as the number of copper oxide planes per
conducting layer (i.e., per formula unit) was increased to 3, but then it decreased
with the addition of more planes. This is generally true for the copper oxide
superconductors, including the more recently discovered mercury materials, which
are discussed in the next section. In both of these families no change in
stoichiometry is necessary to achieve hole doping of the copper oxide planes.
Tl2Ba2Ca2Cu3O10
Figure 2.7. Structures of the T1-Ba-Ca-Cu-O superconductors. Members of the Bi-Sr-Ca-Cu-O family
of superconductors have the same structures. (Adapted from Torardi et al., Ref. 21.)
38 CHAPTER 2
Figure 2.8. Transition temperature as a function of the number of copper oxide planes in the conduction
layers of the Hg, T1, and Bi superconductors.
2.1.4. Mercury Superconductors

In the spring of 1993 a new superconductor series, HgBa2Can–1CunO2n+2, was
synthesized. The n = 3 compound with a transition temperature to the supercon-
ducting state of 133 K has the tetragonal unit cell sketched in Fig. 2.9, with
alternating binding and conducting layers, and the three copper oxide planes of the
conducting layer separated from each other by layers of calcium ions (7). It has
been found that some oxygen atoms are located in the interstitial site in the Hg layer,
shown at the top of the figure by the half-shaded circle, and that these oxygens are
more weakly bound to their sites than the other oxygens in the material. Since the
properties of the superconductor such as the transition temperature depend on the
oxygen concentration, which affects the hole concentration in the copper oxide
planes, this material displays some instability with respect to oxygen content.
However, it has been found that substitution of Pb for one-third of the Hg atoms
makes this material more stable (8). Unlike most of the copper oxide superconduc-
tors, applying pressure of up to 140 kbar increases the transition temperature to 147
K, halfway to room temperature, as shown in Fig. 2.10. Pressure can also be
produced chemically in this material by replacing the Ba2+ ion by the smaller Sr2+,
but unfortunately when this was done, it was found that the transition temperature
decreased to 127 K. Another interesting property of the mercury compound is that
the application of magnetic fields up to 10 T at 77 K does not cause the resistance
to increase, suggesting that this material may more strongly pin flux at 77 K than
Figure 2.9. Unit cell of the Hg-Ba-Ca-Cu-O, n = 3 superconductor. The half-shaded circle at the top
indicates that some of these sites can be partially occupied with oxygen.
the other copper oxide superconductors. Furthermore, it has also been found that
the material can be grain aligned. Both of these results suggest that Hg-Ba-Ca-Cu-
O may be able to carry more current at 77 K than the other copper oxide
superconductors, and perhaps with its fabrication into wires, superconducting
magnets that operate at liquid nitrogen temperature will be possible.
2.1.5. Infinite-Layer Phases

In 1993 superconductivity was discovered in a series of compounds having the
general formula Srn+1CunO2n+1+x (9). The n = 1 compound Sr2CuO3.1 with Tc = 70 K
has the same structure as La2CuO4, but with a large number of oxygen vacancies in
the Sr2O2 layers. These oxygen-deficient layers constitute charge reservoir layers
that serve to dope the copper oxide planes. The n = 2 compound Sr3Cu2O5+x has two
copper oxide layers between the Sr2O2 layers and a Tc of 100 K. The limit of the
series is the infinite-layer phase SrCuO2 whose structure is shown in Fig. 2.11.
40 CHAPTER 2
Figure 2.10. The transition temperature of the n = 3, Hg-Ba-Ca-Cu-O superconductor as a function of

applied pressure.
However, recent work shows that the infinite-layer phase may not be supercon-
ducting, and that the observed superconductivity, which is always a small fraction
of the sample for these materials, may be associated with intergrowths of
Srn+1CunO2n+1+x. These compounds require high pressure to synthesize, and the
results have not been extensively studied or reproduced in other laboratories.
2.1.6. Ladder Phases
Recent theoretical calculations of the properties of the so-called copper oxide
ladder phases, most of which have the general formula Srn–1CunO2n–1, have sug-
gested that these materials could be high-temperature superconductors (10). As
shown in Fig. 2.12, the structure of the copper oxide planes differs from that of the
known copper oxide superconductors. Essentially the structure consists of ladder-
like chains connected by oxygen bonds. Dagotto and Rice (10) have predicted that
compounds in the series having oxygen contents ON of N = 3,7, 11 . . . . (i.e., n =
2,4,6, . . . ) will be frustrated quantum antiferromagnets and have spin gaps. This
means that pairs of S = ½ Cu2+ ions can couple to form singlet states, with the spin
gap being the energy difference between the ground singlet and the excited triplet
Figure 2.12. Arrangement of the copper and oxygen atoms in the ladders of the so-called ladder phase
LaCuO2.5 materials. The horizontal Cu-O distances are 2.29 Å and the vertical Cu-O distances are
1.95 Å.
42 CHAPTER 2
state of the pair. The pairing occurs across the rungs of the ladder. If the exchange
coupling between Cu2+ions parallel to the ladders, J||, is smaller than the J^ between
the ladders, then the spins on adjacent ladders can pair to form singlet states that
lower the energy of the system. It is further predicted that when it is lightly doped
with holes, the spin gap will remain open and the materials may become high-tem-
perature superconductors. However, if J|| is approximately equal to J^, charge
density waves may exist along the chain and decay more slowly than supercon-
ducting correlations. For superconducting correlations to dominate, J^ must be
larger than J||. Azuma et al. (1 1) have been able to synthesize these materials under
high pressure and using nuclear magnetic resonance and magnetic susceptibility
measurements, have shown that SrCu2O3 has a spin gap but that Sr2Cu3O5 does not,
which is in agreement with the predictions of Rice et al. However, to date there have
been no observations of superconductivity in these materials, perhaps because of
the difficulty in doping the planes with holes under high-pressure synthesis.
There have, however, been some tentative hints that superconductivity may
exist in these materials, in some instances perhaps even toward room temperature.
For example, very large surface resistance drops have been observed in another
ladder phase type of material, Sr14–xCaxCu24O41+d (12), which does not belong to the
general class Srn–1CunO2n–1 discussed earlier. The effects are very sensitive to
oxygen exposure and occur in the outer regions of the sample, within about one
microwave penetration depth of the surface. The very large surface resistance drops
were followed by subsequent large increases in surface resistance. The effects were
attributed to superconducting fluctuations followed by a metal-to-insulator transi-
tion, as discussed in Sect. 5.4.4.
2.2. GENERAL PROPERTIES OF COPPER OXlDE

SUPERCONDUCTORS
The properties of the individual copper oxide superconductors are summarized
in Table 2.2, which is borrowed from Ref. 13. Some are tetragonal (T) and some
are orthorhombic (O), but close to tetragonal. Some, such as the yttrium and
mercury compounds, are the aligned type (A) with one formula unit per unit cell,
and others, such as the lanthanum, bismuth, and thallium compounds, which are
denoted by S to indicate staggered positions, are body centered with two formula
units per unit cell. In the aligned compounds, all of the copper ions in successive
conduction layers lie one above the other, while in the body-centered compounds,
the copper ions in the planes alternate in position (i.e., are staggered) in successive
conduction layers, as may be seen from a close scrutiny of Fig. 2.7. We see from
the table that all of the cuprates have the cell dimension a0 @ 3.85 Å, but they differ
in c0, which increases with the number of atoms in the unit cell.
44 CHAPTER 2
2.2.1. Commonalities of the Cuprates

In addition to the properties listed in Table 2.2, there are a number of
characteristics that are common to all of these materials. These common features
are important because they suggest the directions to go to raise Tc and provide the
background needed for finding a theoretical explanation of the origin of the
superconductivity in the cuprates. The most important commonality is the presence
of conduction layers and binding layers that alternate in position along the c-direc-
tion, as sketched in Fig. 2.13. They have the following features and play the
following roles:
1. The conduction layers consist of copper oxide planes separated by layers

of calcium ions, or in the case of Y-Ba-Cu-O, separated by yttrium ions, as shown
in Fig. 2.14. They exhibit little variation from compound to compound. Electrical
conduction in both the normal and the superconducting states takes place mainly
by hole hopping, which is confined to the copper oxide planes of the conduction
layers. In the neodymium compound, the conduction is via electron hopping.
2. The binding layers exhibit greater variations in constitution, and their
common cases are sketched in Fig. 2.15. These binding layers structurally support
Figure 2.13. Layering scheme of the copper oxide superconductors. Figures 2.14 and 2.15 sketch the
conduction layers and the binding layers, respectively, of individual cuprates.
Figure 2.14. Sketches of the conduction layers of several individual copper oxide superconductors.
the conduction layers and also serve as charge reservoirs that provide the proper
amount of hole doping in the copper oxide planes. We see from the figure that the
CuO chains of the yttrium compound are structurally in the binding layer, but
nevertheless they are responsible for some of the current flow. Figure 2.1 1 shows
that the infinite-layer phase lacks binding layers.
There are also some magnetic commonalities among the various cuprates.
They are:
• the presence of magnetic copper ions

• evidence for short-range antiferromagnetic correlations within the planes
46 CHAPTER 2
Figure 2.15. Sketches of the binding (charge reservoir) layers of several individual copper oxide
superconductors.
• dependence of the superconducting transition temperature Tc and the Néel

temperature TN of nonsuperconducting-related phases on the hole concen-
tration
2.2.2. Energy Bands

Let us discuss the implications of these properties. The fact that the current is
largely confined to the copper oxide planes means that the band structure of the
material can be approximated by a two-dimensional model. Figure 2.16 shows the
energy versus density of states for a simple two-dimensional array of copper and
oxygen atoms where each copper atom is bonded to four nearest-neighbor oxygen
atoms. The top occupied band is formed from the highest occupied molecular
orbitals (HOMO) of the atoms, and the first unoccupied band is formed from the
first empty orbitals of the atoms. In this simple model, the energies of the filled
lower band EL(K) and the empty upper band EU(K) are,
EU(K) = EU+ 2tU(cosKxa + cosKya) (2.1)
EL(K) = EL+ 2tL(cosKxa + cosKya) (2.2)
Figure 2.16. Illustration of density of states for two-dimensional copper oxide planes showing the van
Hove singularities. The highest occupied and lowest unoccupied molecular orbital regions, HOMO and
LUMO, respectively, are indicated.
48 CHAPTER 2
where EU and EL are the energies of the free atom orbitals and tL and tU are the
corresponding overlap integrals. The peak in the density of states near the middle
of each band is common to two-dimensional systems and is known as a van Hove
singularity (14). It is a result of the many combinations of Kx a and Ky a giving the
same energy.
A number of attempts to explain superconductivity in the copper oxide
superconductors draw on the existence of this van Hove peak in the density of states
near the Fermi level. This large density of states at EF means that many single
electron states at the top of the conduction band are available to form Cooper pairs.
In the weak coupling form of the BCS theory Tc is given by
Tc = 1.14(Eg/kB)exp[–1/VD(EF)] (2.3)
where the activation energy V contains the interaction between the holes forming
the Cooper pairs and D(EF) is the density of states at the Fermi level. Note that a
larger D(EF) means a higher Tc. Because of the reduced dimensionality, the band
gap is anisotropic, having values approximately 1.75kBTc parallel to the c-axis and
2.7kBTc parallel to the copper oxide planes. The energy gap in the ab plane is
substantially higher than that predicted by weakly coupled BCS theory, correspond-
ing to the limit VD(EF) << 1, which means that the Cooper pairs are more strongly
Figure 2.17. Plot of Bc2 versus temperature near Tc for Y-Ba-Cu-O for the magnetic field parallel to
the c-axis (O) and perpendicular to the c-axis (D), respectively (after Welp et al., Ref. 15).
bonded than in the low-temperature metallic superconductors. A stronger V in Eq.

(2.3) also would provide a higher Tc. However, Eq. (2.3) may not be applicable in
the stronger coupling limit where the exponential factor exp[–1/VD(EF)] is replaced
by the expression { 2sinh[–1/VD(EF)]}–1. The separation between the holes of the
Cooper pairs in the copper oxide planes is typically on the order of 20 Å, which is
significantly smaller than in the low-temperature metallic superconductors, where
this distance can be as large as 10,000 Å. Since the Ginzburg–Landau parameter
k = l/x is on the order of 100, the copper oxide superconductors, as discussed
earlier, are very much Type 11. This stronger binding of the Cooper pairs also means
that the upper critical magnetic fields and critical current densities will be larger.
Figure 2.17 shows the results of a measurement of Bc2 near Tc parallel to c and
perpendicular to c in YBa2Cu3Ox. At absolute zero the value of Bc2 is estimated to
be several hundred tesla, but this cannot be measured reliably. Another consequence
of the two-dimensional nature of the copper oxides is the anisotropy of the electrical
transport both in the superconducting and in the normal states. The conductivity
parallel to the planes is about 2 to 4 orders of magnitude greater than that
perpendicular to the planes. Figure 2.18 shows measurements of the resistance
perpendicular to and parallel to the c-axis in YBa2Cu3O7.
2.2.3. Cooper Pair Binding

The nature of the force that binds the holes into Cooper pairs remains unclear
and has been a subject of intense research. At present two models are receiving the
most attention. One suggests that the charge pairing is mediated by vibrations of
the highly polarizable oxygen ions. This idea, which is a BCS-like mechanism, in
conjunction with the existence of a van Hove singularity in the density of states
near the Fermi level, is at present considered by some as a possible mechanism.
Because of the intimate relationship between the existence of antiferromagnetism
and superconductivity exemplified in Figs. 2.3 and 2.5, as well as the existence of
short-range antiferromagnetic correlations of the Cu spins in the superconducting
state, magnetic pairing mechanisms are also being investigated. It has been pro-
posed that magnetic interactions between antiferromagnetic fluctuations of the Cu
spins and the charge carriers cause the pairing interactions. The idea is that as a
charge carrier moves by, it disrupts the magnetic spin of one ion, which flips the
spin of a neighbor, thus attracting a second charge carrier of the opposite spin. This
model requires the wave function describing the Cooper pair to have d-symmetry.
At present a great deal of effort is being made to determine the symmetry of the
Cooper pairs, and much evidence has accumulated in favor of d-wave pairing.
Electromagnetic absorption measurements constitute one approach used to inves-
tigate this issue. This is discussed in greater detail in Sect. 5.4.3.
50 CHAPTER 2
Figure 2.18. Resistivity versus temperature parallel (a) and perpendicular(b) to the copper oxide planes
in Y-Ba-Cu-O. Note the change in the ordinate scales.
2.3. PEROVSKITE SUPERCONDUCTORS

The compound Ba1–xKxBiO3–yforms for x > 0.25 and crystallizes in the cubic
perovskite structure illustrated in Fig. 2.19. It was found to be a superconductor in
1988 and has Tc @ 40 K for x @ 0.4 (16). This compound has the variable-valence
bismuth ion and utilizes oxygen vacancies to achieve charge compensation. Its
structure has similarities to those of the cuprates, but it lacks copper. The distorted
perovskite BaPb1–xBix03 is tetragonal, and in 1975 was found to superconduct for
x in the concentration range 0.3 ≥ x ≥ 0.05 with Tc up to 13 K (17). Bednorz and
Muller knew about this work and referred to their "metallic, oxygen-deficient . . .
perovskite-like mixed valence copper compound" samples in their pioneering 1986
article.
Figure 2.19. Cubic unit cell of Ba1–xKxBiO3–y perovskite.
2.4. CA RBON -6 0 SUPERCONDUCTORS

In 1990 the synthesis of a new molecule consisting of 60 carbon atoms bonded
to each other in a spherical soccer ball-like arrangement was reported (18). The
molecule, whose structure is shown in Fig. 2.20, has 12 pentagonal and 20
hexagonal faces symmetrically arranged to form a molecular ball, which is now
known as fullerene after the architect Buckminister Fuller, who invented the
geodesic dome. These ball-like molecules can form a crystal lattice having the
face-centered cubic structure shown in Fig. 2.21. In the lattice each C60 molecule
is separated from its nearest neighbors by 10 Å (center-to-center distance of the
molecules). There is empty space in the unit cell between the C60 molecules, making
it possible to put small alkali atoms such as potassium in tetrahedral and octahedral
interstitial positions, as shown by the black circles in Fig. 2.21. The alkali atoms
ionize to form cations such as K+ by transferring electrons to the fullerene mole-
cules. The transferred electrons become delocalized among the conjugated or
alternating single-double bond arrangement of the fullerenes, and they become
charge carriers by hopping between adjacent fullerene molecules to make the
material a conductor.
In 199 1 A. F. Hebard and co-workers (1 9) at Bell Telephone Laboratories made
the surprising discovery that alkali-doped C60 crystals superconduct. For example,
the K3C60 material is superconducting at 18 K, and other alkali atoms doped into
the lattice also make it superconduct, The transition temperature has been shown
to depend on the size of the cation (20), which increases in the order K < Rb < Cs.
The large cations increase the volume of the unit cell, and it is found that the
transition temperature correlates with this volume, as shown in Fig. 2.22.
One of the important issues that arose shortly after the discovery of supercon-
ductivity in these materials was the nature of the mechanism responsible for it. A
critical experiment for testing whether the mechanism is BCS is to measure the
effect of isotopic labeling on the transition temperature. C60 made from the carbon-
52 CHAPTER 2
Figure 2.20. Illustration of the C60 (fullerene) soccer ball-like molecule.
Figure 2.2 1. Structure of A3C60 showing small alkali atoms in the tetrahedral and octahedral interstitial
sites around the large C60 molecules arranged on a face-centered cubic (FCC) lattice.
Figure 2.22. Transition temperature T c of A3C60 superconductors plotted against the lattice parameter
(adapted from Hebard, Ref. 20).
Figure 2.23. Magnetization as a function of temperature for K312C60 (♦) and K313C60 (O) superconduc-
tors (adapted from Chen and Lieber, Ref. 21).
54 CHAPTER 2
13 isotope is 8.3% heavier than C60 made from the normal carbon-12, and so the
phonon-mediated BCS theory predicts a downward shift of the transition tempera-
ture in K313C60 compared with K312C60. This was checked by measuring the tem-
perature dependence of the magnetization in both materials. The results presented
in Fig. 2.23 (21) indicate that the isotopically labeled material becomes supercon-
ducting 0.4 K below that of the nonlabeled material. Unfortunately the result does
not unambiguously confirm the BCS mechanism since the theory predicts that the
downward shift should be 0.8 K.
Because the alkali atoms can diffuse out of the lattice, the bulk form of these
materials as first synthesized had to be kept in sealed tubes under a slight excess of
inert gas pressure. This meant that four-probe resistance measurements could not
be made on the materials. Instead, surface resistance drops as well as magnetization
measurements of the type presented in Fig. 2.22 were used to determine the onset
of superconductivity (19).
References
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3
Experimental Methods and

Complementary Techniques
The main purpose of the remaining chapters of this book is to survey and explain
electromagnetic absorption in superconductors in the microwave region of the
spectrum, and to a lesser extent in the radio frequency (RF), infrared, and optical
regions. This chapter introduces the reader to some of the experimental methods
that are employed to carry out those electromagnetic absorption studies that are of
the nonresonant type. Radio frequency and microwave techniques have also been
employed to study resonant absorption in superconductors, studies that are gener-
ally termed magnetic resonance, and this chapter also reports on some of these
results. Standard nuclear magnetic resonance (NMR) and electron paramagnetic
resonance (EPR) spectrometers, particularly the latter, can be adapted for carrying
out the nonresonant absorption experiments, and most microwave absorption
studies involve using adapted EPR spectrometers. The essence of a magnetic
resonance experiment is the measurement of the precession of nuclear or electronic
spins in a strong magnetic field. Other particles with spin that have been employed
to probe superconductors are muons, positions, and inelastically scattered neutrons,
and some of this work is described here. A great deal of research has also been
carried out on superconductors using frequencies beyond the infrared, such as
X-rays, and this work is commented upon briefly.
Thus the remainder of the book covers radio frequency, microwave, infrared,
and optical absorption in superconductors, and this chapter reports on techniques
for carrying out this work as well as techniques that complement this work.
3.1. RADIO FREQUENCY MEASUREMENTS USING LC

RESONANT CIRCUITS
Radio frequency electromagnetic absorption in the superconducting state can
be studied by a technique originally developed by Schawlow and Devlin (1) in
55
56 CHAPTER 3
which the sample is located in the coil of an LC circuit and the change in the
frequency of the RF oscillator during the absorption process is measured. Figure
3.1 shows a schematic of the original experimental method. Clover and Wolf (2)
have described a simple inexpensive marginal oscillator that can be used for this
measurement. The sample is placed in a cylindrical quartz tube and a coil wound
around the tube forms the inductance part of the LC tank circuit of an RF marginal
oscillator that operates in the kilohertz to megahertz range. The coil containing the
tube may be mounted on the cold tip of a cryogenic Dewar or immersed in a
cryogenic fluid as shown in Fig. 3.1. For dc field measurements, the coil is placed
between the poles of an electromagnet with its axis, and hence its RF B field,
perpendicular to the dc magnetic field direction. When the dc magnetic field is
increased with the sample in the superconducting state, the penetration depth of the
RF field into the sample increases, This changes the effective permeability of the
sample and hence the inductance of the coil because the inductance of a coil is
proportional to the permeability µ of the material inside it. Since the oscillation
frequency w is given by
(3.1)
Figure 3.1. LC oscillator apparatus for measuring the penetration depth. The sample is contained in a
coil that forms part of the LC circuit of an RF oscillator.
EXPERIMENTAL METHODS AND COMPLEMENTARY TECHNIQUES 57
and the change in inductance DL is small, the result is a shift in the oscillation
frequency Dw of the magnitude (1)
(3.2)
For a cylindrical coil, the change in the penetration depth l is related to the change
in the frequency by (1)
(3.3)
where r is the radius of the sample rod and A is the cross-sectional area between
the rod and the coil. One advantage of this method is that it allows a determination
of the frequency dependence of the dc magnetic field-dependent part of the
absorption. The frequency dependence of the RF penetration depth is obtained by
measuring Dw/w0 versus B for different choices of w0.
For this geometry with the coil axis perpendicular to the dc magnetic field, the
electric current that circulates around the coil has components that are both parallel
to and perpendicular to this dc field. The vortices in the sample are parallel to the
dc field and they experience the Lorentz force J × B arising from the perpendicular
component of the current density J. The vortices that are set in motion by the Lorentz
force experience a viscous retarding force, and the result is energy dissipation. To
study this vortex-induced dissipation, it is desirable to enhance the component of
the current perpendicular to the dc field, and this can be done by using a rectangular
wire-wound inductor having a width much greater than its thickness, and aligning
the dc magnetic field perpendicular to the large surface of the inductor. For an LC
circuit containing a rectangular inductor of dimensions a,b, the frequency shift of
the resonator is related to the penetration depth by (3)
(3.4)
where a0 and b0 are the dimensions of the sample, we is the frequency for the empty
inductor, and w0 is the initial frequency with the superconductor in place in the coil
and the applied magnetic field B0 = 0. In an experiment, the frequencyω is measured
for various values of B0 and T.
This method can also be used to determine the temperature dependence of the
RF power absorption at zero field or in a constant dc magnetic field. Figure 3.2
shows, as an example, a measurement of the absorption of Y-Ba-Cu-O powder in a
cylindrical coil at 10 MHz in which the frequency increases with the temperature.
An explanation for this absorption in the normal state is given in Chap. 4, and that
in the superconducting state is given in Chapters 5 and 7.
The measured frequency shift must be corrected for the frequency shift of the
empty coil. It is especially important to make this correction when using samples
58 CHAPTER 3
Figure 3.2. Measurement of the temperature dependence of the frequency shift at 10 MHz for the
cylindrical coil of an LC circuit filled with apowder sample of Y-Ba-Cu-O.
having a small fraction of superconducting component, or samples that do not fill

the volume of the coil. Figure 3.3 shows the temperature dependence of this
frequency shift for the empty coil used to obtain the data presented in Fig. 3.2. This
shift is mainly a result of the temperature dependence of the resistivity of the wire
used to form the coil since expansion and contraction effects would tend to be
negligible. A typical coil made of 10-mil copper wire capable of resonating at 350
Hz can have a resistance decrease from 6 ohms to 1 ohm on cooling from room
temperature to liquid nitrogen temperature. Since the frequency w of an inductance-
capacitance-resistance (LCR) circuit is given by
(3.5)
we see how a decrease in the resistance R produces the increase in the frequency
shown in Fig. 3.3. One approach to dealing with this problem is to use two identical
coils, one of which contains the sample, and measure the difference in frequency
or ratio of the frequencies of the coils as a function of temperature.
The use of phase-sensitive detection can enhance the sensitivity of the system,
and there are a number of different ways to accomplish this. One approach
modulates the oscillator frequency and utilizes a phase-sensitive detector to com-
pare its phase with that of a reference signal of the same initial frequency. When
the frequency of the oscillator changes because of a change in the penetration depth,
Figure 3.3. Temperature dependence of the shift in the resonant frequency of the empty coil used to
collect the data plotted in Fig. 3.2. The observed slight shift in frequency is due to the temperature
variations of the resistivity of the coil.
the phase of the modulation with respect to the reference changes, and the phase-
sensitive detector produces a dc output voltage proportional to this phase difference.
3.2. MICROWAVE MEASUREMENTS USING CAVITY

RESONATORS
The method most commonly used to measure electromagnetic absorption in
high-temperature superconductors in the gigahertz frequency range employs a
microwave bridge and a cavity resonator (4). A standard x-band electron paramag-
netic resonance spectrometer is easily adapted for making this measurement at 9.2
GHz. The absorption of microwaves as a function of the dc magnetic field is
determined by measuring the reflection coefficient G(B,T) of a resonant cavity
containing the sample in the superconducting state. Near optimal coupling where
the cavity is impedance matched to the waveguide, the changes in G(B,T) are
proportional to changes in the surface resistance of the sample.
The experimental arrangement, shown in Fig. 3.4, consists of a microwave
bridge with the cavity containing the sample mounted in one arm of the bridge, The
microwave power source, either a klystron or a Gunn diode, is tuned initially to the
resonant frequency of the cavity. This is accomplished by slightly varying the
frequency of the klystron by mechanically tuning the size of the klystron cavity or
by adjusting the voltage of the Gunn diode until there is a dip in the microwave
60 CHAPTER 3
Figure 3.4. Microwave bridge and cavity resonator arrangement for measuring absorption at 9.2 GHz.
energy reflected to the detector arm of the bridge as indicated by a drop in the diode
current.
For greater sensitivity, the magnetic field can be modulated and phase-sensitive
detection employed. The microwave interaction with the sample produces a change
in the cavity frequency called dispersion, and a change in the quality factor or Q of
the cavity called absorption. Usually an automatic frequency control (AFC) system
is employed to ensure that the frequency of the microwave source remains locked
on the resonant frequency of the cavity so the frequency change that occurs during
absorption is not detected. The absorption by the sample changes the power
reflected from the cavity to the arm of the bridge containing the diode detector. The
change in the dc current measured across this diode is directly proportional to the
microwave power absorbed by the sample.
Ordinarily the sample is located in the center of a TE102 rectangular resonant
cavity or in the center of a TE011 cylindrical resonant cavity where the RF magnetic
field strength is strongest and the RF electric field is zero. Another approach is to
replace the end wall of the cavity by the superconducting material (5). This method
is suited to thin films having a surface area large enough to be made into the wall
of a cavity. In both cases the change in the Q of the cavity can be measured as the
sample temperature is lowered below Tc.
To measure the effect of a magnetic field on the microwave absorption, the

microwave cavity is placed between the poles of an electromagnet as indicated in
Fig. 3.4. The sample may be cooled by containment in a double-walled quartz glass
tube inserted through a hole in the microwave cavity. The temperature is regulated
by the flow of cold nitrogen or helium gas through the tube in conjunction with a
regulated heater and diode sensor interfaced with a controller. This method of
measurement is quite sensitive, but because the klystron must be tuned to the
resonant frequency of the cavity, frequency-dependent measurements are not
feasible. One can, of course, carry out measurements with instrumentation operat-
ing at different microwave frequency bands.
Cavities have also been used to determine the surface resistance in the upper
megahertz frequency range (6). Figure 3.5 illustrates a cavity system for such a
measurement. The resonator consists of a cylindrical copper cavity 10 cm in
diameter and 80 cm long for measurements below 600 MHz. The sample is
contained in a long thin quartz tube that lies along the axis of the cylinder. The RF
Figure 3.5. Cavity for measuring absorption in the 600-MHz frequency range (from Delayen and Bohn,
Ref. 6).
62 CHAPTER 3
Figure 3.6. Microwave bridge for measuring the transmission of microwave energy through a sample
material.
is coupled into the cavity at the top, and at the side is a pickup probe where changes
in the RF due to absorption in the sample are detected. The arrangement allows a
measurement of the dc field, temperature, and frequency dependence of the absorp-
tion.
Transmission of electromagnetic radiation through samples can be measured
by the experimental arrangement shown in Fig. 3.6 (7). In this case no microwave
cavity is used, but the sample is situated in the waveguide between the microwave
source and the detector. The measurement compares the detector current when the
microwaves are sent though the arm of the system containing the sample with that
obtained when the microwaves are routed through the empty arm. This method,
however, is not as sensitive as the cavity method.
3.3. ELECTRON PARAMAGNETIC RESONANCE

Electromagnetic absorption in the gigahertz range arising from precessing
electron spins can be studied using an electron paramagnetic resonance spectrome-
ter. Examples of spins that produce this resonance absorption are unpaired electrons
in free radicals, first transition series ions such as Cu2+ (3d9) and Mn2+ (3d5), which
have unfilled 3d-electron shells, and the rare earth ion gadolinium, Gd3+ (4f7), which
has a half-full 4f-electron shell. Especially favorable for detection are those transi-
tion metal ions with odd numbers of electrons. Free radicals associated with defects
or radiation damage can be detected.
The spectrometer with the block diagram presented in Fig. 3.7 contains the
microwave bridge–electromagnet system sketched in Fig. 3.4 (8) together with
Figure 3.7. Block diagram of a 100-kHz modulated electron paramagnetic resonance spectrometer
equipped with automatic frequency control (AFC) and phase-sensitive detection.
some highly sophisticated electronic components. In this experiment the dc mag-

netic field is slowly scanned with the microwave frequency held constant. Reso-
nance absorption occurs when the condition
hv = gbB (3 .6)
is satisfied, where h is Planck’s constant, v is the microwave frequency, g is the

dimensionless Landé factor and b is the Bohr magnetron. For the x-band (9.2 GHz)
and g @ 2, the EPR absorption occurs for fields near 0.32 T. The presence in acuprate
superconductor of a Cu2+ EPR absorption signal in the range g ≅ 2.05 to g ≅ 2.27
64 CHAPTER 3
is indicative of the presence of a nonsuperconducting fraction such as the “green

phase” Y2BaCuO5, which is often present in poorly made Y-Ba-Cu-O samples. In
well-made superconducting samples, the Cu2+ ions are “EPR silent” so no absorp-
tion is detected.
The scanning dc magnetic field is generally ac modulated at a frequency of
100 kHz. This modulation is supplied by an RF generator through a pair of coils
mounted on the side walls of the microwave cavity. The modulation of the
absorption results in a time-varying ac output signal at the crystal diode which
changes phase by 180 degrees at the peak of the absorption signal, as shown in Fig.
3.8. Phase-sensitive detection is employed which compares the phase of this output
with that of a reference signal, thereby causing the derivative of the absorption to
be recorded. This reduces noise and enhances the sensitivity.
As we discuss later, electron paramagnetic resonance has been used to study
nonresonant low magnetic field-induced absorptions at fields of tens of millitesla
in the copper oxide superconductors. In the case of nonresonance absorption, the
shape of the detected signal depends upon the slowly increasing dc magnetic field
and the superimposed ac magnetic field modulation. Modulation effects are par-
ticularly pronounced at high modulation amplitudes. The effect of the modulation
can be eliminated by directly detecting the change in absorption. Such direct
absorption signals from superconductors are easier to interpret, but the sensitivity
is lower, Conventional EPR, on the other hand, is invariably carried out using
modulated scanning fields.
Figure 3.8. Illustration of how ac magnetic field modulation affects the signal at the detector.
Figure 3.9. Shift of the ESR signals from paramagnetic markers located on the side and end of a
YBa2Cu3O7– d sample from their superimposed position (A) above Tc to different field positions (B,C)
below Tc. The separation of the lines is proportional to the susceptibility [From Farach et al., Ref. 9].
3.4. PARAMAGNETIC PROBES

The magnetic field inside a superconducting sample can be probed by placing
a free radical marker at the face of a specimen normal to the magnetic field direction
and another at a face of the specimen that is parallel to the external magnetic field
(9). In the superconducting state, the two markers experience different local
magnetic fields, so the resonant positions of the lines shift in the manner shown in
Fig. 3.9. The observed shift occurs because the free radicals respond to the surface
field, and this differs from the applied field B0 in accordance with Eq. (1.21a) and
the boundary conditions Bin = Bsurf perpendicular to and Hin = Hsurf parallel to the
Figure 3.10. Temperature dependence of the susceptibility of YBa2Cu3O7–d determined by the ESR
probe method of Fig. 3.9 [From Farach et al., Ref. 9].
66 CHAPTER 3
surface. Thus the observed shift in line position is a measure of the magnitude of
the internal field Bin within the sample, and assuming that the demagnetization
factor N is known, this permits the temperature dependence of the susceptibility x
to be evaluated from Eq. (1.21a), with the results presented in Fig. 3.10. This
probing technique can also be carried out by NMR, using for example, a silicone
oil coating.
3.5. STRIPLINE AND PARALLEL PLATE MICROWAVE

RESONATORS
We have discussed microwave experiments that employ standard waveguide
resonant cavities. Other types of resonators are also available for use. For example,
stripline resonators have been employed to study the dc magnetic field dependence
of the surface resistance of superconductors (10). A typical resonator, shown in Fig.
Figure 3.11. A stripline resonator (a) for measuring the surface resistance of a deposited supercon-
ducting film strip. The resonator is located (b) between two ground planes. [From Revenaz et al., Ref.
10].
3.11, consists of a patterned thin film strip of a superconductor deposited on a

substrate such as LaA1O3. The strip ofsuperconducting transmission line, patterned
by photolithography, has a length of one-half of the wavelength of the microwave
energy at the resonant frequency. Overtone resonances occur at multiples of the
characteristic resonant frequency, wn = nw0. Thus measurements at overtone fre-
quencies allow a determination of the frequency dependence of the surface resis-
tance Rs. The quality factor Q and the resonant frequency w0 are measured and the
surface resistance is calculated from these values with the aid of the expression:
Rs = Gw0/D(l/d)Q (3.7)
where G is a geometric factor, D(l/d) is a correction factor calculated from the

current distribution in the stripline, l is the microwave penetration depth, and d is
the film thickness. Magnetic field-dependent studies are carried out by applying the
dc magnetic field perpendicular to the stripline, as shown in Fig. 3.1 1, which places
B parallel to the c-axis of the superconductor. This method is only applicable to
materials that can be made into thin films.
Another resonator method uses the plates of the resonator as the supercon-
ducting sample to be studied (11). The two parallel plates are separated by a thin
Figure 3.12. A parallel plate resonator for measuring the surface resistance of superconductors that
form the plates in the resonator. (From Taber, Ref. 11]).
68 CHAPTER 3
dielectric spacer about 75 µm thick using the arrangement shown in Fig. 3.12. The
samples, which are the parallel plates, are pressed together by dielectric posts. The
container is made of brass and the inner surfaces are gold plated. Two coupling
probes are shown at the top of the container. These coupling probes are made by
soldering 50-ohm microstrips to the ends of rigid coaxial cable. The vertical
position of these probes can be varied to control the amount of coupling. Microwave
energy is coupled in through one probe and out through the other.
3.6. NUCLEAR MAGNETIC RESONA NCE

Nuclear magnetic resonance absorption occurs when a nucleus with a nonzero
nuclear spin I in an applied magnetic field Bo is radiated with the frequency ω,
which satisfies the same resonant condition [Eq. (3.6)] as EPR, but in the NMR
case a different notation is used
w = gB0 (3.8)
where gb = hg. The gyromagnetic ratio g, sometimes called the magnetogyric ratio,
is characteristic of the particular nucleus, and it is normally three orders of
magnitude less for NMR than it is for the EPR case. Typical NMR measurement
frequencies range from about 60 to 400 MHz. The isotopes of TI and Y are
particularly favorable for NMR because they have a nuclear spin I = 1/2, so they
lack a quadrupole moment and their lines are not broadened by noncubic crystalline
electric fields. The dominant isotope of oxygen, 16O, which is 99.76% abundant,
and the dominant isotope of carbon, 12C, which is 98.9% abundant, both have I = 0
so they do not exhibit NMR.
The importance of NMR arises from the fact that the value of g is sensitive to
the local chemical environment of the nucleus, and it is customary to report the
chemical shift d
(3.9)
which is the extent to which g deviates from gR of a reference sample, where for
proton reference samples, gR/2p is close to 42.576 MHz/T. Chemical shifts are
small, and are usually reported in parts per million (ppm). Cuprates enriched with
the I = 7/2 oxygen isotope 17O provide spectra that distinguish the oxygens at the
different sites in the Cu-O ligand, and the NMR spectra of the isotope 63Cu in natural
abundance differentiate the copper ions at different positions in the lattice (12–16).
NMR studies of 89Y nuclei in YBa2Cu3O7–d provided information on the penetration
depth and the homogeneity of the magnetic field inside the superconductor. NMR
spectroscopy using the 1.1 % abundant 13C isotope, which has nuclear spin I = 1/2
has been instrumental in confirming the structures of fullerenes such as C60 and C70
(13).
3.7. NUCLEAR QUADRUPOLE RESONANCE

A nucleus with spin I = 1/2 has an electric quadrupole moment, and the
crystalline electric fields at an atomic site with symmetry less than cubic split the
nuclear spin levels in a manner that depends on the site symmetry. These spacings
are measured experimentally by the technique of nuclear quadrupole resonance
(NQR), which requires no applied magnetic field and operates at frequencies
similar to those used for NMR. Table VI-14 of Ref. 17 lists the point symmetries
for some of the atomic sites in several high-temperature superconductors. NQR can
provide information on the site symmetries of the various Cu sites in the cuprates,
and can probe changes in symmetry at these sites that result from variations in the
oxygen content (16, 18). When changes in temperature produce nonuniform
compression of the different Cu sites, this is reflected in the NQR spectrum.
3.8. MUON SPIN RELAXAT/ON

The negative muon µ– acts in all respects like an electron and the positive muon
µ like a positron except that they have a mass 206.77 times larger. When polarized
+
muons are implanted into a sample located in a magnetic field, their precession at
the frequency gµ/2p = 135.5 MHz/T provides a microscopic probe ofthe distribution
of local magnetic fields; in particular, the width of the muon spin relaxation (µSR)
signal from a superconductor provides an estimate of this field distribution and the
penetration depth l, (16, 19).
As an example, the temperature dependence of the penetration depth lab(T)
was measured by Harshman et al. (19) in a single crystal of YBa2Cu3O7–d with an
11 T applied magnetic field B0 aligned parallel to the c-axis (θ = 0). This orientation
of B0 automatically gives values of the lab(T) component, and a fit to the expression
(3.10)
provided the zero Kelvin temperature value lab(0) = 141.5 nm. Next, measurements
of the angular dependence of the average internal magnetic fields for the applied
field B0 oriented at different angles q relative to the c-direction provided a determi-
nation of the effective mass ratio m*c /m*ab > 25. Since the penetration depth is
proportional to the square root of the effective mass through the expression
(3.11)
70 CHAPTER 3
where e* = 2e, and fGL is a temperature-dependent parameter in the Ginzburg–Lan-

dau theory, we obtain lc/ lab > 5, which gives lc > 700 nm.
3.9. POSITRON ANNIHILATION

In positron annihilation spectroscopy (PAS), a sample is irradiated by a
radioactive source such as 22NaCl, which emits high-energy (545 keV) electrons
with positive charges e+ called positrons and a 1.28 MeV g-ray. When the positron
enters the solid, it rapidly loses most of its kinetic energy and approaches thermal
energy, ≈ (3/2)kBT≈ 0.04 eV, in the short time of 0.001 to 0.01 ns. After thermali-
zation, the positron diffuses like a free particle, although its motion is correlated
with nearby conduction electrons, until it encounters an electron e– and annihilates
in about 0.1 ns, producing two 0.5 1 MeV g rays in the process
e+ + e– ⇒ g + g (3.12)
The electron moves much faster than the positron, and momentum balance causes
the two g-rays that move off in opposite directions to make a slight angle with
respect to each other, The angular correlation of this annihilation radiation (ACAR)
is one of the important parameters that is measured. The positron lifetime τ is the
time delay between the emissions of the 1.28 MeV and 0.51 MeV g-rays. The
positron is sensitive to the details of the local electronic environment, and these are
reflected in its mean lifetime t, its angular correlation, and its Doppler broadening
parameters S and W (16, 20). These parameters exhibit discontinuities at the
transition temperature. The positron annihilation characteristics are determined by
the overlap of the positron and electron densities, and positron density plots provide
estimates of the electron distributions between the various atoms in the supercon-
ductor. A two-dimensional angular correlation technique called 2D-ACAR samples
the anisotropy of the conduction electron motion and provides information on the
topology of the Fermi surface.
3.10. MÖSSBAUER RESONANCE

Mössbauer resonance measures gamma rays emitted by a recoilless nucleus
when it undergoes a transition from a nuclear ground state to a nuclear excited state.
For 57Fe, the gamma ray has an energy of 14.4 keV and the line width is typically
5 × 10–9 eV, The g-ray can shift in energy, called an isomer shift, or its spectrum
can split into a multiplet by the hyperfine interaction from the nuclear spin, by
crystal field effects, or by the quadrupole interaction. Line broadening and relaxa-
tion provide additional information. These factors are sensitive to the chemical
environment of the nucleus in the lattice. Mössbauer workers frequently quote
energy shifts in velocity units, mm/s.
In a typical experiment, one of the atoms of a superconductor, such as Cu, Y,

or T1, is partially replaced by a small concentration of a nucleus such as 57Co, 57Fe,
151Eu, or 119Sn, which is favorable for Mössbauer studies. Sometimes the replace-
ment is 100%, as in the compound EuBa2Cu3O7–d. The partial substitution can have
the effect of lowering the transition temperature, particularly when Cu is being
replaced. The spectra provide information on the valence state of the nucleus (e.g.,
Fe2+ or Fe3+), whether it is high spin (e.g., S = 5/2) or low spin (e.g., S = 1/2), the
identity of the dominant substitutional site [e.g., Cu( 1) or Cu(2)], etc. Antiferro-
magnetic ordering due to the presence of Fe has been observed.
3.11. PHOTOEMISSION AND X-RAY ABSORPTION

Photoemission spectroscopy (PES) measures the energy distribution of the
electrons emitted by ions in various charge and energy states. These electrons have
energies characteristic of particular atoms in particular valence states. To carry out
this experiment, the material under study is irradiated with ultraviolet light (UPS)
or X-rays (XPS), and these incoming photons eject electrons from atomic energy
levels. The emitted electrons, called photoelectrons, have a kinetic energy KE which
is the difference between the photon energy hvph and the ionization energy Eion
required to remove an electron from the atom, as follows
KE = hvph – Eion (3.13)
The detector measures the kinetic energy of the emitted electrons and since hvph is
known, the ionization energy is determined from Eq. (3.13). Each atomic energy
state of each ion has a characteristic ionization energy, so the measured kinetic
energies provide information about the energy levels of the atoms. In addition, many
ionization energies are perturbed by the surrounding lattice environment, so this
environment is probed by the measurement. PES can furnish spectra of the outer
or valence electrons, and also of the inner electron energy levels called core levels.
In addition, PES can provide information on the energy bands and the density of
states (16, 21, 22).
It is also possible to carry out the reverse experiment, called inverse photoelec-
tron spectroscopy (IPS), in which the sample is irradiated with a beam of electrons
and the energies of the emitted photons are measured. When UV photons are
detected, the method is sometimes called Bremsstrahlung isochromat spectroscopy
(BIS). A related experiment is electron energy loss spectroscopy (EELS), in which
one measures the decrease in energy of the incident electron beam (23). Another
technique called Auger electron spectroscopy involves a radiationless transition in
which an X-ray photon generated within an atom does not leave the atom as
radiation, but ejects an electron from a higher atomic level.
72 CHAPTER 3
An energetic photon is capable of removing electrons from all occupied atomic

energy levels that have ionization energies less than the photon energy. When the
photon energy drops below the largest ionization energy corresponding to the K
level, then the n = 1 electron can no longer be removed, and the X-ray absorption
coefficient abruptly drops. It does not, however, drop to zero because the X-ray
photon is still energetic enough to knock out electrons in the L (n = 2), M (n = 3),
etc., levels. The abrupt drop in absorption coefficient is referred to as an absorption
edge; in this case it is a K-absorption edge, Acronyms are used: for example, X-ray
absorption spectroscopy (XAS), X-ray absorption near edge structure (XANES),
X-ray absorption fine structure (XAFS), and extended X-ray absorption fine
structure (EXAFS) spectroscopy.
Another way to obtain absorption edges, called electron energy loss spectros-
copy, is to irradiate a thin film with a beamofmonoenergetic electrons with energies
of, for example, 170 keV. When the electrons pass through the film, they exchange
momentum with the lattice and lose energy by exciting or ionizing atoms, and an
electron energy analyzer determines the energy Eabs that is absorbed. This energy
equals the difference between the kinetic energy KE0 of the incident electrons and
the kinetic energy KEsc of the scattered electrons
Eabs = KE0 – KEsc (3.14)
When the intensity of the scattered electrons is plotted as a function of the absorbed
energy, then peaks are found at the binding energies of the various electrons in the
sample.
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15. R. D. Johnson, D. S. Bethune, and C. S. Yannoni,Acc. Chem. Res. 25, 169 (1992).
16. C. P. Poole, Jr., H. A. Farach, and R. C. Creswick, Superconductivity,AcademicPress, NewYork
(1995).
17. C. P. Poole, Jr., T. Datta, and H. A. Farach, Copper Oxide Superconductors, Wiley, New York
(1988).
18. P. K. Babu andJ. Ramakrishna, Supercond. Rev. 1,75 (1992).
19. D. R. Harshman, L. F. Schneemeyer, J. V. Waszczak, G. Aeppli, R. J. Cava, B. Batlogg, L. W.
Rupp, Jr., E. J. Ansaldo, and D. LI. Williams, Phys. Rev. B39,851 (1989).
20. S. J. Wang, S. V. Naidu, S. C. Sharma, D. K. De, D. Y. Jeong, T. D. Black, S. Krichene, J. R.
Reynolds, and J. M. Owens, Phys. Rev. B37,603 (1988).
21. Z. X-. Shen, W. E. Spicer, D. M. King, D. S. Dessau, andB. O. Wells, Science 267, 343 (1995).
22. H. M. Meyer and J. H. Weaver, in Physical Properties of High Temperature Superconductors, D.
M. Ginsberg, ed., Vol. 2, Chap. 6, World Scientific, Singapore (1990).
23. N. Nücker, H. Romberg, M. Alexander, and J. Fink, in Studies in High Temperature Supercon-
ductors, A. V. Narlikar, ed., Nova Sci. Publ., New York (1992).
4

Normal State
In this chapter we begin by presenting some background material on the resistivity

of metals. Then we discuss the properties of the surface resistance of metals and
semiconductors in the normal state and show how measurements of the surface
resistance as a function of temperature and magnetic field can be used to explore a
range of phenomena, such as metal–insulator transitions, ferromagnetic and antif-
erromagnetic ordering, and giant magnetoresistive effects.
4.1. METALLIC STATE

4.1.1. Electrical Conductivity
When a potential difference exists between two points in a conducting wire,
an electric field E is established in the wire that exerts the force F = –eE on the
conduction electrons of the charge –e. A typical electron is accelerated, undergoes
a collision, is accelerated again, collides again, etc. The collision time or average
time between collisions is denoted by t; typical values for metallic elements are
listed in Table 4.1 (1). The result is that the electron moves forward at an average
velocity vav, and the n electrons per unit volume produce the current density J
J = nevav (4.1)
This current density is proportional to the electric field through Ohm’s law
J= σ 0 E = E/ρo (4.2)
where s0 is the dc electrical conductivity and its reciprocal r0 is the dc resistivity.

The conductivity is proportional to the collision time t
75
76 CHAPTER 4
ELECTROMAGNETIC ABSORPTION IN THE NORMAL STATE 77
78 CHAPTER 4
(4.3)
where m is the mass of the electron.

When a harmonically varying electric field E=E0 exp(–iwt) acts on the
conduction electrons, the conductivity s assumes the form
(4.4)
withthereal andimaginary parts s1 ands2
(4.5)
We see from Table 4.1 that for good metals t @ 2 ×10–13 s at 77 K and t @
4 × 10–14 s at 273 K. In the microwave region, w/2p = 1010 Hz, so ωτ << 1 and
s1 >> s2, making the electrical conductivity real.
The data in Table 4.1 show that t decreases as the temperature is increased.
Far below and far above the Debye temperature QD, the relaxation time has the
following respective limiting temperature dependencies
(4.6a)
(4.6b)
which determine the temperature dependencies of the resistivity.

4.1.2. Surface Resistance
In a waveguide or resonant cavity made from a perfect conductor, the boundary
conditions require that at the walls the H field be parallel and the E field be
perpendicular to the surface. If the walls are made from good but not perfect
conductors, then in addition to the transverse field Ht there will be a small transverse
field Et at the surface, and the ratio of these fields gives the complex surface
impedance Zs
(4.7)
where Rs is the surface resistance and Xs is the surface reactance. For a metal with
a complex electrical conductivity (4.5), the surface impedance Zs (w) is given by
(4.8)
In the normal metallic state at microwave frequencies s1 >> s2, and with the aid of
the identity
(4.9)
we see that the surface resistance Rs equals the surface reactance Xs in accordance
with the expression
(4.10)
where we write σinstead of s1 here and in Eqs. (4.12) and (4.13).

The electric and magnetic fields Et and Ht at the surface penetrate into the metal
and decay exponentially inside. For the magnetic field component, the field inside
Hin is given by expression
(4.11)
and a similar expression can be written for Ein. The quantity d given by
(4.12)
is called the skin depth, and it is a measure of how far the fields penetrate into the
metal. Figure 4.1 shows how the skin depth and the surface resistance depend on
the frequency for the metal copper and the cuprates in the normal state. The factor
ix/d in Eq. (4.11) indicates that the exponential decay exp(–x/d) is accompanied by
a phase shift. The quantity d is also a measure of the thickness of the surface layer
of the metal within which the energy dissipation occurs. Comparing Eqs. (4.10) and
(4.12) provides the especially simple expression
(4.13)
for the surface resistance.
4.1.3. Power Dissipation

At the surface of the metal, the magnetic field Ht immediately outside induces
a current per unit width Ks directly inside given by
Ks = n × Ht (4.14)
where n is a unit vector pointing outward from the surface so Ks\ is perpendicular
to Ht, Near the surface inside, there is a current density J(x, t) = J(x) exp(iwt), which
decays with distance in accordance with the expression
80 CHAPTER 4
Figure 4. 1. Frequency dependence of the skin depth d and the surface resistance Rs of copper and the
cuprate superconductors (HTSC) in their normal state.
(4.15)
in analogy with Eq. (4.11). The surface current per unit width is obtained by an
integration
(4.16)
(4.17)
For a sample of width w, the total current IT induced by a uniform field Ht at the
surface is
(4.18)
Figure 4.2 helps to explain the relationships (4.18) between J, Ks and IT , The power
loss per unit area dP/dA arising from the surface current Ks is given by
(4.19)
Thus we see that the energy absorbed when electromagnetic radiation is incident
on a metal is proportional to the surface resistance. Equations 4.10 and 4.15 provide
Figure 4.2. Surface layer of thickness d, width w, and length L showing the directions of the current
flow (4.18) and of the magnetic field Ht at the surface.
the basis for explaining many of the surface resistance effects in metals and
semiconductors.
4.1.4. Temperature Dependencies
The resistivity r of a metal is the sum of a contribution from impurity scattering
ri and a contribution from photon scattering rph(T)
(4.20)
The temperature dependence of the resistivity arises from the photon scattering term
rph, and at high temperatures, i.e., above the Debye temperature QD, with the aid of
Eqs. (4.3) and (4.6b), r (T) can be written
(4.21)
The presence of the temperature-independent ri term explains why the resistivity

of the sample does not go to zero at 0 K. Above room temperature, impurity
scattering is small compared with phonon scattering, so the resistivity becomes
linearly dependent on the temperature and thus the surface resistance depends on
the temperature as T1/2. This T1/2 temperature dependence of Rs is typical for the
cuprates in their normal state.
At low temperatures, far below the Debye temperature QD, we have from Eq.
(4.6a), t ⇒ T–3. When we include an additional phonon scattering correction factor
proportional to T2, the resistivity has the low-temperature dependence
(4.22)
82 CHAPTER 4
an expression often referred to as the Bloch T5 law. Thus the surface resistance will
depend on the temperature as
(4.23)
an expression applicable to classical superconductors in their normal states at

sufficiently low temperatures.
4.2. SEMICONDUCTORS
In an intrinsic semiconductor the resistivity depends on temperature as
(4.24)
where D is the band gap. The surface resistance in a semiconductor, from Eq. (4. 10),
will thus have the temperature dependence
(4.25)
Figure 4.3 shows a measurement of the temperature dependence or the surface

resistance of silicon at 9.2 GHz. A surface resistance measurement in an intrinsi-
Figure 4.3. Temperature dependence of the surface resistance of silicon.

cally semiconducting material can be used to determine the band gap of the material
from the slope of a plot of lnRs versus 1/T. If the material is doped, the situation is
more complicated because donor and acceptor ionization energies are much less
than the band gap and hence dominate the conductivity process for semiconductors.
4.3. METAL-INSULATOR TRANSITION

A metal–insulator transition in which there is an abrupt increase in the
resistivity of the sample as the temperature is lowered can be observed by a
temperature-dependent surface resistance measurement. Figure 4.4 shows the
temperature dependence of the surface resistance through the semiconductor-to-in-
sulator transition in nickel sulfide (NiS) at 264 K . This is an example of an
antiferromagnetically induced semiconductor-to-metal transition because both the
susceptibility and the resistivity increase as the temperature is lowered through the
transition (2). We see from the figure that Rs undergoes an abrupt rise from the lower
value in the semiconducting state above the transition to a higher value in the
insulating state below the transition.
4.4. ANTI FERROMAGNETIC TRANSlTlON

Typically an antiferromagnetic transition is accompanied by a pronounced
kink in the susceptibility at the Neé1 temperature TN, as shown in Fig. 4.5 for MnO,
Figure 4.4. Temperature dependence of the surface resistance of NiS showing the metal insulator
transition close to 260 K.
84 CHAPTER 4
Figure 4.5. Temperature dependence of susceptibility x of MnO showing the rise in x with decreasing
temperature above TN = 116 K, followed by a drop in the antiferromagnetic state below TN. (Adapted
from Nagaimiya et al., Ref. 3.)
which becomes antiferromagnetic at TN = 116 K (3). Since the permeability µ and

the susceptibility χ are related bv the expression,
(4.26)
the surface resistance [Eq. (4.10)] for a magnetic material becomes
(4.27)
with the result that the permeability and hence the surface resistance display
discontinuities at TN. Figure 4.6 shows a measurement of the temperature depend-
ence of the surface resistance at 9.2 GHz in MnO, which exhibits an anomalous
peak at 116 K, where the material becomes antiferromagnetic (4).
4.5. FERROMAGNETIC TRANSITION

In a ferromagnetic transition, the magnetization M(T) of the sample increases
at the Curie temperature, Tc. The magnetization in the ferromagnetic phase has been
found empirically to depend on temperature as (5)
ELECTROMAGNETlC ABSORPTION IN THE NORMAL STATE 85
Figure 4.6. Measurement of surface resistance of MnO through the antiferromagnetic transition at
TN = 116 K.
(4.28)
where M(0) is the magnetization at 0 K and c is a constant. Since by definition χ(T)

= M(T)/H, and the permeability and the susceptibility are related by Eq. (4.26), the
permeability µ(T) below Tc has a dependence on temperature given by
(4.29)
where χ0 = M(0)/H is a constant. The temperature dependence T> QD of the surface

resistance from Eqs. (4.10) and (4.21) in the ferromagnetic state will then be
(4.30)
Thus the onset of the ferromagnetic state will be indicated by a rapid increase
in the surface resistance of the sample. Figure 4.7 shows the temperature depend-
ence of the surface resistance of gadolinium, which is ferromagnetic below 293 K.
In the ferromagnetic state the permeability is dependent on the magnetic field
strength, increasing rapidly at low dc magnetic fields, reaching a maximum, and
then decreasing somewhat. Figure 4.8 shows that the permeability of gadolinium
86 CHAPTER 4
Figure 4.7. Increase in the surface resistance of gadolinium (Gd) with the decrease in temperature
below the transition to the ferromagnetic state near 293 K.
Figure 4.8. Plot of relative permeability µ/µ0 of Gd versus dc magnetic field in the ferromagnetic state
at 77 K (from Urbain et al., Ref. 6).
at 77 K plotted against the applied dc magnetic field exhibits this behavior (6). The
maximum in the permeability is temperature dependent, shifting to higher magnetic
field values at lower temperatures. At constant temperature, the field dependence
of the surface resistance will reflect the magnetic field dependence of the perme-
ability. Figure 4.9 shows the surface resistance versus magnetic field strength at
184 K in gadolinium (4).
Since Rs is proportional to µ1/2 the initial rise of the surface resistance to its
maximum value will generally be nonlinearly dependent on the dc magnetic field
strength. Thus an electron spin resonance spectrometer can be used to observe the
derivative of the field dependence of electromagnetic absorption. Figure 4.10 shows
half of the derivative signal obtained in the ferromagnetic state of Gd recorded at
184 K for upward and downward sweeps of the dc magnetic field (4). The derivative
is centered about zero field, and the other half is obtained by reversing the dc field
sweep direction. Note that there is hysteresis because on the downward sweep the
maximum of the derivative occurs at a lower field. The onset of the ferromagnetic
state can also be monitored by measuring the amplitude of the derivative signal at
a constant dc magnetic field as a function of temperature. Figure 4.1 1 presents the
results of such a measurement in Gd showing that the onset of the existence of the
derivative signal occurs at the Curie temperature (4). Since derivative detection is
Figure 4.9. Surface resistance of Gd versus dc magnetic field in the ferromagnetic state at 184 K.
88 CHAPTER 4
Figure 4.10. Low field derivative of microwave absorption by Gd versus dc magnetic field in the
ferromagnetic state at 184 K for upward and downward sweeps of the magnetic field.
Figure 4.71. Temperature dependence of the derivative signal in Gd through the ferromagnetic
transition at 290 K showing the onset of the signal as the field is decreased through the transition.
very sensitive, this technique is a useful tool for studying weakly ferromagnetic
materials such as Gd2CuO4 and EuTbCuO4 (7,8).
4.6. MAGNETORESISTANCE
Magnetoresistance refers to a phenomenon in which a dc magnetic field causes
either an increase or a decrease in the resistance of the sample. Recently there has
been a great deal of interest in the subject because of the discovery of materials that
display very large magnetoresistive effects referred to as giant or colossal magne-
toresistance (CMR). These materials may have a number of application possibili-
ties, such as in devices in magnetic recording heads or sensing elements in
magnetometers.
The perovskite-like material, LaMnO3, in which La3+ is partially replaced with
ions having a valence of 2+ such as Ca, Ba, Sr, Pb, and Cd, has been shown to
exhibit very large magnetoresistive effects. The substitution of the 2+ ion for the
3+ ion results in a mixed valence system of Mn3+/Mn4+, thereby creating mobile
charge carriers. The unit cell of the crystal is sketched in Fig. 4.12. The system
La0.67Ca0.33MnOx displays more than a thousand fold change in resistance with the
application of a 6-T dc magnetic field. Figure 4.13 shows how the resistivity of a
thin film of the material exhibits a pronounced decrease with increasing values of
the dc magnetic field (9). The temperature dependence of the resistivity also
Figure 4.12. Unit cell of the orthorhombically distorted perovskite structure of LaMnO3.
90 CHAPTER 4
Figure 4.13. Magnetoresistance behavior of epitaxial La-Ca-Mn-O films (after Jin et al., Ref. 9).
Figure 4.14. Temperature dependence of the resistivity in sintered samples of La-Ca-Mn-O (after
Radaeilli et al., Ref. 10).
Figure 4.15. dc magnetic field dependence of surface resistance of bulk La-Sr-Mn-O in the ferromag-
netic state at room temperature.
displays unusual behavior, as shown in Fig. 4.14, which plots the resistivity versus
the temperature through the Curie temperature (10).
Besides displaying large magnetoresistive effects, La1–xSrxMnO3 undergoes a
variety of magnetic transitions that depend on the value of x. For x between 0.2 and
0.5, the material becomes ferromagnetic, with the value of the Curie temperature
depending on x. While these systems have not yet been extensively studied by
surface resistance methods, such methods should provide a convenient way to
investigate the phenomenon (1 1,12). The surface resistance exhibits very large
changes in the presence of a dc magnetic field. Figure 4.15 shows a measurement
of the dc field dependence of the fractional change in the surface resistance at 9.2
GHz at room temperature in La0.8Sr0.2MnO3. Figure 4.16 presents a measurement
of the temperature dependence of the surface resistance showing the onset of the
ferromagnetic transition in this sample near 380 K (1 1). Note that there is an initial
drop in the surface resistance, followed by an increase. This is in contrast to the
temperature dependence of the bulk resistivity, which decreases at the Curie
temperature. This difference occurs because the surface resistance depends on two
92 CHAPTER 4
Figure 4.16. Temperature dependence of the surface resistance of bulk La-Sr-Mn-O showing the drop
in surface resistance at the onset of the ferromagnetic state at 380 K.
parameters, namely, the permeability and the resisitivity. The initial decrease in the
surface resistance is due to the temperature-dependent decrease in bulk resisitivity,
but as the ferromagnetic alignment progresses, the permeability starts to increase,
thus causing an increase in the surface resistance, which is reflected in the appear-
ance of the cusplike behavior shown in Fig. 4.16. The dependence of the surface
resistance on both the permeability and the resistivity explains why Rs has a much
stronger dependence on magnetic field in the ferromagnetic phase than the bulk
resistivity. This strong dependence of the surface resistance on the magnetic field
in these materials may have application potential in microwave devices. The
ferromagnetic transition can also be detected by the presence of the low field cusp
in the microwave absorption derivative signal shown for this material in Fig. 4.17,
and its temperature dependence shown in Fig. 4.18 (1 1). These results show that
measurements of the dependence of the surface resistance on the temperature and
on the dc magnetic field provide a method for characterizing the properties of
materials displaying colossal magnetic resistance.
The penetration depth at RF frequencies, measured by the LC coil method
discussed in Chap. 3, has also been shown to be strongly dependent on the dc
magnetic field. Figure 4.19 shows a plot of the measured frequency shift versus dc
magnetic field at 10 MHz in La0.7Sr0.3MnO3 at room temperature (13). Equation
(3.3) shows that this frequency shift Dw/w0 is proportional to the penetration depth.
Figure 4.17. Derivative of the microwave absorption versus the dc magnetic field in the ferromagnetic
state of bulk La-Sr-Mn-O at room temperature.
Figure 4.18. Temperature dependence of the derivative of the microwave absorption in bulk La-Sr
Mn-O showing the onset of the signal at the Curie temperature.
94 CHAPTER 4
Figure 4.19. dc magnetic field dependence of frequency shift at 10 MHz in bulk La0.7Sr0.3MnO3 at
room temperature. This shift is proportional to the penetration depth.
References
1. C. P. Poole, Jr., H. A. Farach, and R. J. Creswick, Superconductivity, Academic Press, San Diego
(1995).
2. J. T. Sparks and T. Komoto, Rev. Mod. Phys. 40, 752 (1968).
3. T. Nagaimiya, K. Yosida, and R. Kubo, Adv. Phys. 4, 1 (1955).
4. E J. Owens (unpublished).
5. B. E. Argyle, S. Charap, and E. W. Pugh, Phys. Rev. 132, 2051 (1963).
6. G. Urbain, P. Weiss, and F. Trombe, Compt. Rend. 200, 2132 (1935).
7. M. D. Sastry, J. K. S. Ajayakumur, R. M. Kadam, G. M. Phatak, and R. M. Iyer, Physica C 170,
41 (1990).
8. B. Oseroff, D. Rao. E. Wrigth, D. C. Vier, S. Hultz, J. D. Thompson, Z. Fisk, S. W. Cheung, M.
F. Hundley, and M. Tovar, Phys. Rev. B41,1934 (1990).
9. S. Jin, M. McCormack, T. H. Tiefel, and R. Ramesh, J. Appl. Phys. 78, 6929 (1994).
10. P. G. Radaeilli, D. E. Cox, M. Marezio, S. W. Cheong, P. E. Schiffer, and A. P. Ramirez, Phys.
Rev. Lett. 75, 4488 (1995).
11. E J. Owens, J. Phys. Chem. Solids 58, 1311 (1997).
12. S. E. Lofland, S. M. Bhagat, S. D. \ Y. M. Muskovskii, S. G. Karabashev, and A. M.
Balbashov, J. Appl. Phys. 80, 3592 (1996).
13. F. J. Owens, J. Appl. Phys. 82, 3054 (1997).
5
Zero Magnetic Field Microwave

Absorption
In this chapter we discuss the absorption of microwave radiation in the supercon-

ducting state in the absence of any applied magnetic field.
5.1 ELECTROMAGNETIC ABSORPTION AND THE TWO-FLUID

MODEL
As the temperature of a superconducting sample is lowered below Tc there is
a pronounced reduction in the surface resistance and thus in the absorption of
electromagnetic energy. Figure 5.1 shows a representative microwave measurement
of the surface resistance at 9.2 GHz in Hg-Pb-Ba-Ca-Cu-O (1). The earliest attempts
to explain this reduction in electromagnetic absorption in superconductors were
based on the expression (Eq. 1.9) for the penetration depth derived from the London
theory using the two-fluid model. Qualitatively, this model envisions the supercon-
ducting state as involving a mixture of normal nn and superconducting ns electrons,
where the sum nn + ns equals the total number of conduction electrons. We now
know that the superelectrons are Cooper pairs. These superconducting charge
carriers are not scattered by phonons, they experience no resistance and they cannot
absorb electromagnetic radiation. As the temperature is lowered below Tc , the
number of superconducting charge carriers increases; the number of normal elec-
trons decreases; and consequently the London penetration depth given by Eq. (1.9)
decreases and the sample becomes less absorbing to electromagnetic radiation. In
this model the temperature dependence of the reduction in the penetration depth is
given by Eq. (1.17). Measurements of the temperature dependence of the penetra-
tion depth in tin by Pippard (2) show that it could be described well by Eq. (1.17)
at low temperatures but deviated from this dependence as T approached Tc.
95
96 CHAPTER 5
At the time of the development of the theory, researchers did not know about
the superconducting gap. The presence of a gap opening up with a temperature
dependence of (T – Tc)1/2 significantly enhances the absorption process near the
transition because at some temperature near Tc, depending on the energy hv of the
incident radiation, the gap will equal the energy of the radiation and absorption will
occur because of excitations across the gap. The importance of the role of the energy
gap in the absorption of electromagnetic radiation in the superconducting state is
seen in measurements of the energy or frequency dependence of the surface
resistance at constant temperature. Figure 5.2 is a plot of the surface resistance in
aluminum at T/Tc = 0.7 in the superconducting state normalized to a value above
Tc and plotted versus hw/kBTc. The sharp increase in the surface resistance just
above hw/kBTc = 2.5 occurs because the photons of the incident radiation are
causing transitions across the gap, in effect breaking up Cooper pairs to form normal
carriers which can then absorb electromagnetic energy. This kind of measurement
can be used to obtain the value of the superconducting gap.
Figure 5.1. Temperature dependence ofsurface resistance through the transition to the superconducting
state in a granular pellet of Hg-Pb-Ba-Cu-O.
ZERO MAGNETIC FIELD MICROWAVE ABSORPTION 97
Figure 5.2 Frequency dependence of the ratio of the microwave absorption determined surface
resistance in the superconducting state to that in the normal state in aluminum at a constant temperature
of 0.83 K, where Tc = 1.18 K.
5.2. SURFACE IMPEDANCE

In this section we discuss the theory of electromagnetic absorption in the “local
limit” where the current density J is determined by the local value of the vector
potential A. This limit applies when the penetration depth is greater than the
coherence length, corresponding to the condition for Type II superconductivity.
Since the copper oxides are Type II superconductors, with k = l/x >> 1, a
description of electromagnetic absorption in the local limit applies.
The surface impedance Zs of a metal or superconductor, which was introduced
in Sect. 4.1.2, is a complex quantity with real and imaginary parts
Zs = Rs + iXs (5.1)
where Rs is the surface resistance and Xs is the associated reactance. The complex
electrical conductivity
s = s1 + is2 (5.2)
98 CHAPTER 5
is related to the surface impedance bv the expression (3,4)
(5.3)
We showed in Sect. 4.1.2 that for a metal in the normal state s1 >> s2, which
gives
(5.4)
The reason s1 is greater than s2 is that normal electrons have very low inertia,
responding promptly to an ac field, and thus the current induced by the ac
electromagnetic field is close to being in phase with the ac field, and there is little
inductive reactance.
For superelectrons s1 is very large, but superelectrons have such a pronounced
inductive response that s1 << s2 in the microwave region below Tc. If Eq. (5.3) is
expanded in a power series for this limit, we obtain the approximate expression
(5.5)
Recalling Eq. (4.3) for the dc conductivity so of normal state electrons, we make
the assumption that an analogous expression applies for superelectrons
(5.6)
and we write t = 1/w to obtain s and Zs from Eqs. (5.2) and (5.3), respectively
(5.7)
(5.8)
where use was made of Eq. (1.9) for the penetration depth. This gives for the
resistive and the reactive parts of the surface impedance
(5.9a)
(5.9b)
The surface resistance Rs measures the absorption due to electronic excitations and
the thermally activated dissociation of Cooper pairs, and the surface reactance Xs
is the inductive response of the superconducting condensate. Thus a measurement
of the surface reactance allows a direct determination of the penetration depth l,
and a measurement of both the surface resistance and reactance provides a deter-
mination of s1. Once the penetration depth is known, the superfluid density ns can
be calculated from Eq. (1.9), namely
(5.10)
5.3. ELECTROMAGNETIC ABSORPTION IN THE BCS THEORY

There are two features of the BCS theory that bear strongly on the nature of
electromagnetic absorption in the superconducting state. One aspect, which has
been mentioned above, is the existence of the superconducting energy gap. For a
photon hv of energy less than the gap at 0 K, D(0), the absorption process will be
enhanced near Tc when the gap has closed to a value comparable to hv, allowing
excitations across the gap. At low temperatures (T < 1/2 Tc), the temperature
dependence of the penetration depth, which by Eq. (5.10) is inversely proportional
to the square root of the superfluid density ns, can be described by thermally
activated behavior in the BCS formalism, i.e, (5)
(5.11)
and,
(5.12)
The second important characteristic of the BCS model that has a major
influence on electromagnetic absorbing properties in the superconducting state is
the existence of singularities in the density of states at the edge of the supercon-
ducting gap. In the weak coupling limit discussed in Sect. 2.2.2, the density of states
Ns (E) in the superconducting state is given by (6)
(5.13)
where Nn(E) is the density of states in the normal state. Figure 5.3 gives a schematic
of the density states in a superconductor. Near Tc as the superconducting gap closes
and approaches the energy of the incident photon, the photon energy overlaps the
energy region where there is a rapid increase in the density of states, and thus an
increase in the number of superfluid electrons available for excitation. This results
in a peak in the temperature dependence of the conductivity s1 near Tc as shown in
Fig. 5.4. This peak is known as the coherence peak. In the temperature region
between 1/2 Tc and Tc, the BCS formalism does not yield simple analytical
expressions for the temperature dependence of l, Rs, and s. However, computer-
generated numerical solutions have been obtained for a given set of parameters
which will be shown to illustrate the BCS predictions (7). Figure 5.5 presents a plot
1 00 CHAPTER 5
SUPERCONDUCTOR
Figure 5.3, Density of states in the neighborhood of the superconducting gap in a BCS superconductor.
Figure 5.4. Real part of the conductivity s1 of a BCS superconductor plotted against the temperature
assuming a Tc of 90 K (after Bonn and Hardy, Ref. 4).
ZERO MAGNETlC FIELD MICROWAVE ABSORPTION 101
Figure 5.5. Plot of l2(0)/l2(T) versus temperature for a BCS superconductor (after Bonn and Hardy,
Ref. 4).
Figure 5.6. Plot of the logarithm of surface resistance versus temperature for a BCS superconductor
(after Bonn and Hardy, Ref. 4).
1 02 CHAPTER 5
of l2(0)/l2(T) versus temperature calculated on a BCS model. The existence of an

energy gap leads to a leveling off, with l(T) ⇒ l(0) at low temperature, as shown
in the figure. The surface resistance shown in Fig. 5.6 exhibits a rapid drop just
below Tc due to the onset of screening by the supercurrents, and exponential
behavior at lower temperatures. Near Tc , the coherence peak is not evident in the
temperature dependence of the surface resistance because it is dominated by the
rapid increase in the penetration depth as the temperature approaches Tc from below.
5.4. COPPER OXIDES

5.4.1. Penetration Depth Measurements
The penetration depth and surface resistance have been measured in high-qual-
ity single crystals of Y-Ba-Cu-O, and ordinarily reports from different research
groups are in agreement with each other. Figure 5.7 shows a representative result
for a high-quality single crystal of YBa2Cu3O6.95 for the ab orientation of the
Figure 5.7. Measured dependence of l2(0)/l2(T) on the temperature for a single crystal of
YBa2Cu3O6.95.
orthorhombic unit cell (8). The most striking feature of the data is that at low
temperature they do not display the leveling-off behavior of Fig. 5.5 that is predicted
by the BCS theory; rather, l2 (0)/l2(T) is linearly dependent on temperature below
about ½Tc. At much lower temperatures there is a deviation from the linear
dependence on T, with an observed dependence closer to T2. The crossover
temperature T* from the T to the T2 behavior depends on the impurity content of
the crystal. Measurements have also been made on epitaxial films where the
crossover to the T2 dependence occurs at a higher temperature, near 30 K (9). The
difference between the crystals and the films has been attributed to a higher impurity
content of the films. The effect of impurity content on the functional dependence
of the penetration depth has been investigated in single crystals. Figure 5.8 shows
a plot of the l(T)/l (0) in single crystals in which some of the copper ions have been
replaced by zinc, corresponding to the formula YBa2(Cu1–xZnx)3O6.95 (10). The data
show that the crossover temperature from the T dependence to the T2 dependence
increases as the impurity content increases. Because in the copper oxides the
superconducting current flows primarily in the ab plane, the penetration depth is
expected to be anisotropic. The measurement of the temperature dependence of
l2(0) /l2(T) parallel and perpendicular to the c-axis presented in Fig. 5.9 shows that
l^ c(T) > l || c(T) (11).
Another interesting feature of the penetration depth data is their behavior near
Tc. Figure 5.10 is a plot of l3(0)/l3(T) versus temperature near Tc. The almost
straight line indicates a cubic dependence of 1/λ on temperature, which is consistent
with critical behavior of a three-dimensional superfluid (12).
Figure 5.8. Temperature dependence of the penetration depth l(T) of Zn-doped Y-Ba-Cu-O for 0.31%
Zn for 0.15% Zn (◊), and for no Zn ( ) present (from Bonn et al., Ref. 10).
•
1 04 CHAPTER 5
Figure 5.9. Plot of l2(0)/l2(T) versus the temperature parallel to the c-axis (•) and parallel to the a-axis
(D) of Y-Ba-Cu-O (from Hardy et al., Ref. 11).
Figure 5.10. Plot of l3(0)/l3(T) of Y-Ba-Cu-O versus the temperature in the neighborhood of T c (from
Kamal et al., Ref. 12).
ZERO MAGNETIC FIELD MlCROWAVE ABSORPTION 105
The most significant result of these studies is that the temperature dependence
of l(T) for the copper oxide superconductors does not follow the predictions of the
phonon-mediated BCS theory at low temperatures. Does this then mean the
mechanism of superconductivity in the copper oxides is not phonon based? The
answer to this question requires further research. There are other explanations for
the linear dependence of 1/l2(T) on temperature below Tc/2. For example, it has
been shown that if some of the copper oxide layers are not superconducting but are
sandwiched between layers that do superconduct, a linear temperature dependence
of 1/l2(T) could be expected. We will return to this question later in the context of
the s-wave versus d-wave question.
5.4.2. Surface Resistance Measurements

As seen in Eq. (5.8), the surface resistance depends on s1. We know from Eq.
(4.5) that s1(T) can be written in the form
(5.14)
where the scattering time t depends on the temperature in accordance with Eq. (4.6),
and so clearly Rs will depend on the impurity content because impurities affect the
scattering time t. In fact, substitution of impurities will decrease the scattering time
and thus decrease the microwave losses. Somewhat contrary to intuition, samples
with higher concentrations of impurities will have lower surface resistance in the
superconducting state. Measurements of the surface resistance in the copper oxides
generally confirm the importance of the role of impurities. Figure 5.11 shows that
the surface resistance in the ab plane of a high-quality pure single crystal of
YBa2CU3O6.95 exhibits a rapid drop at Tc followed by a broad peak at intermediate
temperatures and then a decrease at lower temperatures (8). The figure also shows
that the doped crystal has a lower surface resistance and lacks the broad peak.
The most prominent feature reported by different workers is the broad peak at
40 K. Measurements of the temperature dependence of l do not exhibit such a peak
so it is concluded that this peak must be associated with s1. Since this peak does
not occur near Tc, it is clearly not associated with the singularity in the density of
states near Tc that is responsible for the coherence peak in BCS superconductors.
The broad peak has been attributed to a temperature-dependent increase in the
quasi-particle lifetime. If t in Eq. (5.14) is temperature dependent then a peak can
appear because of the combined effect of the normal fluid lifetime that increases
with temperature and the normal fluid density that decreases with temperature. It
is known that the impurity content strongly affects t, and the lower curve in Fig.
5.11 shows how the substitution of 0.75% Ni for Cu in Y-Ba-Cu-O significantly
lowers the surface resistance in the region of the broad peak. The prediction of Eq.
(5.9) that the surface resistance in the superconducting state increases with the
frequency of measurement is confirmed by the data plotted in Fig. 5.12 (10).
106 CHAPTER 5
Figure 5.11. Temperature dependence of the surface resistance of a pure crystal of Y-Ba-cu-O
showing a broad peak below Tc and in a doped crystal (∆ ) in which 0.75% of the Cu ions are replaced
by Ni (from Bonn et al., Ref. 8).
Figure 5.12. Temperature dependence of the logarithm of the surface resistance in the ab plane of a
10).
•
crystal of Y-Ba-Cu-Oat two differentfrequencies: 34.8 GHz ( )and 3.8 GHz (from Bonn et al., Ref.
5.4.3. Penetration Depth Measurements as a Probe of s- and

d-Wave Symmetry
One of the important unresolved questions involving the cuprates is the nature
of the wave function describing the hole Cooper pairs. For a standard BCS
superconductor, the wave function is isotropic, corresponding to an s-state (L = 0).
Some of the proposed mechanisms for pairing of the holes, such as those of a
magnetic type, require the Cooper pair wave function to be d-like, having L = 2.
BCS s-wave pairing results in an exponentiallly activated temperature dependence
of many dynamic and thermodynamic parameters. One such parameter is the
penetration depth, and at low temperature it reflects changes in the density of pairs
that are respcnsible for screening electromagnetic fields. In s-wave weak coupling
BCS theory, the change in the penetration depth with temperature is given by Eq.
(5.11). However, for d-wave pairing, the penetration depth has a different depend-
ence on temperature (1 1), and for Dl = l(T) – l(0) we have
(5.15)
where D0 is the maximum value of the gap that occurs at T = 0. Thus for d-wave
pairing, the penetration depth is predicted to have a linear dependence on tempera-
ture well below Tc whereas by contrast s-wave pairing is not linear. These predic-
tions have motivated detailed measurements of the temperature dependence of l(T)
at low temperatures in order to address the question of s-wave versus d-wave
pairing. A difficulty with relying on penetration depth measurements to clarify the
nature of the pairing is the strong dependence of l(T) on the impurity content, as
demonstrated by the Y-Ba-Cu-O single-crystal data presented in Fig. 5.8. Theoreti-
cal treatments of systems having d-wave gaps and strong impurity scattering yield
a penetration depth that depends on T2 below a crossover temperature T*, above
which the dependence is linear (13). The data in Fig. 5.8 do show a linear
dependence of l on the temperature for T greater than a temperature T*, and a
nonlinear dependence below T* that is in qualitative agreement with these predic-
tions. However, the strong influence of impurities on the temperature dependence
does not make this unequivocal evidence for d-wave pairing.
5.4.4. Electromagnetic Absorption Due to Fluctuations

The transformation to the superconducting state in the absence of an applied
magnetic field is a second-order phase transition. Common to second-order transi-
tions is the existence of pretransitional fluctuations. A somewhat oversimplified
way to view superconducting fluctuations is to consider them as small transitory
droplets of superconductivity with the radius of a coherence length that form and
dissipate in a short time. Superconducting fluctuations above Tc manifest them-
selves by small decreases in the resistance or susceptibility occurring above the
108 CHAPTER 5
main transformation to the superconducting state. Their existence can be seen

clearly in the temperature dependence of the resistance of the Hg-Pb-Ba-Ca-Cu-O
superconductor shown in Fig. 1.2. The main transition to the superconducting state
denoted by the half value of the resistance is 133 K; however, a slight deviation due
to fluctuations from the linear decrease of the normal state can be seen as high as
150 K. The lower the dimensionality of the system sustaining superconductivity,
the higher the temperature above Tc at which fluctuations appear. Just as the bulk
resistance starts to deviate from its normal decrease above Tc, so it is with the surface
resistance. In the fluctuation regime the surface resistance Rs has been shown to
depend on the temperature as (3)
Rs~(T–Rc)” (5.16)
where the exponent n depends on the dimensions of the system, expected values
being 1/2 for a three-dimensional system, 1 for a two-dimensional system, and 3/2
for a one-dimensional system. Surface resistance measurements have not been
widely employed to study fluctuational effects, but they may be a very useful tool
for this because direct electrical contact with the sample is not required. Small
deviations in the resistance near Tc can be masked by surface contact resistance
effects. Lehoczky and Bruscoe (14) studied the temperature dependence of the
surface resistance above Tc at 24 GHz in films of lead whose thickness was less
than the coherence length, making them in effect two-dimensional superconduc-
Figure 5.13. Plot of surface resistance (normalized to normal state surface resistance) versus reduced
temperature, T/Tc, in films of lead with thickness less than the coherence length, making them essentially
two dimensional (from Lehoczyy and Briscoe, Ref. 14).
Figure 5.14. Sketch of the unit cell of the one-dimensional organic conductor TTF-TCNQ showing a
TCNQ molecule C6H4(C3N2)2 in the center and TTF molecules (C3S2H2)2 along the cell edges [from
Owens and Poole, Ref. 17, p. 174].
tors. Figure 5.13 shows Rs/Rsn versus T above Tc in lead, showing evidence for
fluctuations.
It is interesting that superconducting fluctuations were observed by microwave
absorption in the mid-1970s in the one-dimensional organic conductor TTF-TCNQ
(15). The unit cell shown in Fig. 5.14 consists of one-dimensional chains of donor
and acceptor molecules. Measurements of the microwave absorption at 10 GHz in
these materials showed large drops in the absorption to a minimum in the vicinity
of 50 K, followed by a subsequent rapid increase, as shown in Fig. 5.15 (15).
Although there was some controversy concerning the origin of these surface
resistance cusps at the time, it is now generally believed that they are a result of
superconducting fluctuations followed by a charge density wave-driven metal
insulator transition.
It is widely accepted that purely one-dimensional systems cannot sustain
conventional superconductivity because of the existence of charge density wave
instabilities, but apparently they do show fluctuations as though they want to
become superconducting. In fact, the organic material TTF-TCNQ was eventually
made to be a superconductor by inserting additional molecules into the lattice,
which increased the interaction between the chains, thus raising the dimensionality
above one. Clearly this provides an approach for synthesizing higher temperature
110 CHAPTER 5
Figure 5.15. Surface resistance (normalized to the value R n at 300 K) versus temperature of the organic
superconductor TTF-TCNQ (from Cohen et al., Ref. 15).
superconductors. One might look for one-dimensional materials that display super-
conducting fluctuations and then seek appropriate dopants to enhance the interac-
tion between the chains. For example, the ladder phase materials discussed in Chap.
2 contain copper oxide ligands that are of a dimension between one and two. Indeed,
large microwave absorption cusps similar to those observed in TTF-TCNQ have
been noticed at temperatures as high as 280 K (16) in the ladder phase-type material
Sr14–xCaxCu24O41+d. The structure of this material consists of alternating parallel
planes and chains of copper oxide which have the ladder structure shown in Fig.
2.12. Figure 5.16 shows a sharp drop in surface resistance in the metallic region
between 230 K and 270 K where the superconducting fluctuations occur, the onset
of the metal insulator transition at the 230 K minimum, and a rise in Rs in the
insulator phase below 230 K. The onset of the drop in the surface resistance shifts
to lower temperature with increased calcium content x, as shown in Fig. 5.17 (16).
Superconductivity has been observed in this material when it has the very high
calcium content of x = 13.6. The Tc for this calcium content, the solid circular point
in Fig. 5.17, lies nicely on the plot of the temperature of the surface resistance
minimum versus calcium content, suggesting that these surface resistance drops
could well be associated with superconductivity.
Figure 5.16. Plot of the temperature dependence of the surface resistance RS in the ladder phase Sr14–x
CaxCu24O41.
Figure 5.17.Plot of the temperature of surface resistance drops in the ladder phase material Sr14–x
CaxCu24O41 , versus calcium content x. The large dark circle at the lower right designates the
superconducting transition temperature of the sample with x = 13.6.
112 CHAPTER 5
References
1. E J. Owens, A. G. Rider and Z. Iqbal, Physica C233, 30 (1944).
2. A. B. Pipard, Proc. Roy. Soc. London A216, 547 (1953).
3. M. Tinkham, Introduction to Superconduclivily, McGraw-Hill, New York (1996).
4. D. A. Bonn and W. N. Hardy in Physical Properties of High Temperature Superconductors, Vol.
V, D. M. Ginsberg, ed., World Scientific, River Edge, N.J. (1996).
5. D. C. Mattis and J. Bardeen, Phys. Rev. B111, 412 (1958).
6. J. Bardeen, L. N. Cooper and J. R. Schrieffer, Phys. Rev. 106, 162 (1957).
7. J. Halbritter, Z. Phys. 266, 209 (1977).
8. D. A. Bonn, P. Dosanjh, R. Liang and W. N. Hardy, Phys. Rev. Lett. 68, 2390 (1992).
9. Z. Ma, R. C. Taber, L. W. Lombardo, A. Kapitulnik, M. R. Beasley, P. Merchant, C. B. Eom, S.
Y. Hou, and J. M. Phillips, Phys. Rev. Lett. 71, 781 (1993).
10. D. A. Bonn, S. Kamal, K. Zhang, R. Liang, D. J. Baar, E. Klein and W. N. Hardy, Phys. Rev. B50,
4051(1994).
11. W. N. Hardy, D. A. Bonn, R. Liang, S. Kamal and K. Zhang, in Proc. Seventh Int. Symp. on
Superconductivity(1966).
12. S. Kamal, D. A. Bonn, N. Goldenfeld, P. J. Hirschfeld, R. Liang, and W. Hardy, Phys. Rev. Lett.
73,1845(1994).
13. D. J. Scalapino, Physics Reports 350, 331 (1995).
14. S. L. Lehoczyy and C. V. Briscoe, Phys. Rev. Lett. 23, 695 (1969).
15. M. J. Cohen, L. B. Coleman, A. F. Garito, and A. J. Heeger, Phys. Rev. B10, 1298 (1974).
16. F. J. Owens, Z. Iqbal, and D. Kirven, Physica C267, 147 (1996).
17. E J. Owens and C. P. Poole, Jr. The New Superconductors, Plenum Press, New York (1996).
6
Low Magnetic Field-Induced

Microwave Absorption
6.1. INTRODUCTION
When a dc magnetic field is applied to a material in the superconducting state,
the surface resistance increases. From the point of view of the absorption mecha-
nism, three regions of dependence on the applied magnetic field can be distin-
guished. Figure 6.1 is a generalized plot of the surface resistance behavior as a
Figure 6.1. Generalized diagram of the effect of an applied magnetic field B on the surface resistance
R s showing three major regions in which the increase in Rs arises from different mechanisms.
113
114 CHAPTER 6
function of the applied field. Initially there is a very rapid increase at low fields, in
the vicinity of the lower critical field Bcl, followed by a more slowly increasing
absorption as a function of the dc field strength. At higher fields, above the
irreversibility line, the dissipation increases somewhat more strongly with dc
magnetic fields. This chapter is concerned with the nature of the absorption at the
lowest applied fields.
6.2. PROPERTIES OF LOW MAGNETIC FIELD ABSORPTION

DERIVATIVE
The absorption in the low dc magnetic field limit was first observed as a
derivativeof the absorption versusdcmagneticfieldusing anelectronparamagnetic
resonance spectrometer (1-5). The intensity of the derivative increased as the
temperature was lowered below Tc. The field position of the center of the derivative
was independent ofthe microwavefrequency, indicatingthatthe signal did notarise
from a resonant absorption. The existence of a derivative signal having a phase
opposite to a resonant signal implied a strong nonlinear increase in absorbed
microwave energy as afunction ofincreasing magnetic field atquite low fields, less
than 10 mT. There had actually been an observation of the derivative in the organic
superconductor (TMTSF)2ClO4 by a French group in 1983, but no further studies
were made nor was a mechanism proposed (6). This low-field microwave absorp-
tion (LFMA) in the copper oxides has been the subject of investigation by numerous
groups. Many studies of its properties have been reported and several mechanisms
have been proposed to explain it. Here we review the properties of the absorption
and discuss the mechanism responsible for it.
Because the absorption increases nonlinearly with magnetic field, the deriva-
tive of the absorption versus dc field can be readily detected with an EPR spec-
trometer. A comprehensive list of early observations is contained in Ref. 7. Figure
6.2 is a typical result showing one half of the absorption derivative signal plotted
against increasing magnetic field in a ceramic sample of the N = 3 superconductor
Bi1.5 Pb0.5Sr2Ca2Cu3O10 for sweeps of the magnetic field from zero to 6 mT and back
at two different temperatures (8). The other half of the derivative signal is obtained
by sweeping in the negative B direction. The modulation for this observation was
1 mT. The two derivatives shown in Fig. 6.2 illustrate many of the properties of the
absorption. The figure shows that the intensity increases as the temperature is
lowered below Tc. Note that this is in contrast to the surface resistance, which
decreases as T is lowered below Tc. Figure 6.3 is a plot of the temperature
dependence of the intensity of the derivative signal in this material. These data are
fairly representative of the temperature dependence observed in pure single-phase
samples. As the temperature is lowered, the negative peak of the line shifts to higher
LOW MAGNETIC FIELD-INDUCED MICROWAVE ABSORPTION 115
Figure 6.2. Low dc magnetic field microwave absorption derivative signal for the N = 3, Bi-Pb-Sr-Ca-
Cu-O superconductor for upfield and downfield scans at two different temperatures.
Figure 6.3. Temperature dependence of the microwave absorption derivative intensity measured at the
dc magnetic field of 1 mT in N = 3, Bi-Pb-Sr-Ca-Cu-O material.
116 CHAPTER 6
magnetic field and the line width increases. Figure 6.4 shows a plot of the line width
and field at the peak versus temperature.
The LFMA measurements that we have described were all made by sweeping
to the same magnetic field at each temperature, in this case 6 mT. This is necessary
because the peak of the line and its width are both affected by the magnetic history
of the sample and by the method of application of the dc magnetic field, such as
whether it is applied before or after the sample is cooled below Tc. The derivative
of the absorption signal displays a hystersis that is evident in Fig. 6.2, which
presents a sweep upfield from zero followed by a return to zero field. We see from
the figure that the signal during the return downfield sweep is weaker than it was
for the initial upfield sweep. This hysteresis depends on the maximum range of the
sweep, and it is more pronounced for larger applied fields. The magnitude of the
hysteresis is defined as the shift in the magnetic field position of the negative peak
for an upfield scan followed by a downfield one. Figure 6.5 shows how this
magnitude depends on the maximum value of the magnetic field applied to the
Bi1.5Pb0.5Sr2Ca2Cu3O10 sample at 77 K. There is also hysteresis in the line width in
that it appears broader on the return sweep. It is also noted that on the sweep up
after the application of a magnetic field, the peak of the line occurs at a higher
•
Figure 6.4. Plot of line width ( ) and field position at the peak of the microwave absorption
derivative signal plotted against temperahue for the N = 3, Bi-Pb-Sr-Ca-Cu-O superconductor.
LOW MAGNETIC FIEL D-INDUCED MICROWAVE ABSORPTION 117
Figure 6.5. Magnitude of microwave absorption derivative signal hysteresis versus maximum dc
magnetic field applied at 77 K for the superconductor N = 3, Bi-Pb-Sr-Ca-Cu-O,
magnetic field position and this upward shift increases with larger maximum
applied fields. Figure 6.6 shows this effect. The magnitude of the upward shift
corresponds to the magnitude of the hysteresis, for a sweep up to a given field and
back. The hysteresis for a sweep to a constant magnetic field also increases as the
temperature is lowered below Tc.
The low-field microwave absorption displays a time dependence after the
removal of a magnetic field (9). This measurement is made by cooling the sample
below Tc in a zero magnetic field and then applying a field of 100 mT. The field is
then removed and the LFMA is rapidly recorded on the down scan for different
elapsed times after the removal of the field. Figure 6.7 shows a representative result
for the high-temperature superconductor Tl0.5Pb0.5Sr2CaCu2O7 at 77 K. The inten-
sity grows as a function of time, and the position of the line shifts to the lower field.
We will see later that many of the properties of the absorption are a result of the
flux-trapping behavior of the sample, and measurements of this type can clarify the
nature of this flux trapping.
The absorption derivative signal has also been observed in crystals and thin
films (10–12). In the case of films, the properties of the absorption depend to some
extent on the film quality. At temperatures close to Tc , films that are not perfectly
118 CHAPTER 6
Figure 6.6. Magnetic field position of the center of the absorption derivative signal of the N = 3,
Bi-Pb-Sr-Ca-Cu-O superconductor at 77 K plotted against the maximum of the dc field sweep applied
before recording the scan of the derivative signal.
crystalline produce absorption derivatives that resemble those from composites.

The major difference in the films is that the absorption signal depends on the
orientation of the applied field with respect to the normal to the surface of the film.
Figure 6.8 is a plot of the intensity of the absorption at 77 K versus the orientation
of the applied magnetic field with respect to the normal to a film of YBa2Cu3O7–x
deposited on an MgO single crystal. The c-axis of the orthorhombic cell is
perpendicular to the film surface. The intensity decreases as the dc magnetic field
is rotated away from the perpendicular to the surface. This particular measurement
was made on a film in which most of the crystals are arranged so that c is
perpendicular to the substrate but in which there is some misalignment about the
c-axis (12). In a high-quality film, no low dc magnetic field-induced derivative
signal is detected when the dc magnetic field is parallel to the surface of the film.
It is also observed in the films that the magnitude of the hysteresis depends on the
orientation of the dc magnetic field, being larger when the magnetic field is
perpendicular to the film surface. Figure 6.9 shows a plot of the hysteresis at 77 K
versus the applied field in a film of YBa2Cu3O7–x for the dc field parallel and
perpendicular to the c axis. Results similar to these have been observed in single
crystals of the cuprates at high modulations and at temperatures close to Tc.
Figure 6.7. One half of the microwave absorption derivative signal in TI-Pb-Sr-Ca-Cu-O at 77 K for
an upfield scan (top) and downfield scans made immediately (0 s) and 78 s after the removal of a 100-mT
dc magnetic field.
At low temperatures and low modulations, fine structure is sometimes ob-

served superimposed on the broad lines from crystals, and in some instances
well-defined sharp lines are observed instead of a broad line (13–15). Figure 6.10
shows a spectrum obtained for a single crystal of YBa2Cu3O7–x by Vichery et al.
(15). This spectrum is observed at low magnetic fields using modulations of 1.25
µT. The separation between adjacent lines has the constant value of 7 µT. The
spacing between the lines depends on the orientation of the dc magnetic field as
(cos q)–1. The q = 0 orientation gives the minimum separation, and does not
correspond to any significant direction in the crystal. Sometimes several sets of
lines distinguished by different spacings between them and different directions in
which q = 0 were observed. This was attributed to the presence of Josephson
junction loops with planes oriented in several particular directions.
120 CHAPTER 6
Figure 6.8. Intensity of microwave absorption derivative signal in a thin film of Y-Ba-Cu-O at 77 K
versus orientation of dc magnetic field with respect to the perpendicular to film surface.
6.3. PROPERTIES OF LOW-FIELD DIRECT MICROWAVE

A BSORPTlON
The previous section provided details on the LFMA signal obtained when the
scanning magnetic field is modulated. It is not clear how to sort out the effects due
to the scanning applied field and those arising from the modulation. To obtain a
clearer understanding of the microwave absortion process, the modulation was
eliminated and direct microwave detection was employed (16,17). To accomplish
this, a 9.3-GHz home-built superheterodyne spectrometer was employed, and
detection was accomplished at the 30-MHz intermediate frequency by mixing the
main 9.3-GHz signal with that from a Gunn diode local oscillator. A digital signal
analyzer was employed to average signals obtained from repeated magnet scans.
A typical signal obtained from a zero field-cooled (ZFC) granular Y-Ba-Cu-O
at 5 K during a magnet scan from –2 mT to +2 mT is presented in Fig. 6.1 1. The
small shift of the minimum from zero is due to a small hysteresis of the magnet.
Cycling the applied field over a range of less than 2 mT caused the absorption curve
to repeat itself. However, if the applied field was increased above the critical field
Bcl , the absorption signal exhibited hysteresis, which was attributed to the penetra-
tion into and pinning of flux in the bulk of the sample. Subsequent low-field sweeps
Figure 6.9. Effect of orientation of the dc magnetic field with respect to Y-Ba-Cu-O film surface on
hysteresis of derivative signal at 77 K: parallel •
and perpendicular ( ) to the surface.
exhibited no hysteresis. When the sample was field cooled (FC), the minimum in
the absorption shifted to the value Bm in the direction of the cooling field in the
manner illustrated in Fig. 6.12. The observed shift in the minimum is proportional
to the cooling field up to BFC of about 40 mT, and above this value the curve levels
off in the manner illustrated in Fig. 6.13. Thus the trapped flux is proportional to
BFC for small cooling fields, and it saturates for high cooling fields.
To test the behavior of the remnant magnetization of the field-cooled samples,
the samples were reduced to zero field as before, rotated through an angle q relative
to the cooling field direction, and then scanned in the field. Figure 6.14 presents
absorption signals obtained for the rotation angles q = 0°, 90°, and 180°, and Fig.
6.15 shows how the minimum in the absorption curves, Bmin, has a cosine depend-
ence on the angle
B min(q) = Bm cos q (6.1)
The dependence of the absorption signal χ'' plotted in Figs. 6.1 1,6.12, and 6.14 on
the applied fieldB and the angle θ could be approximated by the following empirical
equation
122 CHAPTER 6
Figure 6.10. Low magnetic field multiline microwave absorption derivative signal obtained for a single
crystal of Y-Ba-Cu-O. (From Vichery et al., Ref. 15.)
(6.2)
where from Fig. 6.13 Bm ≈ 2 mT for BFC = 4 mT. The parameter x”0 establishes the
zero for the ordinate scale, and the factor A converts field values to susceptibility
units. The empirical constant B0 accounts for the rounding at the bottom of the
absorption curves on Figs. 6.1 1,6.12, and 6.14.
Figure 6.11.Direct microwave absorption signal for a zero field-cooled sample of granularY-Ba-Cu-O.
(From Pertile et al., Ref. 17.)
LOW MAGNETIC FIEL D-INDUCED MICRO WAVE A BSORPTlON 123
Figure 6.12. Direct microwave absorption signals of field-cooled granular Y-Ba-Cu-O scanned from
0 to 8 mT. Spectra are shown for field coolings carried out at BFC = 8, 10, and 12 mT, (From Pertile et
al., Ref. 17.)
Figure 6.13. Dependence of the field Bm for minimum absorption on the field cooling field B FC at the
temperature of 10 K. (From Pertile et al., Ref. 17.)
124 CHAPTER 6
Figure 6.14. Direct absorption spectra of Y-Ba-Cu-O taken after 2-mT field cooling and measured at
the angles q = 0°, 90°, and 180° relative to the field cooling direction. (From Mzoughi et al., Ref. 16.)
Figure 6.15. Angular dependence of the minimum field B min normalized relative to B min (0) = Bm on
the angle q relative to the field cooling direction for Y-Ba-Cu-O cooled in 2 mT to 5 K. The data fit a
plot of cos q. (From Mzoughi et al., Ref. 16.)
6.4. ORIGIN OF LOW MAGNETIC FIELD DERIVATIVE SIGNAL

6.4. 1. Loops and Josephson Junctions
Consider a small loop of superconducting wire with a cross-sectional area A
of 1 µm2 held at a temperature below Tc. If a dc magnetic field is applied
perpendicular to the loop, as shown in Fig. 6.16a, and slowly increased in magni-
tude, the magnetic flux F = BA through the loop will not increase continuously, but
will increase in quantum steps F0 in the manner shown in Fig. 6.16b, where
F0= h/2e is the quantum of flux. When the applied flux BA equals an integral
number of fluxons nF0, there is a jump in the flux F through the loop. This jump
takes place in a time Dt on the order of 10–12 s and produces a voltage
V = –dF/dt = –F0/Dt in the loop, which in turn produces a current. Because Dt is
small, the induced current will be large, and can exceed the critical current of the
superconductor. This will momentarily remove the superconducting state from the
loop and there will be a pulse of normal current. If microwave radiation were
incident on the loop as the dc magnetic field was increased, every time a flux jump
occurred the pulse of normal current would result in increased microwave absorp-
Figure 6.16. (a) Square current loop of area A equal to 1 µm2. (b) Flux passing through this loop as a
function of the applied dc magnetic field. (c) Surface resistance determined by microwave absorption
versus applied field for the same loop.
126 CHAPTER 6
tion. The LFMA spectrum as a function ofdc magnetic field would look like a series
of sharp lines, as shown in Fig. 6.16c. The separation between the lines would be F0/A
corresponding to the loop area
A = F0/DB (6.3)
Note the resemblance of this spectrum in Fig. 6.16c to that shown in Fig. 6.10
for a superconducting single crystal at low applied magnetic fields. This suggests
that micron-sized current loops with the areaA given by Eq. (6.3) may be the cause
of the absorption lines in Fig. 6.10. Setting DB = 7 µT and F0 = 2.07 mT(µm)2, we
obtain for the area of the loop
A = 300 (µm)2 (6.4)
which is a reasonable value. In order to understand how these loops can arise, it is
necessary to grasp the nature of a Josephson junction.
A Josephson junction consists of a thin insulating material, about 10 to 20 Å
thick, sandwiched between two superconducting metals, as sketched at the top of
Fig. 6.17. In many instances the insulating layer is a thin oxide coating on an
evaporated metal film. A voltage is applied to the junction and it is then cooled
below the transition temperature of the superconductor, When the voltage is turned
Figure 6.17. Illustration of Josephson junction (top) formed by insulating layer between two super-
conductors and (bottom) curtent-voltage characteristics of the junction.
off, it is observed that a dc current continues to flow through the junction as though
the sandwich were one continuous slab of superconductor. Cooper pairs pass readily
through the nonsuperconducting insulating layer without breaking up. The phe-
nomenon is the result of tunneling in which quantum mechanically there is some
probability that a Cooper pair can traverse the insulator even if its energy is less
than the barrier height between the superconductor and the insulator. The effect is
very pronounced in the superconducting sandwich because of the large wavelength
of the Cooper pairs, on the order of the thickness of the insulator, and the fact that
all pairs have the same wavelength and are in phase with each other. The bottom
part of Fig. 6.17 shows the current-voltage characteristics for the junction. No
current flows across the insulator until the applied voltage V is such that 2Ve is equal
to the superconducting gap of the superconductor.
Now consider a current loop formed by two Josephson junctions as shown in
Fig. 6.18. It turns out that the relative phase of the waves in the lower and upper
superconducting wires can be changed by the application of a magnetic field
perpendicular to the plane of the loop. Figure 6.19 shows how the current through
the junction is changed as the strength of this applied magnetic field is increased.
The points where there is no current are the points where the currents on each side
of the loop are a half wavelength out of phase. The current in a Josephson junction
is very sensitive to a small magnetic field, and magnetic field measuring devices
(i.e., magnetometers) have been designed based on this effect. They are called
SQUID magnetometers, the name being an acronym for superconducting quantum
interference device. Note that there is a maximum dc magnetic field, BJc2, above
which no current flows. For higher applied fields, the two superconductors are
decoupled.
Figure 6.18. Current loop containing by two Josephson junctions, each formed by an insulator
connecting two superconducting wires.
128 CHAPTER 6
Figure 6.19. Current flowing in Josephson junction loop of Fig. 6.18 as a function of dc magnetic field
applied perpendicular to the loop.
6.4.2. Absorption Mechanism

Consider a superconducting current loop enclosing an area A on the order of
1 µ 2 located in a perpendicular applied magnetic field, and assume that the loop
contains a Josephson junction. The current I flowing across the junction depends
on the relative phases Q1 and Q2 of the Cooper pairs on each side of the junction in
accordance with the expression:
(6.5)
When the applied field B0 is increased, the flux through the loop F = B0A increases
in discontinuous steps because of flux quantization in the superconducting state.
Thus as the field increases, flux jumps occur when BA = nF0. This in turn causes a
phase jump given by 2pF/F0. These jumps occur in a very short time, on the order
of 10–12 s, and produce voltage pulses given by
(6.6)
These jumps produce a current in excess of the critical current for the junction,
meaning that in effect they produce normal current flow. If microwaves are incident
on the loop, then there will be energy absorption by the normal current produced
by the flux jump.
Xia and Stroud (1 8) have calculated the derivative spectrum of the absorption
as a function of increasing field for this situation, and the result is shown in Fig.
6.20. The spectrum is a series of equally spaced sharp lines and the magnetic field
separation between adjacent lines is F0/A. If the magnetic field is rotated away
from the normal to the loop, the separation of the lines will change as F0/Acosa
where a is the angle between the field and the normal to the loop. The striking
similarity of the predicted spectrum to the sharp line spectra obtained in the single
crystals, as well as the observed angular dependence of the line separations,
indicates that flux jumping through superconducting loops is the likely cause of the
microwave absorption at low magnetic fields. The absorption only occurs at low
magnetic fields because of the low values of the upper critical field BJc2 for
Josephson junctions. In a composite of YBa2Cu3O7–x, the average BJc2 of the
junctions has been estimated to be about 6 mT at 77 K (19).
This mechanism is also the cause of the broad line observed in composite
samples where, instead of every loop having a single area and orientation, there is
a distribution of loop areas and orientations with respect to the applied magnetic
field. It has been shown that the shape of the derivative of the absorption as a
function of applied magnetic field can be accounted for by assuming that the
distribution of loop areas is determined by a Boltzmann function of the energy BAI
of a loop of area A carrying a current density I in a magnetic field B (20):
f =f0exp(–BAI/kBT) (6.7)
Figure 6.20. Calculated multiline microwave absorption derivative spectrum, dl/dH, for a 1 µm2
superconducting loop as a function of the strength of a dc magnetic field applied perpendicular to the
loop (from Xia and Stroud, Ref. 18).
130 CHAPTER 6
The line shape can be simulated by a sequence of narrow derivative lines centered
at each magnetic field of the sweep for each area A of the distribution that meets
the flux jump condition (6.3). The height of each derivative line is made propor-
tional to f. Figure 6.21 shows the simulated derivative signal in the
Bi1.5Pb.5Sr2Ca2Cu3O10 superconductor at 77 K. The temperature dependence of the
line intensity at a given field is proportional to both the current I flowing in the loop
and to the distribution function. Thus the intensity will depend on the temperature
as
I(T) exp[–BAI(T)/k BT] (6.8)
and close to Tc the current I(T) will vary with temperature as (Tc – T)1/2.
Although the model can account for the observed sharp line spectra in single
crystals, the broad line in composites, and the temperature dependence of the
intensity, nevertheless it does not account for other properties of the absorption,
such as the field and temperature dependence of its line width, position, and
hysteresis. These latter effects are believed to be manifestations of the flux trapping
behavior of the materials. The hysteresis of the field position of the center of the
derivative on the up- and down-sweep for a given applied field is a result of flux
being trapped in the sample. The difference in the field position for up- and
down-sweeps measures the remanent magnetic field in the sample. Thus the
hysteresis is a direct measure of the trapping of flux in the sample, and its value
will depend on whether the sample is cooled below Tc in a magnetic field or in a
zero field, being larger for field cooling. As shown in Fig. 6.5, the hysteresis
increases at a constant temperature with the magnitude of the maximum magnetic
field applied to the sample, but it eventually levels off or saturates for high fields.
•
Figure 6.21. Simulation (-------) and experimental data ( ) for half of the derivative of a microwave
absorption signal versus dc magnetic field for polycrystalline N= 3, Bi-Pb-Sr-Ca-Cu-O at 77K assuming
a Boltzmann distribution of loop areas as described in the text.
In some instances it increases to a maximum and then decreases, as shown in the

case of the thin films in Fig. 6.9. The upward shift of the magnetic field position of
the center of the line as a function of the size of the previously applied field at
constant temperature is also a result of flux trapping effects.The magnitude of the
upward shift for a given previously applied field has been shown to equal the size
of the hysterersis for a sweep up and back down to that field. One can use the
hysteresis and the upward shift of the line to measure Bc1 for the sample at a given
temperature. It is at the field Bc1 that the hysteresis or upward shift of the line is first
observed.
The broadening of the derivative as a function of a previously applied magnetic
field is not well understood, but is probably related to flux trapping. It is noted that
the broadening begins at the same magnetic field where the upward shift and
hysteresis first appear. The broadening may be aresult of a change in the distribution
of loop areas with trapped flux. Current loops formed by Josephson junctions have
upper critical magnetic fields BJc2 above which superconducting current cannot flow
in the loop. Since there is a distribution of loop areas, there will be a distribution
of critical fields. Magnetic fields associated with trapped flux may exceed the
critical fields of some of the junctions and drive those junctions normal, thereby
altering the distribution of Josephson loops.
The temperature dependence of the field position and the width and hysteresis
of the derivative reflect the temperature dependence of the ability of the sample to
trap flux. The temperature dependence of the magnetization of a Type II supercon-
ductor is given by (21)
M = Jc(kBT/EA) ln(t) (6.9)
where EA is an activation energy and t is the time. It has been shown that Jc/EA in
YBa2Cu3O7–x depends on the temperature as (1 – T/T c) (22). In measuring hyster-
esis, the experiment can be carried out so that the time to sweep up and back in a
field is constant for a sweep to a given magnetic field. Under these conditions the
temperature dependence of the hysteresis and the line shift should depend on the
temperature as T( 1 – T/T c). The time dependence of the hysteresis and the absorp-
tion intensity after the removal of a dc magnetic field are a result of flux decay,
which can be described by Eq. 6.9 (9).
The dependence of the magnitude of the hysteresis on the orientation of the dc
magnetic field in crystals and films is a reflection of the anisotropy of flux trapping,
The data in Fig. 6.9 indicate that more flux is trapped when the dc magnetic
field is parallel to the c-axis of the orthorhombic unit cell of Y-Ba-Cu-O than in
the ab plane orientation. This result is in agreement with magnetization meas-
urements in single crystals which show that the pinning barriers are larger in
the c direction (22).
132 CHAPTER 6
6.5. MAGNETIC FIELD ABSORPTION IN ALTERNATING APPLIED

FIELDS
A difficulty in studying the properties of low magnetic field absorption in the
derivative mode is that the imposed magnetic field modulation may also cause
microwave absorption in addition to that caused by the scanning dc magnetic field
and as will be shown, these absorptions are not independent. Figure 6.22 is a plot
of the intensity of the derivative signal versus the amplitude of the modulation in a
polycrystalline sample of YBa2Cu3O7–x showing quite different behavior from a
resonant signal. The presence of a discontinuity between curved and linear regions
is not understood. Figure 6.23 shows that the temperature dependence of the
absorption depends on the modulation amplitude, but it is not clear why there is
such a difference between the low and high modulation behaviors. An RF magnetic
field may induce absorption in a superconductor through a number of processes.
As discussed by Halbritter (23) in the context of the two-fluid model, there will be
resistive losses because some ac current is carried by nonpaired holes or electrons
that are present in the superconducting state. There can be dissipation due to
ac-induced flux oscillation, especially involving intergranular flux, and losses due
to the flux jump process discussed earlier.
Figure 6.22. Intensity of a microwave absorption derivative signal versus the amplitude of an ac applied
magnetic field at 85 K in a ceramic sample of Y-Ba-Cu-O (adapted from Blazey and Huhler, Ref. 11).
Figure 6.23. Temperature dependence of microwave absorption derivative signal in Y-Ba-Cu-O at a

low (- - - - - ) and at a high (––––) modulation amplitude (adapted from Blazey and Huhler, Ref. 11).
When the frequency of the ac magnetic field was increased from 25 kHz to
100 kHz, there was an increase in the 9.2-GHz microwave energy absorbed in the
superconducting state at 77 K, as shown in Fig. 6.24 for modulation amplitudes up
to 4 mT. This increase in absorption was only about 20% for an ac modulation
amplitude of 0.5 mT, whereas for ac amplitudes of 3 to 4 mT, the absorption at 100
kHz was twice that at 25 kHz. The data also showed that for both frequencies the
absorption intensity increased nonlinearly with the peak-to-peak amplitude of the
ac magnetic field. No dc magnetic field was present during this measurement.
The temperature dependence of this ac microwave absorption is shown in Fig.
6.25, measured at a constant amplitude and plotted as the difference in the absorp-
tion at zero ac field P(0) and that at an ac field of 2.5 mT peak-to-peak amplitude
P(Bac) in order to separate out the temperature dependence of the microwave
absorption in a zero magnetic field. This decrease in P(Bac) – P(0) with temperature
provides evidence for the nature of the mechanism giving rise to ac magnetic
field-induced absorption. A microwave absorption arising from intergranular flux
motion or normal carrier flow would increase as the temperature approached Tc
from below, not decrease as observed here. However, an absorption arising from
ac-field induced flux jumps through current loops formed by weak links decreases
134 CHAPTER 6
Figure 6.24. Microwave absorption intensity versus the magnetic field modulation amplitude in
polycrystalline Y-Ba-Cu-O at 77 K for 25 kHz (D) and 100 kHz modulation frequencies. The units
on the y-axis are arbitrary.
as the temperature approaches Tc from below, which is similar to the case of a slowly
increasing dc magnetic field, as discussed in the previous section. Consider a single
superconducting loop formed by a weak link and having its area A perpendicular
to the ac magnetic field. The current flowing in the loop depends on the relative
phase difference Dq of the waves of the Cooper pairs on each side of the link:
I = I0 sin DQ (6.10)
The ac magnetic field perpendicular to the loop causes time-dependent changes in

the relative phase given by
(6.11)
whereF(t) is the time-dependent flux through the loop due to the ac magnetic field,
ω is the frequency, F0 = h/2e is the quantum of flux, and B0 is the amplitude of the
ac field. Because the flux through the loop is quantized, there are phase jumps at
the instant the applied ac flux becomes an integral multiple of the quantum of flux.
The flux jumps occur in short times, on the order of 10–12 s, and produce voltage
pulses given by (see Eq. (6.6))
Figure 6.25. Temperature dependence of the difference between the microwave absorption signal at
2.5 mT peak-to-peak field modulation amplitude and the zero field absorption, P(Bac) – P(0). The
results are for polycrystalline Y-Ba-Cu-O at 77 K. The units on the y-axis are arbitrary.
(6.12)
These voltage pulses produce current pulses whose magnitude exceeds the critical
current of the loop formed by the weak link. In the ac field case, the flux jumps
repeat periodically, depending on the frequency of the ac field, with more jumps
per unit time at higher frequencies.
For each weak link there is a magnetic field BJc2 above which the link cannot
exist. The magnitude of BJc2 is temperature dependent, decreasing as the tempera-
ture approaches Tc from below. Thus at a given magnetic field, the number of
effective weak links decreases as the temperature increases, resulting in a decrease
in the microwave absorption with temperature.
Further evidence that the ac magnetic field-induced absorption is a result of
this mechanism comes from the effect of a small dc magnetic field on the ac
absorption. Figure 6.26 gives the results of such a measurement showing that the
difference in the microwave absorption, P(Bac) – P(0), decreases with increasing
136 CHAPTER 6
Figure 6.26. Dependence of the difference between the microwave absorption signal at 2.5 mT
peak-to-peak field modulation amplitude and the zero ac field absorption, P(Bac) – P(0), on an applied
dc field. The data are for polycrystalline Y-Ba-Cu-O at 77 K. The units on the y-axis are arbitrary.
dc magnetic field. The critical dc magnetic field BJc2 is related to the area of the
loop A by (24)
(6.13)
Because there is a distribution of loop areas, as the dc magnetic field is increased,

it exceeds an increasing number of effective critical fields for loops, and the number
of weak links is reduced. Thus the decrease in P(Bac) – P(0) with increasing dc
magnetic field is consistent with the ac field-induced absorption arising from flux
jumps in loops formed by weak links.
6.6. LOW MAGNETIC FIELD DERIVATIVE SIGNAL AS A

DETECTOR OF SUPERCONDUCTIVITY
The appearance and growth of the intense low dc magnetic field derivative
signal with the onset of superconductivity allows the use of an electron paramag-
LOW MAGNETlC FIELD-INDUCED MICROWAVE ABSORPTION 137
netic resonance spectrometer as a sensitive detector of the presence of supercon-

ductivity. It can be used to search for small fractions of a superconducting compo.
nent embedded in various types of fabricated materials, such as sintered pellets,
thin films, and crystals. It has been estimated that this method can detect supercon-
ducting fractions as small as 1 µg. It requires no physical contact with the sample
and is therefore particularly convenient for samples that must be maintained in
sealed tubes because of sensitivity to moisture or lack of stability in air. For
example, when the material A3C60 was first synthesized in bulk, it had to be stored
in a sealed tube under an overpressure of an inert gas to prevent the alkali substituent
from diffusing out of the material, and thus four-probe resistance measurements
were not feasible. The LFMA in conjunction with a susceptibility measurement of
the Meissner effect was used as evidence of superconductivity (25).
However, there are some pitfalls in using the LFMA signal as an indicator of
superconductivity. In Chap. 4 we saw that a low dc magnetic field derivative signal
can be obtained in a ferromagnetic material, and its intensity grows as the material
enters the ferromagnetic phase. There are, however, some very clear differences
between the LFh4A obtained from a superconductor and that from a ferromagnet.
In a ferromagnetic material, the signal intensity depends on the frequency as w1/2,
whereas in the superconductor it is independent of the frequency. The hysteretic
effect is another distinguishing feature. In the ferromagnetic case, the derivative
signal generally appears at a lower dc magnetic field when sweeping downward
from a given field than when sweeping upward. For a superconductor, the reverse
is true. Thus when a derivative microwave absorption signal is observed at a low
dc magnetic field, it is necessary to make sure that it is not arising from a
ferromagnetic phase. One clear way of distinguishing between these two possibili-
ties is to measure the direct surface resistance against temperature. In the ferromag-
netic case, it increases as the material is cooled below the transition temperature
and becomes ferromagnetic, while in the superconducting case, there is a decrease
upon cooling below the transition temperature Tc. An additional advantage is that
the low-field microwave absorption method is more sensitive than the direct surface
resistance method for detecting the presence of superconductivity.
References
1. K. W. Blazey, K. A. Müller, J. G. Bednorz, W. Berlinger, G. Amoretti, E. Buluggiu, A. Vera and
F. C. Matacotta, Phys. Rev. B36,7241 (1987).
2. D. Shaltiel, J. Genossar, A. Grayevesky, Z. H. Kalman, B. Fisher, and N. Kaplan, Solid State
Commun. 63, 987 (1987).
3. C. Rettori, D. Davidov, I. Belaish, and I. Felner, Phys. Rev. B36, 4028 (1987).
4. J. Stankowski, P. K. Kahol, N. S. Dalal, and J. S. Moodera, Phys. Rev. B36,7126 (1987).
5. R. Dumy, J. Hautala, S. Ducharme, B. Lee, 0. G. Symko, P. C. Taylor, D. J. Zheng, and J. A. Xu,
Phys. Rev. B36, 2361 (1987).
6. J. M. Delrieu, N. S. Sullivan, and K. Bechgaard, J. Physique C3,1033 (1983).
7. F. J. Owens, Synthetic Metals 33, 225, (1989).
138 CHAPTER 6
8. F. J. Owens, Phys. Status Solidi B162, 565 (1990).

9. F. J. Owens and Z. Iqbal, Physica C238, 171 (1990).
10. J. T. Suss, W. Berlinger, A. M. Portis, and K. A. Müller, Solid State Comm 71, 929 (1989).
11. K. W. Blazey and A. Huhler, Solid State Commun. 72, 119 (1989).
12. F. J. Owens (unpublished).
13. K. W. Blazey, A. M. Portis, K. A. Muller, J. G. Bednorz, and E Holtzbcrg, Physica C153, 56
(1988).
14. A. Dulcic, R. H. Crepeau, and J. H. Freed, Physica C160, 223 (1989).
15. H. Vichery, E Beuneu, and P. Lejay, Physica C159,823 (1989).
16. T. Mzoughi, H. A. Farach, E. Quagliata, M. A. Mesa, C. P. Poole, Jr., and R. J. Creswick, Phys.
Rev. B46,1130 (1992).
17. A. Pertile, O. A. Lopez, H. A. Farach, R. J. Creswick, and C. P. Poole, Jr., Phys. Rev. B52, 15475
(1995).
18. T. Xia and D. Stroud, Phys. Rev. 39, 4792 (1989).
19. A. D. Vedeshwar, Solid State Commun. 74 , 23 (1990).
20. F. J. Owens, Physica C171,25 (1990).
21. P. W. Anderson, Phys. Rev. Lett. 9,309 (1962).
22. Y. Yeshurun and A. P. Malozemoff,Phys. Rev. Letters 60, 2202 (1988).
23. J. Halbritter, Z Physik 266, 209 (1974).
24. M. Tinkham and C. J. Lobb, in Solid State Physics, H. Ehrenreich and D. Tumbull, eds. Vol. 42,
p. 91, Academic Press, New York(1989).
25. A. F. Hebard, M. J. Rosslinsky, R. C. Haddon, D. W. Murphy, S. H. Glarurn, T. T. M. Palstra, A.
P. Ramirez, and A. R. Korton, Nature 350,600 (1991).
7
Electromagnetic Absorption Due to

Vortex Motion
In this chapter the effect of vortex motion on the surface resistance in the supercon-
ducting state of the cuprates is discussed. It is shown how the nature of the vortex
dynamics affects electromagnetic dissipation by radio frequency and microwave
radiation.
7.1. THEORY OF ELECTROMAGNETIC ABSORPTlON DUE TO

VORTEX DISSIPATION
7.1.1, Penetrating Fields
The application of a dc magnetic field B0 perpendicular to the surface of a Type
II superconductor causes vortices F0 to form inside. The further application of an
RF or microwave field Hµ(t) parallel to the same surface induces via Eq. (4.14) an
oscillating surface current Ks(t) = n× Hµ, where n is a unit vector pointing outward
from the surface. Inside the surface there is an associated current density J(x, t), in
accordance with Eqs. (4.15) to (4.18), which exerts the Lorentz force F (t) = J ×
F0 on the vortices. Figure 7.1 shows the geometric arrangement of these vectors.
Since the force F(t) is perpendicular to the vortex axis, it sets the vortex into a
transverse oscillation that can propagate further into the material than the current
density J, in effect increasing the effective penetration depth. The transverse motion
will be retarded by a viscous damping force that dissipates energy and hence
contributes to RF and microwave absorption. Vortices that are pinned can oscillate
in their potential wells. The dynamics of the oscillation as well as the details of the
dependence of the surface resistance on the dc magnetic field depend in turn on the
vortex state—whether it is a solid or liquid; the transition from the solid to the liquid
state can be observed from these studies.
139
140 CHAPTER 7
Figure 7.1. Geometry used to model vortex-induced electromagnetic dissipation in superconductors.
7.1.2. Flux Creep, Flux Flow, and Irreversibility

At low temperatures the vortices remain fixed in position on the regular
two-dimensional hexagonal lattice sketched in Fig. 1.22a. This lattice state is
analogous to a two-dimensional solid configuration, and the pinning centers that
are present hold the vortices more strongly to their lattice sites. When the tempera-
ture is raised, the vortices undergo random thermal motions about their equilibrium
positions on the hexagonal lattice, and if the temperature is raised high enough, the
thermal energy will dominate and cause the vortex lattice to transform to a
two-dimensional liquid or fluid state characterized by continuous vortex motion.
This transformation is often referred to as a pinning-depinning transformution; the
flux solid phase is called the flux pinned state; and the flux liquid is called the flux
flow state. The transformation from the solid to the liquid phase can be brought
about by either raising the temperature or by increasing the strength of the applied
magnetic field.
The relationships between these phases are easily depicted on a plot of applied
field B0 versus temperature T called a magnetic phase diagram; a representative
diagram is depicted in Fig. 7.2. We see from the figure that there is a Meissner state
of perfect flux expulsion below the temperature-dependent lower critical field
Bc1(T), and the material becomes normal (nonsuperconducting) above the tempera-
ture-dependent upper critical field Bc2(T), The flux solid and flux liquid phases are
separated by the temperature-dependent depinning field B*( T), also called the
depinning line or flux melting line
flux melting line = B*(T) (7.1)

which plays an important role in explanations of microwave absorption in super-
conductors, and is indicated in Fig. 7.2. The same B* line can be considered as a
ELECTROMAGNETIC ABSORPTION DUE TO VORTEX MOTION 141
Figure 7.2. Magnetic phase diagram of a Type II superconductor showing the Meissner, flux solid, and
flux liquid phases, together with the lower critical field Bc1(T), the upper critical field B C2(T), and the
depinning temperature B*(T) lines that separate the phases. The values of the critical temperature Tc
and critical fields B c1 and B c2 at T = 0 are indicated.
field-dependent depinning temperature T*(B). In other words, a point on this line

at the particular position B', T' can be designated by the notation B*(T') or by the
notation T*(B').
When a transport current flows through a superconductor in the presence of a
magnetic field B0 applied perpendicular to the current direction, the vortices
experience the Lorentz force per unit length given by
F/L = J× F0 (7.2)
and if this force exceeds the pinning forces, then the vortices begin to move in a
direction perpendicular to both J and F0. When the pinning forces dominate, there
can be a very slow motion called flux creep, and when the Lorentz force (7.2)
dominates, there is a faster motion of the vortices called flux flow. The latter faster
motion is characteristic of the flux liquid phase. In a typical case there can be a
range of pinning strengths, and flux creep might occur when the Lorentz force
unpins some vortices and sets them in motion, but their motion is hindered by
encounters with others that remain in place at pinning sites. The situation can be
quite complicated to describe as successively higher fields unpin more and more
vortices.
Another factor to take into account is the magnetic field-dependent irre-
versibility temperature Tin. This is the temperature above which field-cooled and
zero field-cooled magnetization and susceptibility data superimpose, and below
which ZFC measurements lie below FC ones. A plot of the applied field dependence
of Tin(B0) is called the irreversibility line. The presence of irreversibility manifests
142 CHAPTER 7
itself in the appearance of hysteresis effects. In other words, the susceptibility,

magnetization, and other properties have values that depend on the previous
magnetic history of the sample, such as the order in which applied magnetic fields
and temperatures have been varied.
7.1.3. Coffey–Clem Model
Coffey and Clem (1) have developed a unified theory to explain the effect of
vortex oscillation on the surface impedance Zs of Type II superconductors. Their
model takes into account the effects of the flux pinned and the flux flow states. It
includes coupling of the supercurrent density to vortex displacements, dynamic flux
creep effects, and normal-like quasi-particle excitations. The result of their theory
is a complex penetration depth which is a function of the dc magnetic field, ac
frequency, and temperature. Fortunately, however, most of the measurements of the
dc magnetic field dependence of microwave absorption which have been made at
low fields near Tc can be accounted for by using the limiting cases of weak and
strong pinning in the Coffey–Clem model. Here we present a simplified version of
the theory that does not include all the effects mentioned above, but yields
expressions that correspond to weak and strong pinning limits, and in addition
provides some insight into the physics of the process.
The movement of vortices at the velocity v brought about by the time-depend-
ent microwave field Hµ(t) produces an electric field E(t, x) through the v × B0
interaction of the vortices with the applied dc magnetic field B0. The surface
impedance Zs is defined by Eq. (4.7) as the ratio of E(t, x) to Hµ(t, x) at the surface
where x = 0:
(7.3)
where Rs is the surface resistance and Xs is the surface reactance. The microwave
absorption is proportional to the surface resistance, which is the real part of Zs.
For the geometry of Fig. 7.1, the incident RF magnetic field Hµ(t) penetrates
exponentially into the superconductor in accordance with the expression
(7.4)
The microwave magnetic field amplitude Hµ , is assumed to be much smaller than

the dc applied field Hµ< < B0/µ0, and the penetration depth λ is assumed to be
greater than the spacing between vortices. The time-varying microwave field
produces a current in the y direction which can be obtained from Eq. (7.4) using
Maxwell's curl relation (1.7). ∇×H = J, yielding:
(7.5)
where µ0 is the permeability of free space. This current produces a time-varying

force J × F0 on the vortices in the z direction, as indicated in Fig. 7.1, given by
(7.6)
where F0 = h/2e is the quantum of flux. The movement of the vortices along z is
described as an oscillation at their pinning sites in apotential having a force constant
K, or as a flow in the liquid phase having a viscosity h . The governing equation of
motion for the position z of an individual vortex in both the liquid and the solid
phases is then
(7.7)
Assuming a solution of the form,
(7.8)
and substituting into Eq. (7.7) to evaluate the constant z0, we obtain for the vortex
velocity
(7.9)
The surface impedance can be evaluated from Eqs. (7.3), (7.4), and (7.9),
noting from Fig. 7.1 and Eq. (7.3) that E is perpendicular to both v and B0, which
gives the magnitude E = |v × B0| = vB0, so the surface impedance has the form
(7.10)
The surface resistance is the real part of Zs , giving
(7.11)
In this model the penetration depth of the microwaves l depends on whether

the superconductor is in the creep or flow region. Campbell (2) has shown that in
the creep region l is given bv
(creep region) (7.12)
and since in this region K2 >> h2w2, the surface resistance is

144 CHAPTER 7
In the vortex liquid state where h2w2 >> K2, the penetration depth has been shown
to be (3)
(flow region) (7.14)
to give for the surface resistance
Thus the theory predicts that in the creep and flow regions of the vortex state, the
microwave absorption increases as B01/2 but has a different slope in each region as
well as a different frequency dependence. The model also predicts that the tempera-
ture dependence of the absorption will be different in each region. In the flux creep
region, the temperature dependence of Eq. (7.13) will be via h/K3/2. Taking the
temperature dependence of h as given by (1–T/T c) and that of K as
[ 1 – (T/Tc)2]2 leads to the following temperature dependence of Rs (1)
In the flux flow region, the temperature dependence is through h, which is given
by (1 – T/T c), meaning that the surface resistance (7.15) will depend on Tas
Figure 7.3. Magnetic field dependence of surface resistance (log scale) versus reduced temperature at
1.5 T for Y-Ba-Cu-O calculated from the Coffey–Clem model (Ref. 1). Curve a is with no magnetic
field present; curve b has vortices present but there is no motion; and curve c allows flux creep and flux
flow.
Thus the theory predicts that the temperature, frequency, and dc magnetic field
dependencies of vortex-induced electromagnetic dissipation will be different in the
vortex fluid and vortex solid phases, and therefore it should be possible to observe
the vortex solid-to-liquid transition through surface resistance measurements.
Experimental verification of these predictions is discussed in the following sections.
The complete Coffey–Clem model, which includes the local supercurrent
density modifications arising from vortex displacements, does not yield simple
analytical expressions relating surface resistance to dc magnetic field and tempera-
ture such as Eqs. (7.11), (7.13), and (7.15) to (7.17). However, it is possible to
calculate the surface resistance for a specific set of material parameters. Figure 7.3
gives the surface resistance versus reduced temperature at an applied field of 1.5 T
for parameters appropriate to Y-Ba-Cu-O (1). The curve labeled a is for zero dc
magnetic field; curve b has vortices present but not flux creep; and curve c has
vortices that are undergoing flux creep and flux flow.
7.2. EXPERIMENTAL RESULTS

7.2.1. RF Penetration Depth Measurements
In the region of applied dc magnetic field and temperature where the vortices
are pinned, the dependence of the penetration depth on the field is given by Eq.
(7.12). In the liquid vortex state where the vortices are not pinned, the dependence
of the penetration depth on field and frequency is given by Eq. (7.14). Thus the
transition between the flow and pinned regimes should be manifested by a change
in the slope of a plot of the penetration depth versus B01/2 when the applied field
B0 equals the depinning field B* at that temperature. Equations (7.12) and (7.14)
also predict that the frequency dependence of the penetration depth should be
different in each phase, being independent of frequency in the pinned regime but
having a 1/w1/2 dependence in the flow regime.
Wu and Sridhar (4) reported the first magnetic field-dependent studies of the
penetration depth in a cuprate for dc magnetic fields up to 0.1 T using single crystals
ofYBa2Cu3Oy. Representative results are presented in Fig. 7.4 for the magnetic field
parallel to the c-axis at 9.7 K. Notice that Dl = 0 in the Meissner state until the
critical field Bcl(||)is reached at 10 mT (100 G). The break at the lower critical field
Bc1 is sharp, and provides a much clearer signature of this critical field than
magnetization measurements. A measurement of the field dependence of the
penetration depth at a number of different temperatures allows a determination of
the temperature dependence of the lower critical field, which was found to follow
the BCS prediction. The measured field dependence at constant temperature was
consistent with Eq. (7.12), and the temperature dependence of the pinning force
146 CHAPTER 7
Figure 7.4. Change in penetration depth Dl versus magnetic field for a single crystal of Y-Ba-Cu-O at
9.7 K for the applied field parallel to the c-axis (from Wu and Sridhar, Ref. 4).
constant was shown to be [(1 – (T/T c)2]2. The measurements were not made at a
high enough dc magnetic field or temperature to observe the predicted cross-over
to the liquid vortex state.
The first observation of the melting of the vortex lattice in a cuprate determined
from the dc magnetic field dependence of the penetration depth was in a Bi-Pb-Sr-
Ca-Cu-O superconductor in which the transition occurs at lower magnetic fields
than in Y-Ba-Cu-O (5). Figure 7.5 is a plot of the frequency shift Df from 7.9903
MHz versus a dc magnetic field at 77 K in the superconductor Bi-Pb-Sr-Ca-Cu-O.
We know from E2q. (3.3) that Df/f0 is proportional to the change A1 in the RF
penetration depth; hence the scale for Dl added to the right side of Fig. 7.5. Figure
7.6 is a plot of the frequency shift versus B01/2 at two frequencies in the megahertz
range at 77 K in Bi-Pb-Sr-Ca-Cu-O. The data show that the penetration depth
depends on B01/2 and that there is a change in slope at the depinning field B* which
marks the transition from the pinned to the depinned phase of the vortices.
Equations (7.12) and (7.14) indicate that the slope of the dependence of the
penetration depth on B01/2 in the flux flow regime should be larger than in the pinned
region, contrary to the experimental results in Fig. 7.6. The reason for this discrep-
ancy is not clear, but perhaps is associated with increased misalignment of vortices
from the direction of the applied dc magnetic field in the fluid vortex phase, which
Figure 7.5. Shift of frequency Df in LC coil experiment versus dc magnetic field at 77 K in

superconducting Bi-Pb-Sr-Ca-Cu-O.
would have the effect of lowering the dissipation. This conclusion is supported by
other work which demonstrates that there is some dissipation even when the RF
current is parallel to the dc magnetic field (6).
The frequency dependence of the dc magnetic field-dependent penetration
depth in the pinned region can be determined by measuring the slope of Df/f0 versus
B1/2 for different frequencies f0 below the depinning field B*. The measurement
shows the penetration depth to be independent of frequency, which is in agreement
with Eq. (7.12). However, the same measurement above B* shows that the penetra-
tion depth decreases as the frequency increases, as predicted by Eq. (7.14), but the
studies have not been detailed enough to quantitatively verify the 1/w1/2 dependence.
Figure7.7 shows how the slope of Df/f0 versus DB1/2 above B* shifts to lower values
at higher frequencies. Figure 7.8 shows how the depinning field B* decreases in
value when the frequency increases. This result is in agreement with theoretical
predictions of the frequency dependence of the irreversibility line. Experimental
measurements of the irreversibility temperature Tirr in Bi-Sr-Ca-Cu-O at constant
dc magnetic field show that Tirr increases with increasing frequency (7,8). Since B*
and Tirr are related by the equation (7)
148 CHAPTER 7
Figure 7.6. Frequency shift Dfin LC coil versus square root of applied dc magnetic field at 7.99 MHz
•
and 4.343 MHz ( ) in Bi-Pb-Sr-Ca-Cu-O at 77 K. Each vertical arrow indicates the change in slope
at the field B*.
(7.18)
where A and the exponent q are constants, the field B* would be expected to decrease
with increasing frequency, as observed.
7.2.2. Microwave Bridge Measurements

We have seen that in the superconducting state the application of a dc magnetic
field increases the surface resistance of the sample, and this is shown in Fig. 7.9 for
Hg0.7Pb0.3Ba2Ca2Cu3O8+x (9). The theoretical treatments of the dc field-enhanced
surface resistance due to vortex oscillation discussed earlier show that the surface
resistance depends linearly on B01/2 in both the strong and the weak pinning regimes,
but the slope is different in each region. In Fig. 7.10 the microwave absorption is
plotted versus B01/2 at 77 K for both an increasing and decreasing dc magnetic field.
The data show that the microwave absorption depends linearly on B01/2 and that there
is achange of slope at the depinning field B*. On the downsweep ofthe dc magnetic
field, there is an onset of hysteresis in the data starting at B*, clearly demonstrating
that B* corresponds to the irreversibility transition. Below B*, flux is more strongly
pinned in the sample, while above it, the vortices are more free to move. Similar
Figure 7.7. Frequency dependence of slope of the frequency shift Df/f0 versus (DB)1/2 above B* at 77
K in Bi-Pb-Sr-Ca-Cu-O.
Figure 7.8. Plot of frequency dependence of B *, the dc magnetic field at which the transition from the
pinned to the depinned vortex fluid phase occurs.
150 CHAPTER 7
Figure 7.9. Dependence of the surface resistance R s at 9.2 GHz on the dc magnetic field at 122 K in
the N = 3, Hg-Pb-Ba-Ca-Cu-O superconductor.
results have been obtained in other copper oxide superconductors such as the
T1-Ba-Ca-Cu-O and Bi-Sr-Ca-Cu-O types (10,11).
Figure 7.11 is a plot of the surface resistance versus B01/2 at two different
temperatures showing the change in slope, which shifts to a lower field value at the
higher temperature. A measurement of the field dependence of the microwave
absorption at a number of different temperatures allows a determination of the
temperature dependence of B* and thus provides a plot of the B-Tirreversibility line
at 9.2 GHz. This irreversibility line furnishes the temperature at which the vortex
lattice melts for each applied field. Figure 7.12 is a plot of B* versus (1 – T/T c), and
the line through the data is a fit to Eq. (7.18) with A = 367 mT, the exponent q =
0.724, and Tirr set equal to T to make the plot.
Generally the irreversibility line determined from the field dependence of the
surface resistance gives a smaller B-T reversible region than a determination by
bulk techniques such as magnetic susceptibility. This may occur because in the
surface resistance determination, the electromagnetic energy is only probing the
surface regions of the sample where the defect structure may not reflect the situation
in the bulk. Pinning is known to be strongly dependent on the character and number
of defects in a sample. It also has been pointed out that the measurement of the B-T
Figure 7.10. Change in the surface resistance versus the square root of the dc magnetic field at 77 K
for increasing and decreasing (O) magnetic field showing that the onset of irreversibility occurs at
the field B* where the slope changes. The data are for the N = 3, Hg-Ba-Ca-Cu-O superconductor.
irreversibility line depends on the frequency of the probing radiation, which would
mean that ac and dc susceptibility measurements of the B-T line would yield
different results (7,8).
There are some variations in the behavior of the dc field dependence of the
dissipation in different superconductors. In the TI-Ba-Ca-Cu-O and Bi-Sr-Ca-Cu-O
materials, the dependence of the surface resistance on the dc magnetic field is
weaker in the flux flow state, in contrast to the Hg0.7Pb0.3Ba2Ca2Cu3O8+x material,
and is not in agreement with the prediction of the theoretical model (10,11). As in
the case of the RF penetration depth measurements discussed earlier, this could be
due to increased misalignment of vortices in the fluid phase in these materials, but
further studies are needed to clarify the issue.
Measurements of magnetoelectromagnetic absorption on single crystals allow
investigation of the anisotropy of the dissipation. In single crystals of
Bi2Sr2CaCu2O8+x , for example, magnetic field-induced electromagnetic absorption
is observed to be larger when the dc magnetic field is parallel to the c-axis of the
unit cell, i.e., perpendicular to the copper oxide planes (12). This is consistent with
152 CHAPTER 7
Figure 7.11. Change in surface resistance versus square root of dc magnetic field at 97 K and at 91
K (O) for the N = 3, Hg-Pb-Ba-Ca-Cu-O superconductor. These results show that the magnetic field
B* where the slope changes, indicated by vertical bars, depends on the temperature.
magnetic field-dependent resistivity data which show lower pinning barriers to flux
motion when the field is parallel to the c-axis.
While the plots of the microwave absorption versus B01/2 shown in Fig. 7.1 1
appear to suggest that the depinning transition is first order, detailed studies of the
dc magnetic field dependence of the surface resistance at small field intervals in the
transition region reveal a deviation from the B01/2 dependence. Figure 7.13 shows
the results of such a study at constant temperature in the Bi-Sr-Ca-Cu-O supercon-
ductor, revealing the existence of anomalous behavior at the transition. The three
points at the beginning and the three points at the end of the curve provide the slopes
below and above the transition, respectively. The curvature in between is not
resolved on broader scans of the type presented in Fig. 7.1 1. This anomaly has been
attributed to a magnetic field-dependent distribution of pinning barriers in the
material, and the existence of a critical depinning barrier U* (13). Those vortices
arriving at sites having barriers less than U* at a given temperature will be in the
fluid phase, while those with barriers greater than U* will be in the solid phase. The
possibility of a distribution of pinning barriers has been indicated by a number of
experiments, such as magnetic relaxation studies (14). A distribution of critical
Figure 7.12. The temperature dependence of the irreversibility field at 9.2 GHz for the superconductor
N = 3, Hg-Pb-Ba-Ca-Cu-O. The ordinate is the magnetic field B* for the crossover between reversible
and irreversible behavior.
pinning barriers U*, could account for the anomaly shown in Fig. 7.13 at the
depinning transition.
7.2.3. Strip Line Resonator Measurements

The stripline resonator method enables surface resistance determinations at
much higher frequencies and over a broader range of frequencies than the RF
oscillator method. However, since the stripline of the resonator is deposited as a
thin film, the measurements can only be made on films. Figure 7.14 illustrates a
measurement of the dc magnetic field dependence of the surface resistance in
YBa2Cu3Ox strips at 4.3 K and 13.8 GHz (15). The data, which were taken at much
higher magnetic fields than previous measurements, show a nearly linear depend-
ence of the surface resistance on the dc magnetic field strength. A measurement at
1.24 GHz gives a weaker dependence, with Rs varying with the applied field
approximately as B00 8. These results are not in agreement with the predictions of the
theory for the strong pinning limit that might be expected to be applicable at 4.3 K
in this material. It is possible that the disagreement is aresult of the field dependence
of the pinning force constant K, which may be more in evidence at higher magnetic
field measurements of these studies. From Eq. (7.1 1) a linear dependence of the
surface resistance on dc magnetic field would imply that the force constant depends
154 CHAPTER 7
Figure 7.13. Plot of surface resistance versus applied B1/2 measured at very small field intervals in the
depinning transition region of single crystals of Bi-Sr-Ca-Cu-O at 77 K, showing the deviation from a
B1/2 dependence on the applied field in this region.
Figure 7.14. Surface resistance versus dc magnetic field at 4.3 K and 13.8 GHz in Y-Ba-Cu-O films
(from Revenaz et al., Ref. 15).
Figure 7.15. Frequency dependence of surface resistance of Y-Ba-Cu-O films at 4.3 K measured in
•
zero dc magnetic field ( ) and a 3.5 T field. (O) (from Revenaz et al., Ref. 15).
on the field as B0–1/3. Another possibility is that at the higher magnetic field strengths,
where the vortex density is greater, the vortex–vortex interactions affect the
dynamics. The simple theory outlined at the beginning of this chapter does not take
this into account.
Figure 7.16. Temperature dependence of the surface resistance in film strips measured at different
magnetic field strengths of 0.5 T, 1 T, and 3 T (from Revenaz et al., Ref. 15).
156 CHAPTER 7
Figure 7.15 presents a measurement of the frequency dependence of the

surface resistance in a zero dc magnetic field and in a field of 3.5 T at 4.3 K. In such
a dc field at 4.3 K, the material is likely to be in the pinned state, and therefore the
contribution of vortex dissipation to the surface resistance obtained by the differ-
ence between Rs at B = 0 and Rs at B = 3.5 T at a given frequency should increase
with frequency, as predicted by Eq. 7.13. Although there is considerable scatter the
data seem to show that the two lines converge, suggesting that there is a frequency
decrease. Figure 7.16 is a plot of the surface resistance at 1.46 GHz versus
temperature measured at three different magnetic field strengths (15). The data
show a change in the dependence of Rs on temperature from a weak somewhat linear
behavior at low temperature to a much stronger dependence at higher temperatures.
The crossover region shifts to a lower temperature at higher magnetic fields,
suggesting that it may be associated with the vortex solid-to-liquid transition.
However, further quantitative analysis of the data and perhaps additional measure-
ments would be needed to verify this,
7.3. CONCLUDING REMARKS

Measurements of the dc magnetic field dependence of the surface resistance
in the superconducting state can provide useful information about the flux pinning
behavior of superconductors, particularly in the surface regions of materials. In the
case of thin films, the method should provide a way to characterize their properties,
and because the film thickness can be compared with the penetration depth of the
radio frequency, the results may be comparable to bulk measurements. Most of the
dc magnetic field-dependent measurements of the surface resistance have been
made at relatively low dc fields near Tc using either the LC coil or the microwave
cavity method. The results can generally be accounted for by the Coffey–Clem
model in the weak and strong pinning limits, which predicts that Rs has the applied
field dependence B01/2. There is therefore a need for further work at higher dc
magnetic fields where the density of the vortices is higher and vortex–vortex
interactions may play a role in determining the dynamics.
The stripline resonator measurements, which are limited to thin films and have
generally been carried out at higher dc magnetic fields, show some agreement and
some disagreement with the theory. There is a need for a more quantitative
comparison between theory and experiment at higher magnetic fields.
References
1. M. W. Coffey and J. R. Clem, Phys. Rev. Lett. 67, 386 (1991).
2. A. M. Campbell, J. Plays. C2, 1492 (1969).
3. W. Tomasch, H. A. Blackstead, S. T. Roggiero, P. J. McGinn, J. R. Clem, K. Shen, J. W. Weber,
and D. Boyne, Phys. Rev. B37, 9864 (1988).
4. D. Wu and S. Sridhar, Phys. Rev. Lett. 65, 2074 (1990).
5. F. J. Owens, Solid State Commun. 81, 97 (1992).

6. E. K. Moser, W. Tomasch, P. J. McGinn, and J. Z. Liu, Physica C176, 235 (1991).
7. A. P. Malozemoff, T. K. Worthington, Y Yeshurun, F. Holtzbergmand P. H. Kes, Phys. Rev. B38,
7203 (1988).
8. Y.Yeshurun,A.P.Malozemoff,T.K.Worthington,M.Yandropski,L.Krvsin-Elbank,F.Holtzberg,
T. R. Dinger, and G. V. Chandrashekar, Cryogenics 29, 258 (1989).
9. E J. Owens, A. G. Rinzler, and Z. Iqbal, Physica C233, 30 (1994).
10. F. J. Owens, Physica C178, 456 (1991).
11. F. J. Owens, Physica C195, 225 (1992).
12. F. J. Owens, Z. Iqbal, and E. Wolf, J. Phys. Condens. Matter 4, 205 (1992).
13. F. J. Owens, J. Phys. Chem. Solids 55, 167 (1994).
14. M. Reissner and W. Steiner, Supercond. Science Techn. 5, S367 (1992).
15. S. Revenaz, D. E. Oaks, D. Labbe-Lavigine, G. Dresselhaus, and M. S. Dresselhaus, Phys. Rev.
B50, 1178 (1994).
8
Infrared and Optical Absorption
The preceding few chapters have been concerned mainly with microwave absorp-
tion and to a lesser extent with radiofrequency absorption. In this chapter the
frequency range is extended to the infrared, visible, and ultraviolet (UV) (1). In this
region the absorption is explained in terms of the imaginary part of the dielectric
constant, and the Kramers–Kronig technique is useful for the data analysis. From
a spectroscopic viewpoint, infrared absorption is concerned with vibrational tran-
sitions and normal modes. In addition, the energy gaps of high-temperature super-
conductors are in the infrared region, so infrared absorption in the neighborhood
of the gap energy Eg = 2D
hv = Eg (8.1)
can give us information on these gaps.
8.1. ABSORPTION IN THE INFRARED

When the intensity of light I0 is incident on a sample, it is partly transmitted,
It, and partly reflected, It, so the amount Ia that is absorbed is given by
Ia = I0 – Ir – It (8.2)
as shown in Fig. 8.1. Transmission spectrometers measure It, generally when Ir is

small, while reflectance spectrometers measure Ir, generally when It is small. Either
way, the spectrometer provides the frequency dependence of the ratio Ia/I0, and a
maximum in Ia indicates the center of an absorption line. In a single-beam meas-
urement, the absorption Ia itself is determined, and with a double-beam technique,
the absorption of a sample is measured relative to that of a reference material.
Superconductors tend to be opaque at infrared and visible frequencies, so reflec-
tance techniques apply. The reflection Ir is measured and the absorption Ia is
159
160 CHAPTER 8
Figure 8.1. Absorbed (Ia), transmitted (It), and reflected (Ir) components of incident light beam of
intensity I0
deduced from Eq. (8.2) by assuming It = 0. At higher frequencies, in the X-ray

region, the radiation can penetrate and transmission detection of It is generally
employed.
Infrared spectroscopists report their results in several different energy units,
and if we had standardized this chapter by, for example, converting all energies to
joules, it would be difficult to compare the results presented here with those found
in the literature. The appropriate conversion factors are
100 cm–1 = 0.0124 eV = 3 THz (8.3)

where the velocity of light c = 2.9979 × 1010 cm/s is the conversion factor between
reciprocal centimeters and hertz.
8.2. DETECTING MOLECULAR AND CRYSTAL VIBRATIONS

Thermal energy causes atoms in molecules and solids to vibrate about their
equilibrium positions, and the frequencies of the normal modes of vibration are
ordinarily in the infrared region (2,3). These normal modes involve coherent
oscillations of atoms in the unit cell relative to each other at a characteristic
frequency with the center of gravity preserved. They have a maximum frequency
vmax that may be estimated by equating the energy hvmax with the Debye energy
kBQD
(8.4)
where QD is the Debye temperature, or vmax may be estimated from the well-known
formulal minvmax = vs, which provides the expression
(8.5)
INFRARED AND OPTICAL ABSORPTION 161
where vs is the velocity of sound in the material, and the distance a between atoms
is related to the shortest vibrational wavelength through a ≈ lmin/2. Incident infra-
red radiation can induce transitions between these vibrational states. These transi-
tions typically fall in or near the range 1012 to 1013 Hz, which is within the frequency
band of infrared spectrometers.
In infrared spectroscopy, an IR photon hv is absorbed directly to induce the
vibrational transition (1), while in the case of Raman spectroscopy, an incident
optical photon of frequency hvinc is absorbed and another optical photon hvemit is
emitted, with the energy of the n = 1 vibrational level hv related by the difference
(8.6)
where vinc > vemit for what is called a Stokes line and vinc < vemit for an anti-stokes
line. The wavelength of hvemit is measured by the Raman spectrometer. The
fundamental vibrational energy levels have the energies
(8.7)
where the vibrational quantum number nv = 0, 1,2,3, . . , is a positive integer, and

v0 is the characteristic frequency for aparticular vibrational mode. Transitions occur
for the condition
(8.8)
and the lowest frequency transition with n’v = nv = 1 is called a fundamental band.
The frequency v of the radiation that induces the transition of Eq. (8.8) can come
either directly from an incident infrared photon hv, or in the Raman case, indirectly
from an optical photon hvinc, which induces a transition upward to a virtual level
followed by the emission of another optical photon hvemit due to a downward
transition to the final vibrational level n’v.
Infrared spectral lines are caused by a change in the electric dipole moment
µD
µD = dq (8.9)
of the molecule where q is the charge and d is the charge separation. Raman lines
appear when the incoming radiation field brings about a change in the polarizability
P, which is defined as the ratio of the induced dipole moment µ ind to the electric
field E of the incident radiation.
(8.10)
162 CHAPTER 8
Figure 8.2a. Raman spectra of twin free YBa2Cu3O7 recorded with the laser beam directed along the
c-axis and the indicated polarizations. The x-axis is the baseline for the lower spectrum, and the dashed
lines indicate the baselines of the three upper spectra. (From McCarty et al., Ref. 4.)
These measurement techniques are complementary because some vibrational tran-

sitions are IR active and some are Raman active, meaning that some of them can
be detected by direct infrared absorption and others only by the Raman process.
In conventional Raman spectroscopy, an incident unpolarized laser beam
simultaneously excites many Raman active modes. Polarized light enhances some
of these modes and diminishes or eliminates others, and a variety of directions and
polarizations can be employed to sort out and identify the modes, as illustrated by
the data for twin free YBa2Cu3O7 presented in Fig. 8.2 (4). This occurs because the
selection rules for the transition are affected by the symmetry of the molecule or
by the symmetry of the unit cell of the lattice. Isotopic substitutions are helpful for
identifying modes, such as enrichments with the abundant isotope 65Cu and the rare
isotope 18O at particular lattice sites.
Figure 8.2b. Raman spectra of twin free YBa2Cu3O7 recorded with the laser beam propagating in the
x,y plane. Note the scale factor change for the two middle spectra. (From McCarty et al., Ref. 4.)
8.3. SOFT MODES

A second-order structural phase transition is one in which the low- and
high-temperature crystal structures differ by only small lattice displacements, with
no abrupt change in configuration taking place. In many cases the order parameter
changes gradually with the temperature, and exhibits the behavior (Tc – T)1/2 in the
neighborhood of the transition temperature Tc. The force constant can become zero
at Tc for one of the modes of vibration called a soft mode, and for this mode the
frequency also ideally drops to zero at Tc. Most vibrational modes increase in
frequency as the temperature is lowered, so soft modes can be identified by a
decrease in frequency as the temperature is lowered at the approach to Tc from
below. Well below the transition, the frequency begins to increase again, and
sometimes there is a split into two modes because of a lowering of the lattice
symmetry below Tc . The phase transition from the normal to the superconducting
164 CHAPTER 8
Figure 8.2c. Raman spectra of twin free YBa2Cu3O7 recorded with the laser beam directed along the
c-axis, and the indicated polarizations selected to enhance different modes than Fig. 8.2a. Note the scale
factor change for the lower Ag mode spectrum. (From McCarty et al., Ref. 4.)
state is second order in zero field and first order in the presence of a magnetic field.
In the former case there is no latent heat; in the latter case there is a latent heat; and
both cases exhibit a discontinuity in the specific heat. This superconductivity phase
transition can involve a change in crystal structure in which individual atoms
undergo very small shifts in position.
8.4. DIELECTRIC CONSTANT AND CONDUCTIVITY

We saw in previous chapters that electrical conductivity plays a crucial role in
determining the characteristics of microwave absorption in superconductors, and
the same can be said for infrared absorption. This is because, as we show in the next
section, the reflectance of light arises from the dielectric constant ε, which has real
and imaginary parts, e' and e", respectively
lNFRARED AND OPTICAL ABSORPTION 165
(8.11)
and the imaginary part e" depends on the conductivity s. To see this for a conductor,
we write the definition of the electric flux density D assuming a high enough
frequency so vibrational effects on the dielectric constant can be neglected, i.e.,
assuming e = e0
D = e0E (8.12)
and we substitute this and Ohm’s law
J= sE (8.13)
into the inhomogeneous Maxwell curl equation
(8.14)
for the case of a harmonic time dependence exp(iw t) to obtain
(8.15)
Comparing this with Eq. (8.11) provides us with the identification
(8.16)
8.5. REFLECTIVITY
The reflectance or reflectivity R is the fraction of light reflected from the
sample
R = Ir/I0, (8.17)
At frequencies where there are no absorption bands, the dielectric constant e = e'
is real, and for this case the reflectance at normal incidence is given by
(8.18)
an expression that is easily solved for e'. For oblique incidence, the reflectivity
depends on the angle. If we assume that the same expression applies to the case of
a complex dielectric constant, we obtain
166 CHAPTER 8
(8.19)
in which the square root factor (ε' + iε")1/2 may be written
(8.20)
with d defined through what is called the loss tangent
(8.21)
This means that different choices of e' and e" give the same value of R, so e’(w)
and e"(w) are not uniquely determined by measurements of the reflectivity. The
next section describes a way to resolve this dilemma.
8.6. KRAMERS–KRONIG ANALYSlS

A method called Kramers–Kronig analysis has been developed to obtain the
conductivity from reflectivity measurements. It is based on the fact that the
frequency-dependent quantities e' (w) and e"(w) are not independent of each other,
but are linked together through the Kramers–Kronig relations
(8.22a)
(8.22b)
where the integration is carried out over w'. With the aid of these expressions, the
frequency dependence of e'(w) and e"(w) can be extracted from measurements of
the reflectivity.
8.7. DRUDE EXPANSlON

It is often possible to fit the frequency-dependent complex dielectric constant
e(w) determined by a Kramers–Kronig analysis to an expression containing Drude-
like terms as follows
(8.23)
where fi is the oscillator strength and the relaxation times ti are responsible for the
broadening of the resonances. This expression can be written in terms of its real
and imaginary parts
(8.24)
where the factors A'i and A"i are real with the following frequency dependencies
(8.25a)
(8.25b)
For the usual limit of narrow lines, witi >> 1, these expressions simplify to
(8.26a)
and
(8.26b)
Figure 8.3. Normalized line shape of the dielectric constant e = e' + iε" showing the real part ε' called
dispersion, which is antisymmetric and passes through zero in the center where w = wi and the imaginary
part e" called absorption, which reaches a maximum at w= w i.
168 CHAPTER8
Figure 8.4. Infrared spectrum of an Nd2CuO4 single crystal at 10 K showing (a) reflectance and (b)
the imaginary part of the dielectric constant e" obtained from a Kramers–Kronig analysis using the
value e∞ = 6.8. (From Crawford et al., Ref. 5).
corresponding to Lorentzian line shapes. The sketches of these functions in Fig. 8.3
show that the real (A'i, dispersion) and imaginary (A"i , absorption) parts produce
resonant lines centered at wi.
The limiting dielectric constant for large w, denoted by e∞ in Eq. (8.23), is
obtained from a fit to the data, so it is a limiting value for the range of frequencies
under investigation, rather than the ultimate limit e0 of free space. The summation
terms of Eq. 8.23 are Lorentz oscillator types that account for features arising, for
example, from rotational, vibrational, or electronic processes.
Many experimentalists measure the infrared reflectivity and then report their
results asplots of e" = Im[ε(ω)] versus the frequency, while others present plots of
the high-frequency conductivity s = we" versus the frequency. We see from a
comparison of Figs. 8.4a and 8.4b (5) that e" plots (as well as s plots) are superior
to reflectance plots for the determination of the positions wi and widths 1/ti of
individual absorption lines arising from the summation terms of Eq. (8.24). This is
because the reflectance plotted in Fig. 8.4a is a mixture of absorption and dispersion
and hence it cannot provide the resonant frequencies wi with any precision. Some
review articles are available on infrared (6,7) and Raman (8.10) spectroscopic
studies of superconductors.
8.8. PLASMA OSCILLATIONS

At very high frequencies, the conduction electrons of a metal act like a plasma,
that is, an electrically neutral ionized gas in which the negative charges are mobile
electrons and the positive charges are the background lattice of cations. When the
frequency of an incident electromagnetic wave is much higher than the frequencies
w i of all the Drude terms of the summation in Eq. 8.23, then the contributions of
these Drude terms can be neglected and the frequency-dependent dielectric constant
e(w)becomes
(8.27)
where the plasma frequency w p
(8.28)
is the characteristic frequency of oscillation of the conduction electron plasma.

To obtain Eq. (8.27) we dropped the damping factor iw/tp and made the
identification e∞ = fp= e0 in (8.23). This high-frequency plasma dielectric constant
ε(ω) is associated with oscillations of the conduction electrons relative to the
positive charge background set up in the plasma by the incoming electromagnetic
wave.
8.9. ENERGY GAP

Tunneling and vibrational spectroscopy are complementary ways to determine
the energy gap of a superconductor. In this section we say a few words about the
infrared determination of gaps; the alternative tunneling method has been described
elsewhere (1).
For a superconductor at absolute zero, we expect light with frequencies v lower
than Eg/h to be reflected to a greater extent than frequencies v > Eg/h, as in the case
of a normal metal. Above absolute zero, these latter frequencies can excite quasi-
particles and induce aphotoconductive response. Figure 8.5 shows low-temperature
experimental data R(T)/R0 for the reflection of infrared radiation at frequencies
below the gap value Eg ≈ 70 cm–1, and the drop in reflectivity for frequencies above
1 70 CHAPTER 8
Figure 8.5. Infrared reflectance spectra showing the abrupt change in transmission at the energy gap
for the superconductor Ba0.6K0.4BiO3. The upper figure plots data for the temperatures T= 11, 14, 17,
and 21 K, and the lower figure demonstrates the suppression of the low-frequency reflectivity enhance-
ment by successively increasing applied magnetic fields Bapp = 0, 1,2, and 3 T. (From Schlesinger et
ai., Ref. 11.)
this value for the cubic perovskite superconductor Ba0.6K0.4BiO3 (1 1). Similar
reflectivity results have been obtained for many other superconductors.
Figure 8.5a shows how increasing the temperature decreases the frequency at
which the reflectivity undergoes a sharp drop in value. This is explained by the
temperature dependence Eg(T) of the energy gap, which often has the form
(8.29)
where Eg = Eg(0), with the BCS value given by Eg = 3.52 kBTc. Figure 8.5b shows
how increasing the applied magnetic field produces the same effect as increasing
the temperature. This occurs because for many superconductors the critical mag-
netic field Bc(T) depends on the temperature through the expression
(8.30)
where Bc = Bc(0). Equation 8.30 can be inverted by considering T the critical

temperature Tc(B) as a function of the applied field
(8.31)
where we write B in place of Bc(T) and Tc is the critical temperature for B = 0. It is

now clear that Tc(B) decreases as the applied field increases. In the presence of a
magnetic field, the gap equation (8.29) becomes
(8.32)
Figure 8.6. Temperature dependence of the normalized microwave surface resistivity r/rn of alumi-
num (upper figure) for microwave frequencies in the range 12 to 80 GHz , where r n is the normal state
surface resistivity. Each curve is labeled with its equivalent kBTc value. The plot of the normalized
resistivity r/rn at the reduced temperature T/Tc = 0.7 versus kB/Tc (lower figure) exhibits a break at
the energy 2.6 kBTc corresponding to the energy gap Eg = 2.6 kBTc (From Biondi and Garfunkel, Ref.
12.)
172 CHAPTER 8
a formula that is only valid for T < Tc(B). This expression clarifies that the energy
gap decreases when either the temperature or the magnetic field increases. Increas-
ing either T or B also decreases the Cooper pair concentration ns, which causes the
reflectivity peak below the gap to decrease in magnitude, as in the figures.
The infrared method of measuring energy gaps can be applied at much lower
frequencies to elemental and other classical superconductors that have much lower
transition temperatures Tc. As an example consider the temperature dependence of
the normalized microwave resistivity r(T)/rn of aluminum, which is shown in Fig.
8.6 (upper figure) for five microwave frequencies v in the range from 12 to 80 GHz
(12). Each curve is labeled by its microwave photon energy hv expressed in the
units kBTc where Tc = 1.2 K for aluminum, and a temperature of 1 K is equivalent
to 20.84 GHz. The three lowest curves extrapolate to zero resistivity, which
indicates that superelectrons are not excited above the gap, and the two upper curves
extrapolate to a finite resistivity, which is indicative of the presence of excited
quasi-particles, The lower figure shows a plot of the microwave resistivity of each
frequency at the temperature of T = 0.7 Tc versus the energy. We see that the slope
of the curve is small up to the energy 2.6 kBTc, and larger beyond this point,
indicating a gap energy of Eg ≈ 2.6 kBTc, a value somewhat less than the BCS
prediction, Eg ≈ 3.53 kBTc. The more rapid rise in resistivity beyond this point is
attributed to the superelectrons that have become excited to the quasi-particle state.
8.10. ABSORPTION AT VISIBLE AND ULTRAVIOLET

FREQUENCIES
Visible (13,000 to 25,000 cm–1, or 1.6 to 3.0 eV) and ultraviolet (3.1 to 40 eV)
radiation has been employed to detect crystal field split electronic energy levels in
insulating solids containing transition ions, and to determine energy gaps in
semiconductors as well as the locations of impurity levels within these gaps. The
response of metals to incident optical radiation depends on the plasma frequency
wp (Eq. 8.28), which lies in the near infrared region for high-temperature supercon-
ductors and in the ultraviolet for many good conductors such as alkali metals.
As an example of the interaction of optical radiation with superconductors in
the normal state we examine the optical reflectance (reflectivity) of the series of
La2–xSrxCuO4 compounds prepared for the composition range from x= 0 to x = 0.34
(13). The broad spectral scan, up to 37 eV, that is shown in Fig. 8.7 exhibits three
reflectivity edges. The highest frequency edge near 30 eV falls off as 1 / w4, and it
was attributed to excitations involving valence electrons. The midfrequency band
from 3 to 12 eV was assigned to interband excitations from oxygen 2p valence
bands to La 5d/4f orbitals, with the semiconductor La2CuO4 having an optical
energy gap of about 2 eV. The low-frequency edge is absent in the x = 0 insulating
compound and it is very high, off the scale on Fig. 8.7, in the two doped conductors.
Figure 8.7. Optical reflectivity with the E vector polarized in the ab plane for La2–xSrxCuO4 single
crystals for three compositions x. (From Uchida et al., Ref. 13.)
Figure 8.8. Frequency dependence of the optical conductivity s(w) of La2–xSrxCuO4 obtained from a
Kramers–Kronig analysis of the reflectivity spectra of Fig. 8.7 for the E vector polarized in the ab plane.
Results for several compositions x are shown. (From Uchida et al., Ref. 13.)
1 74 CHAPTER 8
A Kramers–Kronig analysis carried out for the reflectance spectra of Fig. 8.7
provided the conductivity spectra presented in Fig. 8.8 for the low-energy range
from 0 to 4 eV (8). We see that s(w) at these low frequencies increases continuously
with the level of doping x, being low for the insulators (x = 0,0.2,0.6), high for the
superconductors (x = 0.1, 0.15, 0.2) and highest for the nonsuperconducting metal
(x = 0.34). Recall that La2–x,SrxCuO4 is a hole superconductor. A similar set of
spectra obtained for the electron superconductor Nd2–x,CexCuO4–y exhibited the
same dependence of the low-frequency conductivity on x as in the hole case.
References
1. C. P. Poole, Jr., H. A. Farach, and R. I. Creswick, Superconductivity, Academic Press, San Diego
(1995).
2. C. Kittel, Introduction to Solid State Physics, Wiley, New York (1996).
3. N. W. Ashcroft and N. D. Mermin, Solid State Physics, Saunders, Philadelphia (1976).
4. K. F. McCarty, J. Z. Liu, R. N. Shelton, and H. B. Radousky, Phys. Rev. B41, 8792 (1990); B42,
9973 (1990).
5. M. K. Crawford, G. Bums, G. V. Chandrashekhar, F. H. Dacol, W. E. Farneth, E. M. McCarron,
III, and R. J. Smalley, Phys. Rev. B41, 8933 (1990).
6. A. P. Litvinchuk, C. Thomsen, and M. Cardona, in Physical Properties of High Temperature
Superconductors, Vol. 4, Chap. 6, World Scientific, Singapore (1994).
7. T. Timusk and D. B. Tanner, in Physical Properties of High Temperature Superconductors, Vol.
1, Chap. 7, World Scientific, Singapore (1994).
8. M. Cardona, Physica C 185C–189C, 65 (1991).
9. E. Faulques and R. E. Russo, in Applications of Analytical Techniques to the Characterization of
Materials, (D. L. Perry, ed.), p. 59, Plenum, New York (1991).
10. C. Thomsen and M. Cardona, in Physical Properties of High Temperature Superconductors, Vol.
1, Chap. 8, World Scientific, Singapore (1989).
11. Z. Schlesinger, R. T. Collins, J. A. Calise, D. G. Hinks, A. W. Mitchell, Y. Zheng, B. Dabrowski,
N. E. Bickers, and D. J. Scalapino, Phys. Rev. B40, 6862 (1989).
12. M. A. Biondi and M. P. Garfunkel, Phys. Rev. 116, 853 (1959).
13. S. Uchida, T. Ido, H. Takagi, T. Arima, Y. Tokura, and S. Tajima, Phys. Rev. B43,7942 (1991).
9
A PPL ICATIONS
In this chapter we give an overview of some of the many applications of supercon-

ductors that are based on their electromagnetic absorbing properties.
9.1. THIN FILMS

In the microwave region of the spectrum, many of the devices that employ
superconductivity, such as delay lines, involve a microwave signal passing through
strips of superconducting material. It is important therefore that these materials have
low surface resistance in order to reduce the loss on transmission through the strip.
The main advantage of using superconductors is that below Tc they have signifi-
cantly lower surface resistance than other materials.
A thin film is a layer of material a few lattice parameters thick, typically 350
nm, deposited on another material called a substrate. Superconducting thin films
of Y-Ba-Cu-O have been made which have a surface resistance of 0.1 milliohms at
77 K and 10 GHz. The surface resistance of copper under the same conditions is
8.7 mohms. The resistance of the material also depends on its form. Figure 9.1
presents a plot of the frequency dependence of the surface resistance at 77 K of
Y-Ba-Cu-O in bulk form, and also in thick and thin films of the material (1). Data
for copper at 77 K are included for comparison. The graph shows that below about
10 GHz at 77 K, the thin films of Y-Ba-Cu-O have a significantly lower surface
resistance than copper.
Figure 9.2 shows an apparatus used to make thin films of Y-Ba-Cu-O. The
component starting materials Y2O3, BaCO3, and CuO are contained in three heated
holders located inside an evacuated chamber, along with the substrate on which the
film is to be deposited. The holders are heated to temperatures high enough (1000°C
and above) to allow the materials in them to evaporate. The substrate is maintained
at a lower temperature, typically around 375°C. The evaporated materials condense
on the substrate to form YBa2Cu3O7. Since the superconducting properties of
175
176 CHAPTER 9
Figure 9.1. Plot of surface resistance versus frequency for various forms of superconducting Y-Ba-Cu-
0 compared with copper at 77 K (from Porch, Ref. 1).
Figure 9.2. Vacuum chamber system for vapor deposition of thin films on a heated substrate. The
starting materials for forming the film are placed in the heated holders.
APPLICATIONS 177
Y-Ba-Cu-O depend on its oxygen content, oxygen gas is introduced into the
chamber after the film has been deposited. The film is generally annealed (heated)
in an oxygen atmosphere at 850°C for a number of hours to achieve the proper
oxygen stoichiometry and thereby convert the material to a 90 K superconductor.
The substrate must be a single crystal whose lattice parameters are compatible with
Y-Ba-Cu-O. Single crystals of MgO cut with an exposed [001] plane have been
used. Besides having very low surface resistance in the superconducting state, the
films also display very sharp resistance drops at the superconducting transition, as
shown in Fig. 9.3 (2). As we will discuss later, these sharp drops can be the basis
for infrared and optical sensors. The films also have high critical current densities,
on the order of 106A/cm2.
There are other ways to make thin films, such as sputtering and laser ablation.
In the sputtering technique, positive ions such as argon are accelerated in a vacuum
chamber to impinge on a target of the material to be made into a film, as illustrated
in Fig. 9.4. The incident argon ions knock atoms out of the target material, and these
atoms migrate to the cooler substrate where they condense to form the film. In the
laser ablation method, a high-power pulsed laser beam incident on the target
material, causes the surface layers of the target to evaporate. The film is formed
when this evaporated material condenses on the cooler substrate.
Figure 9.3. Temperature dependence of the resistance of a thin film of Y-Ba-Cu-O showing the very
sharp drop at the transition temperature (from Hopfengärtner et al., Ref. 2).
178 CHAPTER 9
Figure 9.4. Illustration of a device for making films by the sputtering process.
9.2. DELAY LINES

A delay line is usually a long microstrip or a coplanar line that is deposited on
a substrate. It is used to delay in time one incoming signal with respect to another
by sending one signal through a longer path. Figure 9.5 illustrates a delay line. It
is essential that the deposited strip have as low a surface resistance as possible in
order to minimize attenuation as the signal passes through the strip. Since super-
conductors below Tc have lower surface resistance than other materials, supercon-
ducting delay lines constitute an important application. Delay lines made of
Y-Ba-Cu-O films and operating at 77 K, such as the one in Fig. 9.5, have been found
capable of delaying a signal at 10 GHz for a nanosecond with only a few decibels
of loss. Both the thickness and the width of the strip influence the loss. Typical
substrates used in delay lines are around 10µ thick, so they are essentially thin films
themselves. Fig. 9.6 compares the loss as a function of frequency for delay lines
made of copper and Y-Ba-Cu-O maintained at 77 K (3,4). The figure shows that the
use of superconducting film greatly reduces the loss of the delay line.
9.3. STRIPLINE RESONATORS

A resonator is a structure that can sustain an oscillatory electromagnetic field
at a number of discrete frequencies. The resonant frequencies depend on the
geometry of the system. As in the delay lines, it is important to minimize losses in
APPLICATIONS 179
Figure 9.5. Delay line made by depositing a thin film strip of a high-temperature superconductor on a
substrate such as MgO.
Figure 9.6. Comparison of the loss versus the frequency at 77 K of a delay line made of copper and
another made of a Y-Ba-Cu-O superconductor (after Hammond, Ref. 3).
180 CHAPTER 9
resonators. These losses primarily arise from the surface resistance of the material
from which the resonator is constructed. Resonators are used in microwave circuits
as filters to separate out specific frequencies from a broadband incoming signal.
An important parameter used to characterize the resonator is the quality factor
Q, which is defined as
Q0 = 2p (energy stored)/(energy dissipated per cycle) (9.1)
A resonator made of a low surface-resistance material has a higher Q and hence

less power loss. Figure 9.7 shows a stripline ring resonator made by depositing a
material such as copper or a superconductor on a substrate with dimensions such
that it resonates at 3.4 GHz. Figure 9.8 compares the Q of ring resonators made of
copper and Y-Ba-Cu-O at 77 K deposited on sapphire (3). The graph shows that
below 10 GHz the ring resonator made of the superconductor has a Q that is more
than an order of magnitude better than copper at the same temperature. Figure 9.9
shows another kind of stripline resonator in the form of a meander line of Y-Ba-Cu-
0 deposited on LaAlO3 (4). The superconducting strip is one half the wavelength
of the fundamental frequency f0, which in this case is 1.24 GHz. The strip is clamped
between copper plates and a lower loss dielectric material. The surface resistance
of this strip at 4.2 K is 2 × 10–5 ohms, which is quite low.
Bandpass filters are used in receiving signals. It is desirable that the receiver
have a band width comparable to the band width of the incoming signal and that it
Figure 9.7. Illustration of a ring resonator made by depositing an annular strip of Y-Ba-Cu-O on a
substrate. The dimensions were chosen so resonance occurs at 3.4 GHz (after Hammond, Ref. 3).
APPLICATIONS 181
Figure 9.8. Comparison of the Q of Cu and Y-Ba-Cu-O resonators at 77 K plotted against the frequency
(from Hammond, Ref. 3).
reject frequencies outside this range. The filter should pass frequencies within the
band width with minimum dissipation and distortion. Bandpass filters are con-
structed by depositing on a substrate a series of strips of materials having low
surface resistance, with each strip having a geometry that resonates at a different
frequency. Figure 9.10 shows a common type of bandpass filter. Figure 9.11
compares the performance at 77 K of a filter made of copper with one made of
Y-Ba-Cu-O as a function of frequency. Again because of the lower surface resis-
tance, there is much less loss in the superconducting filter than there is in the copper
one.
9.4. CAVITY RESONATORS

A cavity resonator is usually a cylindrical or rectangular metal container whose
dimensions are multiples of the guide half-wavelength of the microwave radiation
that is coupled into it to form a standing wave pattern. Cavity resonators are
important components in microwave circuitry, and they are used as filters to
separate out a specific frequency. They are also employed as the main element in
feedback oscillators. When the exciting power source is turned off, the standing
electromagnetic field inside the cavity decays in time because of losses due to
leakage, owing to the finite conductivity of the cavity walls and the presence of any
dissipative dielectric material. Quality factors add as reciprocals, so the overall Q
arising from these three factors is (5)
182 CHAPTER 9
Figure 9.9. Illustration of a stripline resonator made in the form ofa meander line: (a) overall side view
and (b) top view of center conductor transmission stripline (from Oates et al., Ref. 4).
(9.2)
The Q due to the conductivity losses is given by
(9.3)
where, from Eq. (4.10),
Rs = (wµ 0/2s)1/2 (9.4)
and G is a parameter related to the geometry of the cavity. Constructing the walls
of the cavity from a superconducting material and operating at a temperature below
Tc can significantly increase Qc For example, making the cavity walls from a thin
film of Y-Ba-Cu-O, which has a surface resistance at 77 K of 10–5 ohms at 1 GHz,
would increase the Qc by a factor of 103 over a cavity made with silver walls.
APPLICATIONS 183
Figure 9.10. Illustration of a bandpass filter made by depositing a series of thin microstrips of
Y-Ba-Cu-O of different geometries on a substrate.
As discussed in Chap. 3, cavities in which one wall has been replaced by a

superconducting thin film are often used to make surface resistance measurements
on superconductors. If such a cavity with dielectric material excluded (1/Qe ≈ 0) is
strongly undercoupled so the leakage losses can be neglected (1/QL ≈ 0), the overall
Q then becomes
Figure 9.11. Comparison of the transmission loss at 77 K of a bandpass filter made of Cu (———)
and another made of Y-Ba-Cu-O (- - - - -) (from Hammond, Ref. 3).
184 CHAPTER 9
Figure 9.12. Illustration of a microwave cavity used to measure the surface resistance of a thin
superconducting film by making one wall of the cavity from the film.
(9.5)
where QTC is the contribution to the Q of the total cavity interior, excluding the extra
wall, and QWc is the contribution to Q from the superconducting wall. The surface
resistance is obtained by measuring the overall Q of the cavity as a function of
temperature to determine QWc(T) and then making use of Eq. (9.3) to determine
Rs, where the factor G is now a parameter specific to the superconducting wall.
Figure 9.12 shows an example of a cavity used to measure the surface resistance of
superconducting films (1).
9.5. TRANSMISSION LINES

One kind of superconducting microwave transmission line, shown in Fig. 9.13,
consists of two infinitely long plates of superconducting material, usually with films
deposited on the inner surfaces of the substrates separated by a small distance h,
and with the plates having a width w >> h. Again, the low surface resistance of the
superconducting plates reduces the losses on transmission. The velocity cz of the
APPLlCATIONS 185
Figure 9.13. A microwave transmission line made of two infinitely long parallel superconducting films
with the close spacing h, and width w >> h. The films of thickness t are deposited on the inside surfaces
of the substrate plates. The figure shows the films but not the substrates.
signal down the transmission line depends on the spacing h between the plates, as
shown in Fig. 9.14. The reduced velocity of the signal c2/c0, where c0 is the velocity
of light in free space, decreases with decreasing spacing because of the increased
penetration of the signal into the film, which increases the inductance but not the
capacitance. In addition, the attenuation of the signal also increases when the
spacing decreases, as shown in Fig. 9.15.
Figure 9.14. Plot of the reduced signal velocity cz/c0 versus the spacing h/l of the plates of Fig. 9.13
for two different film thicknesses t > l (———) and t = l (- - - - -) (adapted from Lancaster, Ref. 14).
186 CHAPTER 9
Figure 9.75. Plot of the attenuation coefficient versus the spacing h/l of the plates of Fig. 9.13 for two
different film thicknesses t > l (———) and t < l (- - - - -) (adapted from Lancaster, Ref. 14).
9.6. SUPERCONDUCTING ANTENNAE

Antennae are geometrical arrays of conducting material arranged in such a
way so as to effectively radiate electromagnetic energy (transmitting operation), or
to pick up an incoming signal (receiving operation). An antenna with dimensions
d comparable to the wavelength l of the radiation constructed from conventional
metal conductors can be quite efficient, and making one from superconductors does
not greatly improve its performance. For smaller sizes, d << l , the efficiency
decreases due to ohmic losses, and making a small antenna from superconducting
materials improves its efficiency.
One of the important issues in antenna design is the matching of the antenna
impedance to the source impedance in order to optimize the transfer of radiation
between the source and the antenna. This matching becomes more difficult with a
smaller antenna made from superconductors because of the reduction in impedance.
Making the matching circuitry from superconducting materials can help. Figure
9.16 shows a small dipole antenna made by depositing a superconducting film on
a substrate (6). A small antenna of this kind has a large capacitive reactance and a
small inductive reactance. The low value of the reactance in the superconducting
APPLICATIONS 187
Figure 9.16. Dipole antenna made by depositing Y-Ba-Cu-O strips on a substrate.
state causes the antenna to have a high Q. Figure 9.17 plots the Q versus the
efficiency for a small dipole antenna of the kind shown in Fig. 9.16.
Certain transmission situations require high signal directionality. A superdi-
rective antenna array using high-temperature superconductors has been demon-
strated (7). It consists of two dipoles half a wavelength long placed side by side a
distance d apart, as shown in Fig. 9.18. The signal is fed into the two dipoles at the
bottom of the figure from a coaxial cable and capacitor, which form a single stub
tuner-matching circuit at the bottom. This allows the dipoles to have equal and
opposite currents as required for enhanced directivity.
Figure 9.17. Comparison of a plot of Q versus efficiency at 77 K for a dipole antenna made of copper
(- - - -) and one made of Y-Ba-Cu-O (———) (adapted from Lancaster, Ref. 14).
188 CHAPTER 9
Figure 9.18. Sketch of a two-element highly directive antenna array made of superconducting mate-
rials. The double dipole radiator is shown at the top, and the source coaxial cable with its associated
single stub tuner is sketched at the bottom.
9.7. INFRARED AND OPTICAL SENSORS

There are many applications of the electromagnetic absorbing process in parts
of the electromagnetic spectrum other than the microwave region, and this section
describes infrared and optical applications. An infrared detector is a device that
indicates how much infrared radiation is present. An efficient radiation detector can
make use of the sharp change in the resistance of a Y-Ba-Cu-O film, shown in Fig.
9.3, in the neighborhood of its transition temperature Tc = 90.5 K. This resistance
change occurs over the narrow temperature range of about 0.3 K. Suppose that the
temperature is maintained at precisely 90.7 K so that the resistance of the material
is half of its value above Tc. If infrared radiation strikes the superconductor, it will
heat the material and raise its temperature, and this temperature change will be
reflected by an increase in resistance, thereby providing a measure of the amount
of radiation that is present. The drop in resistance at the transition is so sharp that
a temperature change of 0.0001 K results in a detectable change in resistance.
An illustration of a device based on such a principle is shown in Fig. 9.19, The
main part of the detector is a superconducting film deposited on a substrate such as
mica, and this lies on a copper block in contact with liquid nitrogen. Tiny wire leads
are attached to the superconductor to measure its resistance, and the film is enclosed
in a vacuum container to isolate it from its environment. A small heater on the block
maintains the temperature at a constant value near Tc. When infrared radiation
strikes the film, its resistance increases; this is detected by applying a small current
and measuring the voltage across the resistance leads.
One could also design an optical and IR detector based on the sharp drop of
the surface resistance of a superconductor shown in Fig 5.1 (8). Figure 9.20 shows
what such a detector might look like. It would have a source of microwaves
APPLICATIONS 189
Figure 9.1 9. Sketch of an infrared and optical light sensor employing a thin film of Y-Ba-Cu-O.
Figure 9.20. Block diagram of an optical sensor that employs the sharp change in microwave surface
resistance at the transition temperature illustrated in Fig. 9.3 as the radiation detection mechanism.
190 CHAPTER 9
provided, perhaps, by a Gunn diode located in a microwave bridge of the type

sketched in Fig. 3.4. The superconducting sample held below Tc would be located
in the cavity, which would be provided with an aperture and focusing lenses to direct
the light to the sample, as shown.
9.8. MAGNETOMETERS
There have been a number of proposals to use the dc magnetic field dependence
of electromagnetic absorption as the sensing element in magnetic field detectors
(9, 10). In principle, magnetometers employing field-dependent microwave absorp-
tion could approach the sensitivity of SQUID magnetometers. In Chap. 6 we saw
that a very low-strength dc magnetic field applied to a single crystal of Y-Ba-Cu-O
in the superconducting state produces a very sharp derivative signal that can be
detected by an electron paramagnetic resonance spectrometer. This spectrum is a
result of flux jumps arising from intrinsic weak links in the materials formed at twin
boundaries in the crystal, The separation of the lines in the spectrum shown in Fig.
6.10 is less than 0.1 mT, so in effect this system could be the basis of a reasonably
sensitive magnetometer, albeit an expensive one.
A somewhat less expensive magnetometer can be designed around the effect
of a dc magnetic field on the direct absorption of microwave energy in the
superconducting state using a microwave bridge arrangement analogous to the
infrared one sketched in Fig. 9.20. In this application, a cavity without an aperture
containing the superconducting sample becomes the magnetic sensor. Figure 9.21
is a plot of the change in the diode current versus the dc magnetic field for an
epitaxial film of Y-Ba-Cu-O on an MgO substrate acting as a sensor (1 1). Below 1
mT (i.e. < 10 G) this magnetometer would have a sensitivity of 5 µA per millitesla.
A magnetometer that senses a dc magnetic field by the change in the frequency
of an RF LC circuit in which the coil contains the sample could also be quite
sensitive (12). The device would consist of an LC oscillator and a frequency meter
as shown in Fig, 3.1. Clover and Wolf (13) have described a simple tunnel diode
oscillator employing a germanium IN37 12 diode powered by a 1.4-V Duracell
battery which can be built for less than $100. The magnetic sensing element of the
instrument is the coil of the oscillator LC circuit wound around a thin quartz
cylindrical holder containing the as-sintered sample of the superconductor. The
strength of the dc magnetic field is determined by measuring the frequency shift of
the oscillator. Figure 9.22 shows the shift in frequency as a function of dc magnetic
field for a sintered sample of the 133-K Hg-Ba-Ca-Cu-O superconductor located
in the coil of the LC circuit. Below 50 mT this magnetometer would have a
sensitivity of 7 × 10–4 mT/Hz. In principle, with a stable oscillator and an accurate
measurement of frequency, this could be a very sensitive magnetometer.
APPLICATIONS 191
Figure 9.21. Plot of the change of detector current in a microwave bridge as a function of magnetic
field applied to the cavity of the bridge containing a thin film of Y-Ba-Cu-O. This result shows that such
a bridge could be the basis of a magnetometer.
Figure 9.22. Frequency shift of an LC circuit versus applied dc magnetic field strength in which the
coil is filled with the 133-K superconductor Hg-Ba-Ca-Cu-O at 77 K. These data demonstrate that such
an arrangement could be developed into a sensitive magnetometer.
192 CHAPTER 9
References
1. I. A. Porch, Microwave Surface Impedance of YBaCuO, PhD Thesis, University of Cambridge
(1991).
2. B. Hopfengärtner, B. Hensel, and G. Saemann-Ischenko, Phys. Rev. B44, 741(1991).
3. R. Hammond, Supercurrents 6, July (1989).
4. D. E. Oates, A. C. Anderson, D. M. Sheen, and S. M. Ali, IEEE Trans. Microwave Theory and
Techniques39, 1522 (1991).
5. C. P. Poole, Jr., Electron Spin Resonance, Chap. 5, Wiley (New York) 1983; reprint edition, Dover,
NewYork(1997).
6. G. C. Liang, R. S. Withers, B. E Cole, S. M. Garrison, M. E. Johansson, W. S. Ruby, and W. G.
Lyons, IEEE Trans. Appl. Superconductivity 3, 3037 (1993).
7. Y. Huang, M. J. Lancaster, T. S. M. MacLean, Z. Wu, and N. McN. Alford, Physica C180, 267
(1991).
8. F. J. Owens, Patent pending.
9. B. E Kim, J. Bohandy, F. J. Adrian, and K. Moorani, Appl. Phys. Lett. 56, 2037 (1990).
10. S. Tyagi and M. Barsoum, Supercond. Sci. Technol. 1,20 (1988).
11, E J. Owens, unpublished.
12. F. 1. Owens, Appl. Superconductivity 2,51 (1994).
13. R. B. Clover and W. P. Wolf, Rev. Sci. Instr. 41, 617 (1970).
14. M. J. Lancaster, Passive Microwave Applications of High Temperature Superconductors, Cam-
bridge Univ. Press, Cambridge (1997).
Index
Abrikosov lattice, 25,26 Bessel function, modified, 24

Absorption, 60 Binding layer, sketch, 44,46
direct detection, 64 Bi-Pb-Sr-Ca-Cu-O
modulation detection, 64 microwave absorption, 1 14–1 17,
X-ray edge, 72 130
AI, 171 penetration depth, 146–148
Antenna, 186, 187 structure, 36
dipole, 188 transition temperature, 32
Antiferromagnetic transition, 83 Bi-Sr-Ca-Cu-O
Antiferromagnetism, 83 microwave absorption, 154
La-Sr-Cu-O,32 structure, 36
MnO, 84 transition temperature, 32, 38
ordering, 75 Bohr magneton, 63
phase diagram, 33 Bremsstrahlung, 71
temperture dependence, 84
Y-Ba-Cu-O, 35
Antistokes’ line, 161 Carbon 60: see Fullerene, 5 1
Argon, 178 Cavity resonator, 59, 18 1, 184
Attenuation coefticient, 186 600 MHz figure, 61
Auger electron, 7 1 Chain of Cu-O atoms, 35
Automatic frequency control (AFC), 60, 63 Charge density wave, 109
Charge transfer layer, 46
Ba-K-Bi-O, 50 Chemical shift, 68
infrared, 170 Co, 71
structure, 51 Coffey–Clem model, 142, 156
Band complete, 145
conduction, 1 Coherence
diagram, 47 length, 12
Bandpass filter, 183 peak, 99, 102
BCS theory Collision time, 75
Cooper pair, 7 Colossal magnetoresistance, 89
electromagnetic absorption, 99 Conduction layer
penetration depth, 105 aligned, 42
weak coupling, 3, 48 sketch, 44, 45
193
194 INDEX
Conductivity Density of superelectrons, 13

AC, 78 Density of states, 47, 48, 99
BCS, 100 figure, 100
complex, 78 Depairing current density, 19
electrical, 75 Depinning
optical, 173 barrier, 152
temperature dependence, 100 field, 146, 147
Cooper pair, 2,4 line, 140
binding, 4,49 temperature, 141
binding mechanism, 5 transition, 152
breakup, 3, 19,96 Dewar, 56
Josephson junction, 127 Diamagnet, perfect, 7
phase, 134 Dielectric constant
phase coherence, 6 complex, 164, 165, 167
phonon mechanism, 5 conductivity, 164, 165
wave function, 7.23, 107 Dimensionality, 109
Copper oxide plane Dipole
aligned, 42 antenna, 187, 188
figure, 33, 37, 38 field of sphere, 16
number, 37,38 Dispersion, 60
staggered, 42 Double beam, I59
transition temperature, 38 Drude model, 166
Copper oxides, see cuprate, 42 D-wave pairing, 105
Critical current density, 9, 10
Josephson, 128 Effective mass, 69
penetration,10, 11 Electromagnetic absorption, 99, 107
temperature dependence, 19, 20 due to vortex motion, 139
Critical field Electron
lower, 17, 25 conduction, 34, 75
slope, 18 scattering, 1
thermodynamic, 17,19 superconductor, 174
upper, 17,25 valence, 1
upper-figure, 48 Electron paramagnetic resonance: see EPR, 62
Crossover temperature, 103, 107 Electron spin resonance: see ESR, 62
Cu, 62, 63, 64,68, 69, 71, 162 Ellipsoid, 14, 15
Cuprate, 42 oblate, 14, 15
commonalities, 44, 45 prolate, 14, 15
general properties, 42 Energy band, figure, 47
Hg, 2 Energy gap, 2, 169
individual compound properties, 43 A1, 171
orthorhombic, 42 infrared, 2, 171
tetragonal, 42 microwave, 2
Curie temperature, 84, 87,91 temperature dependence, 17 1
Current-transport, 141 Energy surface, 2 1, 22
EPR, 55
Debye bridge block diagram, 63
energy, 160 silent, 64
temperature, 78,81, 160 spectrometer, 190
Delay line, 175, 178, ESR see EPR, 55
Y-Ba-Cu-O, 179 Eu, 71
Demagnetization factor, 14 Experimental techniques, 55
INDEX 195
Fe, 70, 71 Hg-Ba-Ca-Cu-O ( cont.)

Fermi magnetometer, I9 1
level, 47 pressure, 40
surface, 1 resistivity temperature dependence, 28
Ferromagnetic transition, 84 structure, 39
Ferromagnetism, 84 transition temperature, 32, 38, 40
microwave absorption, 88 Hg-Pb-Ba-Ca-Cu-O, 38
ordering, 75 frequency shift, 150
Fieldcooling(FC),121, 123, 124, 130 microwave absorption, 95, 96, 148–
Fluctuations, 107–109 153
Flux resistivity, 3
creep, 25, 113, 140, 141 surface resistance, 108
expulsion, I5 Hole conduction, 34
flow,25, 113, 140, 141, 151 Hysteresis, 120, 142
jump, 133, 135 LFMA, I14
melting line, 140 microwave absorption, 130
penetration, 8 modulation, 114
quantization, 23
solid, 141 Impedance of surface, 78
trapping,20, 117, 121, 131 In, 4
Fluxon, 26 Infinite layer phase, 41
Free energy, Gibbs, 2 1, 22 figure, 41
Fullerene Infrared, 55
doped-figure, 52,53 absorption, I59
magnetization, 54 active, 162, 163
structure figure, 52 Ba-K-Bi-O, 170
transition temperature, 53, 54 detector, 188, 189
Fundamental band, 161 energy gap, 2
In, 4
Gap Nd-Ce-Cu-O, I68
anisotropy, 48 sensor, 188, 189
energy, 2 spectroscopy, I61
superconducting, 96, 169 spectrum, 168
Ta, 5 Y-Ba-Cu-O, 189
Gd, 36,62, 85, 86, 87 Irreversibility, 140, 151
Geodesic dome, 53 line, 25,26, 141, 147, 153
g-factor, Landé, 63 Y-Ba-Cu-O,26,27
Giant magnetoresistance, 75, 89 Isotope effect, 4
Gibbs free energy, 21,22
Ginzburg–Landau Josephsonjunction, 119, 125, 126
parameter, 2 1, 49 loop, 128
theory, 70 pair of, 127
Green phase, 64 Y-Ba-Cu-O, 129
Gunn diode, 59, 120 Josephson loop, 134
Gyromagnetic ratio, 68
Klystron, 59
Helmholtz equation, 9 Kramers–Kronig analysis, 159, 166, 173, 174
Hg, 4
Hg-Ba-Ca-Cu-O La-Ba-Cu-O,32
figure, 39 transition temperature, 32
magnet, 190, 19 1 La-Ca-Mn-O, 90
196 INDEX
Ladder phase, 40, 4 1, 110 Magnetoresistance, 89

exchange coupling, 42 magnetic field dependence, 90
figure, 41 temperature dependence, 90
Laser ablation, 177 Magnetoresistivity, 75
La-Sr-Cu-O, 174 Maxwell
antiferromagnetism, 32 curl equation, 9, 165
phase diagram, 33 equations, 8
transition temperature, 32 Meander line, 180
unit cell, 3 I, 32 Meissner
visible region absorption, 172–1 74 effect, 7,8
La-Ca-Mn-O,89,90 region, 113
La-Sr-Mn-O, 89, 91–94 state, 20, 141
Latent heat, 164 Melting line, 140, 141
LC oscillator, 56 Metal-insulator transition, 75, 83, 109
LCR circuit, 58 Metallic elements, table, 76, 77
LFMA, I13 MgO, 118
alternating fields, 132 Microwave
Bi-Pb-Sr-Ca-Cu-O, 114–1 17, 130 bridge, 60
Bi-Sr-Ca-Cu-O, 154 bridge block diagram, 62
derivative, I14 energy gap, 2, 171
direct detection, 122, 123 measurement, 59
Hg-Pb-Ba-Ca-Cu-O,95,96, 148, 150–1 53 Microwave absorption: see LFMA, 1 I3
hysteresis, 114, 117, 13I angular dependence, 120
indicator of superconductivity, 136, 137 explanation, 140
mechanism, 128 ferromagnetism, 88, 93
modulation, 114, 133 multiline derivative spectrum, 129
origin, 125 zero field, 95
sharp line structure, 122 Mn, 62
sweep range, 116 MnO, 83
temperature dependence, 115 antiferromagnetism, 84
thin film, 117, 118 surface resistance, 85
time dependence, 1 17, 131 Modulation, 64
Y-Ba-Cu-O, 118-124, 131-146,153–155 Mossbauer resonance, 70
London penetration depth, 9 Muon spin relaxation, 69
Lorentz force, 26, 139
Lorentzian shape, I68 Nb–Ge transition temperature, 31
Low magnetic field induced microwave absorp- Nd, 36
tion, see LFMA, 113 Nd-Ce-Cu-O,34, 174
electron conduction, 34
Magnet, 190, 191 Kramers–Kronig, I68
Magnetic field, 14 structure, 34
internal, 14–17 Néel temperature, 32, 83
slope, 18 Ni, 36, 105, 106
Magnetic moment of sphere, 16 NiS, 83
Magnetization Normal mode, 160
ferromagnetism, 85 Nuclear quadrupole resonance, 69
remnant, 121
temperature dependence, 8, 85 Ohm’s law, 75,165
Magnetoelectromagnetic absorption, 151 Optical, 55
Magnetogyric ratio, 68 conductivity, 173
Magnetometer, 127, 190, 191 detector, 188
INDEX 197
Optical (cont.) Plasma (cont.)

reflectivity, 173 oscillation, 169
sensor, 188, 189 Polarized light, 162
Organic conductor, 109 Positron annihilation, 70
Oscillator, feedback, 181 Power dissipation, 79
Pressure, 40
Parallel plate resonator, 66, 67
Paramagnetic Quality factor Q, 60, 180, 184
marker, 65 addition by reciprocals, 182
probe, 65
Penetration depth, 1 1 Radio frequency, 55
anisotropy, 69 Raman
BCS, 101 active mode, I62
creep region, 143 spectroscopy, I6 I
Bi-Pb-Sr-Ca-Cu-O, 146–148 Y-Ba-Cu-O, 162–164
flow region, 144 Reactance of surface, 79
frequency dependence, 147 Reflectance, 159
frequency shitt, 149 Reflectivity, 165
London, 9 complex, 166
low temperature, 102 Remnant magnetization, 121
magnetic field dependence, 21, 92 Resistance
measurement, 57, 145 drop at Tc, 3
temperature dependence, 13,95, 10 1, 102, residual, 1
103, 104, 107 surface, 78
Y-Ba-Cu-O,69, 102–104, 145, 146 zero, 1
Permeability Resistivity
Gd, 85 anisotropy, 50
Gd temperature dependence, 86 frequency dependence, 176
Perovskite Hg-Ba-Ca-Cu-O, 29
cubic, 50, 170 Hg-Pb Ba-Ca-Cu-O,3
figure, 51 moving vortices, 28
structure, 89 semiconductor, temperature dependence, 82
Phase jump, 134 temperature dependence, 8 1
Phase diagram Resonant cavity, 59
La-Sr-Cu-O,33 600 MHz figure, 61
magnetic, 140 Resonator
universal, 33 cavity, 181, 184
Y-Ba-Cu-O,35 parallel plate, 66, 67
Phase sensitive detector, 58, 63 Q comparison, 181
Phonon ring, 180
exchange, 6 stripline, 67, 153, 156, 178, 182
scattering, 8 1 superconducting, I80
Photoemission, 71 Y-Ba-Cu-O, 180, 181
Pinning
barrier, 152 Scattering
force, 153 electron,1
line, 140 phonon, 8 1
vortex, 146 Screening supercurrrent, 102
strong, 153 Selection rule, 162
Plasma Semiconductor, 82
frequency, I69 resistivity, 82
198 INDEX
Sensor Ta, 4, 5
detector, 188 TCNQ, 109
infrared, 188, 189 Temperature dependence
optical, 189 density of superelectrons, 12
Skin depth, 79,80 magnetization, 7
Sn, 71 penetration depth, 12
Soft mode, 163 resistivity, 28, 50
Sputtering, 177, 178 Thin film, 175
SQUID, 127 preparation, 177
Stokes' line, 161 resistivity, 177
Stripline resonator, 67 TI, 68, 7 I
measurements, I53 TI-Ba-Ca-Cu-O
Structure, 43, 76 structure, 36,37
Bi-Pb-Sr-Ca-Cu-O,36 transition temperature, 32, 38
Hg-Ba-Ca-Cu-O, 39 TI-Pb-Sr-Ca-Cu-O, 117, 119
La-Sr-Cu-O,31, 32 TMTSF, 14
Nd-Ce-Cu-O,34 Transition temperature
TI-Ba-Ca-Cu-O,37 BCS relation, 48
Y-Ba-Cu-O, 34 number of copper oxide planes, 38
Substitution, 36 pressure dependence, 40
Substrate, 175 Transmission line, 184, 185
Superheterodyne spectrometer, 120 Transmittance, 159
Surface energy, 2 1, 22 Transport current, 141
Surface impedance, 78,97,98, 143, 144 TTF-TCNQ, 109
Surface reactance, 79 surfaceresistance, 110
Surface resistance, 78 Twin free crystal, 162, 163, 164
BCS,101 Two fluid model, 8.95
creep region, 143, 144 Type I superconductor, 17
depinning transition, 154 Type II superconductor, 17
energy gap, 171
ferromagnetic, 85, 87, 91, 92 Ultraviolet absorption, 172
flow region, 144, 145
fluctuations, 108 Valence electron, 1
frequency dependence, 80, 97 Van Hove singularity, 48
Gd, 86 Vapor deposition, 176
Hg-Pb-Ba-Ca-Cu-O, 108 Velocity, reduced, I85
magnetic field dependence, 87, 91, Vibrational state, 160, 161
113 Visible absorption, I72
measurement, 105 La-Sr-Cu-O, 172-174
microwave, 171 Vortex, 20
MnO, 85 bundle, 28
semiconductor, 82 density, 26
temperature dependence, 86, 92, 96, 101, distance dependence, 24
110, 111 drag coefficient, 27
Y-Ba-Cu-O, 105–107, 175–177 energy barrier, 28
Susceptibility equation of motion, 143
definition, 7 fluid, 113
microwave, 65 force, 26
temperature dependence, 84 lattice, 25
Y-Ba-Cu-O,65 liquid, 25
S-wave pairing, 105 melting, 25, 146
INDEX 199
Vortex (cont.) Y-Ba-Cu-O (cont.)

motion, 139 infrared, 189
oscillation, 139 irreversibility line, 26, 27
radius, 24 LFMA, 118–124,131–135, 144 _146, 153–155
solid, 113 Josephson junction, 129
thermal hopping, 28 magnetization temperature dependence, 7
two dimensional liquid, 27 magnetometer, 190, 191
Vortex-vortexinteraction, 155 oxygen content, 177
penetration depth, 69, 102-104,145, 146
Wave function phase diagram, 35
Cooper pair, 107 Raman spectrum, 162, 164
D-wave, 107 resistivity temperature dependence, 50
S-wave, 107 resonator, 180, 181
Weak link, 133, 134 surface resistance, 105–1 07, 175–1 77
susceptibility, 65
X-ray absorption, 71 transition temperature, 32
twin free, 162, 163, 164
Y-Ba-Cu-O, 102 unit cell, 34
antenna, 187
antiferromagnetism, 35 Zero field cooling (ZFC), 120, 122
delay line, 179 Zn, 36, 103

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Electromagnetic Absorption in the

Copper Oxide Superconductors

CASE STUDIES IN SUPERCONDUCTING MAGNETS

Charles P. Poole, Jr.

KLUWER ACADEMIC PUBLISHERS

©2002 Kluwer Academic Publishers

All rights reserved

Created in the United States of America

Visit Kluwer Online at: http://www.kluweronline.com

In 1987 a major breakthrough occurred in materials science. A new family of

Frank J. Owens and Charles P. Poole, Jr.

Chapter 1. The Superconducting State

Chapter 2. The New Superconductors

Chapter 3 . Experimental Methods and Complementary Techniques

Chapter 4 . Electromagnetic Absorption in the Normal State

Chapter 5 . Zero Magnetic Field Microwave Absorption

Chapter 6. Low Magnetic Field-Induced Microwave Absorption

6.3. Properties of Low-Field Direct Microwave Absorption . . . . . . . . . 120

Chapter 7 . Electromagnetic Absorption Due to Vortex Motion

Chapter 8. Infrared and Optical Absorption

9.8. Magnetometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190

The Superconducting State

1.1. ZERO RESISTANCE

Figure 1.2. Temperature dependence of the resistance of the Hg-Pb-Ba-Ca-Cu-O superconductor

Eg(0)=2D (0) = 3.52kBTc (1.1)

1.1.2. Cooper Pairs

1.2. THE MElSSNER EFFECT

Figure 1.7. Temperature dependence of the magnetization M of a single crystal of a Y-Ba-Cu-O

The one-dimensional solutions of these two equations for a direction x perpen-

1.2.2. Temperature Dependencies

Figure 1.13.Temperature dependence of the penetration depth l(T) below Tc.

1.2.3. Applied and Internal Fields

where N is a dimensionless geometrical coefficient with the range of values 0 £ N

Figure 1.14 shows the dependence of the demagnetization factors on this

where q is the angle with respect to the applied field direction.

where k is defined by Eq. (1.25).

and this is plotted in Fig. 1.18.

1.2.5. Quantization of Flux

1.2.6. Vortex Configurations

where K0(r/l) is the zero-order modified Bessel function. At large distances,

1.2.7. Flux Creep and Flux Flow

magnetic properties are reversible. Figure 1.23 shows a determination of the

A regular array of vortices in a superconductor produces an average magnetic field

Since the resisitivity r is defined by

Figure 1.24.Measurement of resistance normalized relative to the room temperature resistance Rn

HgBa2Ca2Cu3O10 (17) superconductor. As we will see later, the movement of flux

The New Superconductors

2.1. THE COPPER OXIDES

Table 2.1.Progress in Raisingthe Transition Temperatures ofCuprate

The concentration of holes in the copper oxide planes of La2CuO4 is increased

Sr concentrations where the antiferromagnetic phase no longer exists. However,

The majority of the copper oxide superconductors carry current by means of

2.1.2. The Yttrium Superconductor

Figure 2.4. Orthorhombic unit cell of YBa2Cu3O7–x .

The replacement of copper in the planes by a transition ion such as Ni or by

Bi,Pb 2223 Bi,Pb 2212

Figure 2.6. Crystal structures of two Bi-Pb-Ba-Ca-Cu-O superconductors.

the formula Tl2Ba2Can–1CunO2n+4. This series of compounds is isomorphic with the

2.1.4. Mercury Superconductors

2.1.5. Infinite-Layer Phases

Figure 2.10. The transition temperature of the n = 3, Hg-Ba-Ca-Cu-O superconductor as a function of

2.2. GENERAL PROPERTIES OF COPPER OXlDE

2.2.1. Commonalities of the Cuprates