Copyright © 2013 American Scientific Publishers Journal of

All rights reserved Surfaces and Interfaces of Materials

Printed in the United States of America Vol. 1, 1–23, 2013

Review the High Temperature Superconductor (HTSC)

Cuprates-Properties and Applications
Abida Saleem and S. Tajammul Hussain∗
Nano Science and Catalysis Division, National Centre for Physics, Quaid-i-Azam University Campus, 45320 Islamabad, Pakistan

This review illustrates the synthesis and properties of High temperature Superconductors, discov-
ered twenty six years ago in the copper oxides. This discovery has created tremendous activity
in the researchers in this field. In high temperature superconductor cuprates, superconductivity is
confined within CuO2 planes. The highlighting feature of this type of superconductors that is more
attractive for application point of view is the very high upper critical field. The article gives a sum-

REVIEW
mary of the prevailing arguments of researchers to relate the material to cuprates and also the
comparative features of many families of superconductors. The existing challenges, such as flux
pinning, inter-grain Josephson losses due to population of voids and attempts towards the solution
of these problems have been made by researcher have also been discussed.
Keywords: High Temperature Superconductors, Type I and Type II Superconductors, X-Ray
Diffraction, Scanning Electron Microscopy.

CONTENTS In superconductors electric conduction arises from the

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 pairing of charge carriers into cooper pairs.1 Supercon-
2. Conventional Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . 1 ductivity is believed to be a universal phenomenon, and
3. High-Temperature Superconductors (HTSC) . . . . . . . . . . . . . . . 2
3.1. Carrier Concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 is a collective state existing in electron population of
3.2. Families of Hole-Doped HTSC . . . . . . . . . . . . . . . . . . . . . 3 a material. From superconducting cosmic strings created
3.3. Effect of Transition Metals (TM) Doping . . . . . . . . . . . . . 8 as topological defects in the early universe2 or proton
3.4. HTSC Preparation Techniques and superconducting cores in neutron stars3 to color supercon-
Composition Features . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.5. Superconductivity of HTSC at
ductivity in quark matter.4
Surfaces and Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4. Room Temperature Superconductivity . . . . . . . . . . . . . . . . . . . . 14 2. CONVENTIONAL SUPERCONDUCTORS
5. Magnetic Properties of Superconductors . . . . . . . . . . . . . . . . . . 14
In 1911, Kamerlingh Onnes first discovered the
5.1. Type-I Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5.2. Type-II Superconductors . . . . . . . . . . . . . . . . . . . . . . . . . . 14 phenomenon of superconductivity in mercury5 by an
6. Inter-Grain Weak Links and Nano-Particles Doping . . . . . . . . . 14 experimental error, such as an accidental short circuit.
7. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 Later on careful repetition assured him that he had in fact
7.1. Transmission of Commercial Power . . . . . . . . . . . . . . . . . . 18 discovered a new electronic phase. The discovery of van-
7.2. Bio-Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
7.3. Electronic Switches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 ishing resistivity in several other elements such as tin and
7.4. Scientific Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 lead soon followed.
8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 The second characteristic of superconductivity, expul-
References and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 sion of magnetic flux from the superconducting state, was
discovered by Meissner and Ochsenfeld in 1933.6 Major
1. INTRODUCTION advances were made with the London theory7 in 1935
Superconductors are the interesting materials used and and the Ginzburg–Landau theory8 in 1950. A universally
studied today. A superconductor can be distinguished by accepted microscopic theory of the phenomenon was put
following two properties: (i) Vanishing of electric resis- forth by Bardeen, Cooper, and Schrieffer (BCS) in 1957.9
tivity below a critical temperature (Tc ). (ii) Expulsion of They ascribed superconductivity to an attractive interac-
external magnetic field below a critical field (Hc ). tion between two electrons through electron–phonon inter-
action nBCS theory of superconductivity. One electron
∗
Author to whom correspondence should be addressed. interacts with a positive ion in the lattice and deforms the

J. Surf. Interfac. Mater. 2013, Vol. 1, No. 2 2164-7542/2013/1/001/023 doi:10.1166/jsim.2013.1025 1

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

lattice; a second electron of compatible momentum value 3. HIGH-TEMPERATURE

interacts with the ion in the distorted lattice so as to mini- SUPERCONDUCTORS (HTSC)
mize the energy. The interacting electrons are said to form A history of the increase in record Tc is shown in
a pair. The electrons of a pair have equal and opposite Figure 1. In 1986, a startling discovery reopened the
momentum; one in spin up state and the other in spin down field of superconductivity research. Bednorz and Muller,
state, so that the total spin of a pair is zero. The electron working at IBM in Switzerland, discovered a new class
pairs are called Cooper pairs. The important feature of of superconducting materials starting with LaBaCuO, hav-
Cooper pair is that excitation can take place in only pairs ing Tc up to 30 K.17 The very next year, liquid nitrogen
of electrons; i.e., if the state with +k and spin up (↑) is temperature barrier (77 K) was broken with the discov-
occupied, the corresponding state with −k and spin down ery of YBa2 Cu3 O7− , superconducting at 90 K.18 Since
(↓) is also occupied and if the state with +k is vacant, the CuO2 plane is the common component in all these new
state with −k is also vacant. HTSC, these materials are referred to as the “cuprates.”
Two of the main experimental facts that led to the BCS Due to some reasons, the discovery of superconductivity
understanding were: in the cuprates was very surprising. In their stoichiomet-
(a) The density of states is gapped at the Fermi surface. ric form; with no additional oxygen or other dopant atoms
This was determined experimentally first by the measure- added, these materials are anti-ferromagnetic Mott insu-
ment of an exponential specific heat.10
11 This led to the lators. It is ordinary understanding that magnetism can-
realization that some kind of pairing is occurring and elec- not coexist with superconductivity. Abrikosov and Gor’kov
showed that magnetic impurities disrupt superconductivity
REVIEW

trons are thermally activated across a gap with Boltzmann

and depress Tc 19
20 The evident differences between these
probability. The gap was later confirmed by electromag-
new HTSC and the conventional superconductors created
netic absorption in aluminum and lead.12–14
a great deal of stimulation. Rapidly, all the old experi-
(b) The Tc was found to vary as the inverse square root
ments which had lead to the unifying theory of conven-
of the nuclear mass, so the phonons concern was shown
tional superconductors were repeated. But the results were
experimentally by the √ isotope effect.15
16 Since the phonon
often confusing and/or contradictory.
frequency varies as k/M, the discovery of the iso- In distinction to the deep Fermi sea of quasi-free elec-
tope effect led to the understanding that phonons are trons in the case of classical metals (kB Tc  EFermi ) where
involved. the cooper-pair condensed electrons amount only to a
Numerous details were filled in over the next few small part of the valence electron system. In these layered
decades, but the problem of superconductivity was largely cuprate compounds, there is only a shallow reservoir of
considered solved by BCS in 1957. charge carriers (kB Tc ∼EFermi ) which have to be introduced

Abida Saleem

S. Tajammul Hussain

2 J. Surf. Interfac. Mater. 1, 1–23, 2013

Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

3.1. Carrier Concentration

The most prominent factor in the HTS is the existence
of a whole new parameter. This new parameter is called
carrier concentration, which can easily be tuned. This
can be explaining by 3-dimensional phase diagram rather
than the simple temperature versus B-field phase diagram
of the conventional superconductors. The stoichiomet-
ric parent compounds are insulators in HTSC materials,
and by adding charge carriers these materials become
superconducting. Normally charge carriers in the form
of holes are added by doping oxygen interstitially e.g.,
Bi2 Sr2 CaCu2 O8+ . Also, by substituting a mono-valent
atom with a divalent atom e.g., replacing La with Sr in
La2−x Srx CuO4 , or by removal of oxygen from their stoi-
chiometric positions e.g., YBa2 Cu3 O7− . In any case, the
properties of the material depend strongly on the carrier
concentration. Many electron-doped superconductors have
also been discovered, that is just about the mirror image of
the hole-doped materials.

REVIEW
3.2. Families of Hole-Doped HTSC
There are three major families of hole-doped HTSC stud-
ied today. However, much of the misunderstanding in the
study of HTSC results from the reality that each material is
reachable to different experimental techniques. An inclu-
Fig. 1. Time evolution of Tc . sive summary of many of the known hole-doped HTSC
in the insulating anti-ferromagnetic (AF) stoichiometric materials along with an explanation of the variant Tc ’s is
parent compound by appropriate doping. Thus generated given by Eisaki et al.25
normal state corresponds to a bad metal in which Coulomb
correlations strongly link the charge and spin degrees 3.2.1. La1−x Mx Cu4 O
of freedom. This intrinsic closeness of metal-insulator, Bednorz and Müller in 198617 discovered the lanthanum
magnetic and SC transitions continues to present a great family of HTSC, which was the first family of materials to
challenge to theory, which is sensibly more complicated be discovered by them. Synthesis of alkaline-earth-doped
than the classical superconductivity problem. The SC La1−x Mx Cu4 O; M = Ca, Sr and Ba of K2 NiF4 structure
instability in the structurally and chemically related lay- with Tc up to 35 K is achieved by the ceramic method.
ered cobaltate and ruthenate compounds as well as in Typically, the synthesis is carried out by reacting stoichio-
cuprate HTSC is hence believed to stem predominantly metric quantities of the oxides/carbonates around 1300 K
from a magnetic and not from a phononic interaction. in air.26–28 Furthermore, a few groups have annealed the
Whereas in the case of the classical metallic superconduc- samples after the sintering step in an oxygen atmosphere at
tors, magnetism plays only the role of unusual, intrinsi- 673 K.29 Metal nitrates have also been used as the starting
cally antagonistic long range instability. materials for the synthesis.30–32 Since the hydrated metal
It is generally accepted that there is a dx2 −y2 wave gap nitrates have low melting points leading to a uniform melt
in the density of states. However in conventional super- in the initial stage of the reaction, so a more homogeneous
conductors, simple symmetric s-wave gap is found. This starting mixture is obtain by starting with metal nitrates.
was shown by flux modulation measurements in YBCO To obtain the necessary oxygen content Nitrates are used,
DC-SQUID21 and then more explicitly by flux quantiza- which provide necessary oxidative atmosphere. Politis et al.
tion in a tri-crystal YBCO junction.22 From the gap in the observed high Tc superconductivity in the single crys-
density of states, it is usually decided that electrons are talline La18 Sr02 CuO4 with Tc onset up to 42 K. They
paired. By the measurement of h/2e flux quanta,23 it was prepared and studied the properties of La Ba Cu O
shown explicitly that the charge carriers have charge 2e. At and La Sr Cu O compounds. By substituting Sr for
low carrier concentration, magnetism is known to play a Ba in such type of compounds an increase in Tc onset in
role in the crystal, so many arguments strongly support the La18 Sr01 Ba01 CuO4 from 24 K to 35 K was observed.33
point that electron pairing in HTSC is caused by magnons The LSCO is physically the hardest of the three materials,
or other magnetic consequences. But the pairing is indeed and with stronger bonds it is easier to grow large single
caused by phonons have also carried strong arguments.24 crystals (> 1 cm); structure is shown in Figure 2(a).

J. Surf. Interfac. Mater. 1, 1–23, 2013 3

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain
REVIEW

Fig. 2. Crystal Structure of the high temperature superconductor families (a) La2−x Srx Cu4 O (b) YBa2 Cu3 O7− (c) Bi2 Sr2 CaCu2 O8+ 25

3.2.2. YBa2 Cu3 O7− many domains, separated by “twin boundaries” in which
The YBCO discovery followed that of LSCO within a the chains run in orthogonal directions. YBCO crystals
year18 break the 77 K temperature limit. The optimal may be “de-twinned” by application of pressure for more
Tc of YBCO is now around 90 K. Superconducting careful studies, but many presented results on YBCO are
YBa2 Cu3 O7− , having orthorhombic structure can be eas- confusing due to twin domains.
ily prepared by the ceramic method. Most of the inves- YBCO is so ordered that all atoms of a particular type
tigations of the YBa2 Cu3 O7− have been carried out on will live in the same electronic environment. YBCO has
the materials prepared by reacting Y2 O3 and CuO with been used in nuclear magnetic resonance (NMR) studies,
BaCO3 34
35 It is remarkable that Rao et al.36 obtained which investigate the spatial distribution of magnetic field.
mono-phasic YBa2 Cu3 O7− , as the x = 10 member of the
Y3−x Ba3+x Cu6 O14 series. The stoichiometric quantities of 3.2.3. Bi2 Sr2 CaCu2 O8+
high-purity Y2 O3 , BaCO3 and CuO are ground thoroughly BSCCO was discovered in 1988,35 can have one, two, or
and heated initially in powder form around 1223 K for a three CuO planes, whereas Tc increases with the num-
period of 24 h for preparing YBa2 Cu3 O7− . After the calci- ber of planes; structure is shown in Figure 2(c). Although
nations step, the powder is ground, pelletized and sintered the ceramic method is widely in use for the synthesis
at the same temperature for another 24 h. Annealing is car- of superconducting bismuth cuprates of the type Bi2 (Ca,
ried out in an atmosphere of oxygen around 773 K for 24 h Sr)n+l Cun O2n+4+ , due to different factors. It is usually dif-
to obtain the orthorhombic YBa2 Cu3 O7− phase show- ficult to obtain mono-phase compositions.37
38 Both ther-
ing superconductivity at 90 K. YBCO has been the most modynamic and kinetic factors are clearly concerned in
highly studied because it is the most ordered and cleanest determining the ease of formation as well as phase purity
crystal; structure of YBCO is shown in Figure 2(b). There of these cuprates. The member 2201 (n = 1) of the for-
are two CuO2 planes: the square plane and the chain plane. mula Bi2 Sr2 CuO6 appears to be stable around 1083 K
By analogy with the other HTSC families, it is thought and the member Bi2 (Ca Sr)3 Cu2 O8 ; 2122 (n = 2), around
that the superconductivity originates in the square plane, 1113 K. The n = 3 member, Bi2 (Ca Sr)4 Cu3 O10 (2223),
but it is hard to isolate the behaviors of the planes. Fur- can be obtained close to the melting point; 1123 K after
thermore, the one-dimensional chains make difficult the heating for several days or even weeks. The n = 2 mem-
study of YBCO crystals, because as-grown crystals exhibit ber (2122) seem to be most stable of all the members

4 J. Surf. Interfac. Mater. 1, 1–23, 2013

Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

of the Bi2 (Ca, Sr)n+1 Cun O2n+4+ a family. Bi2 O3 melts The nine phases in the TBCCO system can be represented
at around 1103 K, Increasing the reaction temperature by the homologous series. Tlm Ba2 Can−1 Cun O2n+m+2 ; m =
leads to preferential loss of volatile Bi2 O3 . This results in 1, n = 1–5, are the ‘single Tl–O layer’ phases, and m = 2,
micro-in-homogeneities and the presence of the un-reacted n = 1–4, are the ‘double Tl–O layer’ phases. The phases in
oxides in the closing product. Impurity phases in the final the TSCCO system are described as TlSr2 Can−1 Cun O2n+3 ;
product cannot easily be avoided due to partial reaction n = 1–3.57 These are iso-structural with the single Tl–O
between various pairs of oxides, as these materials con- layer TBCCO phases, with Sr on the Ba sites. However,
tain so many cations. Green et al. achieved the zero resis- these compounds have low Tc and difficult to manufac-
tance at temperatures exceeding 100 K by doping Pb to the ture without partial substitution of Tl by Pb or Bi.59–63
above system. The highest value of zero resistivity temper- Pb or Bi Doping increases Tc to 75–90 K.65–67 Simul-
ature Tc0 = 107 K is obtained for Bi18 Pb02 Ca2 Sr2 Cu3 Oy 39 taneously doping the Ca site with Y increases Tc above
Most of the above problems have been solved by 100 K.60
68
69 Cation doping also has the effect of chang-
employing the matrix reaction method.40
41 This method ing the average Cu oxidation state in the superconductor,
reduces the number of reacting components and gives bet- which controls the concentration of charge carriers.70
71
ter products. The synthesis is carried out by reacting the This results in a maximum Tc value at some optimum dop-
oxide matrix made from CaCO3 , SrCO3 and CuO with ing level. Presland et al.72 investigated the effects of oxy-
Bi2 O3 in the temperature range of 1083–1123 K in air for a gen stoichiometry on the physical properties of Tl-based
minimum period of 48 h. The matrix reaction method gives and Bi-based HTSC compounds. They have found that the
mono-phasic n = 2 (2122) and n = 3 (2223) compositions

REVIEW
optimum doping level is at 0.17 holes per unit CuO2 plane
showing Tc values of 85 K and 110 K respectively.42
43 and this shows general feature of all cuprate superconduc-
Quenching the samples in air from the sintering temper- tors. The optimum doping level for Pb and Bi doping in
ature or heating in a nitrogen atmosphere get betters the the TSCCO system appears to be around 50% Tl3+ site
superconducting properties of bismuth cuprates. Bismuth
substitution,65
68
73
74 and for coincident Y doping the opti-
can also be replaced with thallium or mercury, which
mum level is 20% Ca2+ site substitution.66 Politis et al.75
results in the highest Tc material known i.e., 153 K. YBCO
synthesized the Tl2 Ba2 Ca2 Cu3 O10 by ceramic methods and
has been used in magnetic field applications because it is
observed onset of Tc around 130 K. Nakajima et al.76
easier to pin flux in it and BSCCO competes with YBCO
found that the substitution of the rare-earth elements Nd,
as the most technologically useful material. YBCO can
Gd or Y, the optimum level of doping for the for Ca in Tl
be used to grow high-Tc SQUIDS with grain-boundary
(1212) was at 30% Ca2+ site substitution. From the chem-
Josephson junctions. Their higher operating temperature
istry of Ba and Sr, it would be expected that the TSCCO
than conventional SQUIDs makes them practical in the
study of living biological materials. BSCCO has been and TBCCO compounds can be doped with Ba and Sr
more useful so far in bulk applications, has been formed respectively. The introduction of Sr to the TBCCO sys-
into superconducting wires and placed into the Detroit. tem has the result of stabilizing the single Tl–O layered
Politis44 studied multi phase Sr–Bi–Ca–Cu–O with the phases.77
78 The Tl-2223 phase can only be synthesized
nominal composition of SrBiCaCu2 O6 and observed onset up to a Ba:Sr ratio of 1:1.77 Therefore, there is a wide
of Tc around 120 K and observed double transitions in range of cation compositions over which Tl-based HTSC
many samples. phases can exist and from which the composition with the
most appropriate properties must be selected for the future
3.2.4. Tl–Ba–Ca–Cu–O (TBCCO) application. The structure of Tl-2201, Tl-2223 and Tl-2212
Tl–Ba–Ca–Cu–O (TBCCO) superconductors, discovered are shown in Figure 3.58
in 1988 by Sheng and Hermann45–50 are the best among
all other cuprates due to their high transition tem- 3.2.5. Hg–Ba–Ca–Cu–O
perature [Tc (0)], transport critical current densities [Jc ] In Hg-based high temperature superconductors, the
and low microwave surface resistances [Rs ]. There are Hg1 Ba2 Ca2 Cu3 O8+ prepared at normal pressure has
two Tl-based superconducting families, Tl–Ba–Ca–Cu–O highest Tc around 135 K. The critical temperature of opti-
(TBCCO) and Tl–Sr–Ca–Cu–O (TSCCO). TBCCO mate- mally doped phases HgBa2 Cam−1 Cum O2m+2+ ; m = 1–3
rials have perovskite-like Ba2 Can−1 Cun O2n+1 layers and have been studied. The Tc of HgBa2 Cu1 O4+ is 94 K,
tetragonal crystal structures.51–57 The Cu–O sheets stack whereas Hg1 Ba2 Ca1 Cu2 O6+ and Hg1 Ba2 Ca2 Cu3 O8+
vertically above one another in the single Tl–O layer phase has shown Tc around 135 K. The Tc of later
phases. In the double Tl–O layer phases each perovskite two phases has shown dependence on oxygen content in
layer is translated in the x and y directions by a/2, in this HgBa2 O4− charge reservoir layer. The highest Tc attained
manner doubling the lattice parameter along the c-axis; as for Hg-based Hg08 Tl02 Ba2 Ca2 Cu3 O8 superconductor is
shown in Figure 3.58 The exception is Tl2 Ba2 CuO6 which 138 K up to now. The resistivity of these compound under
also exhibits orthorhombic and monoclinic symmetry. pressure have shown Tc (0) around 160 K.79

J. Surf. Interfac. Mater. 1, 1–23, 2013 5

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

Fig. 3. Crystal structures of the layered Tl–Ba–Ca–Cu–O compounds.59

Fig. 4. Crystal structures of the layered Cu–Ba–Ca–Cu–O

3.2.6. Cu Ba2 Can−1 Cun O2n+4 compounds.91
92
Since stronger coupling between CuO2 planes in high
temperature superconductors lowers the anisotropy and synthesis of these compounds is not simple, but the super-
REVIEW

in sequence improves the superconducting properties i.e., conducting phases are easily obtained by normal pres-
Tc (0), critical current density (Jc ) and irreversibility field sure synthesis by introducing thallium into the charge
(Hirr ). Any superconducting material having these proper- reservoir layer. The substitution of Tl in Cu-12n − 1n
ties will be very useful from application point of view. Tl- compounds results in appearance of a new subfamily
1223 superconductor has least anisotropy and higher Tc (0) Cu1−x Tlx -12n − 1n. The crystal structure of Cu-1223,
among all members of single Tl–O layer compounds, but Cu-1234 and Cu-1245 are shown in Figure 4.91
92
the toxicity of Tl hinders its use for application.
Superconducting materials, CuBa2 Can−1 Cun O2n+ ; n = 3.2.7. (Cu, Tl)–Ba–Ca–Cu–O
1
2
3    [Cu-12n − 1n] prepared under high pressure, Since the discovery of superconductivity in both
is thought to be the most promising due to their Jc and CuBa2 Can Cun+1 ; Cu-12nn + 1) and TlBa2 Can Cun+1 ; Tl-
higher Tc 80–86 The members of Cu-12n − 1n family have 12nn + 1), their broad characterization have been carried
copper in the charge reservoir layer i.e., CuBa2 O4n+ ; and out. These systems are iso-structural excluding the position
have same tetragonal structure as that of Tl-12n − 1n. of oxygen in the charge reservoir layer. The carrier con-
The conducting charge reservoir layer of these compounds centration could be control by applying external pressure,
makes them least anisotropic as compared to Tl-based by varying oxygen contents and by cation substitution.93
94
superconductors. The members of Cu-12n − 1n super- These compounds are synthesized under high as well
conductor family with higher number of CuO2 planes are as normal pressure and have superconducting properties
thought to have higher Tc (0) because of the optimum very close to Cu-based compounds.95–98 The members of
valency of copper, which is responsible for higher criti- this family have semi insulating charge reservoir layer
cal temperature. Theoretically, n = 11 is predicted for the Cu1−x Tlx Ba2 O4n− which to some extent increases the
maximum increase of critical temperature.85 anisotropy of these superconductors but the anisotropy
There is another member of Cu-12n − 1n family hav- remains lower than that of Tl-based compounds. A contrast
ing carbon instead of Tl in the charge reservoir layer. The of the anisotropy parameter and technological critical tem-
n = 3 member of this family; (Cu, C)-1223 has high Tc and perature for superconductors of different families is shown
low anisotropy.87 The Tc of this compound is 120 K and in Figure 5.
lattice parameters a = 3862 Å and c = 14.80 Å, analogous The Cu1−x Tlx Ba2 Ca2 Cu3 O10− ; Cu1−x Tlx -1223 super-
to that of Cu-1223 superconductors.87
88 But (Cu, C)-1223 conductor of this family has highest Tc ; Tc 0 = 130 K and
does not have the ability of significant Tc (0) enhancement Jc 90 This compound with anisotropy parameter ( = 5)
by self doping89 because it has carbon in the charge reser- has Cu1−x Tlx Ba2 O4− charge reservoir layer and three
voir layer in comparison to Cu1−x Tlx Ba2 Ca2 Cu3 O10− in CuO2 planes in the unit cell; shown in Figure 6.99 It fol-
which change of state of thallium promotes the optimum lows P4/mmm space group and has tetragonal structure.99
holes doping in CuO2 planes. The two Ca atoms in the unit cell separate CuO2 planes
Among all the superconducting phases in this family from each other, while superconducting CuO2 plane linked
the highest Tc belongs to n = 3 phase, Cu-1223 (Tc 0 ∼ with Ba atom in the unit cell is pyramid type and is
120 K) and next higher member Cu-1234 has Tc of 118 K. called p-plane. A plane sandwiched between the p-planes
These two compounds have least anisotropy;  = 16, and is called central planes or s-plane. The p-planes are over-
long coherence length along c-axis.90
91 The high-pressure doped with the carriers while s-planes are optimally doped.

6 J. Surf. Interfac. Mater. 1, 1–23, 2013

Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

30 60

25 50

Z = (Tc/γ1/2)K
20 40
γ = (ξab/ξc)

15 30

10 20

5 10

0 0
Bi-2223 TlBi-1212 Tl-1223 Y-123 CuTl-1223
Superconducting Compounds

Fig. 5. A comparison of anisotropy and technological critical tempera- Fig. 7. The energy level diagram of Tl 6s level in Cu1−x Tlx -1223 super-
ture of high temperature superconductors.91 conductor before and after post-annealing in nitrogen.91
114

The p-planes also present as a bridge for the supply of completed by the reduction of Tl+3 to Tl+2 states, shown

REVIEW
the carriers from charge reservoir layer to s-plane. The Cu in Figure 7.112–114
atoms in the s-plane are named as Cu(2) and the oxygen It is concluded from the above detailed review
atom in this plane is named as O(4), however, the Cu of high temperature superconductor families that the
atoms in the p-plane are Cu(1) and the oxygen atom in superconductors of Tl-12n − 1n and Cu-12n − 1n
this plane is called O(1). The oxygen atom bridging the families in contrast to other cuprate families are superior
Cu1−x Tlx Ba2 O8− charge reservoir layer and p-plane is candidates for device fabrication. These compounds due
apical oxygen atom and is named as O(2) atom. to their lower anisotropy have the capability to carry very
The Cu1−x Tlx -1223 superconductor has been synthe- high current densities of the order of 104 –106 A/cm2 in
sized both in the form of thin films and bulk samples.99–104 applied magnetic fields. In both these families the higher
The thin films of this compound have Jc of the order of critical temperature belongs to n = 3 member. The Cu-
107 A/cm2 (77 K, 0T) and 105 A/cm2 (77 K, 10T).104 1223 has lower anisotropy than that of Tl-1223 but its
The superconducting properties of Cu1−x Tlx -1223 can preparation is possible only under high pressure. The high
further be enhanced by post-annealing and by substitu- pressure synthesis prevents the preparation of this com-
tion of different cations.96
107–111 The Tc of this material pound for large scale applications. But the substitution of
increases by self-doping mechanism when post-annealed Tl at the Cu site in the charge reservoir layer of Cu-1223
in nitrogen atmosphere. The self-doping mechanism is outcome in a new compound CuTl-1223 at normal pres-
sure, which has low anisotropy, higher Tc and Jc .
The as-prepared samples of CuTl-12nn + 1 supercon-
ductor are in the over-doped regime and the density of
states near the fermi level DEF  are greater than that of
the optimum value. Thallium with Tl+1 has lower quan-
tity of oxygen with it whereas Tl+3 has more oxygen, so
by these experiments we can optimize the charge state
of Tl atoms from Tl+3 to Tl+1 . The more oxygen in the
charge reservoir layer prevents the flow of electron to
the conducting CuO2 planes; oxygen controls this through
its higher electro-negativity. The carrier concentration in
CuO2 planes can be brought to optimum level by changing
of oxidation state.115
The doping of various cations, especially the transition
metals at the planar site and at charge reservoir layer has
a strong effect on the properties of HTSC. Whereas the
substitution of magnetic ions, such as Ni+2 , Co+3 , Fe+3
etc., causes strong changes in the structural and supercon-
ducting properties due to the magnetic ordering inside the
Fig. 6. Crystal structure of CuTl-1223 unit cell. plane and at the charge reservoir layer.

J. Surf. Interfac. Mater. 1, 1–23, 2013 7

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

3.3. Effect of Transition Metals (TM) Doping contrast, they found that Cu–O system had the smallest
Since the discovery of high temperature superconductivity p–d separation and the largest p–d hybridization. They
(HTSC), on-site substitution-al studies have proved very also found that removing an electron from these systems
practical in understanding the mechanism of HTSC.113
114 further enhanced the p–d hybridization.
In all the high Tc (R = 0) systems such as YBCO,
BSCCO, TBCCO and Hg-based systems, the Cu ions have 3.3.2. YBCO System
a particular importance. (i) Because they constitute the Hongjie et al.122 studied the thermoelectric power of the
very important structural part of all these systems, (ii) the La-214 systems doped with Zn, Mg and Ni. Their exper-
superconductivity is mainly supposed to reside in the CuO2 imental observations were rooted in variations of the spin
planes. The coordination of Cu(2); Figure 6 remains in gen- correlation induced by substitutions of Zn, Mg and Ni
eral invariant, except in special cases as described earlier,118 for Cu site in La214 systems. Their analysis recom-
while that of Cu(1) vary with the oxygen content. mended that magnetic scattering mechanism plays a key
role in the ST  behaviors. Furukawa et al.123 performed a
3.3.1. La2−x Srx CuO4 System NMR study to study the electronic state microscopically in
Sedky et al.119 investigated the structural and transport (La1−x Cax O) Cu1−x Nix S. They suggested that the density
properties of La185 Sr015 Cu1−x Mx Oy (M = Li, Ni, Co, Mn, of states (DOS) at the Fermi level increased with increas-
and x = 000, 0.15, 0.30) ceramic samples. They showed ing x, although those values are rather small.
that the magnetic doping elements caused lattice deforma- Van Bael et al. observed that substitution of Ni or Co
in the copper positions of Y-124 significantly changed
REVIEW

tion resulting in fast increase in the resistivity more effi-

the Tc .124 Nickel substitution had the most harmful effect
ciently than the non-magnetic doped samples and direct
on Tc ; only 3% Ni destroys superconductivity but did not
to the largest change in the transport properties of La-
change the Y-124 structure or the oxygen stability. Cobalt
214 systems. Normal state resistivity versus doping con-
substitution changed Tc less obviously, but the structure
tent for La185 Sr015 Cu1−x Mx Oy ceramic samples is shown
was largely affected. The observed effects upon Ni and Co
in Figure 8. They supposed that the Mn was not well sub-
substitution suggested that both dopants were substituted
stituted in the CuO2 planes of La-214 systems and it might
in different Cu sites; Ni substitutes the Cu(2) sites and Co
be dissolved in some other sites which had less effect substitutes the Cu(1) sites.
on superconductivity. Xiao et al.120 showed accurately the Verma et al.125 investigated that Co substitutes preferen-
relations between Tc and doping level as well as the crit- tially in the CuO chains [Cu(I)] while Ni prefers the CuO2
ical doping levels xc for the Fe-, Co-, Ni-, Zn-, Ga-, and planes [Cu(II)]. Surplus substitution of Co may cause the
Al-doped La-214 systems. conversion of the double CuO chains to single ones result-
They suggested that every dopant, magnetic or non- ing in a disordering of the CuO chains and a damage of
magnetic, either carries an intrinsic magnetic moment or orthorhombic-city. An orthorhombic to tetragonal transi-
induces a net moment on the Cu–O2 plane. The size of the tion occurs in the Co doped Y-124 structure. Co substitu-
moment was correlated with the inhibition of superconduc- tion destabilizes the Y-124 structure. Different occupation
tivity, consistent with the magnetic-pair-breaking effect. sites of Co in Y-124 as compared to Ni, results in a faster
Similarly, Chen et al.121 found that all ions (Cr, Mn, Fe, decrease in superconducting properties and a higher rate of
Co, Ni) substituting for Cu ion in La2−x Srx CuO4 system suppression of Tc . CuO chains may play a far more essen-
possessed local magnetic moments. Through a systematic tial role for occurrence of superconductivity in the Y-124
system, whereas CuO2 planes are thought to play a very
important role in the Y-123 system.
From the Raman scattering study of YBa2 (Cu1−x Mx 4 O8
(M = Ni, Zn) samples in the normal and superconduct-
ing phases, Payne et al.126 reported that the frequency
of the Cu(1) chain Ag mode was observed to soften by
about 11 cm−1 over a Ni doping range of 0–2.5%, while
other modes exhibited shifts of 0–4 cm−1 . Raman frequen-
cies of the Cu coupled modes in YBa2 (Cu1−x Nix 4 O8 as
a function of Ni concentration is shown in Figure 9. Lal
et al.124 reported the causes of Tc degradation in YBa2
(Cu1−x Mx 4 O8 (M = Ni, Fe) system was due to local-
ization and the carrier impurity scattering of magnetic/
potential origin might not be the cause of Tc inhibition in
the Fe- and Ni-doped Y-124 system.
Fig. 8. Normal state resistivity versus doping content for Pringle et al.128 reported the effect of doping and impu-
La185 Sr015 Cu1−x Mx Oy ceramic samples.119 rities on the oxygen isotope effect in HTSC cuprates.

8 J. Surf. Interfac. Mater. 1, 1–23, 2013

Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

both Zn and Ni substituted for Cu in the planes, from the

full pattern analysis. Analogous results are found by Faber
et al.134 from anomalous dispersive XRD analysis. Hoff-
man et al.135 recommended that in YBa2 (Cu1−x Nix 3 O7−
system over 95% of Ni dopants occupy the Cu(2) site
in the copper oxide planes, with negligible occupation
of Cu(1)copper oxide chain sites. Yin et al.136 mea-
sured Cu nuclear quadrupole resonance (NQR) spectra
of YB2 (Cu1−X Nix 3 O7− at room temperature. The asym-
metric broadening of Cu(1) could be recognized with
the emergence of a new peak, whereas the Cu(2) sig-
nal showed symmetrical broadening. Their results sup-
ported that Ni substitute not only for Cu(2) on the
conducting plane but also for Cu(1) on the chain in
Fig. 9. Raman frequencies of the Cu associated modes in YB2 (Cu1−X NiX 3 O7− .
YBa2 (Cu1−x Nix )4 O8 as a function of Ni concentration.126 Tomimoto et al.137 investigated the effects of impurity
on the superconducting coherence length in Zn or Ni-
They suggested that the hole-concentration- and impurity- doped YBa2 Cu3 O69 single crystals. They reported that

REVIEW
concentration-induced changes in the isotope-effect coef- coherence length () increased along both the in-and
ficient in YBa2 (Cu1−x Nix 4 O8 superconductors could be out-of-plane directions. They concluded that increased
continually modeled by including the effect of the normal- coherence length () along both the in-and out-of-plane
state pseudo-gap. Itoh et al.129 presented an application directions could be well explained by the pair-breaking
of impurity-induced nuclear spin-lattice relaxation theory68 theory of d-wave superconductivity and the modification
for; Cu NQR in YBa2 (Cu1−x Nix 4 O8 to obtain indepen- in the inter-plane coupling of the order parameter due to
dently the planar Cu nuclear spin-lattice relaxation rate the presence of impurities respectively. Kaplan et al.138
(1/T1 HOST due to the host Cu electron spin fluctuations studied the effect of Zn and Ni substitution on the local
and the Ni-induced Cu nuclear spin-lattice relaxation rate electronic structure of the YBa2 Cu3 O7 superconductor.
(1/1 . They showed that the Ni impurity with low x did The calculated increase of positive charge for both impuri-
neither annihilate the host Cu anti-ferromagnetic correla- ties, compared with substituted Cu, show that the impurity
tion nor the pseudo spin-gap. atoms lost more negative charge than Cu. As a result, all
Bichile et al.130 studied the effect of nickel substitution nearest CuO2 units around impurity lost their holes: com-
on flux pinning and critical currents in YBa2 Cu3 O7− pletely in the Zn case and partly in the Ni case. This lead
superconductors. Their magnetization measurements rec- to the breaking of the hole pairs in the area of impurity
ommended large flux pinning as temperature approaches and associated with an increase of the coherence length in
Tc . They believed that the flux pinning arise due to the Zn- and Ni-doped Y123 crystals measured by Timomoto
preferential substitution of Ni on the Cu(2) site, which et al.137 The superconducting Raman responses in impu-
acted as a pinning centre. Tarascon et al.131 reported phys- rity substituted optimally doped YBa2 (Cu1−x Mx 3 O7−
ical properties resulting from chemical substitution of Cu (M = Ni/Zn) single crystals were investigated by Tacon
by Co, Fe, Ni, Al and Zn in the YBa2 Cu3−x Mx O7−y et al.139 For both Ni and Zn substitutions, they found that
superconductors. They showed that Tc suppression occur the pair breaking peak energy measured in the anti-nodal
due the increasing doping concentration, whether the dop- regions remained invariant, in comparison with Abrikosov-
ing ion is magnetic or diamagnetic. They suggested that Gorkov’ calculations for a conventional BCS super-fluid
anisotropic oxide structure of these compounds made them condensate. Clayhold et al.140 studied the temperature
different, in behaving with respect to magnetic impuri- dependence of the Hall coefficient RH in Co-doped and
ties, from conventional BCS-type superconductors. The Ni-doped YBa2 Cu3 O7 , and Ni-doped La2−x Srx CuO4 . They
influence of impurities on the physical properties of recommended that the strong T dependence of RH was
YBa2 Cu3 O7− superconducting ceramics was also inves- an anomaly explicit to the unconventional normal state in
tigated by Sanikidze et al.132 Their experimental results almost all high Tc oxide superconductors.
showed a stronger suppression of the superconducting state Kim et al.141 reported the infrared conductivities of Zn
by nonmagnetic impurities, thus confirming the presence doped and Ni-doped YBCO films and concluded that there
of d-state pairs. is no clear proof of superconductivity at temperatures well
Shaked et al.133 performed neutron diffraction mea- below Tc . The influence of magnetic (S = 1) and nonmag-
surements at room temperature on samples of YBa2 netic (S = 0) impurities on the spin dynamics of an opti-
(Cu1−x Mx 3 O7− (M = Zn, Ni); x = 005 to study the site mally doped HTSC in YBa2 (Cu097 Ni003 3 O7 (Tc = 80 K)
preference of Cu substituted Zn and Ni. They found that and YBa2 (Cu099 Zn001 3 O7 (Tc = 78 K) was compared by

J. Surf. Interfac. Mater. 1, 1–23, 2013 9

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

Sidis et al.142 They observed that in the Ni-substituted sys- and 0.04) single crystal so as to discuss the origin
tem, the magnetic resonance peak shifted to lower energy of the drastic changes in the electric resistivity along
with a preserved Er /Tc ratio while the shift was much the b-axis and the space group of the crystals. They
smaller upon Zn substitution. Han et al. performed68
70 concluded that the origin of the strong change in the elec-
Cu NQR measurements on Zn and Ni doped YBCO tric resistivity along the b-axis direction lies in the for-
(YBa2 Cu3−x Mx O7 , M = Zn or Ni, x = 00∼009) super- mation of rows of Ni atoms on the Cu–O plane along
conductors. Clear differences due to the non-magnetic the a-axis direction. Davis et al.151 determine directly the
Zn and the magnetic Ni dopants substituted for copper influence of individual Ni atoms on the local electronic
were compared microscopically based on the plane and structure of Bi2 Sr2 Ca(Cu1−x Nix 2 O8+ using scanning tun-
the chain Cu NQR data. Both spin-lattice and spin–spin neling microscopy (STM). Analysis of the impurity-
relaxation rates decreased for Zn doped YBCO whereas state energies showed that quasi-particle scattering at
they increased for Ni doped YBCO. The effect of Zn and Ni was predominantly non-magnetic. Furthermore, they
Ni substitution in the Cu site on the vortex phase dia- showed that the superconducting energy gap and correla-
gram by resistivity and magnetization measurements in tions were unimpaired at Ni sites. A thorough quantita-
untwinned YB2 (Cu1−X MX 3 Oy (M = Zn, Ni) single crys- tive contrast between theoretical calculations of the local
tals was investigated by Nishizaki et al.143 density of states and recent experimental measurements
of scanning tunneling spectra around Ni impurities in
3.3.3. BSCCO System Bi2 Sr2 CaCu2 O8+ superconductors was presented by Tang
and Flatte.149 The Ni atom induced local changes in hop-
REVIEW

Dissanayake et al.145 reported the superconducting prop-

erties of a series of compounds of supposed composi- ping matrix elements comparable in size to the induced on-
tion (Bi07 Pb03  Sr Ca (Cu15−x Nix 0 (x = 0–1.1). Up to site spin-dependent potential. They found evidence from
x = 02 composition, Tc drops down to 60 K rather fast. the measurements of order-parameter restraint in the vicin-
From x = 02 to 0.95 the material remains superconducting ity of the Ni impurity. Quitmann et al.153 investigated the
with Tc around 50 K. For x ≥ 10, the material becomes influence of Co and Ni doping on the electronic band
semi-conducting. They reported that even the compound structure and the transport properties of Bi2 Sr2 CaCu2 O8+y
with Ni:Cu = 095:0.55 is superconducting with Tc around superconductors. They reported that with the increas-
50 K; the magnetic disorder introduced by Ni is smaller ing doping concentration, the residual resistivity increases
in this material than in Ni-doped YBa2 Cu3 O7− material, strongly accompanied by an almost complete disappear-
where even the samples with Ni:Cu = 075:2.25 have lost ance of the dispersing band like states in angle-resolved
their superconducting properties. From an investigation of photoemission.
XPS core-level spectra, XPD (X-ray photoelectron diffrac- Ilonca et al.154 studied the critical current densities of
tion) patterns and Tc of the Bi2 Sr2 Cal Cu2−x Nix O8+ sys- Fe and Ni doped Bi:2212 superconductors. Low concen-
tem, Man et al.146 proposed that the decrease of Tc with trations of the doping elements increased the pinning force
increasing Ni content was mainly due to distortion of the density and shifted the magnetic irreversibility line towards
crystal structure by the extra oxygen intercalated between higher fields. They concluded that Ni and Fe could cre-
two adjacent BiO layers which then affected the hole con- ate pinning centers in Bi:2212, but it could also increase
centration of the copper planes. Additionally, the decrease the grain boundaries resistance that depressed the criti-
of Tc was suggested to be due to the impurity Ni substi- cal current densities for high dopant content. Electrical
tuted for the Cu in the CuO2 planes. The optical proper- conductivity and magnetization measurements on single
ties of Ni-doped Bi2 Sr2 CaCu2 O8+ superconductors were crystals of the high-Tc superconductor Bi2 Sr2 CaCu2 O8+
studied by Liu et al.147 They analyzed the conductivity with partial substitution of Fe, Ni and Zn for Cu were
within the framework of the two-component and the one- reported by Hedt et al.155 They found that even concentra-
component pictures indicated that the main effect of Ni tion of the doping elements below 1 atm.% caused a strong
substitution was to increase impurity scattering rate. Han- increase of the electrical resistivity, a definite increase of
cotte et al.148 investigated an increase of the superconduct- London penetration depth and a decrease of the correlation
ing energy gap and a decrease of Tc for the Ni substituted length. Celebi et al.156 studied the effect of Ni doping on
Bi2 Sr2 CaCu2 O8+x single crystals yielding an increase of the inter-granular flux pinning properties of Bi16 Pb04 Sr2
the reduced gap ratio 2 /kB Tc . The effect of magnetic (Ca1−x Nix 2 Cu3 0 ceramic superconductors. They found
and nonmagnetic impurities (Ni, Zn) substitution for Cu that the Ni content in the BSCCO system changes both
in Bi2 (SrCa)2+n (Cu1−x Mx 1+n Oy whiskers was studied by the effective volume fraction of the grains and the field
Kuo et al.149 These whisker crystals showed resistance dependence of the inter-granular critical current density as
drops for both the 2212 and 2223 phases, with transition well as transition temperature and inter-granular pinning
widths (10–90%) of 1 K. properties. Haas et al.157 observed that both Zn and Ni
Matsuhata et al.150 investigated the microstructure of impurities produced bound states with a four-fold symme-
Ni doped Bi22 Srl8 Ca1 Cu2−x Nix Oy (for x = 000, 0.02 try, localized around the impurity sites in dx 2−y 2 wave

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Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

superconductors. Impurities with intermediate scattering • The Zn substitution suppresses Tc more slowly in Hg-
strength might have a bound state with a dominant eight- based system than in La-124 and Y-123 systems.
fold symmetry. They indicated that the layered organic
Kandyela et al.163 also investigated the effect of 3d
superconductors had d-wave order parameters as well.
metal ion doping on the structure and superconductivity
Measurements of the AC-susceptibility and the irreversible of (Tl05 Pb05 Sr2 Ca(Cu2−x Mx O7 (M = Co, Ni and Zn)
magnetization of Bi(2212) single crystals doped with up superconductors. The Tc decreased linearly with both Co
to 2 at.% of Fe, Ni, Co and Zn on the Cu position were and Ni concentrations and the rate of Tc decrease was
reported by Noetzel et al.158 Low concentrations of the around − 6.5 and − 7.0 K/at%, respectively. The suppres-
doping elements, typically below 1 at.%, certainly increase sion in Tc in Co and Ni doped samples were attributed
the pinning force density and shift the magnetic irre- to the magnetic pair-breaking mechanism and the decrease
versibility lines towards higher fields. in the carrier concentration. Chen et al.164 fabricated Pr
Mori et al.159 investigated the fluctuation induced con- Ba2 (Cu1−x Mx 3 O7 for M = Al, Co, Fe, Ga, Ni and Zn, and
ductivity above Tc in (Bi, Pb)–Sr–Ca–(Cu1−x ,Nix –O x = 005, 0.10, 0.15, and 0.20 with impurity phases were
superconductors having the 110-K phase. They showed detected for Ni and Zn substituted samples with doping
that temperature dependence of the para-conductivity levels equal to and higher than 15%. At 77 K the electrical
could be described by a power law following Aslamazov– resistivity of these compounds was orders of magnitude
Larkin theory. For un-doped (x = 0) samples, the con- higher than that of PBCO.
ductivity data showed a two-dimensional fluctuation of Varadaraju and Prabhu carried out the investigation of

REVIEW
the order parameter, whereas Ni-doped samples showed RBa2 Cu3−x Mx O7 (R = Sm, Dy; M = Fe, Ni, Zn) sys-
lower-dimensional fluctuations and reduced widths of the tem and find out the effect of the rare-earth ionic size
resistive transition. They observed crossover from two- and magnetic moment on the Tc suppression rate.165 The
to one- (or lower-) dimensional behavior with increasing trend in Tc suppression as a function of concentration
Ni dopant level might be related to a fractal nature for (x) showed deviation from Abrikosov-Gor’kov behavior.
the system. Chattopadhyay et al.160 studied that disordered A metal-insulator transition was observed at higher dopant
short-coherence-length superconductors could exhibit pair concentrations, and the semiconducting phases were found
breaking from spatial fluctuations in the pairing interac- to obey the Mott’s variable range hopping mechanism of
tion, in a manner very similar to that found with magnetic conduction.
impurities. Knizhnik et al.166 investigated the family “CLBLCO”
of 1–2–3 superconductors [(Cax La1−x (Bac−x
3.3.4. Some Other Superconductor Systems La2−c+x (Cu1−z Mz 3 Oy ] for impurity M (Zn, Ni, Co, and
Abou-Aly et al.161 studied the electrical and magnetic Ga) substituting for Cu. They found that although the
maximal value of the transition temperature Tc occurs
properties of Hg03 Tl07 Ba2 Ca3 (Cu1−x Mx4 O10+ , where
at different values of the oxygen content y, the average
M = Ni and Ag (x = 0, 0.1, 0.2, 0.3 and 0.5) supercon-
oxidation state of copper for maximal Tc was found to
ductors. They found that with increasing Ni content, the
be approximately constant. They recommended that the
lattice parameter ‘c’ decreased while it is increased for
oxidation state of Ni in this system appeared to be 3.
Ag-doped samples. The transition temperature Tc showed
Riera et al.167 investigated that nonmagnetic impurities
a decrease in its value by increasing both Ni and Ag con-
were more effective in suppressing pairing than magnetic
tents. The depression in Tc was attributed to the disor-
ones in agreement with experimental studies of Zn- and
der and pair breaking for Ni doped samples, while for Ni-substituted high-Tc superconductors by following two-
Ag-doped samples it was attributed to the formation of a dimensional t–J model. Besides, they determined how
non-superconducting phase and the defects caused by Ag the localization of holes contributes to the suppression of
clusters. The data of activation energy were found to be pairing.
consistent with the variation of Tc with both Ag and Ni Sugiyama et al.168 studied the effect of Co, Ni and Zn
contents. The structural, electrical and magnetic properties doping in the electron doped Nd185 Ce015 Cu O4 supercon-
of Hg07 Cr03 Sr2 Cu1−x Mx O4+ (M = Co, Ni, Zn) systems ductors. They observed that only 0.7% Co or 0.8% Ni
were studied by Kandyel, and Sekkina.162 They made fol- substitution for Cu destroy superconductivity. Contrary to
lowing conclusions from their investigations: this, superconductivity survived even in the 2% Zn sub-
• Both Co and Zn are soluble in the material upto 5% stituted sample (Tc ∼ 9 K). The relationship between Tc
on
whereas the solubility of the Ni extended to 10%. and Ni content x, for Nd185 Ce015 CuO4 superconductor is
• The doping of magnetic ions (Co, Ni) has stronger effect shown in Figure 10. From the normal-state magnetic sus-
on the suppression of Tc than with non-magnetic ions (Zn) ceptibility data, Jayaram et al.169 found that Fe and Ni
• Ni and Co substitution for Cu depress Tc more quickly possessed local moments of the order of 2.2 B and 2 B
in Hg-1201 system than Y-123 system showing that pair in this system, respectively. The observed moment on Ni
breaking effect is stronger in this Hg-based system. was attributed to Ni in a 3+ valence state.

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 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

3.4.1. HTSC Films and Coated Conductors

In-situ and ex-situ methods are to synthesize the films
of HTSC. Film crystallization takes place directly and
epitaxial growth occurs under corresponding conditions
during in-situ method. In ex-situ synthesis method, the
films are deposited initially at low temperature. Necessary
crystalline structure is not form at this temperature, and
films are sintered in O2 atmosphere that leads to the crys-
tallization of the required phase. There are physical meth-
ods of deposition, including all possible evaporation and
scatterings.
Fig. 10. The relationship between Tc , (determined from SQUID mea-
surements) and Ni content x, for Nd185 Ce015 CuO4 . The solid line rep-
3.4.1.1. Vacuum Co-Evaporation. Layer by layer co-
resents the calculated dependence of Tc on x using Abrikosov-Gor’kov precipitation of HTSC components evaporated from var-
theory.168 ious sources by using, electron beam guns or resistive
evaporators. These methods are used in two stage
Brinkmann et al.170 reported results on single crystals of synthesis.172
the Pr2−x Cex CuO4+ high-Tc superconductors doped with 3.4.1.2. Laser Evaporation. Laser evaporation is highly
Ni and Co on the Cu position. These substitutional atoms effective method in the deposition of HTSC thin film.
REVIEW

very well suppressed Tc at a rate of dTc /dy ∼ 20 K/at.%, In this method the advantage is equally well evaporation
and superconducting correlation length strongly increased of all chemical elements contained in the target.173 The
with the concentration of Co and Ni. They reported that main disadvantages of this method are (a) small region for
with the increasing doping concentration, the residual stoichiometric films deposition (b) heterogeneity of their
resistivity increased strongly which indicated that the scat- thickness (c) surface roughness.
tering cross section of the Ni and Co ions for the charge 3.4.1.3. Magnetron Scattering. In this method one can
carriers in the electron-doped high-Tc superconductors is obtain one stage HTSC film (YBCO films). They have
definitely larger than for the charge carriers in the hole- homogeneous thickness and higher smoothness of surface.
doped superconductors. Disorder in the oxygen sub-lattice The plasma formation at magnetron scattering creates high
might increase the residual resistivity in the electron-doped energy atoms and ions, which allow getting HTSC film at
superconductors. They also reported the strong shift of not high temperature in one stage.
the Hall coefficient towards positive values with increas- 3.4.1.4. Chemical Precipitation. In this method the
ing degree of substitution of Ni and Co which indicated a transportation of metallic components in the form of
different impurity scattering rate for the hole and electron streams of volatile metal-organic compounds in a reactor,
type of charge carriers coexisting on the Fermi surface of a mixing with gaseous oxidizer, composition of the stream
the electron doped superconductors. and condensation of the oxide film on substrate. The com-
Brinkmann et al.171 introduced a self-flux-based parative advantages of this method to the previous are
growth procedure for pure and M-substituted (a) a possibility to obtain homogeneous film and possess-
Pr2−x Cex (Cul−y My O4+ (M = Co, Ni) single crystals. ing large area with non-plan configuration;
With their growth process it was possible to partly sub- (b) high rates of precipitation under high quality condi-
stitute Cu- by Co- and Ni-atoms. They tested the other tions;
substitutional elements (M = Fe, Zn, Ga, Sn), did not (c) a flexibility at preliminary stage of technological
enter the 214 structure with a concentration above the
regime.169
resolution limit of their wavelength dispersive X-ray
(WDX) analysis. They mentioned that Co and Ni were The following techniques are most extensive ones:
the only metallic substituents which suppressed Tc in • Two-axis texture preparation of film by using ion-beam-
polycrystalline electron-doped high-Tc superconductors assisted-deposition.174
175
rapidly, whereas the suppression of Tc was much smaller • Electro-phoretic deposition.176
when incorporated with Zn. • Metal-organic chemical vapour deposition
(MOCVD).177
3.4. HTSC Preparation Techniques and • Coated Conductors preparation by metal-organics depo-
Composition Features sition (MOD)178 .
In application point of view, HTSC samples in the form of • Buffer layer preparation by surface oxidation
films at mono and polycrystalline substrates, coated con- epitaxy (SOE),179 electron beam evaporation,178
ductors, tapes and superconducting bulks are very impor- laser ablation,179–182 ion beam sputtering,183
184
185–187
tant. There preparation techniques are discussed below. Rf-sputtering.

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Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

3.4.2. BSCCO Films, Tapes and Wires overdoped (La,Sr)2 CuO4 206 The enhancement in the inter-
Melt-processing,188
189 electrophoretic deposition,190 face of electron–phonon coupling207 and epitaxial strain208
doctor-bladed, 191
dip-coated 192
and organic precursor has been studied to increase the Tc of superconductors.
film193 are the techniques used for the preparation of Cuprate planes act as connectors; whereas cuprates
Bi-2212 thick films on MgO and Ag substrates. In doctor- dopants in the insulating oxide layers provide strong
bladed process, film is made before heat treatment from electron-phonon interactions. Mostly carrier paths simply
the organic/powder mixture by pouring the pool of slurry remain confined to the highly conductive connectors, so
on the piece of glass, then leveling the slurry with a this mechanism by itself is unsuccessful. The density of
straight edge blade, located above the plate. For dip- electronic states N EF ) at the Fermi energy EF is much
coated films, the Ag foil is passed through the mixture, larger than at the dopants, whose effectiveness is further
which adheres to the film. For organic precursor films, decreased by a tunneling transfer factor T . Thus a satis-
organo-metallic compounds solution of Bi, Ca, Sr and Cu factory model is required that connecting cuprate planes
is deposited on the Ag foil. The solvent burns and the be criss-crossed by domain nanowalls. Such nanodomains
are essentially credible in the cuprates because of their
process are repeated until the desired thickness.
marginally stable pseudo-perovskite structures. Evidence
3.4.3. Tapes and Wires Based on Thallium Cuprates provided at the beginning for the existence of cuprate
Techniques for the thallium thin films (Tl-1212, Tl-2012, nano-domains206 has since been supplemented by exten-
Tl-1223, Tl-2212, Tl-2223) are nearly similar to the fab- sive STM studies.210 The nano-domain walls force carriers
rication of YBCO thin films. Substrates like; LaAlO3 and to follow only percolative paths that exchange between

REVIEW
NdGaO3
194–197 and buffer layers; YSZ and CeO2 198 give strong interaction interlayer dopants and cuprate planar
the best results due to the good agreement of their crystal- connectors. The purely planar conductive paths are elimi-
lographic properties. nated by domain walls. This mechanism can occur if the
percolative paths are self organized and can be criticized as
3.5. Superconductivity of HTSC at not likely, but high temperature superconductivity (HTSC)
Surfaces and Interfaces occurs only seldom. The Percolative mechanisms have
HTSC gives an excellent description of HTSC in quasi- increasingly attracted the interest of theorists who have
two-dimensional contexts. With decreasing dimensionality provided further support for them.211–213 Large anisotropy
thermal fluctuations enhanced due to decrease in phase or surface-volume ratios can produce diamagnetic effects
transition temperature Tc , so that surface and interfacial at high T indicative of HTSC at a slightly lower T have
phase transitions occur at lower Tc ’s than bulk Tc ’s. Gen- proved in some recent experiments.214
215
erally this occurs for most superconductive transitions, but There are several new marginally stable families (like
there are some exceptions, for which a percolative mecha- Lix ZrNCl and LaFeAsO1−x Fx 216 of ionic crystals that
nism is attractive.196
197 The carriers can be localized effi- exhibit many similarities to the cuprates. There are many
ciently at strong interaction centers (i.e., centers of strong atoms per unit cell, with tetragonal-orthorhombic lattice
instabilities, vicinal antiferromagnetic phases.217 By bring-
electron–phonon interactions) due to percolative mecha-
ing these new materials into the general framework of
nisms. These centers can be connected by highly con-
self-organized percolative networks, the percolative model
ductive paths (“wires”) where scattering is weak.196 The
simply explains these similarities. This has already been
largest known superconductive Tc ’s were found in layered
done for Lix (Zr, Hf)NCl having Tc ∼ 15 K–25 K.218
superconductors, with metallic cuprate planes separated
A similar mechanism is for the LaFeAsO1−x Fx family
by intervening oxide layers.17 The Tc ’s of most cuprates
with Tc ∼ 26 K–43 K,219 which is much larger and the
increase significantly with pressure. The interplanar stiff- subject of hundreds of recent studies. Unlike effective
ness is smaller than the cuprate planar stiffness, so pressure medium, virtual crystal theories, the self-organized per-
enhances interplanar interactions. Besides the cuprates, colative model makes specific predictions concerning Tc
some marginally stable materials have shown larger Tc ’s at and predicts the least upper bound Tc max (X), where X
surfaces. Qing-Yan et al. reported the high transition tem- is a percolative configuration coordinate. X = R in the
perature superconductivity (77 K) in one unit cell thick case of cuprates; where R is the average number of Paul-
FeSe films grown on a Se-etched SrTiO3 (001) substrate by ing resonating valence bonds. The Pauling’s resonating
molecular beam epitaxy (MBE). They introduced an inter- valence bond concept has been widely abused in the
face engineering method for dramatically raising the Tc of HTSC context, but in the cuprate case it works well with
superconducting films. By growing atomically flat ultrathin R(Cu) = 2; Cu is in a 2+ valence state.219
220 These mate-
films of superconducting phase FeSe201 on STO (001) rials are marginally stable only, so they are strongly dis-
substrates, they got signatures of superconducting transi- ordered when doped and generally far from optimized
tion around 77 K.202 Nax WO3 (Na tungsten bronze) shown (with respect to HTSC). The overall scale for Tc is deter-
bulk Tc = 13 K increases to 88 K at the surface.203–205 mined by marginal lattice stability. The Jahn-Teller dou-
Interfacial enhancement of Tc is reported for insulating and bling of the unit cell of LO phonons correlates linearly

J. Surf. Interfac. Mater. 1, 1–23, 2013 13

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

with Tc
max in the cuprates is associated with the phonon 4. ROOM TEMPERATURE
energy shift.15 The least upper bound Tc
max has a strongly SUPERCONDUCTIVITY
percolative character, as it peaks at R = 2216
217 we There are at least two papers reporting superconductivity
now discuss the point for the LaFeAsO1−x Fx family (hav- above room temperature. In the first paper, Superconduc-
ing Tc ∼ 26 K–43 K) with R(Fe) = 2, Fe is in a 2+ tivity is observed in a thin surface layer of the complex
valence state in a virtual crystal model.218 One calcu- compound Ag Pb6 CO9 (07 < < 1) at 240–340 K.221 The
lated R for un-doped LaFeAsO and obtained R = 25, second paper claims that superconductivity exist in carbon
which places LaFeAsO1−x Fx (Tc = 26 K) very close to based multiwall nano-tubes at T > 400 K.225
Lix ZrNCl. A 60% increase more than cuprates, Tc is max-
imized at 43 K for pressures near 44 GPA,222 The equilib- 5. MAGNETIC PROPERTIES OF
rium cuprate master function Tc max (R ) remains valid for SUPERCONDUCTORS
the Lix ZrNCl and LaFeAsO1−x Fx families, but the pres- Superconductors are divided into two types according
sure dependence in the latter family is larger than in the to their magnetic properties, Type-I superconductors and
cuprates. Due to the larger Pauling electronegativity X dif- Type-II superconductors. Abrikosov theoretically investi-
ferences (X(Fe) = 18, X(As) = 20, X(Cu) = 19, X(O = gated the properties of superconductors in external mag-
35)) in the cuprates, Fe As bonding is more covalent netic fields. In 1957, he discovered that superconducting
than largely ionic Cu O bonding.219 The Tc max (R ) is materials can be separated into two groups, type-I and
determined from bulk data on layered crystals. Determin- type-II superconductors.226
REVIEW

ing R at surfaces and interfaces is much more tricky

than in the bulk, where it is natural to average R over all 5.1. Type-I Superconductors
atoms, as the self-organized structure is marginally stable Superconductors which show a M versus H curve with an
overall. Soft modes that are critically bound to percola- abrupt transition from perfect diamagnetic state to param-
tive superconductive paths should have long wave lengths, agnetic state at Hc are called Type-I superconductors. Most
as Tc max is small compared to the melting temperature. elemental superconductors exhibit this behavior. The value
Similar percolative behavior is estimated in layered thin of critical field Hc is quiet low for these superconductors,
crystalline films with epitaxial interfaces or at doped free not being greater than 0.2 Tesla. These superconductors
are also called soft superconductors. All superconducting
surfaces. In La2 CuO4 -overdoped (La,Sr)2 CuO4 interface,
elements except niobium belong to type-I superconductors.
where Tc ∼ 50 K, after enhancement by exposure to ozone
from ∼ 30 K percolation behavior has been practiced.203
5.2. Type-II Superconductors
The ozone enhancement is readily explained by the addi-
In Type-II superconductors, the transition from a perfect
tion of oxygen dopants, absorbed by La2 CuO4 to M give
diamagnetic state to the paramagnetic state is not abrupt.
La2 CuO4+ with  ∼ 015. However, the maximum Tc
The negative magnetization increases linearly up to a cer-
obtainable in this way was ∼ 30 K for both layers sepa- tain value of magnetic field Hc1 and beyond this, magne-
rately, apparently producing a mystery. tization falls slowly, becoming positive at a much higher
Considering another compound, surface monolayer of magnetic field Hc2 . Up to Hc1 material is a perfect dia-
Ax WO3 , where A is an alkali metal (Na198
200 or Cs202 ). magnet and between Hc1 and Hc2 the material is partly
Bulk Nax WO3 exhibits superconductivity only near 1 K. diamagnetic, i.e., there is some flux penetration into the
For Na superconductivity appears around 100 K, whereas material. At Hc2 material becomes paramagnetic with a
for Cs there are two phase transitions, a bulk one with small positive magnetization. These are also called hard
lower Tc at higher doping, and a reentrant percolative one superconductors.227–229 Niobium, superconducting alloys
with higher Tc at lower doping. Moreover, Na- and Li- and chemical compounds are type-II superconductors.
doped surfaces of nano-clusters of WO3 embedded in a
variety of nanoporous hosts; carbon nanotube paper, car-
6. INTER-GRAIN WEAK LINKS AND
bon inverse opal, or platinum sponge etc. show diamag- NANO-PARTICLES DOPING
netic anomalies with an onset of 130 K223 WO3 with The importance of afore-mentioned experiments is that,
its simpler unit cell, subject only to Jahn-Teller distor- they not only adjust the composition variations but also
tions, itself is nonmagnetic. These data can be combined efficiently dope the conducting CuO2 planes, where pre-
with Tc max (R ) to construct a model of percolative self- dominantly superconductivity occurs. In both of above
organization at surfaces. One must assume R = 2 to mentioned experiments, the composition variations can be
explain Tc ∼ 130 K. In the free surface case203–205 thermal fixed if the termination ends of the crystals are the charge
fluctuations disrupt superconductivity above 100 K. Taking reservoir layer sites. The real story may be different, and
into consideration the fast progress in nano-science, it is the termination ends of the crystals can be any portion
possible to obtain similar pairs of points for other HTSC. of the unit cell. In that case, oxygen incorporation would

14 J. Surf. Interfac. Mater. 1, 1–23, 2013

Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

y=0.0 (Tc=105) As prepared As prepared

4 y=0.05 (Tc=105) 0.02
y=0.10 (Tc=99)
y=0.15 (Tc=105)
0.00
3 y = 0.00

χ(emu/gram)
y = 0.05
ρ(Ω-cm)

–0.02 y = 0.10
y = 0.15
2
ρ∗2 –0.04

1
–0.06

0 –0.08
100 150 200 250 300 80 90 100 110 120 130
T(K) T(K)

Fig. 11. Resistivity versus temperature measurements of Fig. 13. Ac-susceptibility versus temperature measurements of (CuO,
(CuO)y Cu05 Tl05 Ba2 Ca2 Cu3 O10− (y = 0, 5, 10, 15 wt.%) superconductor CaO2 , BaO)y Cu05 Tl05 Ba2 Ca2 Cu3 O10− 244
samples.244

REVIEW
Annabi et al.234 investigated the effect of nanometer
create the oxides of respective elements. The incorporated Al2 O3 addition to (Bi, Pb)-2223 superconductor. It was
alkali metals will be converted to their respective oxides seen that small amount of Al2 O3 within superconducting
which would add to thickness of the grain boundaries. grains produced defects such as dislocations and stacking
The thicker grain boundaries will add to the additional faults, which also enhance the flux pinning and criti-
resistivity of the final compound. cal current density. Nano-oxide addition to high temper-
The inter-grain weak links and weak flux pinning capa- ature superconductors was found to be most practicable
bility are two main limitations of high temperatures appli- technique for the enhancement of flux pinning and criti-
cations. The flux pinning capability of high temperature cal current density.235
236 Koblischka et al.237 observed the
can be enhanced through micro-structural control such as high-Tc superconductor with light rare earth (LRE) ele-
small secondary phases,230 high concentration of disloca- ment instead of Y exhibit nano-scale stripe structures on
tions and planar faults231 and irradiation damage zones.232 the surface observed by atomic force microscopy (AFM)
Jia et al.230 studied the effect of nano-ZrO2 addition in and scanning tunneling microscopy (STM) scans. The
Pb-doped BSCCO high temperature superconductor. They additions of nanoparticles (ZnO2 , ZrO2 ) lead to the forma-
observed that the addition of nano-ZrO2 act as effective tion of nano-lamellae.
flux pinning centers in matrices of Bi-2223 superconductor Awad investigated the effect of nano-MgO addi-
and enhanced the critical current density. tion on the electrical and mechanical properties of
(Cu025 Tl075 -1234 phase.238 He showed that the Vickers
micro-hardness number, grain connectivity and phase
0.04
As prepared y=0.0 (Tc=122K) formation increased with increasing MgO concentrations
y=0.05 (Tc=122K) till 0.6 wt.%, after that it decreased with further increase
y=0.10 (Tc=100K)
0.02 y=0.15 (Tc=122K) of MgO addition. The variation of lattice parameter
0.00
and volume with the thermal expansion coefficient for
(MgO)x Cu025 Tl075 Ba2 Ca3 Cu4 O10− with x = 00, 0.2, 0.6
χ(emu/gram)

–0.02 and 1.0 wt.% at the temperature range 80 K ≤ T ≥ 290 K

were studied. The volume thermal coefficient measure-
–0.04
ments were divided into two regions. In the first region,
–0.06 it decreased rapidly with temperature from 290 K to
160 K, whereas in the second region, it decreased slowly
–0.08 with decreasing temperature. The Debye temperature for
–0.10
this phase was calculated to be lower than that of Tl-
1223 phase.239 Mohammed et al.240 studied the mechanical
80 90 100 110 120 130 properties of nano-SnO2 added (Cu05 Tl05 -1223 supercon-
T(K) ducting phase. The microstructure density increased with
Fig. 12. Ac-susceptibility versus temperature measurements of the addition of nano-SnO2 , also porosity among the grains
(CuO)y Cu05 Tl05 Ba2 Ca2 Cu3 O10− (y = 0, 5, 10, 15 wt.%) superconductor was reduced. The micro-hardness of the studied samples
samples.244 decreased with increasing the applied load up to 1.96 N,

J. Surf. Interfac. Mater. 1, 1–23, 2013 15

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

(a)
REVIEW

(b)

Fig. 14. (a) SEM of the (CuO)y Cu05 Tl05 Ba2 Ca2 Cu3 O10− (y = 0, 5, 10, 15 wt.%) samples.244 (b) SEM of the (CuO, CaO2 ,
BaO)y Cu05 Tl05 Ba2 Ca2 Cu3 O10− (y = 0, 5, 10, 15 wt.%) samples.244

and then it showed a slight decrease (nearly plateau) with Elokr et al.241 studied the effect of nano-sized ZnO on the
the further increase of the applied load. The Vickers micro- physical properties of (Cu05 Tl025 Pb025 Ba2 Ca2 Cu3 O10−
hardness number and modulus of elasticity increased with [(Cu05 Tl025 Pb025 -1223]. The percentage of volume frac-
increasing nano-SnO2 -addition. Thus, nano-SnO2 addition tion, melting point of the major phase (Cu05 Tl025
has a significant effect on improving the micro-hardness Pb025 -1223, superconducting transition temperature and
of the phase. critical current density enhanced up to the concentration

16 J. Surf. Interfac. Mater. 1, 1–23, 2013

Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

of nano-ZnO (y = 08 wt.%), whereas grain boundary (a)

resistance reduced. Further increase in y (y > 08 wt.%)
reduced the volume fraction, melting point, superconduct-
ing transition temperature and critical current density of
(Cu05 Tl025 Pb025 -1223 phase, and increased grain bound-
ary resistance. Anabi et al.242 studied the effect of ZnO
and Zn095 Mn005 O addition on the microstructure and pin-
ning properties of polycrystalline YBCO superconductor.
Samples showed one step transition. Critical transition
temperature decreased with the addition of nano-particles.
Critical current density Jc H  for free and nano-sized
Zn095 Mn005 O and ZnO added samples at 77 K in the mag-
netic field were measured and normalized to their zero field
value, Jc (0). Fabod et al.243 investigated the doping effect
of Ag nano-particles on critical current of YBa2 Cu3 O7−
bulk superconductor. They observed that, with the increase
of nano-particles size, the connectivity among grains and
crystallization of the samples were improved. Also critical (b)

REVIEW
current density increased with the higher Ag concentration.
Ag nano-particles act as effective agent to improve connec-
tions and crystallization of grains.
We have made an attempt to fix the weak intergrain
coupling and flux pinning problems by doping with CuO,
CaO2 , BaO nano-particles in Cu05 Tl05 Ba2 Ca2 Cu3 O10−
superconductors. This is accomplished via using the higher
activation energy of chemical reaction available with the
nano-particles. The nano-particles are prone to higher acti-
vation energy because they have large surface area to vol-
ume ratio and they accomplish their lower energy state via
reacting with other compounds. We have added the nano-
particles in the precursor material in two ways: (1) only the
addition of CuO nano-particles (2) sum of all CuO, CaO2 ,
BaO nano-particles. The main objective behind following
these addition protocols were to see that which of the
two above give us better superconducting properties and (c)
a material with better micro-structure free of voids. The
nano-particles doped (Cu05 Tl05 Ba2 Ca2 Cu3 O10− super-
conductors were synthesized at 860 C and investigated
by X-ray diffraction, resistivity, ac-susceptibility, FTIR
absorption measurements and electron-microscopy mea-
surements. The X-ray diffraction (XRD) studies of these
samples have shown a tetragonal structure. The room
temperature resistivity of the samples was systematically
found to decrease with increased concentration of CuO
nano-particles and best results were achieved with the
15% additions of the nano-particle; Figures 11, 12. The Tc
(R = 0) is not significantly influenced with the incorpora-
tion of nano-particles in these samples, however, the mag-
nitude of the superconductivity is significantly enhanced
with the doping of CuO, CaO2 and BaO nano-particles;
Figure 13. This show that inter-grain material is of the
same composition and increased magnitude of the dia-
Fig. 15. (a) Fluctuation induced conductivity (FIC) analysis of (Cu, Tl)-
magnetism is due to the suppression of inter-grain losses. 1223.245 (b) Fluctuation induced conductivity (FIC) analysis of (Nano-
These inter-grain losses most likely are decreased due CuO)x (CuTl)-1223 (x = 10 wt.%).245 (c) Fluctuation induced conductivity
to the introduction of CuO nano-particles which healed (FIC) analysis of (Nano-CuO)x (CuTl)-1223 (x = 20 wt.%).245

J. Surf. Interfac. Mater. 1, 1–23, 2013 17

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

Table I. The parameters such as normal state resistivity n (290 K), the zero resistivity critical Temperature (Tc ), onset of superconductivity (Tconset ),
cross-over temperatures (To ), mean field critical temperature (Tcmf ), inter-grain coupling constant ( ), zero temperature coherence length along c-axis
{c (0)} and interplan coupling (J ) extracted from the FIC analysis of (CuO)x /(CuTl)-1223: (x = 0, 10, 15, 20 wt.%).245

Wt.% n (290 K) ( cm) Tc (K) Tconset (K) Tc (K) To (K) Tomf (K) = n (0 K) ( cm) c (0) J = 2c 0/d2

0 0.061 105 123 17 113 108 00011 1927 0066

10 0.025 105 117 12 112 108 00010 1936 0067
15 0.051 101 120 19 109 105 00004 2110 0079
20 0.036 96 111 15 105 101 00009 2153 0082

the inter-grain by voids. (Cu05 Tl05 Ba2 Ca2 Cu3 O10− sam- fields. However, in the first generation of SC materials
ples added with CuO, CaO2 and BaO nano-particle (Type-I) superconductivity was easily suppressed by mag-
have also shown a significant decrease in the population netic fields. The magnetic self-field generated by the
of voids and enhancement in the inter-grain coupling; injected current prevented high-field as well as high-
Figures 14(a)–(b). The samples with 15% addition of current applications. A first step towards this goal was
CuO, CaO2 and BaO nano-particles have even shown tex- the discovery of Type-II superconductors where the mag-
tured elongated crystalline with extremely low population netic penetration depth exceeds the Coherence length. This
of voids.244 The fluctuations induced conductivity (FIC) enables a coexistence of superconductivity and magnetic
analysis of (CuO)x /CuTl-1223 composite has been car- fields at least up to a certain critical field Hc2 . The last
REVIEW

ried out by using Aslamazov–Larkin (AL) and Lawrence– ingredient required for technically applicable hard super-
Doniach (LD) models in the temperature regime above conductors was the discovery and engineering of pinning
the critical temperature (T > Tc ). In order to extract the centers which fix penetrated magnetic flux and prevent its
microscopic parameters such as zero temperature coher- Loretnz force driven flow through the superconductor that
ence length along c-axis {c (0)}, inter-layer coupling (J),
otherwise generate power dissipation.
dimensional critical exponent () and inter-grain coupling
constant ( ) etc., the electrical resistivity versus temper-
7.1. Transmission of Commercial Power
ature curves of (CuO)x /CuTl-1223 composite were fitted
by using above mentioned models. It has been observed An idealized application for superconductors is to use
that the cross-over temperature (To ) fits very well the two- them in the transmission of commercial power to cities.
dimensional (2D) and three-dimensional (3D) AL equa- However, due to the high cost and needlessness of cooling
tions and shifts towards the lower temperature regime with miles of superconducting wire to cryogenic temperatures,
the enhanced weight percentage of CuO nano-particles this has only happened with short “test runs.” In May of
Figures 15(a)–(c). The shifting of AL 3D region to 2001 some 150,000 residents of Copenhagen, Denmark,
higher temperature after oxygen post-annealing indicates began receiving their electricity through high-temperature
the restoration of oxygen and optimization of charge carri- superconducting material. That cable was only 30 m long,
ers in conducting CuO2 planes. The gradual decrease in the but proved sufficient for testing purposes. This marked
value of inter-grain coupling constant ( ) with the increase the first time commercial power has been delivered to
of CuO nano-particles content reflects an improvement in customers through superconducting wire. Superconducting
the inter-grain coupling resulting into an increase in the transformers with HTSC windings have been carried out
coherence length (c ) along the c-axis (Table I). Almost in Japan and the USA.248 Super-Foam, synthesized from
all superconductivity parameters have been improved after YBa2 Cu3 Oz may be ideal material for the fault current
oxygen post-annealing. The suppression of superconduc- limiters.249
tivity parameters in the composite with x = 20% lim-
its the optimum doping level of CuO nano-particles in 7.2. Bio-Magnetism
(CuO)x /CuTl-1223 composite.245 An area where superconductors can carry out a life-saving
function is in the field of bio-magnetism. Doctors need a
7. APPLICATIONS non-invasive means of determining what’s going on inside
Due to the unique properties of high temperature supercon- the human body. By impinging a strong superconductor-
ducting materials, their applications are becoming attrac- derived magnetic field into the body, hydrogen atoms that
tive continuously with the improvement in properties exist in the body’s water and fat molecules are forced to
of superconductors.246 The search for applications has accept energy from the magnetic field. They then release
always been a driving force for superconductor materials this energy at a frequency that can be detected and dis-
science.247 Right from the discovery, it had been envi- played graphically by a computer. Magnetic Resonance
sioned that superconducting (SC) coils with high persis- Imaging (MRI) was actually discovered on July 3, 1977.
tent current might be used to produce strong magnetic It took almost five hours to construct one image.

18 J. Surf. Interfac. Mater. 1, 1–23, 2013

Saleem and Hussain Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications

7.3. Electronic Switches the La-214 system. Detailed neutron and X-ray work has
Type-II superconductors can be used to as very fast been devoted to the site preference for the specific sub-
electronic switches due to the way in which a mag- stituents at Cu(1) or Cu(2),133–136 and one finds roughly
netic field can penetrate into the superconductor. Japanese that 3+ ions mainly substitute in the chains while 2+
researchers build a 4-bit computer microchip (compared ions both in the chains and planes but especially at the
to today’s 32-bit and 64-bit processors) operating at about low concentration, the site preference is somewhat contro-
500 times the speed of current processors, where heat versial. The most important work of the studies dealing
output is currently a major problem with typical speeds with the substitution of Cu in Bi-2212 by 3d elements,
approaching the 1 GHz. The military is also search- are the incorporation of magnetic Fe and Co suppress Tc
ing using superconductive tape as a means of reducing linearly with increasing dopant concentration at a rate of
the length of very low frequency antennas employed on 5 K/atm.% and for Ni and Zn the suppression is much less
submarines. pronounced.146–160
The addition of nano-oxides to the high-temperature
7.4. Scientific Research superconductors plays an important role for enhancing the
Magnets for plasma confinement and superconducting critical current density and flux pinning.233–236
240
241 This
cables are two extreme examples of applications for which enhancement is due to trapping of nano-oxide particles
a higher upper critical field at low temperature and a high within the superconducting grains, introducing second
critical temperature are respectively the desired character- phase defects.233 Fabod et al.243 investigated the dop-
ing effect of Ag nano-particles on critical current of

REVIEW
istics to be achieved. Higher fields are desirable to improve
plasma confinement, and probably cannot be achieved YBa2 Cu3 O7− bulk superconductor. They observed that,
with low temperature superconductors.250 Superconducting with the increase of nano-particles size, the connectiv-
magnets have potential application for high-energy physics ity among grains and crystallization of the samples were
research. An accelerator of high energetic charged parti- improved. Also critical current density increased with the
cles (Large Hadron Collider) is constructed in Europe by higher Ag concentration.
CERN consortium in 2007. The parameters of HTSC ori- There is no report of such substitution effects in the
gin are sufficient to produce multi-charged ions.248 CuTl-system. In present work, we focus on CuTl-1223
system in our present work due to following advantages:
(1) under ambient conditions, the possibility to obtain pre-
8. SUMMARY
dominant CuTl-1223 phase is high.
It is well known from the Abrikosov and Gor’kov19
20
(2) The crystal symmetry is high, tetragonal, which permit
theory that the direct interaction of the magnetic ions
us to ignore the in-plane anisotropy.
with the superconducting electrons breaks the Cooper
(3) Tc is high for three layer compound.
pairs and suppresses the Tc . In the new HTSC cuprates,
(4) The difference in nature of charge reservoir layers;
superconductivity is confined within CuO2 planes. To
Cu05 Tl05 Ba2 Ca2 Cu3 O10− has a Cu05 Tl05 Ba2 O4− while
determine whether these materials behave similarly with
all the previous systems had MBa2 O4− ; M = Y+3 , Bi+3 ,
respect to magnetic impurities, numerous studies on the
Tl+3 . The charge reservoir layer of type Cu05 Tl05 Ba2 O4−
transition–metal substitution effect in the Cu-sites have
is more efficient dopant of the carriers to conducting CuO2
been already performed for La-, Y- and Bi-based supercon-
planes whereas MBa2 O4− possibly develops localization
ductor systems.119–161 In the La-214 system, Tc was sup-
of carriers at the trivalent M+3 sites and is therefore less
pressed at the same rate for magnetic and non-magnetic
efficient provider of the carriers.
substituent and about 4 atm.% of the substitution in the Cu
(5) Due to lower anisotropy, high Tc and high Jc capable
position is enough to quench the superconductivity.119–123
candidate for device fabrication.
In the n-type superconductors like Nd-214, the influence is
even stronger, and Ni and Co concentration below 1 atm.% The importance of afore-mentioned experiments is that
suppress the superconductivity completely.165 In the Y-123 they not only adjust the composition variations but also
system, non-magnetic Zn is especially effective in sup- efficient dope the conducting CuO2 planes where predom-
pressing Tc than magnetic Ni and Co.130–144 However, the inantly superconductivity occurs. In both above mentioned
situation in Y-123 is more complex than in the La-124 experiments the only composition variations can be fixed
system, since two different sites, the chain Cu(1) site and if the termination ends of the crystals are the charge reser-
the plane Cu(2) site, exist in the unit cell and a dopant can voir layers site. But the real story may be different and
substitute at Cu(1) or Cu(2). The influence of substitution it is most likely that the termination ends of the crystal
in the plane and chain site on the superconductivity is quite can be any portion of the unit cell. In that case oxygen
different. Substitution in the chain mainly acts indirectly incorporation would create the oxides of respective ele-
via modification of the inter-cell charge transfer and thus ments and the incorporated alkali metals will be converted
the number of holes in the CuO2 planes. Dopants in the to their respective oxides which would add to thickness of
CuO2 planes suppress directly the superconductivity as in the grain boundaries. It is most likely that thicker grain

J. Surf. Interfac. Mater. 1, 1–23, 2013 19

 Review the High Temperature Superconductor (HTSC) Cuprates-Properties and Applications Saleem and Hussain

boundaries will add to the additional resistivity of the final 19. A. A. Abrikosov, L. P. Gor’kov, and Zh. Eksperim, I Teor. Fiz.
compound. In the present studies an attempt is made to 39, 1781 (1960).
fix these problems by doping CuO, CaO2 and BaO nano- 20. A. A. Abrikosov and L. P. Gor’kov, Soviet Phys. JETP 12, 1243
(1961).
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Received: 29 January 2013. Accepted: 13 February 2013.

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