C HAPTER

7
Superconductivity

The phenomenon of superconductivity was discovered by the Dutch physicist Kamerlingh

Onnes while investigating the electrical properties of metals at very low temperatures. Though
it was discovered in 1911, understanding of the subject proceeded very slowly. In this chapter,
we will consider the basics of superconductivity and some of the phenomena associated with
it.

7.1 INTRODUCTION
In 1911, Onnes discovered that for some materials there exists a certain temperature, called
critical temperature or transition temperature TC, below which the resistivity is zero and
the conductivity V  ‡. This phenomenon is called superconductivity. Figure 7.1 shows a
plot of the resistance of mercury versus temperature obtained by Onnes. The critical temperature
for mercury is 4.2 K. The critical temperature varies from material to material, less than 0.1
K for hafnium to 9.2 K for niobium; below this temperature the electrical resistance of the
material is zero. Table 7.1 lists the critical temperatures of some superconducting materials.
Many metallic compounds are also superconductors. The superconducting alloy Nb3Ge,
discovered in 1973, has a critical temperature of 23.2 K. This was the highest critical
temperature known until 1986.
There is no d.c. resistance for a superconductor below TC. Hence, there can be a current
in a ring shaped superconducting material even in the absence of a potential difference. Such
currents are called supercurrents. In fact, steady currents have been observed to persist for
years without loss, in superconducting rings without an electric field.

142
 Superconductivity 143

0.15

0.10
R (W)

0.05

0.00
4.0 4.1 4.2 4.3 4.4
T(K)
Fig. 7.1 Plot of the resistance of mercury versus temperature, showing sudden decrease of the critical
temperature T = 4.2 K.

Table 7.1 TC and BC values at 0 K for some superconductors

Type-I TC BC (at 0 K) Type - II TC BC(at 0 K)

element* (K) (T) compound* (K) (T)

Al 1.175 0.0105 Nb3Sn 18.1 24.5

Cd 0.517 0.0028 Nb3Ge 23.2 34.0
Hg 4.154 0.0411 NbN 16.0 15.3
In 3.408 0.0282 V3Ga 16.5 35.0
Nb 9.25 0.2060 V3Si 17.1 15.6
Os 0.66 0.0070 Pb MoS 14.4 6.0
Pb 7.196 0.0803 CNb 8.0 1.7
Sn 3.722 0.0305 Al2CMo3 9.8 15.6
Tl 2.38 0.0178 Rb3C60 29.0 ?
Zn 0.85 0.0054 Cs2RbC60 33.0 ?

* For Type - I and Type - II superconductors, See Section 7.4.

7.2 MAGNETIC PROPERTIES

Consider a superconductor at a temperature T below its critical temperature TC . When a
magnetic field B is turned on, the critical temperature is lowered compared to the value when
144 Engineering Physics

there is no field. As the magnetic field increases, the critical temperature decreases, as illustrated
in Fig. 7.2. If the magnetic field is greater than BC , called the critical magnetic field,
superconductivity does not exist at any temperature. In a sense, the above diagram is a phase
diagram where the lower left region represents the superconducting state and the upper right
region its normal state. Table 7.1 also gives the values of BC at 0 K.

0.10
BC (0)
0.08 Normal

0.06
BC (T )

BC (T )
0.04
Superconducting

0.02

0 2 4 6 TC 8 T(K)
Fig. 7.2 Variation of the critical temperature with magnetic field for lead.

The magnetic field approaches zero as T approaches TC . The variation of the critical
magnetic field at temperature T can be represented by the relation:

Ë T2 Û
BC (T ) BC (0) Ì1 – 2 Ü (7.1)
ÌÍ TC ÜÝ

where BC (0) is the critical magnetic field at 0 K and TC is the critical temperature at B = 0.

7.3 MEISSNER EFFECT

Another interesting aspect of the magnetic properties of superconductors is the Meissner effect.
Consider a superconducting material in the presence of a small external magnetic field
B < BC at a temperature greater than the critical temperature. The magnetic field lines will be
as illustrated in Fig. 7.3(a). If the material is cooled below the critical temperature TC , it becomes
a superconductor and the magnetic field lines will be as shown in Fig. 7.3(b). In other words,
when a superconductor is cooled below the critical temperature in an external magnetic field,
the magnetic field lines are expelled or cancelled from the superconductor and the magnetic
field inside the superconductor becomes zero.
 Superconductivity 145

Field
direction

T > TC T < TC
(a) The magnetic lines of force around (b) Magnetic flux expulsion from
a superconductor when T > TC . the superconductor when T < TC .

Fig. 7.3 The Meissner effect.

7.4 TYPE–I AND TYPE–II SUPERCONDUCTORS

Depending on the magnetization, superconducting materials can be classified into Type-I and
Type-II superconductors. Only certain superconductors, called type-I or soft superconductors,
exhibit complete Meissner effect. Some of the familiar examples are Al, Cd, Sn, and Zn,
(Table 7.1). Figure 7.4(a) shows the plot of the magnetization (M) times P0 (permeability of
free space) versus the applied magnetic field B for a type-I superconductor. For magnetic fields
less than the critical field BC, the magnetic field induced in the superconductor P0 M is equal
and opposite to the external magnetic field. That is, the superconductor is a perfect diamagnet.
For type-I superconductors, the values of BC are very small (Table 7.1). Hence, such materials
are not useful as coils of a superconducting magnet.

– m0M m0M = –B – m0 M

BC1 BC2
BC B Completely Mixed state Normal
diamagnetic conductor
(a) For type-I super conductor (b) For type-II superconductor

Fig. 7.4 Magnetization versus magnetic field curve.

Type-II or hard superconductors have magnetization curve similar to that given in

Fig. 7.4(b). Such materials are usually alloys or metals that have large resistivities in the normal
state. Type-II superconductors exhibit two critical magnetic fields, BC1 and BC2 [Fig. 7.4(b)].
For applied fields less than BC1, total magnetic flux cancellation will be there and the entire
146 Engineering Physics

sample will be superconducting as in type-I superconductors. For applied fields greater than
BC2, complete penetration of the magnetic field throughout the sample will be there and the
resistivity returns to the normal value. For applied fields between BC1 and BC2 there will be
partial penetration of the magnetic fields, the field lines being confined to flux tubes, also called
vortices. In the flux tubes, the material will have normal resistivity. The surrounding material
remains field free and superconducting. Each flux tube contains one quantized unit of flux,
called a fluxoid (Section 7.7).
For certain type-II superconductors, the critical field BC2 may be several hundred times
larger than the typical values of critical fields for type-I superconductors. For example, Nb3Ge
has a BC 2 of 34 T. Such materials are used to construct high field superconducting magnets.
Figure 7.5 illustrates the critical magnetic fields BC1 and BC2 as a function of temperature.
Below the BC1 curve, the substance exhibits the Meissner effect. Between the two curves is the
mixed state with filaments of normal substance penetrating the superconducting state. Above
the BC2 curve, there is complete magnetic field penetration and the entire sample has normal
resistivity.

0.20

0.15 BC2
B(T)

0.10

0.05 BC 1

0 1 2 3 4 5 T(K)
Fig. 7.5 Critical magnetic fields BC1 and BC2 of a type –II superconductor as a function of temperature.

London penetration depth

In type–I superconductors, magnetic fields are expelled from the interior by the formation of
surface currents. In reality, these currents penetrate the surface to a small extent. Within this
layer, the magnetic field B decreases exponentially from its external value to zero, according
to the expression:
È rØ (7.2)
B r B0 exp É  Ù
Ê OÚ

where the external field is assumed to be parallel to the surface of the superconductor. B0 is
the magnetic field at the surface, r is the distance from the surface to some interior, and O is
 Superconductivity 147

the London penetration depth. The penetration depth varies with temperature according to
the equation as follows:
1

Ë È T Ø4 Û 2
O (T ) O 0 Ì1  É Ù Ü (7.3)
Ì Ê Tc Ú Ü
Í Ý
where O0 is the penetration depth at 0 K. From Eq. (7.3), it follows that at T = TC the substance
changes from its superconducting properties and attains its normal state, as the field penetrates
the whole specimen.

7.5 THE ISOTOPE EFFECT

It has been observed (1950) that the superconducting critical temperature for different isotopes
of superconductors is different. This effect is called the isotope effect. Experimental
observations revealed that TC depends on the isotopic mass according to the relation

M DTC constant (7.4)

where M is the average isotopic mass and D varies from material to material but is typically
about 0.5. The significance of this discovery is that it tells us that the electron-phonon interaction
in crystals cannot be ignored.

7.6 BCS THEORY

For quite some time, it was felt that superconductivity is due to a collective behaviour of the
conduction electrons. The discovery of isotope effect tells us that the electron-phonon
interaction is the one responsible for superconductivity. In 1957, Bardeen, Cooper, and
Schrieffer (BCS) published a theory, now known as BCS theory, which explained most of the
phenomena relating to superconductivity.

7.6.1 Cooper Pairs

According to BCS theory, at low temperatures the conduction electrons in a superconductor are
coupled in pairs. The coupling comes in the following way:
An electron moving through the lattice of positive ions attracts the positive ions nearby,
displacing them slightly, resulting in a region of increased positive charge density (Fig. 7.6).
This region of increased charge density propagates through the material as a vibrational wave
in the lattice, called a phonon.

Fig. 7.6 An electron travelling through the lattice of positive ions generating a wave of increased
charge density, shown by the dotted lines in two dimensions.
148 Engineering Physics

A second electron that encounters the wave of increased positive charge concentration is
attracted towards it by the Coulomb interaction. Thus, the phonon acts as the mediator of the
interaction between the two electrons. Since both the electrons experience an attractive force
toward the region of increased positive charge density, the interaction between the two is an
attractive one. At low temperature (T < TC), the attraction between the two electrons can exceed
the Coulomb repulsion between them. This pair of electrons is called a Cooper pair.

7.6.2 Superconducting Energy Gap

The electrons in a Cooper pair have opposite spins and equal and opposite linear momenta. Thus,
they form a system with zero spin and zero linear momentum. Each Cooper pair may be
considered as a single particle with zero spin. Collection of such Cooper pairs form a system
of bosons. Hence, any number of Cooper pairs may be in the same quantum state with the same
energy. In the superconducting state, the Cooper pairs are correlated, so that they all act together.
Thus, in the ground state of a superconductor (at T = 0), all the electrons are in Cooper pairs
and all the Cooper pairs are in the same state. The electrons in a superconducting state can absorb
or emit energy when the binding of the Cooper pairs is broken. The energy needed to breakup
a Cooper pair is similar to that needed to break up a molecule into its constituent atoms. This
energy is called the superconducting energy gap Eg. According to BCS theory this energy
at absolute zero is predicted to be

Eg 3.5 k TC (7.5)
where k is the Boltzmann constant. As the temperature is increased from T = 0 K, the energy
gap reduces. At T = TC the energy gap is zero.
The energy gap for typical superconductors (~10–4 eV) are much smaller than the energy
gap for typical semiconductors (~1eV). This prediction of the energy gap was verified
experimentally by studying the absorption of electromagnetic radiation by superconductors.

7.7 MAGNETIC FLUX QUANTIZATION

Consider a ring made up of a superconductor in its normal state in a magnetic field illustrated
in Fig. 7.7(a). Cool the ring to a temperature below the critical temperature TC. The magnetic
field in the material of the ring will be expelled. Some of the expelled magnetic field lines will
be trapped inside the ring as in Fig. 7.7(b). A prediction of the BCS theory is that the magnetic
flux inside the ring is quantized, taking on the values:
h
) n (7.6)
2e
where n is an integer and 2e refers to the charge on the Cooper pair that forms the basic unit.
The magnitude of the flux quantum is given by
h
)0 2.0678 – 10 15 Tm 2 (7.7)
2e
 Superconductivity 149

This is referred as the quantum fuxoid. Quantization of magnetic flux has been confirmed
experimentally.

(a) Above the critical temperature TC . (b) Below the critical temperature.

Fig. 7.7 A ring of superconducting material in a magnetic field.

7.8 JOSEPHSON JUNCTION

In barrier penetration (to be discussed in Section 9.22) a single particle tunnels through a barrier.
Consider two superconductors separated by a thin layer (~10–9 m) of insulating material. In
1962, Josephson proposed that Cooper pairs could tunnel from one superconductor to the other
with no resistance, giving rise to a direct current with no voltage across the junction. Such a
superconductor-insulator-superconductor junction is called a Josephson junction (Fig. 7.8).

The d.c. Josephson effect

The current across the junction is given by
I I max sin (I2 – I1 ) (7.8)
where Imax is the maximum current which is dependent on the thickness of the barrier, I1 is
the phase of the wave function on one side of the insulating layer, and I2 is the phase of the
corresponding wave function on the other side. This result is known as the d.c. Josephson
effect.

Insulator
(oxide layer)

Super Super
Conductor Conductor

Fig. 7.8 Josephson junction.

150 Engineering Physics

The a.c. Josephson effect

If a d.c. voltage V is applied across a Josephson junction, there would be an alternating current,
having frequency Q given by

2 eV
Q (7.9)
h
This result is known as the a.c. Josephson effect, and the current is called the Josephson
current. As frequency can be measured very accurately, a.c. Josephson effect is often used as
a voltage standard. The accuracy of the voltage standard with Josephson junction is
approximately one part in 1010. The inverse effect also happens, in which the application of
an alternating voltage across a Josephson junction results in a d.c. current. This has also been
verified experimentally.

7.9 HIGH TEMPERATURE SUPERCONDUCTIVITY

Superconductors can be grouped into low TC and high TC based on their transition temperature.
Substances having TC around or below 24 K are considered as low TC super-conductors
and those above are high TC superconductors. The low TC superconductors range from
ordinary metals and alloys such as Nb(TC = 9.25 K) and Nb3Ge(TC = 23.2 K) to oxides like
BaPb1–xBixO3(TC = 13 K). A class of compounds called A-15, Nb3Ge, Nb3Sn(TC = 18.1 K) and
Nb3Ga(TC = 20.3 K) and others, are the very familiar ones with TC in and around 20 K. The
BCS theory could explain the behaviour of low TC superconductors.
A forward step was the observation of a TC of 40 K in La1–xSrxCuO with x = 0.15 by Bednorz
and Muller (1986), for which they were awarded the Nobel Prize in 1987. Changing lanthanum
by yttrium and strontium by barium a TC of 93 K in YBa2Cu3O7 was reported in 1987. This
compound is referred to as 1-2-3 following the ratio of the three metallic elements. This was
a fantastic advancement, as the observed TC surpassed 77 K, the boiling point of liquid nitrogen.
Another interesting aspect about the type-II copper oxide superconductors is about their
extremely high upper critical fields. For Y Ba2Cu3O7 the upper critical field Bc2 # 100 T at
77 K and about 300 T at 0 K.
A similar compound using bismuth and aluminum Bi Al1–yCaSrCoO7–d with d < 0.45 and
0 < y < 0.3 raised the value of TC to 114 K. The thallium based compound T12 Ba2Can–1 CunO2n+4
is a very interesting since it gives different TC values for different n; TC of 80 K for
n = 1, TC = 110 K for n = 2 and TC = 125 K for n = 3. There is a possibility of reaching
very high TC values if we can make compounds with n > 3. In 1993, a higher TC (113 K) was
achieved in the mercury based copper oxide HaBa2Ca2Cu3O1+x with x being a small positive
number. At extremely high pressures (about 300000 atmospheres) these mercury based
superconductors reach transition temperature of 164 K. Most of these compounds fall in the
category of ceramics.
Another class of superconductors is based on the organic molecule C60. Pure C60 is not a
superconducting element. When C60 is doped with the right amount of potassium, it forms the
compound K3C60 with a TC of 18 K. Combination of C60 with thallium and rubidium increases
the TC to 42.5 K. The dream of the scientists is to achieve a TC of about 300 K, so that they
can eliminate the need for cryogenic fluids.
 Superconductivity 151

7.10 APPLICATIONS
The properties of zero resistance and the Meissner effect make superconductors ideal for many
applications. The cost of cryogenic systems and fluids has also to be taken into account when
we consider the applications. We discuss here some of the important applications.

7.10.1 SQUID
The Josephson junctions are used in devices known as Superconducting Quantum Interference
Devices (SQUID). The SQUID uses a pair of Josephen junctions in a current loop. The current
is extremely sensitive to the magnetic flux applied to the loop. SQUIDS are used for measuring
very small amounts of magnetic flux. They can be used to measure quantum fluxoid to within
one part in 106. As ordinary magnetometers, SQUIDS are capable of measuring magnetic
fluctuations of the order of 10-13 T. The biomedical applications of SQUIDS include the imaging
of soft tissues such as the brain. They have also been used to detect the presence of bacteria,
search for explosives, examine materials for defects, and search for oil.

7.10.2 Generation and Transmission of Electricity

Substantial amount of energy saving is possible if superconductors are used in electrical
generators and motors. Most of the savings come from the replacement of the heavy iron cores
by lighter superconducting magnets. The other part comes from the cutting of resistive losses.
Superconducting transmission lines would save significant amounts of energy. Superconducting
transmission requires no expensive transformers. For normal transmission one has to make the
voltage as large as possible, which is not needed if R = 0. The large current densities possible
in superconducting wires allow the reduction of the number and size of transmission lines.
Superconducting energy storage rings would be of great use to store extra energy generated
during low usage hours in power plants.

7.10.3 Superconducting Magnets

A conventional electromagnet is made by passing current through a metal wire wound in the
shape of a solenoid. A maximum magnetic field of a few millitesla can be generated by this
method. By placing an iron core within the solenoid, the magnetic field can be enhanced to
about 2 to 3 T. The iron core is extremely heavy and cumbersome. Since we can achieve current
densities of 107A/cm2 in superconducting wires, it is possible to produce very large magnetic
fields. An additional advantage is that no iron core is needed in this case. The superconducting
material must have a critical field higher than the maximum field we want to generate. With
type-II superconductors, it is possible to achieve upper critical fields of 50T (Section 7.4).
Superconducting magnets are used for large particle accelerators. Large magnets are used to
confine plasma in fusion research. One of the most important medical applications of large
superconducting magnets is in Magnetic Resonance Imaging (MRI).

7.10.4 Other Applications

Josephson junctions could be used in integrated circuits. Superconducting computers are not
cost-effective. They may have to be re-evaluated when room temperature superconductors
152 Engineering Physics

become available. The Josephson junction is used to measure and maintain voltage standards.
In Japan, a magnetic leviation (maglev) train achieved a speed of 550 km/h. It is designed on
the principle of Meissner effect to levitate the transport system. The idea is to make a more
comfortable travel at higher speeds.

SOLVED EXAMPLES

Example 7.1 A superconducting sample has a critical temperature of 3.722 K in zero magnetic
field and a critical field of 0.0305 T at 0 K. Evaluate the critical field at 2 K.
Ë T2 Û
Solution: We have BC (T ) BC (0) Ì1 – 2 Ü
ÍÌ TC ÜÝ

Ë È 2K Ø2 Û
BC (2 K) (0.0305 T) Ì1 – É Ù Ü
ÌÍ Ê 3.722 K Ú ÜÝ
= 0.0217 T

Example 7.2 A d.c. voltage of 1 PV is applied across a Josephson junction. Calculate the
frequency of the Josephson current generated.
Solution: From Eq. (7.9), the required frequency

2eV 2 1.6 – 10 –19 C (10 –6 V)

Q
h 6.626 – 10 –34 Js
= 482.9 MHz
Example 7.3 Calculate the superconducting energy gap at T = 0 K predicted by the BCS theory
for cadmium. TC for cadmium is 0.517 K.
Solution: Energy gap Eg = 3.5 K TC

3.5(1.38 – 10 –23 J/K) (0.517 K)

Eg
J
1.6 – 10 –19
eV

1.56 – 10 –4 eV
Note: Compare this result with the measured value of 1.5 × 10–4 eV.
Example 7.4 The superconducting energy gap for a material is 1.5 × 10–4 eV. Compute the
wavelength of a photon whose energy is just sufficient to break up a Cooper pair in it.
Solution: Let Q be the frequency of the photon. Then,
 Superconductivity 153

hc hc
Eg hQ or O
O Eg

(6.626 – 10 –34 Js) (3 – 108 m/s)

O
(1.5 – 10 –4 eV) (1.6 – 10 –19 J/eV)

8.28 – 10 –3 m

Example 7.5 Calculate the London penetration depth for lead at 5.2 K if the penetration depth
at 0 K is 37 nm. The critical temperature of lead is 7.193 K.
Solution: London penetration depth is given as
1

Ë È T Ø4 Û 2
O (T ) O 0 Ì1  É Ù Ü
Ì Ê Tc Ú Ü
Í Ý
1

Ë È 5.2 K Ø 4 Û 2
O 5.2 K 37 nm Ì1  É Ù Ü 43.4 nm
ÌÍ Ê 7.193 K Ú ÜÝ

Example 7.6 An isotope of mercury with a mass of 199 amu has a transition temperature of
4.185 K. If the TC of another isotope is 4.153 K, what is its atomic mass. Take the value of
D to be 0.5.
Solution: We have the relation
M DTC Constant
1
M2 È TC1 Ø D
M1 ÉÊ T ÙÚ
C2

2
È 4.185 Ø
M2 (199 amu) É
Ê 4.153 ÙÚ
= 202.08 amu

REVIEW QUESTIONS

7.1 Explain what is superconductivity.

7.2 Explain critical temperature and critical magnetic field with respect to a superconducting
substance. State the relation connecting the two.
154 Engineering Physics

7.3 What is Meissner effect?

7.4 What are type-I and type-II superconductors? Give examples.
7.5 Type-I superconductors are not suitable as coils of superconducting magnet whereas
type-II are. Why?
7.6 Explain what you understand by vortices in type-II superconductors.
7.7 What is isotope effect in superconductivity? Explain its importance.
7.8 What are Cooper pairs?
7.9 What is Josephson tunnelling? Mention some of the applications of Josephson junction.
7.10 Write a note on high temperature superconductors.
7.11 Explain one or two applications of superconductivity.
7.12 What is a.c. Josephson effect? How is it used as a voltage standard?
7.13 Explain briefly magnetic flux quantization.
7.14 Explain Meissner effect and type-I and type-II superconductors. Write a note on high
temperature superconductors.
7.15 How is superconductivity explained on the basis of the BCS theory? Explain some of
the applications of superconductors.
7.16 Discuss the magnetic properties of superconductors.

PROBLEMS

1. A superconducting sample has a critical temperature of 4.1 K in zero magnetic field and
critical magnetic field of 0.0505 T at 0 K. Find the critical field at 2 K.
2. Estimate the critical field for lead at 3.8 K from the following data.
BC(0) = 5.6 × 104 A/m, and TC = 7.193 K.
3. The critical temperature of a superconducting sample is 1.19 K with atomic mass 26.9.
Estimate the critical temperature when the isotope mass change to 32.1.
4. Compute (i) the superconducting energy gap for indium and (ii) the wavelength of a
photon that could just break up a Cooper pair in indium. The transition temperature of
indium is 3.408 K.
5. The London penetration depth of lead (Pb) at 0 K is 390 Å. Calculate the penetration
depth at 2 K. TC of lead is 7.2 K.
6. Calculate the wavelength of the photon, which will be required to break a Cooper pair
in the superconductor Zr whose TC = 0.56 K.