Study of superconducting properties of NiO Nano

particles/CuTl-1223 composite.

LAYIQ ZIA
Department of Physics
Quaid-i-Azam University
Islamabad, Pakistan
2015

Study of superconducting properties of NiO Nano particles/CuTl-1223 composite.

A dissertation submitted to the department of physics, Quaid-i-Azam University,

Islamabad, in the partial fulfillment of the requirement for the degree of

Master of Philosophy
in
Physics
By
LAYIQ ZIA

Material Science Laboratory

Department of Physics
Quaid-i-Azam University
Islamabad, Pakistan
2015

Beginning with the name of ALLAH ALMGHTY the most beneficent and
merciful, and the most sovereign among all of us.

Certificate
This is to certify that Layiq Zia S/O Lajbar Khan has carried out the
experimental work in this dissertation under my supervision in Materials Science Laboratory, Department of Physics, Quaid-i-Azam University, Islamabad and satisfying the dissertation requirement for the degree of Master of
Philosophy in Physics.
Supervisor
Dr. Nawazish Ali Khan
Department of Physics
Quaid-i-Azam University
Islamabad, Pakistan.
Submitted through
Chairman
Prof. Dr. Arshad M.Mirza (S.I)
Department of Physics
Quaid-i-Azam University
Islamabad, Pakistan.

DEDICATED
TO
MY LATE FATHER

ACKNOWLEDGEMENTS
All the praises to Almighty ALLAH, the most merciful and the sovereign
power, who made me able to accomplish this research work successfully. I offer my
humble and sincere words of thanks to his Holy Prophet Muhammad (P.B.U.H)
who is forever a source of guidance and knowledge for humanity.
This work would have not been possible without the invaluable contributions
of many individuals. First and foremost, I wish to thank my supervisor Dr. Nawazish Ali Khan for all of his support, advice, and guidance during the whole period
of my study. I am thankful to chairman, department of physics, for the provision of
all possible facilities and cooperation.
I would like to acknowledge the Higher Education Commission of Pakistan
(HEC) for their financial support by awarding me the fellowship via Indigenous
5000 Ph.D Fellowship Program.
My humble and heartfelt gratitude is reserved for my beloved Parents, and
especially for my respectful brother Asif Zia and sister. Without their prayers, support and encouragement the completion of this study task would have been a
dream.
My sincere regards and thanks are overdue to my best friend Faizullah,Abida Saleem, S.Qamar Abbas, S.Hamza safeer, M.Usman, M.Nadeem, and
all other friends and Lab fellows for their constructive suggestions and technical
guidance.

Layiq Zia

Abstract
Nix/(Cu0.5Tl0.5)Ba2Ca2Cu3O10- composite superconductors samples are synthesized at
normal pressure by two step solid state reaction method. The samples have shown orthorhombic crystal structure with increase in the cell parameters with the increase in the
added concentration of Ni-nano-particles showing that Ni diffuses partially into the unit
cell of final compound. A metallic variation of resistivity from room temperature down to
onset of superconductivity is typical feature of these samples with Tc(R=0) varying between 92 and 94K. The magnitude of diamagnetism is significantly enhanced in 7 and
10% nano-particle added samples. The softening of apical oxygen modes of type Cu(1)OA-Cu(2) has confirmed the diffusion of Ni into the unit cell of the final compound. The
excess conductivity analyses of conductivity data have shown enhancement in the values
of Bc(0), Bc1 and Jc with the addition of Ni-nano-particles. This shows that added Ninano-particles act as efficient pinning centers, which also confirmed in the suppression of
the London penetration depth.

Table of Contents
Chapter 1.1

Superconductivity ................................................................................................................................. 1

1.1.

Electrical Resistivity....................................................................................................................... 1

1.2

Some fundamental facts and historical review of superconductivity .......................................... 4

1.3

High temperature superconductors ............................................................................................. 7

1.4

. Structure of (CuTl) based high temperature superconductors................................................. 10

1.5

Types of superconductors ........................................................................................................... 11

1.5.1 According to their magnetic properties ............................................................................................. 11

I.

Type-(I) superconductors ............................................................................................................ 11

II.

Type-(II) superconductors ........................................................................................................... 12

1.6.

Characteristics and fundamentals of superconductivity ................................................................ 13

1.6.1 Zero resistivity .................................................................................................................................... 13

1.6.2.Meissner effect .................................................................................................................................. 14
1.6.3. Critical temperature .......................................................................................................................... 17
1.6.4. Critical magnetic field ....................................................................................................................... 18
1.6.5. The Isotope effect ............................................................................................................................. 19
1.6.6. Critical current density (

) ............................................................................................................. 20

1.6.7. Correlation of three critical values in superconductivity .................................................................. 20

1.6.8. London penetration depth

......................................................................................................... 21

1.6.9. Coherence length .............................................................................................................................. 22

1.6.10. Specific heat .................................................................................................................................... 23
1.6.11. Energy gap....................................................................................................................................... 23
1.6.12. Vortex formation ............................................................................................................................ 24
1.6.13.Magnetic Flux quantum ................................................................................................................... 24
1.6.14. Josephson Effect ............................................................................................................................. 25
I.DC Josephson effect .................................................................................................................................. 25
II. AC Josephson effect ................................................................................................................................ 25
1.6.15. Order parameter ............................................................................................................................. 25
1.6.16.Proximity effect................................................................................................................................ 25
1.7

Theories and development of superconductors......................................................................... 26

ii

1.7.1. London theory ................................................................................................................................... 26

1.7.2. Ginzburg landau theory .................................................................................................................... 27
1.7.3. BCS Theory ........................................................................................................................................ 28
1.7.3.1. Cooper pair formation ................................................................................................................... 28
1.8. Nano Technology and Nanoparticles ................................................................................................... 29
1.9. Application of superconductors ........................................................................................................... 30
1.9.1. Based on Zero resistivity ................................................................................................................... 30
I.Power transmission line ............................................................................................................................ 30
II. Superconducting motor .......................................................................................................................... 30
1.9.2. Based on magnetic properties .......................................................................................................... 31
II. Superconducting trains ........................................................................................................................... 31
III. Magnetic Resonance Imagining ............................................................................................................. 31
IV. Particle Accelerators .............................................................................................................................. 31
1.9.3. Based on Josephson Effect................................................................................................................ 31
I. SQUID ...................................................................................................................................................... 31
1.10.

References .............................................................................................................................. 32

Chapter 2 44
2.1. Literature review on (Tl-1223) superconductors ................................................................................. 34
2.2.

Literature review on Nano-particle dope High temperature Superconductors (CuTl-1223) ......... 37

2.3.

Literature Reviews on Fluctuation induced conductivity of high temperature superconductors

44

2.4.

References ...................................................................................................................................... 47

Chapter 3 .. 59
3.1. Nanoparticles Synthesis procedure ..................................................................................................... 48
3.1.1. Co-precipitation method................................................................................................................... 48
3.1.2.Synthesis of NiO nanoparticles .......................................................................................................... 49
3.2. Sample preparation ............................................................................................................................. 49
3.3. Characterization of the samples .......................................................................................................... 50
3.3.1. X-ray diffraction technique ............................................................................................................... 50
I.

X-ray diffraction and Braggs law .................................................................................................... 50

II.

X-ray diffractometer ....................................................................................................................... 53

iii

3.3.2.

Resistivity measurements ........................................................................................................... 54

Experimental setup ......................................................................................................................... 56

3.3.3.

Ac magneto susceptibility technique .......................................................................................... 58

Experimental setup ......................................................................................................................... 61

I.

Ac magnetic susceptometer ........................................................................................................... 61

3.3.4. Infrared spectroscopy ....................................................................................................................... 62

3.3.4.1. FTIR Components ........................................................................................................................... 63
I.

Michelson interferometer........................................................................................................... 63

II.

Source and detectors .................................................................................................................. 64

III.

Detectors ................................................................................................................................. 64

IV.

Fourier Transformation ............................................................................................................... 64

V.

Moving mirrors ........................................................................................................................... 65

3.3.4.2.
3.4.

Operating procedure of FTIR Spectrometer ....................................................................... 65

Refrences ........................................................................................................................................ 66

Chapter 4.. 78
4.

Introduction ........................................................................................................................................ 67

4.1.

Experimental ................................................................................................................................... 67

4.2.

Results and Discussion .................................................................................................................... 68

4.2.1. Theoretical Background .................................................................................................................... 68

4.2.2. Nano-superconductor (Ni)x/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt. %) composites ............................. 73
4.3.

Conclusions ..................................................................................................................................... 84

4.4.

References ...................................................................................................................................... 85

Figures of contents
Figure 1.1: (a) Zero resistivity
(b) Perfect diamagnetism..................................... 1
Figure.1.2:(a) lattice site (b) deformation of lattice site (c) attraction of second electron making cooper
pair ................................................................................................................................................................ 4
Figure .1.3: Evolution of Critical temperature(Tc) with time ........................ Error! Bookmark not defined.
Figure.1.4: Unit cell of CuTlBaCaCuO- superconductor ............... Error! Bookmark not defined.
Figure.1.5: Magnetization, versus applied magnetic field, for type-I superconductor. ............................. 12
Figure.1.6: magnetization, curve of a Type II superconductor ...................... Error! Bookmark not defined.
Figure.1 7: shows the expulsion of magnetic flux from superconductor .................................................... 15
iv

Figure1 8: Meissner Effect.......................................................................................................................... 16

Figure1.9: Vanishing resistivity at Tc ......................................................................................................... 17
Figure 1.10: critical magnetic field (Hc) as a function of temperature ....................................................... 19
Figure1 11: Relation of Jc,Hc,and Tc graphically ...................................................................................... 21
Figure 1.12: Dependence of penetration depth , on temperature of superconductor. . Error! Bookmark not
defined.
Figure 1.13: Decay of magnetic field inside the superconducing material ................................................. 27
Figure 1.14: shows cooper pair formation inside superconductors lattice .................................................. 29
Figure 3.1: X-rays diffraction from a crystal................................................................................................ 52
Figure 3.2 X-ray diffractometer .................................................................................................................. 54
Figure 3.3 Phono contribution to the resistivity in normal metals ............................................................. 56
Figure 3.4: (a) Four probe resistivity setup (b) Equivalent circuit............................................................... 58
Figure 3.5: Phase diagram ........................................................................................................................... 61
Figure 3.6: Experimental arrangement of Ac magneto susceptibility ........................................................ 62
Figure 3.7: Systematic FTIR sketch.............................................................................................................. 64
Figure 4.1: X-ray diffraction scans for Ni nano-particles ............................................................................ 73
Figure 4.2: X-ray diffraction scans for Nix/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) nano-superconducting
composites .................................................................................................................................................. 75
Figure 4.2(a): Variation in a,b-axis length because of Ni-contents. ............................................................ 76
Figure 4.2(b): Variation in c-axis length because of Ni-contents. ............................................................... 76
Figure 4.3: Combined resistivities for Nix/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) nano-superconducting
composites. ................................................................................................................................................. 77
Figure 4.4: AC-susceptibility measurements for Nix/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) nanosuperconducting composites ...................................................................................................................... 78
Figure 4.5: F.T.I.R spectrum for Nix/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) nano-superconducting
composites. ................................................................................................................................................. 79
Figure 4.6(a): ln() vs ln() of Nix/CuTl-1223 x = 0 wt% nano-superconducting composites ................. 81
Figure 4.6(b): ln() vs ln() of Nix/CuTl-1223 x = 3 wt% nano-superconducting composites. ................. 82
Figure 4.6(c): ln() vs ln() of Nix/CuTl-1223 x = 5 wt% nano-superconducting composites. ................. 82
Figure 4.6(d): ln() vs ln() of Nix/CuTl-1223 x = 7 wt% nano-superconducting composites. ................. 83
Figure 4.6(e): ln() vs ln() of Nix/CuTl-1223 x = 10 wt% nano-superconducting composites. ............... 83

Table of contents
Table 1: Parameters estimated from ln() and ln() 82
Table 2: Superconducting parameters estimated from excess conductivity... 83

Chapter 1

Introduction and Historical Review

This chapter contains a brief historical review and an explanation of superconductivity,

theoretical models, necessary terms, and some important applications of superconductors. This
chapter also covers some of the fundamental experimental and theoretical facts about superconductors.

Superconductivity
Superconductor are those conductors in which resistivity of the material goes to zero at

the critical temperature and the material become perfect diamagnetic mean all magnetic field
lines expel from the bulk of the material. In classical prospective superconductivity is a phenomena in which the resistivity vanishes and material become perfect diamagnetic below the critical
temperature [1]. The zero resistivity and the perfect diamagnetism are shown in Figure.1.1.

Figure 1.1: (a) Zero resistivity

(b) Perfect diamagnetism

The property that made superconductors attractive is zero resistance and the expulsion of a magnetic field. Before discussing property of superconductor, we have to first review resistive properties of normal materials in comparison with superconductors.

1.1.

Electrical Resistivity
The electrical resistivity is property of material how strongly it opposes the flow of the

current. The flow of the current opposes different in different materials. On the base of electrical

properties, materials classified into three groups, which are conductors, insulators, semiconductors, table 1 show electrical resistivity of these materials.
Materials

Resistivity

Superconductors

0
10-8

Metals
Semiconductors

Variable
1016

Insulators

Table 1: Shows resistivity range of superconductors, metals, semiconductors and

insulators.
Insulators having high electrical resistivity, while semiconductors have temperature dependent electrical resistivity in contrast of these conductors show relatively very low electrical
resistivity. Metals are all conductors having low electrical resistance which is due to the very
large number of free electrons in metals while insulators and semiconductors having very low
free electron density at ambient temperature. Beside of high numbers of free electrons in metals
theirs is electrical resistance to the flow of the electrons when the electric field applied to metals.
The electrical resistance arises from lattice vibration or impurities in the metals. Moving electrons are scattered by lattice vibrations or impurities in the metal. Due to scattering, electron loss
there energy causes reduction in electric current in the metal. Lattice vibration depends on temperature of metal by increasing temperature electrical resistance increase because lattice vibration of metal increase while by decreasing temperature of the metal electrical resistance decreases but did not reach to zero value for normal metals. While the impurities were independents of
the temperature. In superconductors when the temperature goes down the electrical resistance
become zero at the critical temperature and below critical temperature superconductor is in zero
resistance state. In zero resistance, motion of moving electrons wasn't disturbed by the scattering
mechanism. Cooper and Schrieffer explained the zero resistance state giving a complete new
idea of cooper pair formation in the superconducting state. According to them, when normal
metals transform to superconducting state cooper pairs are formed in superconducting state due
to phonon induce electron-electron interaction. When electrons move across the positive core,
i.e. Lattice site they leave behind a small deformation by an account of its negative charge attrac2

tion on the positive lattice site cause the increasing density of positive charge due to the positive
charge on ion core. At this time, another electron attracted by this deformation of lattice site and
hence two electron pairs by this weak attraction. The pairing of the two electrons via phonons
called Cooper pairs [2].
By deformation of lattice sites for a short time due to electron attraction, creating a virtual
phonon which attracts the second electron, and thus two electrons come closer to become a
cooper pair. At this time the energy of the system decrease showing that force is attractive.
In normal metals, charge carriers are electrons or holes, but in superconductors, charge
carriers are cooper pairs. Electrons in normal metals come across the high resistance, but cooper
pairs encounter very low resistance, overall it shows very minimum resistance to electron
movement.
Electrical resistivity is due to lattice vibration and impurities in metals, lattice vibration is
decreasing with temperature and almost become vanishes at 0K, but impurities are independent
of temperature, which is always present in metals, at low temperature there is always residual
resistivity due to these impurities. Beside of these residual impurities metals can be transformed
into superconducting state.
Due to negligible resistance, heat loss is very little in superconductor wire, so they can
caries huge amount of current for a long time without any loss of energy. This huge amount of
caries current ability of superconducting wire challenges scientist and engineers technically to
develop this type of wire for transmission line of electric power supply to overcome energy loss
in transmission lines [3].

(a)

(b)

(c)
Figure.1.2:(a) lattice site (b) deformation of lattice site (c) attraction of second electron making cooper pair

Figure.1.2: shows cooper pair formation in superconducting state, at (a) shows lattice of positively charged ions of superconducting material (b) here a negative charge electron
moving through the positively ions lattice site (c) shows disturbance in positive lattice site increasing density of positive charge as a result another electron is attracted by this disturbance.

1.2 Some fundamental facts and historical review of superconductivity

All conductors show electrical resistance to the electrical current. To find a good conductor that have no resistance scientist are struggling for centuries, in this way 19th century was
very victorious because of the discovery of superconductivity in mercury by Onnes. Onnes discovered the phenomenon of superconductivity, in the mercury during the validity of the Drude
theory. Onnes presented his research in 1911, in an article titled "On the Sudden Rate at
Which the Resistance of Mercury Disappears." Onnes define in that paper that the specific
resistance, became thousands of times less in amount relative to the best conductor at ordinary
temperature. Onnes later overturned the process and found that at 4.2 K, the resistance reimbursed to the material. The next year, Onnes presented more articles about the superconductivi-

ty. Initially, Onnes called the phenomenon "supraconductivity" and, only later, approved the
term "superconductivity." For this research, Nobel Prize in Physics in 1911 granted to Onnes.
Two years later, after the discovery of superconductivity in mercury, conductivity of lead
had investigated in 1913 having superconductivity at 7K. After this long period, there is no such
element or compound was noticeable to have superconductivity. In 1941, Niobium Nitride had
reported to have superconductivity at 16K [4].
To understand this phenomena, different groups of scientist are working on this field
from the time of its discovery and discover a number of different properties and elements having
superconductivity. Up to half century from the discovery of superconductivity, there was no reasonable theory that explains this phenomenon. From the discovery of high temperature superconductors up to now experimental mysteries of superconductors, mention that our knowledge
for understanding the complete phenomena of superconductivity is not enough [5].
In the history of superconductivity, one of the most important discoveries is the Meissner
Ochsenfeld effect. The Meissner effect is the expulsion of magnetic field line from the bulk of
the superconductors. The German physicists Walther Meissner and Robert Ochsenfeld discovered the Meissner effect in 1933 by measuring the magnetic field distribution outside superconducting tin and lead samples. From above transition temperature sample is in normal state and
the field lines are passes through it, but after cooling below the transition temperature, Meissner
and Ochsenfeld observed all field lines ousted from the interior of the sample. The Meissner effect is the unique property of the superconductors, which make superconductors to become perfect diamagnetic. The minimization of energy, of the charge carriers in superconducting state is
the origin of the Meissner effect [6].
The expulsion of magnetic field line and vanishing resistivity in superconductors, shows
that the Maxwell equations are not most enough at superconducting state. To overcome this difficulty London brother in 1935 presented first phenomenological theory, which justifies the presence of Meissner effect. Although, the London theory did not completely describe superconducting state, but was an important step toward understanding the superconductivity. The London
theory had based on two fluid models of super fluidity. London brother assumed that in the superconducting state, there are two types of electrons, normal and superconducting electrons; they
therefor consider two types of charge carries for the first time.

After the London theory, in 1950 there was another theory presented by Ginzburg and
Landau, which explain most macroscopic properties of superconductors. The phenomenological
Ginzburg Landau theory of superconductivity was first formulated by Landau and Ginzburg.
This theory, which joint Landau's theory of second-order phase transitions with a Schrdingerlike wave equation, had great success in clarifying the macroscopic properties of superconductors. It can also be obtained from BCS theory, by applying suitable limits indicated by Gorkov
[7].
Abrikosov indicated that the Ginzburg-Landau theory expects the division of supercon-

ductors into the two types now referred to as type-I and type-II. Abrikosov and Ginzburg were
awarded the 2003 Nobel Prize for their work.
The dependence of the critical temperature of isotope mass had investigated by Maxwell and
Reynolds they observed that the Tc of superconductors is varies with the varying isotope mass.
From this observation, it was shown that phonon-electron interaction was necessary for superconductivity [8].
In 1957 John Bardeen, Leon Cooper and Robert Schrieffer developed a brief theory of
superconductors with the concept of electron pairing via phonon. Elemental and type-(I) superconductors obey this theory, but type two superconductors did not obey this theory and need
modification. Cooper pairs were considered a current carrier in superconductors according to this
theory. Cooper pairs were form when the conductors changes from the normal state to the superconducting state.
The study of superconducting properties with mathematical tools was first time developed by Bogolyubov in 1958 which was an important contribution to this field.
Unification of Ginzburg landau theory with Bardeen, Cooper Schrieffer near the critical temperature was explained by L.P Gorkov in 1959. Gorkov also solved the BCS theory using green
function after one year later in 1958.
Practical use of superconductor was first time come into the world in 1962, when scientists made first superconducting wire of niobium titanium, hence making superconducting magnet.
The tunneling effect was discovered in 1962 by Josephson, which explains the current
flow between two superconducting blocks, which was separated by an insulator, the phenomena
were known as Josephson effect.

1.3 High temperature superconductors

Since after the discovery of superconductors scientists were struggling to find superconductors that have a high critical temperature. More than Half decay after superconductors were
discovered scientists only made superconductors having a critical temperature 18K in Nb3Sn and
23K for Nb3Ge. However, for practical use of these superconductors, low temperatures were required, which made superconductivity to be explored to get high temperature superconductors
for the practical use. Having no such discovery more than half decay, field of superconductivity
was considered to be at a dead end. The 1980's were a decade of unequaled discovery in the field
of superconductivity. Before 1986, in 1964, Bill Little of Stanford University had suggested the
possibility of organic (carbon-based) superconductors. These superconductors are synthesizing
effectively in 1980, by Danish researcher Klaus Bechgaard of the University of Copenhagen and
3 French team members. (TMTSF)2PF6 had to be cooled to an incredibly cold 1.2K critical temperature and exposed to high pressure to super conduct.
Then, in 1986, a true discovery was made in the superconductivity. Alex Mller and
Georg Bednorz (above), researchers at the IBM Research Laboratory in Rschlikon, Switzerland,
made an inelastic ceramic compound that super conducted at the highest temperature then known
30K [9]. This discovery was so remarkable because of that ceramics are normally insulators.
They do not conduct electricity. Because of that, researchers had not dignified them as likely
high-temperature superconductor candidates. The Barium, Oxygen, Copper and Lanthanum
compound i.e. LaBaCuO, which Mller and Bednorz synthesized, behaved in a not yet tacit way.
The discovery of this first of the superconducting copper-oxides (cuperates) won the two men a
Nobel Prize the following year. It was also found that small quantities of this material were in
fact superconducting at 58 K. Mller and Bednorz' discovery started a rash of activity in the field
of superconductivity. Researchers began around the world, making up ceramics of every presumable combination in a quest for getting higher and higher critical temperature.
A research group In January of 1987 at the University of Alabama-Huntsville replaced
Yttrium for Lanthanum in the Mller and Bednorz molecule and attained incredible 92K critical
temperature superconductivity in YBa2Cu3O10- [10]. A material (today referred to as YBCO)
was for the first time had found that would super conduct at temperatures higher than that of
boiling temperature liquid nitrogen, which is an easily available coolant. Further milestones had
done using exotic and frequently toxic elements in the vile perovskite ceramic.
7

These ceramic superconductors are called cuperates because Cu2O is a common constituent in all these high temperature superconductors. The Superconducting behavior of the cuperates was astonishing at that time, because in normal un-dopant form they are Mott insulators.
The superconducting behaviors of these cuperates are depending on the magnetic impurities, these magnetic impurities, reduce the critical temperature of cuperates.
The newly discovered superconductors also called un-conventional superconductors, and
had a clear difference from all conventional superconductors, which obey BCS theory. Scientist
repeated all conventional method on these cuperates for understanding superconductivity in these
cuperates, but did not get any satisfactory results. The importance of Cu2O in high temperature
superconductors were for the first time identified by Anderson, he realizes there is week inter
planer coupling in cuperates, thus the important physics behind superconductivity in cuperates is
quasi two dimensional[11].
The current classes of ceramic superconductors with the highest critical temperatures are
the mercuric-cuperates. In 1993 at the University of Colorado and the team of A. Schilling, M.
Cantoni, J. D. Guo, and H. R. Tot of Zurich, Switzerland for first time synthesis of one of these
compounds. A thallium-doped, mercuric-cuperates included of the elements Mercury, Thallium,
Barium, Calcium, Copper and Oxygen had a highest critical temperature at 138K, and was confirmed in February of 1994 by Dr. Ron Goldfarb at the National Institute of Standards and Technology Colorado. On the application of extreme pressure its T can be increased up higher approximately 25 to 30 degrees more at 300,000 atmospheres.
In 1988, Sheng and Hermann discovered thallium based superconductors [12-13]. Thallium based superconductors are the most finest amongst all other cuperates superconductors, due
to its high critical temperature and having a low surface resistance. Because of these quality efforts had done on thallium-based superconductors, for making thin film and bulks [14-20]. They
are existing in different phases according to its general formula TlpBa2Caq-1CqO2q+2 (p=1, 2; q=1,
2, 3, 4, 5) [21-24].
According to this general formula, different phases are synthesized, in which Tl-2223 is
at best having high critical temperature 127K, having tetragonal symmetry with p4/mmm space
group [25, 26].

In recent years, various discoveries regarding the novel nature of superconductivity have
been made. In 1997 researchers found, an alloy of gold and indium was superconductor and a
magnet near at zero absolute temperature, which contradicts that both a magnet and superconductivity, could not exist at the same time. Since then, more than a half-dozen such compounds
had discovered.
In 2001 magnesium Debride had been found to be a super conduct at 39K, which was an extraordinary discovery because any of the elemental or binary alloy do not super conduct above
30K. However, 39 K is still well below the transition temperature of the high temperature ceramic superconductors.
The most recent groups of superconductors to be discovered are the "pnictides". They are
iron-based superconductors having a high critical temperature at 50K.they are first discovered by
Japanese researcher in 2006. Similar to the high-T copper-oxides, the precise mechanism that
aids superconductivity in them is a mystery.

Figure.1.3: Evolution of Critical temperature (Tc) with time

1.4. The Structure of (CuTl) based high temperature superconductors

Number of characterization has been done on superconducting systems such as CuBa2CanCun+1Oy and TlBa2CanCun+1Oy. Both of these systems are differ because of position of
oxygen in charge reservoir layers. The Charge carriers dominating superconducting properties of
these samples and on change concentration of charge carriers superconducting properties get
change. Charge concentration can be changed by applying pressure or doping cations [27,28].
Addition of TI in Cu-12(n-1)n, results in the growth of a new subfamily Cu1-xTlx-12(n-1)n,
which is quite near to the compound. The Preparation of Cu-Tl compound has been done at normal as well as high pressure, having properties similar to those of Cu-based compounds [29, 3033]. The slight increase in the anisotropy of Cu-Tl superconducting compounds is mainly due to
semi insulating charge reservoir layer Cu1-xTlxBa2O4-, but the anisotropy remains lower as compared to that of Tl-based superconductors.

Figure.1.4: Unit cell of CuTlBaCaCuO- superconductor

10

The member of cuperates family

1-x

has P4/MMM space group and tetrago-

nal structure [34]. In addition, as the result, the prepared compound

1-x

n-1

n 2n+4-

have showed the low anisotropy as well as the critical temperature is high too. In a unit cell,
there are four

planes and a charge reservoir layer. In a unit cell, the four

planes are

separated by three calcium atoms from other. The Ba atom connected the superconducting

planes with each other, making the pyramid, type, unit cell and known as a p-plane. Where, the
central planes or s-planes are those, which come between these two p-planes. When the carriers
are doped to superconductors compounds, the s-planes are optimally doped, whereas p-planes
are over doped. Overall, p-planes play an important role in carrying supplies from the charge
reservoir layer to the s-plane [35]. The Cu atom of the p-plane mentioned as
oxygen atom of the p-plane is termed as
reservoir layer are named as
layer

1-x

2 4-

whereas the

, on the other hand the copper atoms in the charge

[36-37]. The

oxygen atom links the charge reservoir

and the p-plane. The charge passage mechanism is controlled by the

oxygen atom from the p-plane to the charge reservoir layer. The oxygen atom at the center of the
charge reservoir layer
secondary bonding either

1.5

1-x

2 4-

is named as

and

atom [38]. This

oxygen atom has

atoms of the charge reservoir layer.

Types of superconductors
Superconductors have classified into two main types according to their physical and

magnetic properties. However, it can further classify according to our understanding.

1.5.1 According to their magnetic properties

According to their magnetic properties, they are divided into two main types. They are type-(I)
and type-(II).

I. Type-(I) superconductors
These types of superconductors have a lower critical temperature, and have an abrupt transition from
a normal state to a super state in a magnetic field. Type-(I) superconductors are soft superconductors, they
are composed of pure elements, alloys, they have also low critical magnetic field. Type-(I) are consist of
elemental and binary alloy superconductors. The maximum critical magnetic field of type-(I) superconductor is

, which is very low value compare to the type-(I) superconductors. The Type-(I) super-

11

conductor mostly consists of those superconductors, which obeyed BCS theory and called as conventional
superconductors. Figure.1.5. Shows that up to

the material is pure diamagnetic and above

it

becomes paramagnetic.

Figure.1.5: Magnetization, versus applied magnetic field, for

type-I superconductor.

II.

Type-(II) superconductors
They are consisting of all non-conventional superconductors, and having a high critical

temperature. They are mostly made of ceramic, so due to their physical properties they are hard
superconductors. In comparison with type-(I) superconductors, type-(II) superconductors not
have sharp or abrupt transition from a perfect diamagnetic state to a paramagnetic state. As a result, there has a two state combine region, where vortices are formed having a normal core inside
and outside the region is in the superconducting state. Figure.1.5.(b) Shows that negative magnetization rises continuously up to Hc1(T) while above Hc1 it decreases gradually. The material
between Hc1 and Hc2 is partial diamagnetic, i.e. The magnetic field can penetrate into the material and above Hc2 material become paramagnetic.

12

Figure.1.6: Magnetization, versus applied magnetic field, for type-II superconductor

1.6. Characteristics and fundamentals of superconductivity

As any state of matter, has its own elementary properties, so any superconducting state
independently exhibits its own mechanism of superconductivity. Hence, a high temperature superconductor will also exhibit them. The key basic properties of the superconducting state are the
following: zero resistance, the Meissner effect, the Josephson effects, the magnetic flux quantization, the presence of an energy gap, and the proximity effect. An obstacle in specific heat was
marked in all superconducting transition. Finally, the behavior of type-II superconductors, in the
mixed state has the same pattern.

1.6.1 Zero resistivity

At any temperature below the critical temperature all superconductor has zero electrical
resistivity, mean that infinite electrical conductivity, for small amplitude of DC current. The resistivity of a superconductor is smaller than 1023-m. This value is 18 orders of magnitude lesser than the resistivity of copper at ambient temperature. Such a small value of resistivity in a superconductor indicates that in zero magnetic field the current lifetime in a superconducting ring
is not less than 105 years. Superconductors have properties having zero electrical resistivity be-

13

low the critical temperature, which make superconductivity a thermodynamically unique phase
of matter [39]. The relation of electrical resistivity with electrical conductivity is followed as:
(1.1)
Now, as

(1.2)
Here m is the mass of the electron, e represent charge on the electron, is mean free time,
where n is the number of the electron. A scattering of electrons in solid decrease with decrease of
temperature, with resulting of decrease in lattice vibrations in solid. In superconducting state
when scattering of electron with lattice decrease mean free time increases, which results in decrease in electrical resistivity, and at very low temperature below the critical temperature of superconductors, mean free time become so large that resistivity become vanishes and the material
become a superconductor [40]. Electrical resistivity vanishing at below critical temperature is
the intrinsic properties of all superconductors, which is widely used in practical applications.

1.6.2. Meissner effect

Meissner effect is the intrinsic property of all superconductors, below the critical field all
superconductors shows expulsion of magnetic field line from the bulk of the material. It was
first observed by Meissner and Ochsenfeld in 1911, that magnetic flux lower than Hc was expelled by the sample below Tc[41]. Meissner effect is the consequence of perfect diamagnetism
of the superconductors. Every superconductor shows perfect diamagnetism. Inside the superconductor magnetic field is zero in placing in the applied external field. This due to surface current
which arise when superconductor is placed in the external field current was built up on the surface of superconductor which produce magnetization in opposite direction which cancel out the
effect of external magnetic field.

14

Figure.1 6: shows the expulsion of magnetic flux from superconductor

The magnetic field expulsion from superconductor vanishes when the temperature increased or field strength is increased. Surface current remains on the surface of superconductor
in the temperature below the critical field because the resistivity is zero, so a dissipation of energy is zero and the material remain in the perfect diamagnetic state. Relation of external magnetic
field to magnetization is as follows
(1.3)
Here, Hex shows the external magnetic field, M denotes magnetization, and
susceptibility.
But inside the superconductor

at

So equation 1.3 becomes

15

shows magnetic

Also from (1.3)

(1.4)

Negative sign shows opposite magnetization produce inside the superconductor. This
shows that the magnetization of superconductors have ve value and susceptibility of superconductors have -1 value [42].

Figure1 7: Meissner Effect

From a classical point of view every superconductor exhibit perfect diamagnetism, i.e.
B= 0 inside the superconductor, as shown in Figure.1.8. In fact, as we already know to cancel B,
a superconductor creates a DC current on the surface, which gives rise to a magnetization M, so
that in the interior of the superconductor. Since the resistivity of the superconductor is zero, this
surface current does not dissipate energy. If the magnetic field was applied to a superconductor
at T>Tc, and it is then cooled down to T<Tc, in this case, the field will remain inside the superconductor until it will be warmed up again through Tc. This frozen magnetic field will remain
inside the superconductor independently of the presence of the external magnetic field. Probably,
the most spectacular demonstration of the Meissner effect is the levitation effect. A small magnet
above Tc simply rests on the surface of a superconductor having dimensions larger than those of
the magnet. If the temperature is lowered below Tc, the magnet will float above the superconductor. The gravitational force exerted on the magnet is compensated the magnetic pressure occurring due to super current circulation on the surface of the superconductor.

16

1.6.3. Critical temperature

Superconductivity appears in superconductors only below a certain temperature, which is known
as critical temperature. At room temperature the superconductor is a normal state and the current
dissipation occurs due to electrical resistivity. However, when the superconductor material
cooled down below its critical temperature the dissipation of current or energy become vanishes
and the state of the material is defined as superconducting state. Different superconductors have
different critical temperature, which mean that critical temperature depends on the superconductor materials. From the discovery of superconductors scientist remain in struggle for increasing
the critical temperature of superconductors. Although they had no good achievements in this research up to 1986. At that time, the highest critical temperature was below 30K, which is no
good sign of research. In 1986, material having high a critical temperature above 77K was

Figure1.8: Vanishing resistivity at Tc

17

Discovered, and got attention because of having

above liquid temperature. In high tempera-

ture ceramic superconductors, YBa2Cu3O7 have 92K [43], and HgBa2Ca2Cu3 have Tc 133K. Figure 1.9 shows the resistance of normal and superconductor above and below Tc. Where, Table:
1.2 shows critical temperature of different superconductors

Table1.2: Critical temperature of some superconductors

1.6.4.

Critical magnetic field

The superconductivity not only destroyed by the increasing of temperature, above its critical value, but it also destroyed by increasing the external applied magnetic field. Transition
from superconducting to normal state occurs below the critical temperature, by application of
high magnetic field. Therefore, the maximum external field at which the superconductivity destroyed is called a critical magnetic field. This was first observed by Meissner when they analyze
the behavior of superconductors at different magnetic field, they observed that the superconductivity remains only at certain values of the applied external field after which the superconductors
is a normal state. Figure.1.10. Shows critical magnetic field versus temperature at T < Tc.

18

Figure 1.9: critical magnetic field (Hc) as a function of temperature

When the superconductor placed in external fields, induces current flow in the surface of
superconductors, which produce opposite magnetic field, which cancels the applied field and the
expulsion of the field line, occurred. Nevertheless, above a critical value of applied magnetic
field, the current do not present more and as a result, the magnetic field line penetrates into the
bulk and the material become normal. The critical magnetic field depends upon the critical temperate of the sample and on the symmetry of the superconductor sample [44]. The critical magnetic field is low for type-(I) superconductors. In case of type-(II), superconductors, there are
intermediate region so there are different critical fields having mixed region.

1.6.5. The Isotope effect

The dependence of the critical temperature of the mass of the isotope was first observed
by Maxwell indicating that for a material different isotope, has different critical temperature.
From a number of different experiments, it proved, providing an equation between the mass of
the isotope and its critical temperature i.e.
(1.5)
Where a is fitting constant.

19

1.6.6. Critical current density (

In superconducting state the current in the superconductors have zero resistance so the
loss of heat energy is zero its reply that superconductors can carry a huge amount of current
without loss of energy due to resistance but there is a limit above which the loss of energy occurs. Superconductors sustain up to a certain amount of current above which its superconducting
state destroyed. The maximum current at which the superconductivity destroyed is called critical
current density

. The critical current depends on the material, different materials have differ-

ent value of critical current. The transition of state occurs because of the collision of electrons
with lattice site and the breaking of Cooper pairs. The critical current for type-(I) superconductors has low value then type-(II) superconductors. Its because of that type-(I) superconductors
have low Tc and also consists of elements superconductors, there for the electron density is higher than that in type-(II).

1.6.7. Correlation of three critical values in superconductivity

As superconductivity not only destroyed upon increasing temperature, but there are two
other critical values upon which the superconductivity depend as we discuss above, now the dependence of these critical values on each other also importance in superconductors.
For superconductors have superconductivity the temperature, current and applied magnetic field must be below of its critical values for that superconductor. This implies that the material
must be below of all critical values, then it can have superconductivity. In superconducting state
the materials have a lower energy state, so that all electrons that formed cooper pairs has lower
energy state. While electrons that are unpair have higher energy state and they are according to
London theory called normal electrons. The superconductors below its critical temperature at
and

has supercondivity but upon increasing its temperature above its critical value

having no applied field and no current transform into a normal state. Because of breaking up of
cooper pairs become favorable and the current now only fascinated by normal electrons, which
have resistance to its motion.

20

Now, at below Tc increase in current density from its critical value

vanish the super-

conductivity, on similar way when the superconductors placed in strong magnetic field above of
its critical value

the superconducting state vanish beside it has lower value of temperature

and current. Figure 1.11 shows the relation among temperature , magnetic field

, and current

density .

Figure1 10: Relation of Jc,Hc,and Tc graphically

1.6.8.

London penetration depth

From Meissner effect, it was first believed that external magnetic field completely expelled from the interior of the superconductors. Soon after the London theory, it was proved that
external magnetic field could penetrate into a thin layer of the superconductor, which is known
as the London penetration depth denoted as

.The London theory was two fluid model in

which current is flowing by two different ways super electron and normal for which London
used Maxwell equation from which they developed useful equation, which is known as London
equations [45].
By solving London equations it proved that magnetic field exponential decay from the
surface to the interior of superconductors. This decay of the magnetic field is called London penetration depth.
(1.6)

21

Where e represents charge, me represent mass, ns represent density, of electrons

is permeabil-

ity of free space.

London penetration depth also depends on the temperature and the nature of the materials which
is given as
(1.7)
*

Here

is penetration depth at zero T. For

about 1022cm-3,

is nearly 60nm [46]. Fig-

ure.1.12. Shows the dependence of penetration depth on temperature.

Figure 1.11: Dependence of penetration depth , on temperature of superconductor.

1.6.9.

Coherence length

In 1953 Pippard give the idea of coherence length for the first time [47]. The coherence length is
basically the dimension over which the order parameter

varies near the boundary of

superconductor. Abrikosov defined the ratio of penetration depth, and coherence length, as GinzburgLandau parameter. It is denoted by
22

(1.8)
Ginzburg-Landau parameter basically distinguishes between type-I and type-II superconductors,
superconductors having

are termed as type-I superconductors while type-II superconductors has value of

1.6.10.

(1.9)
[48].

Specific heat

Another property that has a nonlinear behavior is specific heat, which has a jump at the
transition point. For normal metals specific heat given as
(1.10)
Specific heat has two parts, one from the conducting electron and second is from lattice vibration
or phonons. In normal metals, specific heat is linear with temperature at low temperature where
phonon contribution is negligible.
In case of superconductors, as the phonon at low temperature have no such contribution
to specific heat, only the electron contributes to specific heat capacity. In superconductors normal electron transforms into Cooper pairs, so that the value of specific heat

has nonlinear be-

havior with temperature for superconductors.

(1.11)
From a thermodynamic of superconductors, define that heat capacity changes exponentially with
the temperature. There is the development of the energy gap, proof of the existence of the superconducting state.

1.6.11.

Energy Gap

Fermi band theory of metals define that electron in metals has a definite energy band,
metals have conduction band having higher energy. In case of superconductors, there is formation of cooper pairs, which reduce energy of electron than its normal state, so there has produced a band gap between normal electron state and pairs electrons states. The width of the
electron energy gap in Fermi surface is 2. This was developed from the BCS theory that the
electron in normal state has a higher energy state than electrons in a super state [49].
(1.12)

23

Here

reperesent Fermi velocity, from equation its show that band gap depends on temperature

of the system. At 0K all electrons are transform to pairs form in superconductors while above 0K
there are two definite electrons normal and paired, above Tc the Cooper pairs are completely
broken.
(1.11)
Represent Boltzmanns constant.

1.6.12.

Vortex formation

For type-(I) superconductor, there is one critical magnetic field, the value at which transition, from the super to the normal state occurs. In case of type-(II) superconductors, there is not
one critical magnetic field where the transition from normal to super state occur, but there are
more than one valued critical magnetic field at which super state transition occurs.
At first critical field the superconductor transforms to intermediate phase in which the
sample having both state normal and super state. In this region, there is formation of vortices
which has a dimension of cooper pair length i.e. coherence length. The Vortices has radius equal
to that of coherence length, and having a normal core inside while outside of vortices is superconducting state.
Due to this normal core vortex external magnetic field can penetrate through this core and
the superconductor has changed its purfying properties of perfect diamagnetic nature.
By increasing external magnetic field, density of these vortices increased which mean normal
region in the sample increase and the material become normal at a point called a third critical
field. Above which there is no superconductivity remain and all of the materials become transferred into a normal state.

1.6.13.

Magnetic Flux quantum

Superconductor has another interesting property of magnetic flux quantization. The applied external magnetic field through a coil of superconductors has properties of quantization
that there is a discrete number of flux cross through that of the coil which is called flux quantization. In 1961, B. S. Deaver and W. M. Fairbank discovered experimentally the phenomenon of
flux quantization [50]. It was predicted first theoretically by London theory 1948. Single magnetic quanta has a value that pass through a loop of a superconductor is
24

(1.12)

1.6.14. Josephson Effect

In 1962, Josephson determined that current through a thin insulating barrier (the order of
a few nanometers thick) between two superconducting blocks flowing due to tunneling of pairs.
This tunneling of cooper pairs through an insulating barrier called Josephson Effect. The Josephson Effect is two types, DC Josephson effect, and Ac Josephson effect.

I.

DC Josephson effect

The current flow during tunneling of Cooper pairs through an insulating barrier at zero-voltage
known as the DC Josephson Effect.

II.

AC Josephson effect
The flow of the oscillating current during tunneling of Cooper pairs across the insulating

barrier at a steady voltage is sustained across a tunnel barrier is known as the Ac Josephson Effect. These two phenomena was proved experimentally soon after its prediction. The oscillating
current in AC Josephson Effect has frequency calculated by Josephson has equal to
(1.13)

1.6.15. Order parameter

There are different parameters, which describe the properties of the system or its state. In
the superconducting state, the order parameter is the one of the most important parameter. This
represents the density of cooper pairs in the superconducting state. The Wave function has an
amplitude and phase the superconductors, wave function written as the order parameter has
unique properties similar to that of the wave function in quantum mechanics.

1.6.16. Proximity effect

When a superconductor is in good contact with normal metal, the cooper pairs from superconductor transfer or tunnel into the thin layer of normal metal and this thin layer of normal
metal behave like a superconductor. This phenomenon, called proximity effect. Every superconductor shows this phenomena when it has a good quality connection with normal metal. During
proximity effect the order parameter from superconducting state alter, and hence inducing super25

conductivity in normal metal within a thin layer of the order of coherence length
[51].Induce superconductivity; depend on the contact of the two conductors, and on the temperature. Below critical temperature, density of cooper pairs is high, so the tunneling from superconductors to a normal state is also high.

1.7

Theories and development of superconductors

Scientists are developing theory on the phenomenon of superconductivity. To fully de-

scribe superconducting state many models and theory were presented at different time having
limitation in explaining the phenomena of superconductivity. In 1947, London brothers present
first phenomenological theory of superconductivity, which was successfully explained electrodynamics of superconductors at that time, but having a limitation of explaining other properties
of superconductors. With the passage of time, theories were produced for explaining a different
aspect of the superconductors, in the same way Ginzburg Landau presents a theoretical model in
which they for the first time introduce quantum mechanics and define a new parameter in a superconducting state called order parameter. The first microscopic theory which explains the behavior of superconducting state at micro level was presented by three scientist Bardeen, Cooper
and Schrieffer in 1967, in which they introduce cooper pairs. In similar ways, Aslamsov and
Larkin presented his work on the thermal fluctuation in superconductors.

1.7.1. London theory

Fritz and Heinz London in 1935 present a phenomenological model of superconductivity,
which explain the macroscopic behavior of superconductors in external magnetic field. They
used the Maxwell equation to describe the electrodynamics of superconductors and considering
the super state as two fluid state in which they considered current in two class one due to normal
electron and other due to super electron, the super electron current has high density when a metal
change from a normal state to superconducting state. As in superconducting, state there is no opposition for current so therefore they take the current in normal state as normal current and in
superconductor

state,

as

superconducting

current.

The

relation

between

magnetic

field, electric field, and current is linear and is described by London equations [52].
The London equations in terms of electric field and magnetic field are
(1.14)

26

is the density and is the velocity of superconducting fluid, is the mass and is

Where

charge of the electron. is the electric field.

The magnetic fields penetrate into the superconductors in a thin, small layer called London penetration depth

as discussed above. This is of the order of

; having de-

pends on the temperature of the sample. Figure.1.17. Shows decay of magnetic field inside the
superconductor.

Figure 1.12: Decay of magnetic field inside the superconducing material

.

1.7.2. Ginzburg landau theory

Ginzburg Landau presented the second phenomenological theory in 1950. The GL theory used quantum mechanics into the explanation of superconductors. GL theory combined
Landau second order phase transition with a Schrdinger wave equation. They consigned a
wave function
conducting

Subject on single distinct coordinate to the whole superelectrons. Electron in superconducting state has coherence behavior because of

single valued wave function

behavior of all electron at single state. Categorically, the GL

theory assigns a single wave function to an electron in super state. The GL theory is only applicable to a small region in the critical temperature range

, because its used second

order phase transition of Landau theory. The Landau second order phase transition associated

27

with thermodynamic variable and singularity arises in the heat capacity. The probability

of

order parameter or wave function, of superconducting electrons gives the density of cooper pairs
in the super state.
From London theory, it was proved that the magnetic field has small penetration depth in
the superconductor. This was also proved in the GL theory that defines the dependent of coherence and penetration depth on temperature.
GL theory shows that the width of the wave function in type-(I) superconductors is larger than
that oh type two superconductors.

1.7.3. BCS Theory

The electron in superconductors has single state, and having lower energy from that of
normal electrons in normal state. This microscopic property of superconductors was first explained by BCS theory, developed by J.Bardeen, L. N. Cooperand J. R. Schrieffer [53] in 1957,
with the idea of attractive interaction between two electrons viva phonons. The BCS theory was
well educated in explaining superconductivity in type-(I) or elemental superconductors. However, it fails to explain type-(II) superconductors.

1.7.3.1. Cooper pair formation

The electron that moves through the conductor, interacts with the nearby positive
charges in the lattice which results in the deformation of the lattice. Lattice deformation brings
another electron, of opposite spin and momentum, to move into the higher positive charge
density region [54] is the basic consideration of BCS theory. According to BCS theory, the atomic excitations produce attractive interaction between two electrons and they form a pair. This
pairing of two electrons, correlate these electrons making a correlated system. Figure.1.18.
Shows the lattice of superconductors and formation of cooper pair.

28

Figure 1.13: shows cooper pair formation inside superconductors lattice

Below the critical temperature, there are high numbers of these electron pairs produced
and all of them correlated with each other so they make a super condensate, which has higher
breaking energy. This suggests that in low temperature the lattice vibration has the small energy
so it cannot break these correlated electrons. In superconducting state these Cooper pairs have no
effect of lattice vibration and thus there is no resistance in motion for these Cooper pairs. The
breaking of any pair destroys the hole condensate of all pairs and the superconductivity dismiss
at that point which is above the critical temperature of superconductor. The coherence length at
which the cooper pair exists is a few angstroms.

1.8.

Nano Technology and Nanoparticles

The term nanotechnology, and nano-science, is commonly used in past decades because it

is including an enormous range of disciplines and technologies. Nanotechnology is the science

that deals with the materials, studying their composition, structure and properties at the nanometer scale [55]. The term nano-science discusses the applied science field, and technology, whose
basic aim is to control the matter at atomic and molecular scale and making of devices that lie
within this size range, most of 100 nanometers or smaller.
The material particles that have the order range from 1-100nm, is called nanoparticles.
They are different in shapes and dimension having zero-dimensional and shaped identical to
spheroids. Nanoparticles exhibit different properties by having size in the dimensions of nano-

29

scale than normal materials. A particle at nano scale has more reactive than from bulk size because of having a greater surface per unit mass. Thus, the material in the nano-particles form will
be more reactive as compared to the mass of material made up of larger particles. The ordered
arrangement of atoms may be of ions in a nano-particle are called nano-crystallites.

1.9. Application of superconductors

Based on the properties of superconductors used in practical life, the applications of Superconductors are categorized as Fellows.

1.9.1.
I.

Based on Zero resistivity

Power transmission line

The Energy loss in power transmission lines From power generation to home or city In-

dustries is 15% of the total power. This is bush energy loss due to resistance, so to remove or
minimize energy loss due to resistance, resistance less wire is needed for which superconducting wine is good choice, because of having no energy loss due to zero resistance.
There are various labs working, and developing superconducting wire for practical use.
One of which is Brookhaven Laboratory produces 50cm diameter of superconducting wire Capable of carrying power up to 1000MW, which is to time more than the power that the normal
conductor of same diameter can carry. Superconducting wires need special en closer that it must
be below from room temperature, because of superconductivity only take place below room
temperature. Niobium titanium wire is used in encloses of liquid helium. BSCCO in a tape form
is also a process of experiments with YBCO in thin film form. For practical application the optimum current density is approximately 1000 A/Cm. This is the largest value of current, incapable by copper wire.

II.

Superconducting motor
Recent motors and generators are efficient, but having large size for the production of

high power requirement. The superconducting coil of bismuth 2223 is used instead of conventional coil; it has small size producing power up to 167HP, demonstrated in 1995 at Navel laboratory. Normal motors having copper wire used as a coil is large in size, it can be reduced in size
using super conducting coil instead of copper coil which make also these motors or Generators to
become more efficient.

30

1.9.2. Based on magnetic properties

II.

Superconducting trains
The Meissner effect of superconductors has useful application in the modern world is

fastest train system. A train system of superconductors can be built having fewer fractions between the rail and train because of no contact due to Meissner effect. Engineering for this assessment was done by oh nan and reported that superconducting trains would be faster and safer
than the conventional trains, The record speed of 32l miles/ hour was recorded in 1997 By magnetic aviation train made by Japanese engineers.

III.

Magnetic Resonance Imagining

In recent day MRI is commonly used for the diagnosis of different diseases. This tech-

nique helps doctors in the treatment of many hidden diseases. For MRI strong and uniform magnetic field is required. For this requirement superconducting magnet are used in modern type of
MRI.

IV.

Particle Accelerators
Particle accelerators require high power electromagnetic field. The LHC in CERN has

several thousand of superconducting magnets producing high magnetic field in the comparison
of normal superconductors, also has less energy requirement of about 10th timeless from normal
electromagnets, with the benefit of producing 4th time more power the that of normal magnets.

1.9.3. Based on Josephson Effect

I.

SQUID
Accuracy is important for any experimental measurement of any experiment. So for most

sensitive magnetic field experiment SQUID use as a magnetic field detector.

The superconducting quantum interference device (SQUID), is made up of two parallel
Josephson junctions. The SQUID device is a very sensitive magnetometer, which can detect extremely small magnetic fields. SQUID can be used to measure very small magnetic fields in beings. It can be used for finding that if there is sufficient magnetism in mouse brains for the navigational property to an internal compass. The SQUIDs sensitivity is linked with measuring variations in magnetic field related to one flux quantum, which can be written;
(1.15)

31

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(1988).

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[27]. B. Morison, D. S. Ginley, J. E. Schirber and E. L. Venturini Physica C 156, 587, 1988
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[29]. H. Ihara, K. Tokiwa, H. Ozawa, M. Hirabayashi, A. Negishi, H. Matuhata and Y. S. Song Jpn. J.
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[31]. K. Tanaka, A. Iyo, N. Terada, K. Tokiwa, S. Miyashita, Y. Tanaka, T.Tsukamoto, S. K. Agarwal,
T. Watanabe and H. Ihara Phys. Rev. B 63 064508, 2001
[32]. T. Shibata, T. Tatsucki, S. Adachi, K. Tanabe, S. Fujihara and T. Kimura Physica C 353 200,
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[33]. N. A. Khan, Y. Sekita, H. Ihara and A. Maqsood, Physica C 377, 43, 2002
[34]. Ihara, K. Tokiwa, K. Tanaka, T. Tsukamoto, T. Watanabe, H. Yamamoto, A. Iyo, M. Tokumoto
and M. Umeda, Physica C 282-287, 957 1997.
[35]. H. Ihara, Physica C 364,289 2001.
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33

Chapter 2

Literature review

2.1. Literature review on (Tl-1223) superconductors

L.Perez. Arrieta et al [1] prepared the

superconductors and

3 x

studied their properties. For the preparation of these samples, they used two step process. They
diffusion conditions at 5500C, they deposit

used a two zone furnace by different thallium

films of

3 x

by spray pyrolysis techniques. From acetylacetonates, precursor of films

was formed and from different oxygen flow rates various

get the pressure of thallousoxide in the range of
used of

pellets. They obtained films of

partial pressure were prepared to

-4

-2

phase having

by the

which is perpen-

dicular to the surface of substrate. They took the conclusion that the film has the mixture of
2

phase and

phase, they got crystalline grain with longest side having super-

conductor behavior best overall for a thallous oxide pressure of

-2

atm. For these films

the (Tc) values were from

The Cu0.5Tl0.5Ba2Ca2Cu3-y FeyO10- specimen were produced by N.Hasan et al [2]. These
specimens were manufactured using a solid phase change of Ca(NO3)2,CuCN,Ba(NO3)2 and
Fe2O3 at 1atm for (y=0.0, 0.01, 0.03, 0.075) examples. They performed the XRD analysis, resistivity, thermo gravimetric analysis, and AC susceptibility measurements, to observe the influence
of Fe doping on them. From the XRD data, they noticed changes in the cell function a and c
but the tetrahedral arrangement of particles remained the identical. The

length was

shortened with the inclusion of Fe concentration in unit cell. From gravimetric analysis, they noticed that on replacing Cu+2 with Fe+2 ions result the existence of oxygen in higher quantity and
produced some Fe-O defects, having influence on conductivity. Through the resistivity and susceptibility calculations they got that by putting Fe doping will damage CuO2 planes, ground effects and greater amount of oxygen will free up carrier to a great extent in turn it will lessen
down the charge density. The influences on the charge localization were studied and it was resulted that Fe occupies different Cu areas in a normal condition. On the annealing of specimen
firstly they got that magnitude of diamagnetism and Tc goes up to three times, they got that due
to annealing the bonding of transporters may cause the meeting of Fe with oxygen hence raising
34

the density of CuO2 planes after annealing. The out of state components of susceptibility is made
will organize high peaks, which is noticed of improvement in the inter-grain coupling. They resulted that increasing diamagnetism may be because of the increase in transporter density in
charge container layer through oxygen diffusion at O areas. Diffusion of oxygen causes the
movement of e restrict CuO2 plane in optimum phase, and thus the electron concentration normalizes at Fe+3 sites. In super conductive state the lesser number of electrons plays role in quantizing the hole density. They got that with Fe doping the electrons in their path of CuO2 are localized that produce high quantity oxygen faults and damages at small level. It will lower down T c
and lowering in electron density is the result.
Y. Shimakava et al [3] studied and produce

samples. They studied the struc-

ture of unit crystal, critical temperature (Tc) and carrier concentration in

They noticed that long range of

samples.

values are clearly co-related in these samples with

length, it was clear that the change in the critical temperature may be due to small change in oxygen content from which it is proved that (Tc) depends on the concentration of carrier. They noticed that

might be increased about at 80K and

length might be alongated 0.4% by

increasing oxygen about 0.1 per formula unit. They show that (Tc) suppress due to increase in
concentration of dopant. They take the conclusion that in

samples, increases in con-

centration of holes might suppress superconductivity while a decrease in concentration of holes

might Enhance superconductivity. The change in

could be because of increase in

number per formula unit. By increasing the number of sheets of

sheet

per formula unit the num-

ber of concentration carrier per sheet became smaller. It was noticed that certain suitable range of
concentration of carrier the superconductivity only exist.
Nae. Lih. Wu et al [4] introduced a new powder synthesis technique for the formation of
2

2 8

and

2 8

single phase compound from a stoichiometric mixtures. For

the preparation of 2122 compound, they used

2 3

and for the formation of 2223 compounds they used

2
2 3

stoichiometric mixture,

4
2

stoicheo-

metric mixture. Those single phase samples which have Tc above than 100K were prepared for a
time between 6 & 23h by one step calcination for 2122 they got the maximum critical temperature of 116K, and for 14h calcination they got 110-118K Tc for 2223 single phase samples. Both
of 2122 & 2223 samples have saturated Meissner effect and sharp transition. With the help of
35

this new powder synthesis method the problem of powder melting was successively reduced,
which occur widely in the conventional method. This reduction was mainly due to the presence
of

in the mixture with the help of which 2122 compounds were formed and lower

temperature calcination was made possible. In the second two step calcination the 2122 compounds worked as a precursor for 2223 compounds. They took the result that the reaction was
due to the inter-calcination of CaO and CuO layers into the present 2122 grains.
S.K Agarwal et al [5] reported the study of superconductor sample CuBa2Ca2Cu3O12- doped
with Mg at Ca sites, prepared in a pressure of 3.5GPa at temperature 10000C. The analysis of
these samples was carried by characterization of these samples by XRD analysis, four probe resistivity measurements, and Hall effect measurements. The lattice parameters a=axis and c=axis
was reported, decreased by the increase of Mg at Ca sites. Holes concentration nH was found to
decreases by the increasing Mg contents at Ca site in the Hall Effect measurements. They did the
critical field measurements and noticed that the anisotropy

in the c=axis in aligned samples

was the least between such samples of high temperature superconductors. Such low value of anisotropy

was due to decrease of hole concentration nH in the charge carrier block they reported,

also they conclude the decrease of holes concentration nH was be the cause of decreasing space
between the inter-superconducting Ca3Cu4O8 block, resulting decrease of c-axis.
S.Mikusu et al [6] prepared the thallium superconducting samples

3 y.

For

the formation of these samples they used the solid state reaction. And the X-rays diffraction,
SEM technique were carried for characterization. They used four probe electrical resistivity and
Quantum design MPMs apparatus to get the critical temperature

the MPMs was also used to

measure the hysteresis loop of DC-magnetization at the temperature of 5-110K for the magnetic
field up to

. They noted that the variation of critical temperature (Tc) values occurs due to

small changes in the starting composition of the system

magnetization, they calculate the current density

3 y.

From DC-

and Birr. And by comparison calculated data

with Hg-1223 they get results that Birr value for Tl-1223 having Tc 130K have higher value than
that of Hg-1223 low Tc sample. Nevertheless, Y-123 has high value of Birr at

then obtained

valued of Tl-1223 samples. From Their result, they suggested that pinning center is necessary for
application at 77K.

36

L. Ruffo et al [7] developed and observed YBa2(Cu1-xMgx)3O7- (x=0 to 0.1) and

La1.85Sr0.15(Cu1-xMgx)O4 (x=0 to x=0.07). They noticed that increase in Mg densities decrease the
length and also decrease critical temperature Tc of there samples. They suggested that
lowering of conductivity was due to magnetic pair breaking influence, as Cu electrons are localized strongly, replacing of non-magnetic dopant for Cu produce a magnetic phase in CuO2
planes. It does not depend on electronic configuration or valence shell, but only effected by replacement of non-magnetic dopant suggested by the results. They noticed from Ac magnetic susceptibility measurement of YBa2(Cu1-xMx)3O7- samples, that with increasing the of weak link
network in CuO2 planes decreased the current density .

Na0.5Co1-xMxO2.1.3H2O and Na0.3Co1-xMxO2.1.3H2O (x=0 to x=0.1, M=Mn, Ti) was

prepared by Y.G Shi et al [8] and studied their superconducting properties. The Superconducting
properties of these superconductors, samples were analyzed by doping Mn and Ti at Co sites.
The Superconducting properties of Na0.3Co1-xMxO2.1.3H2O was varied by slight doping of Ti and
Mn at Co site and were finished the superconducting properties of Na0.3Co1-xMxO2.1.3H2O at Ti
x> 0.01 and Mn at x>0.02 they reported. Resistivity and magnetic measurement of Na0.5Co1xMxO2.1.3H2O sample was done and they reported that the Mn doping is more effective than Ti
doping. This difference of effect suggests that the magnetic order of CoO2 plane was altered by
Mn atom then that of Ti atoms. The transformation of different magnetic state was observed and
concluded that paramagnetic state between x=0 to x>0.3 and ferromagnetic state between x=0.1
to x=0.2 with the doping of Ti or Mn in Na0.3Co1-xMxO2.1.3H2O.

2.2. Literature review on Nano-particle dope High temperature Superconductors (CuTl-1223)

The mechanical properties of nano-SnO2 doped (Cu0.5Tl0.5)-1223 were studied by N.H.
Muhammad et al [9]. With the help of single step solid state reaction method, superconducting
samples of the type (Cu0.5Tl0.5)-1223 were prepared. Nano-SnO2 (Sigma Aldrich) with wt% in
range of 0.0 to 1.0 was mixed with shift powder. It was found from the X-ray diffraction analysis
of (SnO2)xCu0.5Tl0.5Ba2Ca2Cu3O10- where (x=0.0, 0.1, 0.6 and 1.0 wt.%) superconducting samples, that the (Cu0.5Tl0.5)-1223 was the major phase with tetragonal structure and P4/mmm sym37

metry. Some of the peaks of secondary phases like (Cu0.5Tl0.5)-1212 and BaCuO2 were also observed. Related to SnO or Sn there was no peak in the diffraction pattern. From X-ray diffraction
analysis the volume fraction calculation showed that the percentage of the main phase
(Cu0.5Tl0.5)-1223 increase with the addition of nano-SnO2 up to x= 0.6wt%, It showed a slight
retardation beyond this addition percentage. The addition of the high concentration of SnO2 (x >
0.6 wt.%) affects the viscosity of transient liquid formed at the reaction temperature, its homogeneity and the formation rate of (Cu0.5Tl0.5)-1223 phase. It was observed from the EDS analysis of
SnO2)xCu0.5Tl0.5Ba2Ca2Cu3O10- with x = 0.2.wt% that the nano-SnO2 did not enter the structure
of the phase, but occupied the interstitial places between the superconducting grains. With the
addition of nano-SnO2 the porosity decreases. SEM micrograph indicated a large plate like
grains, which was indication of (Cu0.5Tl0.5)-1223 phase formation. As x increasing from x=0.0 to
x = 0.4 wt.%, the number of plates like grains also increased with the addition of nano-SnO2 the
porosity decreases and the microstructure density increases. Addition of small amount of nanoSnO2 heals micro-cracks and the continuity between the (Cu0.5Tl0.5)-1223 grains increases.
Among the grains the spherical SnO2 grains were observed at x = 0.4 wt.%, which showed that
the nano-SnO2 particles remained as discrete nano-particles after the sintering process. Microhardness values of (Cu0.5Tl0.5)-1223 phase was found to be increased gradually with the addition
of nano-SnO2. It was also found that Micro-hardness values decreased with increase in applied
load up to 1.96N. With the help of Mayer's law the indentation size effect (ISE) was analyzed.
With the increase of density and nano-SnO2 addition the elastic modulus increased whereas it
decreased with the applied load from (0.49 to 2.94)N.
The effect of nano-SnO2 and nano-ln2O3 additions on the microstructure, phase formation
and mechanical properties of (Cu0.5Tl0.5)-1223 superconducting phase was studied by N.H Muhammad et al [10]. With the help of solid state reaction method they prepared superconducting
samples of the type Cu0.5Tl0.5Ba2Ca2Cu3O10- added by nano-SnO2 and nano-ln2O3 (0.0 - 1.0
wt.%). Nano-SnO2 (Sigma Aldrich, particle size 20-50 nm ) was mixed with shifted powder with
concentration (x) changed from 0.0 to 1.0 wt.% of the sample total mass. Also, nano-ln2O3 (Sigma Aldrich, particle size 20-50 nm) was mixed with shifted powder with concentration (x)
changed from 0.1 to 1.0 wt.%. It was clear from the X-ray diffraction pattern of
(SnO2)yCu0.5Tl0.5Ba2Ca2Cu3O10- and (ln2O3)xCu0.5Tl0.5Ba2Ca2Cu3O10- with x = 0.0, 0.1, 0.2, 0.4,
0.6 and 1.0 wt.% that samples were mainly consist of (Cu0.5Tl0.5)-1223 phase with tetragonal
38

structure and p4/mmm symmetry, some of the peak of secondary phase like (Cu0.5Tl0.5)-1212 and
BaCuO2 were also observed. With the addition of nano-SnO2 up to z = 0.6 wt.% the volume fraction of (Cu0.5Tl0.5)-1223 increased while nano-ln2O3 could not change the main phase, for all
values of x. It was found from the SEM micrograph for (SnO2)xCu0.5Tl0.5Ba2Ca2Cu3O10- and
(ln2O3)xCu0.5Tl0.5Ba2Ca2Cu3O10- with x = 0.0 and x = 0.6 wt.% that sample morphology composed of randomly oriented plate like grains. Nano oxides homogeneously spread in (Cu0.5Tl0.5)1223 matrix and porosity decreased. The normal state resistivity increased up to x = 1.0 wt.% for
nano-SnO2 added samples, while it increased for x = 0.1 wt.% for nano-ln2O3 added samples. For
nano-SnO2 added samples the superconducting transition temperature Tc increased up to x = 0.6
wt.% and consistent with volume fraction. Whereas Tc slightly varies with x for nano-ln2O3 added samples and this was also consistent with the volume fraction calculation. Micro-hardness
values increased up to x = 1.0 wt.% of nano-SnO2 added samples, while in case of nano-ln2O3
micro-hardness increased with concentration x = 0.1 wt.%. Mechanical parameters like yield
and fracture toughness were calculated and results indicated that the values of these parameters were much higher for nano-SnO2
added samples than those calculated for nano-ln2O3 added samples for all applied loads. Moreover the addition of nano-oxides increased the ductility and decreased the brittleness index of
(Cu0.5Tl0.5)-1223 phase.
Mansoor Fabod et al [11] studied the doping effect of Ag nano-particles of critical current
of YBa2Cu3O7- bulk superconductor. Using chemical reduction in aqueous media Ag nanoparticles were prepared. Superconducting samples were prepared using the solid state reaction
method. Two sets of samples of superconducting powders were prepared with Ag concentration
of 1.0 and 2.0 wt.% with average sizes of 30, 200, 500, 700, 800 and 100nm. It was clear from
the SEM micrograph of pure YBCO and the doped samples with 1 and 2 wt.% of 30, 200, and
700 nm of Ag nano-particles that the continuity between the grains and crystallization of samples
were improved by increasing the nano-particles comparison of the samples of the same size Ag
nano-particles which were doped with 1 and 2 wt.% showed that with higher concentration of Ag
addition in sample improved the continuity and crystallization between the grains. The X-ray diffraction pattern of the samples doped with 1 and 2 wt.% of Ag nano-particles showed that their
crystallization increased with the size and concentration of added nano-particles. By increasing
size up to 700nm critical current density increased monotonically. It also increased with higher
39

Ag concentration. Ag nano-particles help in improving the connections and crystallization of the

grains.
The artificial addition of nano-ZrO2 to Pb doped BSCCO high temperature superconductor was investigated by Z.Y. Jia et al [12]. With the help of solid state reaction method BSCCO
was synthesized, x mole percent of nano-ZrO2 particles with a size of 10nm were added to
(ZrO2)xBi1.8Pb0.4Sr2Ca2.2Cu3O10+ (where x = 0, 5, 10, 20, 30, 50 mol.%). It was observed from
the X-ray diffraction patterns of different concentration of nano-ZrO2 added samples that Bi2223 phase was formed with a few peaks of low intensity belonged to Bi-2212 and other unknown non-superconductor phases. X-ray diffraction could not observe the peaks of ZrO2. With
x < 20 mol.% the transition width and Tc of the samples were about 3K and 110K respectively.
When the temperature was 5K, magnetic hysteresis loop of samples having x = 10, 20 mol.%
was larger than that of the nano-ZrO2 doped and un-doped samples. Nano-ZrO2 behaved as effective flux pinning centers in the matrices of Bi-2223 superconductor and increased critical current density. This increment us due to the trapping of nano-oxides particles within the grains of
high temperature superconductors, which acted as a secondary phase in the grains final compound. SEM studies showed that nano-ZrO2 particles dispersed homogeneously in Bi-2223 matrices. It was found from the energy dispersive X-ray spectroscopy that there are 50 to 100nm
features consisting of Zr with small amount of Sr and Cu from the BSCCO matrix.
The influence of nano-MgO on the electrical and mechanical properties of
(Cu0.25Tl0.75)-1234 phase was studied by R. Awad [13]. With the help of solid state reaction
method Cu0.25Tl0.75Ba2Ca3Cu4O12- samples were synthesized with various concentrations (x) of
nano-MgO (x = 0.0, 0.2, 0.4, 0.6 and 1.0 wt.%). Using simple mixing and grinding the nanoMgO (Sigma Aldrich) with particle size of 40-60nm has been added. It was observed from the
X-ray diffraction studies that with a few peaks of low intensity (Cu0.25Tl0.75)-1234 phase was
formed related to (CuTl)-1223 and Ba2Cu3O8- superconducting phases. Related to MgO or Mg
compounds, no pattern was observed. From SEM studies, it was found that nano-MgO particles
introduced between the superconducting grains. With the addition of nano-oxides up to x = 0.6
wt.% the grain connectivity, phase formation, transport critical current density and microhardness were improved. However, large amounts of MgO introduced between the grains and
hence reduced phase formation, grains connectivity, critical current density and micro-hardness.

40

MgO behaved like effective flux pinning centers in the matrices of (Cu0.5Tl0.75)-1234 and hence
increased critical current density. Nano-MgO particles remained as discrete particles even after
sintering process.
The variation of volume and lattice parameter with a thermal expansion coefficient
for (MgO)xCu0.25Tl0.75Ba2Ca3Cu4O12- with x = 0.0, 0.2, 0.6 and 1.0 wt.% at the temperature
range of 80K to 290K were investigated. With the help of single step solid state reaction method
the superconducting samples were synthesized. It was observed from the X-ray diffraction studies that the (CuTl)-1234 was a main phase with space group p4/mmm and tetragonal unit cell. In
the pattern a few peaks of (CuTl)-1223 and Ba2Cu3O6 were also observed. No phase corresponding to MgO or Mg rich compound was found. With the increase of concentration of MgO-nano
particles

in

the

sample,

the

crystalline

size

decreased.

From

SEM

images

for

(MgO)xCu0.25Tl0.75Ba2Ca3Cu4O12- superconducting samples, the plate like grains were found.

With an increase in concentration of MgO-nano particles in the sample, porosity reduced. It was
observed from the EDS analysis that there was the existence of Mg in the bulk sample of
(MgO)xCu0.25Tl0.75Ba2Ca3Cu4O12- with x = 1.0 wt.%. The addition of nano oxides up to x = 0.6
wt.% increased the phase formation, grains connectivity and decrease the thermal expansion coefficient with increase in x from 0.0 to 0.6 wt.% the volume fraction of (CuTl)-1234 increased by
88% to 96% and then decreased. With decrease of temperature both "a" and "c" lattice parameters were decreased. Critical temperature increased slightly up to x = 0.6 wt.% and for x > 0.6
wt.% it decreased. In the volume thermal coefficient measurement two regions were observed. In
the first region, it reduced rapidly with temperature range of 290K to 160K while in second region, it reduced slowly with decrease in temperature. For x = 1.0 wt.% the value if thevolume
coefficient of thermal expansion increased and that was the probability due to the decrease of
volume fraction of (CuTl)-1234 the calculated volume thermal expansion coefficient data were
will fitted to the metallic model, for the first region. The Debye temperature was calculated to be
lower for this phase than that of Tl-1223 phase [14].
The effect of ZnO and Zn0.95Mn0.05O addition on the microstructure and pinning properties
of polycrystalline YBCO superconductor was investigated by M. Anabi et al [15]. With the help
of solid-state reaction method the pure sample of YBCO added by ZnO and Zn0.95Mn0.05O particles of 25nm diameter were introduced separately to the precursor powder of YBCO by mixing

41

and grinding both powders. Temperature dependent resistivity measurement for free and 0.2
wt.% ZnO0.95Mn0.05O or 0.2 wt.% ZnO added samples exhibited linear temperature dependence
at higher temperature, having a different magnitude of resistivity at room temperature and a superconducting transition to zero resistance. Also, in all samples one step transition was observed.
By adding nano particles, the critical transition temperature reduced. Critical current density
c

for free and nano-sized Zn0.95Mn0.05O and ZnO added a sample at 77K in a magnetic field

was been measured and normalized to their zero field value

field the

. With the increase in applied

monotonically decreased. When magnetic field was applied, the samples

with 0.2 wt.% added Zn0.95Mn0.05O had the best performance compared to all samples. From
transmission electron microscopy (TEM) and EDX analysis, it was found that there were the
twin bands which are characteristics of orthorhombic structures. TEM images of samples indicated the existence of nanometer scale particles incorporated within the Y-123 matrix. It was
found that the magnetic dots were effective pinning centers. The presence of defects due to the
formation of the nano-metric inhomogeneity and to the magnetic interaction of the Mn magnetic
moment with vortices, showed the increasement of flux pinning in YBCO.

Nanometer Al2O3 addition to (BiPb)-2223 superconductor was studied by M. Annabi et al

[16]. With the help of solid-state synthesis method Bi1.6Pb0.4Sr1.9Ca2.1Cu3O10- was prepared. The
Al2O3 particles having 50nm diameter were introduced to 0.0-1.0 wt.% of the total mass of the
sample and various powder mixtures were formed. DTA for four precursors added with Al 2O3
(0.0, 0.2, 0.5 and 1.0 wt.%) revealed that up to 0.5 wt.%, the onset of melting point slightly increased. However, melting point was decreased with more increase of Al2O3 concentration. It
was found from the study of X-ray diffraction of un-doped Al2O3 that the powder was mainly
consist of (BiPb)-2223 phase, small amount of (BiPb)-2212 phase and an insignificant amount of
secondary phase. In addition, the (BiPb)-2223 phase formation and current density decreased
with the addition of a large amount of Al2O3. Within superconducting grains the addition of
small amounts of Al2O3 produced defects like dislocations and stacking faults, which also increased the flux pinning and critical current density. However, larger concentration of Al2O3
produced agglomeration.

42

I.Bouchoucha et al [17]. Investigated the microstructure and the normal state transport properties of nano-sized Zn0.95Mn0.05O and ZnO (30nm) added polycrystalline YBCO. The orthorhombic structure remained even at the highest concentration of Zn0.95Mn0.05O and ZnO added to
the YBCO. From X-ray diffraction, SEM and TEM studies, it was found that the superconducting properties suppressed with Zn0.95Mn0.05O and ZnO addition, both by decreasing the effective
coupling strength and by destroying the phase coherence.
The superconducting properties of bulk samples of Bi-2212 with nano-sized MgO addition were studied by W. Wei et al [18]. With the addition of MgO there was no change in critical
temperature. It was being observed from the DTA measurements that with the addition of MgO
in Bi-2212 the melting temperature increased slightly. From X-ray diffraction studies, it was being found that MgO nano-oxides remained un-reacted and added as a secondary phase in the Bi2212 matrix. In samples with large MgO contents, it was being found that irreversibility fields
and the width of the magnetic hysteresis loop was increased.
The effect of carbon nano-tubes doping on the critical current density of MgB2 superconductor was studied by S. X. Dou et al [19]. The study of the effect of carbon nano-tubes doping
on lattice parameters,

and flux pinning in MgB2 was under a high range of conditions. The

flux pinning enhanced and critical temperature suppressed due to substitution of carbon nanotubes at the site of B. For nano-carbon particles the optimum doping level is x = 0.05 (2.5% of
B), whereas for carbon nano-tubes doping this level increased to x = 0.2 (10% of B). The addition of carbon nano-tubes and the substation for B was proposed to be the cause of enhancement
of flux pinning in high fields.
With the help of powder-in-sealed-tube (PIST) method, bulk MgB2 samples added with 0,
2, 5, 10 and 15% of SiC nano-particles was being synthesized. From X-ray diffraction studies the
variation in lattice parameter "a" was, observed and FWHM with increasing amount of SiC reveal that carbon is getting substituted at boron site. The carbon substitution results local strain in
MgB2 lattice. Also from DC measurements this is confirmed which showed decreasement of critical temperature. The sharpness of MgB2 grain boundaries loses in heavily doped samples and
more grains combined to form bigger grains. Within the grain the uniformly distributed impurities are nano-sized Mg2Si and SiC, as confirmed by EDS and X-ray diffraction. The Jo(H) and

43

Fp(H) properties increased slightly due to the addition of nano-sized SiC particles as flux pinning
centers and slightly because of C doping [20].
Highly dispersed CuO nano-particles were prepared by J. Zhu et al [21]. Using novel quickprecipitation method. From results, it was observed that the as-prepared CuO nano-particles have
narrow size distribution. The average size of CuO nano-particles is estimated to be 6nm according to the Scherer equation. The spherical particles with high dispersion was been observed from
TEM image of the as-prepared CuO nano-particles.

2.3. Literature Reviews on Fluctuation induced conductivity of high

temperature superconductors
The fluctuation induce conductivity of Bi2Sr2

1Cu2 8+

and Y1-xCaxBa2Cu3Oy samples

were investigated by A.K Ghosh et al [22]. They employed effective medium theory, which was
used for formation of Aslamazov-Larkin (AL) type equations, for these polycrystalline superconductors. Exponent remains unaltered in the

case, since for the

and

direction FICs in the crystal both the exponents are same for these axis. Whereas in

case

there is a complicated situation, in which different temperature dependencies are there in the
counterpart of the crystal. The final results are then compared with the theoretical values obtained from the proposed model. For both the crystals they also measured the exponents, coherence length, and cross over temperature. They observed from the analysis based on the present
model that both superconductors are same, according to their nature of fluctuations. The extent
of a particular fluctuations region exactly differs of on

to another.

The fluctuation induced conductivity in temperature variation of resistivity in the mean

field region was measured for the 110K phase of the (Bi, Pb)-Sr-Ca-Cu-O system analyzed by S.
Ravi et al [23]. With the help of Aslamazov-Larkin (AL) and Lawrence-Deniach (LD) models
they analyzed the resistivity data for the excess conductivity (
-1

usual linear equation

)analysis. Whereas, by using the

they find the normal conductivity (n ) From the fitting of both

models the observed that against the YBa2Cu3O7 there also exist a two dimensional nature in the
fluctuation of the order parameters in the 110K phase of the Bi based system. They estimated the
coherence length values

(0) = 3.96 by changing the inter planner spacing value from theo-

retical fitting.
44

The temperature dependence in plane DC conducting for many high quality epitaxial

3 7

films was observed by R. Hopfengartner et al [24]. They apply the Aslamazov-Larkin (LA),
Lawrence-Deniach (LD) and Maki-Thampson models for the rounding of the resistivity in the
transition region. The short wavelength cutoff parameters influence has been investigated in the
fluctuation spectrum of (AL) and (LD) terms in the framework of time dependent Ginzburg landau approach. This cutoff in the regime in the high temperature superconductor shows a reduction in the Dc excess conductivity in both the theoretical models. 3D anisotropic AL terms were
also predicted the same value of excess conducting taking into account the cutoff value like that
of the original LD term. Although both of these approaches described different systems between
the experimental data and LD term as well as the modified three dimensional anisotropic AL
terms a good agreement was observed in the region
cal value

Tc

for zero temperature GL coherence length

Tc , they estimated numeric(0).

The microscopic effect on superconducting properties was reported by N.A Khan et al

[25]. The microscopic effect because of doping Mg atoms by studying the para-conductivity
analysis of conductivity data of

3-y

4O12-

synthe-

sized at normal pressure. With the help of XRD technique, the tetragonal structure was being
identified with a decrease in unit cell volume by increasing Mg content. Also with by doping of
Mg atoms the transition and offset the temperatures decrease. With the help of an ACsusceptibility technique the maximum diamagnetic magnitude for y = 2 Mg content was observed. The softening of CuO2 planar and Tl-OA-Cu (2) apical oxygen modes was observed from
the

absorption spectrum. From the analysis of fluctuations induced conductivity, the in-

crease of inter-plane coupling and coherence length along c-axis was being observed. The increase of inter-plane coupling was suggested to be due to a small decrease in the value of the order parameter (||2=1) of the carriers of CuO2 planes in doped samples. In addition, the decrease
in values of

C0

C1

was being found which was suggested to be because of

weak coupling of grains induced by the doping of Mg content.

The excess induced conductivity due to thermal fluctuations in Cu0.5Tl0.5Ba2Ca1Cu2O8-
thin films was investigated by A.A Khurram et al [26]. For studying their properties, they performed the analysis of the conductivity data of Cu0.5Tl0.5Ba2Ca1Cu2O8- thin films in the light of
Aslamazov-Larkin (AL) model. It was been found from the FIC result that the dimensionality of
45

fluctuations that induced conductivity in mobile carriers varies due to removal or addition of oxygen content in the charge reservoir layer after post-annealing of these films. They also observed
that in nitrogen environment post-annealing have shown higher Tc(0) with 3D behavior of FIC
over a wide range of temperature in comparison to post-annealing in oxygen environment of these samples. The dimensionality of fluctuations was affected due to (1). The intrinsic properties of
intra grain regions. (2). The nature of the grain boundary junctions. They concluded that the possible resources of 3D fluctuations are strong grains connectivity, large grain size and optimum
carrier concentration, which ultimately brought the transition temperature higher values.
Mi-Ock Mun et al [27] reported FICs analysis of a single crystal

2 x

high

superconductors (HTSC) having fluctuations in order parameter. They did FICs using Aslamazov-Larkin AL model in the temperature range 84K to 245K between 2D regions. They reported
2D 12.6 characteristic length using Aslamazov-Larkin theory, which was in physical acceptable, rang. Using Lawrence-Donaich model LD they found decreasing interlayer coupling
strength along c-axis, giving reason to it that it is intrinsic property of highly anisotropic superconductors. The Maki-Thompson effect was negligible in there sample as they reported. From
conclusion of their result they reported that superconductivity in Bi2Sr2CaCu2Ox was only caused
by 2D thermal fluctuations, having no 2D-3D cross over the effect of cooper pairs fluctuation
and breaking was negligible.

46

2.4. References
[1]. L. Perez. Arrieta and M. Aguilar-Frutis Revista Mexicana Defisica 54 (6) 446 450. Dec(2008).
[2]. Najmul Hassan, Nawazish A. Khan, Journal of alloys and compounds 471 , 39-43 (2009).
[3]. Y. Shimakawa, Y. Kubo, T. manako, and H. Igarashi, Physical review B, Vol 40, No,16, 14 (1989).
[4]. Nae-Lih Wu, Yeong Der Yao, Sern- Nan Lee, S- Yen Wong, and Eli Ruckenstein, physica C 161,

302 (1989).
[5]. S. K. Agarwal, A. Iyo, K. Tokiwa, Y. Tanaka, K. Tanaka, M. Tokumoto, N. Terada, T. Saya, M.

Umeda, and H. Ihara, Physical Review B. Volume 58, number 14(1998)

[6]. S Mikusua, G Watanabea, K Tokiwaa, Y Tanakab, A Iyob, and T Watanabea Journal of Physics:
Conference Series 150, 052161 (2009). 42
[7]. L. Raffo, R. Cacioffu, D. Rinaldi, and F. Licci, Supercond. Sci. Technol. 8, 409-414 (1995).
[8]. Y.G. Shi, H.X. Yang, X. Liu, W.J. Ma, C.J. Nie, W.W. Huang, J.Q. Li , Physica C 432, 299305
(2005).
[9]. N. H. Mohammed, A. I. Abou-Aly, I. H. Ibrahim, R. Awad, and M. Rekaby, J. Alloys compd. 486,
733 (2009).
[10]. N. H. Mohammed, A. I. Abou-Aly, I. H. Ibrahim, R. Awad, and M. Rekaby, J. Supercond. Nov.
Magn. 24, 1463 (2010).
[11]. M. Farbod, and M. R. Batvandi, Physica C 471, 112 (2011).
[12]. Z. Y. Jia, H. Tang, Z. Q. Yang, Y. T. Xing, Y. Z. Wang, and G. W. Qiao, Physica C 337, 130
(2000).
[13]. R. Awad, J. Supercond. Nov. Magn. 21, 461 (2008).
[14]. S. G. Elsharkawy, and R. Awad, J. Alloys Compd. 478, 642 (2009).
[15]. M. Annabi, I. Bouchoucha, F. B. Azzouz, and M. B. Salem, IOP Conf. Series: Materials Sci. Eng
13, 012009 (2010).
[16]. M. Annabi, A. Mchirgui, F. B. Azzouz, M. Zouaoui, and M. B. Salem, Physica C 405, 25
(2004).
[17]. I. Bouchoucha, F. B. Azzouz, M. Annabi, M. Zouaoui, M. B. Salem, Physica C 470, 262 (2010).
[18]. W. Wei, J. Schwartz, K. C. Goretta, U. Balachandran, and A. Bhargava, Physica C 298, 279
(1998).
[19]. S. X. Dou, W. K. Yeoh, J. Horvat, and M.Ionescu, Applied Phys. Lett. 83, 24 (2003).
[20]. N. Varghese, K. Vinod, U. Syamaprassad, and S. B. Roy, J. Alloys Compd. 484, 734 (2009).
[21]. P. K. Khanna, S. Gaikwad, P. V. Adhyapak, N. Singh, and R. Marimuthu, Materials Letters 61,

4711 (2007). [19]

[22]. A. K. Ghosh, S. K. Bandyopadhyay and A. N. Basu JOURNAL OF APPLIED PHYSICS VOLUME 86, NUMBER 6
[23]. S. Ravi and V. Seshu BaiPhysica C 182 (1991) 345-350 North-Holland
[24]. R. Hopfengrtner, B. Hensel, and G. Saemann-Ischenko PHYSICAL REVIEW B VOLUME 44,
NUMBER 2
[25]. Nawazish A. Khan, M. Shamraiz, Saleem Abas, Azhar A. Rizvi. J Supercond Nov Magn DOI
10.1007/s10948-014-2569-1
[26]. A A Khurram, Nawazish A Khan J. Phys. Condense. Matter, 20 (2008) 045216
[27]. M.-O. Mun, S.-I. Lee, S.-H. Suck Salk, H. J. Shin and M. K. Joo, Physical Review B 48 (9),
6703-6706 (1993)
47

Chapter 3

Experimental Technique

Brief explanation of the experimental technique used for the characterization of the superconducting samples and their detailed theoretical background covered is in this chapter.

3.1. Nanoparticles Synthesis procedure

Nano particle can be synthesized by two different methods, which are physical and chemical methods. Physical method is simple in the way that the bulk of material was crushed or broken out in small particle by applying high voltage using discharge electrodes for metal nano particles. Nano particles of metals have large size and different size distribution [1]. In case of
chemical method there are reduction of metal ions or dismantle of atoms from precursor occur,
which produce nano particle having small size as compared to physical method. A Chemical
method is widely used for nano particle preparation, which can be seen from the number of report and review on chemical method [2]. There are numbers of chemical methods for preparation
of nano-particles, including Co-precipitation method, solid-state reaction method, sol-gel method. There are different methods that can be classified on the basis of processing material used i.e.
solid, liquid or vapor [3].

3.1.1. Co-precipitation method

The Co-precipitation method is one of the widely used wet chemical nano particle methods. Properties of the nano particles, i.e. size, morphology, composition, and purity are dependent on the powder properties. In Co-precipitation method nucleation, growth, coarsening, and
agglomeration reaction occur simultaneously [4]. In Co-precipitation method morphology and
composition of nano particles is significantly controlled. Nano particles which are produced by a
Co-precipitation method are ultrafine and having narrow dimensions. The precipitate has a different composition, which can be in the form of carbonates, oxalates, or hydroxides and can be
thermally decomposed into corresponding oxides. In Co-precipitation reaction, precipitation can
be formed by chemical reaction or using the physical electrolytic method [5].

48

3.1.2. Synthesis of NiO nanoparticles

The main materials used for the synthesis of NiO nano-particle were nickel hex hydrate
Ni(NO3).6H2O, sodium hydroxide NaOH, polyvinilpyrolidone (pvp) MW = 65000.
Preparation of these nano-particles consists of two steps. In the first step we prepared two separate solutions; one a solution of 8.9g of Ni(NO3)2 in 60mL of deionized water. Second on a solution of 3g of sodium hydroxide, NaOH in 160mL deionized water was made. One gram of pvp
was added to latter solution and. Then the former solution was added to the latter solution drop
wise.
Then, the mixed solution was stirred drop wise using magnetic stirring apparatus at room
temperature. The resulting sodium was filtered and washed 5 to 10 times with deionized water
and ethanol and dried at 600C for 24 hours. After this, the resultant material was calcined at
2800C for 3hours.
Main reactions of the experiment can be written as;
+
(s)

(NO3)2
2

(s)

(aq)

(aq)

+2
(aq)

3 (aq)

(s)

2(s)

2(s)

(s)

(aq)

(g)

(g)

3.2. Sample preparation

The preparation of highly pure powder is required for practical purpose of superconductors of high

. In superconducting samples, the presence of impurity phase barricades the criti-

cal current density

as a result Flux pinning increases with the decrease in .

The materials, which are involved in high temperature superconductivity are difficult to work
with because these materials are mechanically hard. These materials are made up of hard transition metals and highly anisotropic [6].
The samples (Ni)x/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) were prepared with the help of solid state reaction method in which two stages were involved. We prepared the (Ni)x/CuTl-1223 (x
= 0, 3, 5, 7 and 10 wt%) precursor at first stage by mixing Ba(NO3)2, Ca(NO3)2.4H2O, and Cu(CN) in

appropriate ratios using quartz mortar and pestle for one hour, then put this mixed powder in
quartz boat and placed in furnace for first 24 hours. After 24 hours, the precursor was again
49

grounded using quartz mortar pestle and placed for second firing in furnace for 24 hours using
alumina boats. The precursor was cooled to room temperature after completing two-time firing.
Appropriate amount of

with Ni nanoparticles having different wt.% were added to the pre-

pared precursor and grounded for one hour in quartz mortar, this mixed precursor was pelletized
by hydraulic press applying 3.8 tons/cm2 of pressure. The pellet was then wrapped in gold foil
and placed in the furnace for sintering at 8600C for 10 mints, and quenched to room temperature
forming 1223 stable phase.

3.3. Characterization of the samples

The techniques, which were used for the characterization of the samples, are as follows

X-ray diffraction technique

Four probe resistivity measurement technique

Ac magneto susceptibility measurement technique

Fourier transform infrared spectroscopy technique

3.3.1. X-ray diffraction technique

Using X-ray diffraction technique, we may study the crystal structure of the sample. We
may find that whether the sample is crystalline or not and determine the unit cell parameters using XRD technique.

I.

X-ray diffraction and Braggs law

The process in which the waves are spread by closely placed hurdles is called diffraction.

Diffraction takes place only when the gap between the hurdles is comparable to the wavelength
of incident rays.
The wavelength of the X-rays and atomic spacing of crystalline materials are equivalent,
so when X-rays fall on the surface of the crystalline materials, some portion of these rays is scattered in all directions by the electrons or ions of the crystalline materials. The X-rays which diffract strongly are only detected in those directions in which all scattered waves have the same
phases. If the scattered waves have the different phases in any direction then in that direction no
diffraction is detected.
50

For understanding the necessary conditions for the diffraction of X-rays, suppose three
atomic planes in a direction parallel to each other and having equal Miller indices
let

and

is spacing between these planes. Suppose a coherent and monochromatic beam of wave-

hkl

length is incident on these planes with angle and let two atoms in these parallel planes

Figure 3.1: X-rays diffraction from a crystal.

having positions A, and C, and two parallel rays are scattered by these two atoms, shown in figure.3.1.

It is clear that these two rays have different path lengths, so these waves might be in phase when
they touch the screen if they have an integral multiple of path difference of wavelength between
them.
(3.1)

hkl

Where n is the diffraction order and can be 1, 2, 3

Equation (3.1) is known as Braggs law.
For constant

and

hkl

several values of angles of incidence are expected from which dif-

fraction occurs. There is constructive interference if the Braggs law is obeyed and strong diffraction pattern, otherwise no diffracted waves will be detected and destructive interference will
occur. In the above equation

cant be greater than 1, so we can write;

51

(3.2)

hkl

So,

hkl

The least value of n is 1, while the waves diffracted for n = 0 in the direction of transmitted
waves. So its diffraction may not be detected. So we can write;
(3.3)

hkl

In most cases,

hkl

is 3 or less, thus

cannot be more than 6 [7].

Braggs law is not an appropriate condition for real crystals but only a required condition
for diffraction. This means that diffraction only takes place from the atoms at the cell corners of
a unit cell. However, atoms of other sites contribute as additional scattering points.
For the existence of diffraction, Braggs law should be satisfied. This is very difficult to satisfy
the Braggs law, although different techniques have been established to remove these difficulties.
Some of them are following [8].
1)

Lau method: For Lau method wavelength

changes, while the value of angle of dif-

fraction is constant.
2)

Rotating crystal method: Wavelength is fixed for this method, while the angle of diffrac-

tion changes.
3)

Powder method: For this method wavelength is constant, while the angle of diffraction

changes.
The powder method or Debye-Scherer method is used for the analysis of polycrystalline
materials. In this method, finally powdered sample is placed in the path of incoming X-rays.
These X-rays diffracted by little crystals present in all directions in the sample thus the net result
is same to that of a rotating unit cell of single crystal which in all possible direction rotates and to
all inverse lattice vectors a ring of spreading peaks is there [9]. Because our samples are polycrystalline, therefore we use the powder diffraction method for their analysis.

52

II.

X-ray diffractometer

Figure 3.2: X-ray diffractometer

In figure.3.2, a diffractometer is shown. A specimen is supported by a smooth plate in
such a way that it could rotate about an axis which is in direction perpendicular to the surface of
the paper. Monochromatic X-rays are formed in x-ray tube and are transferred in an absorbed
beam by passing the rays from a divergent slit. The beam fall upon the specimen and diffraction
takes place. The intensities of beams, which are diffracted, are noticed with a counter. The
source of x-rays, specimen and counter all are in one plane. The counter can move and can rotate
about its axis.

53

The angular location of the counter is measured in terms of

. The counter and the spec-

imen are arranged in such a way that if the specimen is rotated through an angle, the counter is
rotated through

because of this the angle of incidence and the reflection angle are remained

constant. As the angular velocity of the counter remains constant the intensities of diffracted rays
is recorded as a function of

The data that is obtained from the diffractometer is examined for finding the crystal arrangement of the specimen. Computer software chekcell is used for finding the matrix parameters and for the identification of crystal arrangement.

3.3.2. Resistivity measurements

Usually, two-probe method is used for measuring resistivity of a material in order of
ohms. However, it cannot be used for resistivity measuring of superconductors. The reason for
this is that superconductor has very low resistance of the order of micro ohm and two-probe
method is not capable of measuring such low resistance of superconductors. Two-probe method
can only be applied to normal conductors this is because of that long length of wire affects the
resistivity results.
For accurate measurement of the resistivity of a superconductor, four-probe method is used. It
eliminates the effect on result due to the long length of wire that arises in two-probe method [10].
Let first discuss the brief characteristic of resistivity in normal metals before going to the
description of the resistivity measurements in superconductors. The resistance in normal metals
arises due to electron electrons scattering, phonons and due to impurities or defects present in the
metals. The total resistivity that arises from the above factors can be expressed as
(3.4)
Here

is contributed due to impurities while

tion and the last term

is due to the electron phonon interac-

is due to electron electron scattering. The electron-electron scattering

takes place within the empty states that appear on the Fermi surface at any temperature Tc
[11,12]. However, on lowering the temperature, the empty space on the Fermi surface suppress
and the net effect from electron-electron scattering is very low.

54

The dependence of
the relation

on temperature is nonlinear below the Debye temperature i.e.

. The phonon modes actually suppress the

by

at low temperature. But at

high temperature the occupation of phonon modes is linear in temperature by the relation
at T >

. From Figure.3.3, it can also be seen by decreasing temperature linear behav-

ior change to nonlinear at round about at

[13].

Figure 3.3: Phonon contribution to the resistivity in normal metals

There are no pure metals on the earth. Every metals on earth has a significant amount of
impurities such as grain boundaries, defects.etc. The contribution due to impurities is independent of temperature. Therefore, they cannot be removed by lowering or increasing the temperature
of the metals.
The relation between the current and voltage from ohms law;
(3.5)

55

From the ohms law at constant temperature the applied potential is directly proportional
to the current of an ohmic conductor. The resistance can be calculated simply if the voltage and
current through the conductors are known. So the above equation becomes
(3.6)
In above equation V and I represent the applied potential and current where R is the resistance of
the conductor. It was experimentally observed that the resistance of the conductors not only depended on the temperature but also on the dimension of the conductor. For any conductor at constant T of the cross sectional area A and length L the resistance is directly proportional to area
and invers to length of the conductor;

(3.7)
Where

is constant at constant temperature having no dependence on the dimension of the con-

ductors.
The resistivity varies with temperature and can be expressed as;
(3.8)
(3.9)

Experimental setup
The resistivity of the superconductors can be determined by four-probe method, which is
shown in Figure. 3.4 below. Most of high temperature superconductors are ceramic and the contacts on the samples or superconductor pellets are made using silver paste. Silver paste is used
for the sake of good quality contacts and having negligible contacts resistance. There are four
contacts used, the inner two contacts are connected to millimeter for measuring voltage while the
external two contacts are connected to the current source providing current to the pellet.

56

Figure.3.4: (a) Four probe resistivity setup (b) Equivalent circuit

Superconductivity arises below room temperature so the sample was cooled by dipping it
in liquid nitrogen. As the resistivity verses temperature measurement is required so there is thermocouple used for measuring temperature. Thermocouple is actually two wires joined at the end
of different metals and alloys. The working principle of the thermocouple is based on the Seebeck effect. According to Seebeck effect, a voltage is generated when the two ends of the wires
are at different temperatures. There are two junctions i.e. measuring junction and the reference
junction. The measuring junction placed in the surroundings whose temperature is to be calculated. For accuracy, the reference junction is kept at a fixed known temperature (in this case placed
in liquid nitrogen). The electromotive force between the two junctions develops across the potentiometer or voltmeter used to find the temperature of the heated junction. The data from the

57

measuring device is noted and using origin computer software, we compute the resistivity and
temperature graph of superconductor.

3.3.3. Ac magneto susceptibility technique

Before going into experimental technique, let briefly review the concept of Ac magneto
susceptibility. Susceptibility is the term used for the response of any material to the externally
applied magnetic field. Every material has magnetic behavior, some show high magnetic behavior i.e. ferromagnetic, some have low magnetic nature i.e. paramagnetic, and others are those that
have magnetic behavior only when they are placed in the externally applied magnetic field.
The origin of the magnetic behavior is microscopic. Since a moving charge produces the
magnetic field so electrons in the atom revolving around the nucleus also produce small currents
which produce a net magnetic moment and spin around its own axis as well producing spin magnetic moment. The magnetic moments of atoms are measured in the units of Bohr-magneton i.e.
. When a material has alignments of both orbital and spin magnetic moments, there is the net
magnetic field arisen and the material becomes a magnet. However, the normal material does not
show this magnetic behavior unless they are exposed to the externally applied magnetic field,
because in normal material the net magnetic moment is zero due to random alignments of the
atomic magnetic dipoles.
The magnetic field through the material is known as magnetic induction represented by
B, while H, called magnetic field strength represents the external field both are related as
(3.10)
is the permeability of free space. When a material is placed in an external magnetic field the
magnetization is produced in the material and the magnetic dipole of the material aligns in the
direction of the applied field as by expression
(3.11)
M is the magnetization of the material. Now dividing by H above equation

58

Now for a medium we have

Where

represent the permeability of the medium,

is the susceptibility of the ma-

terial then

(3.12)
Here

is the relative permeability of the material.

So the susceptibility become

(3.13)
Magnetic materials are name according by the value of susceptibility, susceptibility is
unit less quantity. For ferromagnetic materials

, the material is, and for diamagnetic material

.
Superconductors are diamagnetic having

, due to which superconductors are called perfect

diamagnetic materials.
becomes complex when the superconductor is placed in the varying magnetic field and can be
written as;
(3.14)
Here the imaginary part arises due to the varying magnetic field, showing Hysteresis loss. While
the real part represents the shielding effect of the superconductor.
For AC- magnetic field

can written as
(3.15)

The real part of the complex susceptibility is in phase with the external field while the imaginary
part is out of phase by 90o. This is shown from the phase diagram

59

Figure 3.5: Phase diagram

High temperature superconductors are poly-crystalline materials having complex crystal

structure. The susceptibility transition takes place in these poly-crystalline materials in two-steps.
During the first step, the transition occurs in grain and in the second step the transition takes
place in the decoupling of these grains.
The critical field for decoupling of these grains are lower than that required for the interior transition. The applied field first decouples the grains before going inside the grains. Below
TC i.e. T < TC the current did not pass into the material due to the flux and the bulk of the material reflecting it. Nevertheless, by increasing temperature the current start penetrating into the material. Whereas for T < TC the shielding current near the surface of the material developed due to
induced current that was produced by varying magnetic field. The imaginary part of the susceptibility has broadened peaks by increasing the external magnetic field and at a temperature greater than peak temperature the grain are decoupled [14].
The technique used for the Ac magneto susceptibility became more common after the
discovery of high temperature superconductors, this technique is non-contact and non-inductive.
This makes it better from others techniques. Using Ac magneto susceptibility one can find weak
link, the magnitude of diamagnetism, critical temperature and the characteristics of diamagnetic
behaviors of superconductors.

60

 Experimental setup
I.

Ac magnetic susceptometer
The Ac magneto susceptibility of superconductors is measured by using AC magnetic

susceptometer. Ac magnetic susceptometer works on the principle of mutual induction, the mutual induction is set in the coils of the AC magnetic susceptometer. As shown in Figure.3.6.
Generally, AC magneto susceptometer consist of two coil primary and secondary coil.
The secondary coil is further separated by two oppositely loop coils which pick up the sense of
the diamagnetic signal, and the primary coil produces AC magnetic field. The flux produced in
the secondary coils cancel because of two oppositely loops. There are other parts of AC magneto
susceptometer, which are lock-in amplifier, plotter, and frequency generator.

Figure 3.6: Experimental arrangement of Ac magneto susceptibility

The lock in amplifier has jobs of amplifying the signal that comes from the secondary
coils and produce an amplified signal in the primary coil. The frequency generator produces the
desired frequency, which is needed for the primary coil. The data are taken on the graph that is
plotted by the graph plotter.

61

The basic concept of measurement of AC magneto susceptibility from AC magneto susceptometer is the mutual induction, the sample or pellet of superconductors is held in the secondary coils below Tc by dipping in liquid nitrogen and thermocouple is attached to the pellet for
taking measurement at different temperature scales.
In the measurement of Ac magneto susceptibility of the superconductors sample AC signal of 1volt having 270Hz frequency is applied to the primary coils which induce Emf in the
secondary coils, which shows that the AC magneto susceptometer work as modified bridge network. The signal form the secondary coil is amplified by the amplifier and displayed with the
lock in amplifier.

3.3.4. Infrared spectroscopy

Before 1940, the traditional dispersion instrument used to get infrared spectroscopy. The
dispersion instrument technique is superseded in recent decades, for obtaining IR spectroscopy
Fourier transform infrared spectroscopy is predominantly used now- a- days. The spectra from
any substance in any form liquid, gas or solid can obtained from Fourier transform infrared spectroscopy. Before going to the experimental technique, we let first discuss the brief introduction to
infrared spectroscopy. Any atom above zero k has vibrations. The basic principle for IR spectroscopy is by passing infrared radiation from a sample and examine what fraction of radiation
absorbed by the sample in the given energy band. The sample molecules have vibration frequencies that related to the absorption energy spectra. At above absolute temperature molecules or
atoms are continuously vibrating. The absorption of radiation from an IR waves incident on molecules or atoms only observes when when it is equal to the vibration frequency of atoms in it. A
single frequency in a sample produce more than one mode of vibration, Therefore the observed
spectra have band} less than the fundamental vibration in number. There are other additional
bands produced by the coupling of fundamental vibration and overtone coupling of absorption
frequency overtone and difference in frequency. The absorption of IR waves having sufficient
energy produces stretching and bending in molecules. This absorption of radiation has both discrete and continuous energy levels. There is in polyatomic molecules rotational, translational vibration al motion so their combination produces band absorption rather discrete. Infrared radiation has a wavelength range from 0.78 to l000

62

having wave number inverse of wavelength.

The wave number is the number of waves per unit length in cm. and commonly used because of
its linear relation with the energy of the wave. They are intercom vested by relation
* +

(3.16)

3.3.4.1. FTIR Components

There are three basic components of the FTIR spectrometer, as shown systematically in
Figure.3.7. They are consisting of Michelson Interferometer, Detector, and Source.

I.

Michelson interferometer
Usually Michelson interferometer is use in FTIR spectrometer. Michelson Interferometer

consists of two plane mirrors that are perpendicular to each other. In these two mirrors, one mirror is stationary and the other can moves perpendicular to the first one. There is beam splitter bisecting the plane of these two mirrors which is semi reflecting. The beam splitter material selected differently for different region to be remained. For IR transparent Iron Oxide or germanium is
coated, on potassium bromide or caesium iodide, which creates a beam splitter for near or mid IR
region. Polyethylene terephthalate thin film is used in the far infrared region. The mechanism is
as follows
A beam of monochromatic radiation is projected on the beam splitter, which reflect 50 %
and transmit 50% of the incident radiation. The deflected and transmitted beam, then reflects
back from the mirrors and interferes at beam splitter. Now, at this time again the 50% reflected
beam from the fined mirrors transmitted, through the beam splitter while 50% reflect, back to the

Figure.3.7: Systematic
FTIR sketch
63

Source. Transmitted beam is one which emerges at 90 to the incident beam, and this
transmitted beam is detected by FTlR. The Optical path difference is produced between the two
arms of the interferometer by the moving mirror Constructive interference occur at the path difference of n which is in case of reflected beam. In destructive interference, occur at the path
difference of (n + 1/2) in case of the transmitted beam.

II.

Source and detectors

In the mid IR region, Glober or Nernst source is used. In case of far IR region high pres-

sure mercury lamps are used. For near IR region to be examined the halogens or tungsten lamp
also be used.

III.

Detectors

Usually, For mid IR region two types of detectors are used. For normal routine as normal detector is used which is pyro electric device en corporations deuterium try glycine Sulphate
(PTGS). Mercury Cadmium telluride can be cool to liquid nitrogen temperature, in work that is
more sensitive. These are mid-range detectors. For near IR region lead sulphide photo conductor
is used as a detector. Germanium detectors operating at liquid helium temperature is used for the
far IR region.

IV.

Fourier Transformation

The intensity falling on the detector I

can relate to spectral power density the particular

wave number by Fourier transformation as follows

(3.17)

Which is one-half of a cousin e Fourier transform pair, with the other being

(3.19)

The above two equations are known as Fourier transform pairs. Variation in power density in
path length found from equation (3.17). Equation 3.18 describes the dependence of intensity on

64

the ware number. These two equations are interconvert able using mathematical method called
Fourier transformation.

V.

Moving mirrors
Most sensitive part of the interferometer is the moving mirrors. It must be aligned accu-

rately and capable scanning, two distances. So, one can calculate path difference values. The intensity of wane varies sinusoidal ways when the moving mirror moves with uniform velocity,
yielding interferogram output. Interferogram is to record of interferometer Signal. The whole Information about the IR region for which detector has act are connected with Interferogram. Interferogram transferred to final IR spectrum by the employment of the Fourier transformation. The
Final IR spectrum shows the Intensity verses frequency. For Zero path difference there is largest
Amplitude [15].

3.3.4.2. Operating procedure of FTIR Spectrometer

Background spectrum or interferes gram is collected first, by applying Fourier transform
method on this data. After it, the single beam spectrum of IR is collected. It contains sample and
background's absorption bands.
FTIR technique can be in any form of a Sample solid, liquid, or gas. For FTIR Spectroscopy of High Tc Superconductors KBr is used in FTIR technique as a background spectrum. The
time for obtaining different sample Spectrum varies depending on the instrument and obtaining
necessary resolution. Normally I to 5 minute was taken from each sample for FTIR reading.

65

3.4.

Refrences

1. L. M. Liz-Marzan, P. V. Kamat, Nanoscale Materials, (Kluwer Academic Publishers, Boston,

2003).
2. C. Burda, X. Chen, R. Narayanan, and M. A. El-Sayed, Chem. Rev. 105, 1025 (2005).
3. S. C. Tjong, and H. Chen, Mater. Sci. Eng. 45, 1 (2004).
4. J. Sjoblom, R. Lindberg, and S. E. Friberg, Adv. colloid interface sci. 65, 125 (1996).
5. M. Yoshimura, and S. Somiya, Mater. Chem. Phys. 61, 1 (1999).

6.

Allen M. Hermann, Thallium-Based High-Temperature Superconductors, Marcel Dekker, Inc. P

41 (1994)

7.

London, H., Proc. Roy. Soc, A, 176, 522 (1940).

8.

B. D Cullity, Element of X-ray Diffraction, Adison-Wesley, Second edition, 92 (1978).

9.

M. P Marder, Condensed Matter Physics, John Wiley & Sons Inc, 58 (2002).

10.N. Ashcroft, N. Mermin Solid State Physics (Orlando, FL: Saunders), 31, pp346 (1976).
11.P. Nozieres, Theory of Interacting Fermi Systems (New York, NY: Benjamin) pp92 (1964).
12.C. Kittel, Introduction to Solid State Physics (New York, NY: Wiley) (1976).
13.M. Okada, Supercond. Sci. Technol. 13, 29 (2000).
14.A guide to alternating current susceptibility measurements and alternating current susceptometer
design,Martin Nikolo,Physics department, St. Louis University (1994).

15.Handbook of Instrumental Techniques for Analytical Chemistry Chapter 15 C.-P. Sherman Hsu,
Ph.D. Separation Sciences Research and Product Development Mallinckrodt, Inc. Mallinckrodt
Baker Division 247.

66

Chapter 4
4.

Results and Discussion

Introduction
The impact of superconducting materials from their application point of view can be es-

timated from the values of superconducting critical parameters such as critical temperature Tc,
critical current density Jc, critical magnetic field Hc [1,2]. The values of these superconductivity
parameters are higher in (Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors and their for device fabrication is further enhanced due to their preparation at normal pressure [3-6]. However, one of the
major route causes which can limit the performance of these materials is inter-grains voids which
can produce inhomogeneous macro-defects that limit the transport Jc and other superconductivity
parameters. A convenient way to tackle this problem is the inclusion of metallic nanoparticles at
the inter-grain sites and if such particles are ferromagnetic in nature they may act as efficient
pinning centers. In the presence of external magnetic field the vortex motion is impeded due to
these pinning centers [7-14]. In order to increase the Jc it is necessary to introduce artificial pinning centers in the superconducting matrices. There are various ways of introducing the pinning
centers in the superconducting materials, such as high energy ion irradiation, chemical doping,
and addition of various types of materials for this purpose [15-18]. The addition of various kinds
of nano-particles in the superconductor matrix have shown significant improvement in the healing of inter-grain voids and hence improved the superconducting properties of the final compound [19-30]. Due to a large surface to volume and higher reactivity of the nano-particles the
inter-grain connectivity is significantly improved and the pores are filled up. If these nanoparticles are ferromagnetic in nature, they do not turn superconducting at lower temperature and
act as efficient pinning centers. In the current studies we have, therefore, added ferromagnetic
Ni-nano-particles for this purpose.

4.1. Experimental
Nano-superconductor (Ni)x/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt. %) composites were
synthesized by two step solid state reaction method. Initially, Ba(NO3)2, Ca(NO3)2.4H2O, and
Cu(CN) compounds were mixed in appropriate ratios and ground in a quartz mortar and pestle

67

followed by firing at 860oC in a quartz boat for 24 hours to prepare Cu0.5Ba2Ca2Cu3O10- precursor material. The precursor was furnace cooled to room temperature and ground again for an
hour and again fired at 860oC in an alumina boat for 24 hours. The precursor material was furnace cooled to room temperature after each heat treatment. The nano-particles of Ni were prepared separately by Co-precipitation method. Later on, at the second stage appropriate amount of
thallium oxide Tl2O3 and Ni nanoparticles with different wt.% were mixed in this precursor material and then ground again for 1 h. This ground material was pressed under 3.8 tons/cm2 pressure in the form of pellets and the pellets were then wrapped in gold capsules for sintering at
860C for 10 min followed by quenching to room temperature to get (Ni)x/CuTl-1223 nanosuperconductor composites. The structure and phase purity of the samples were examined by xray diffraction scan using Bruker DX 8 Focus employs CuK radiations of wavelength
1.54056. The cell parameters were determined by check cell computer refinement program.
The superconductivity characteristics of the samples were measured by conventional four probe
resistivity, AC-susceptibility and Fourier Transform infrared spectroscopic measurements. The
FTIR absorption measurements were carried out by using Nicolet 5700 Fourier Transform Infrared Spectrometer (FTIR) in 400-700cm-1 wave number range.

4.2. Results and Discussion

4.2.1. Theoretical Background
The fluctuation induced conductivity (FIC) analysis is a state of the art theoretical analysis on the
experimental data of cuperates, which can play an essential role to unearth the intrinsic properties of the material well above the zero resistivity critical temperature Tc (0), where the Cooper
pair formation starts and imparts additional conductivity. There are two models that can give a
very nice picture of superconducting fluctuations in inter-grains and intra-grains regions. AL
Model can be used for fluctuations both in inter-grains and intra-grains regions, while LD can be
used only for fluctuations in intra-grains regions of layered superconductors [31, 32]. The excess
conductivity is given by

68

where

is the actually measured resistivity, and

is the normal-state resistiv-

ity of the samples extrapolated to resistivity at 0K; the is a intercept and is a slope of straight
line. The excess conductivity generally comprises on two contributions, i.e.,

The first term, according to AL model, is derived using microscopic approach by mean field theory and is considered as a direct contribution to para-conductivity [33]. The fluctuation induced
conductivity according to AL theory is given as

where A is the fluctuation amplitude, is dimensional exponent, is the reduce temperature

is usually referred to as the mean field critical temperature, which separates the mean field
region from the critical region [33, 34], and is determined from the point of inflection of the
temperature derivative of resistivity (d/dT). The exponent determines the dimensionality of
the superconducting fluctuations and is given as = 2-D/2; =3/2, 1 and 1/2 for one, two, and
three dimensional fluctuations, respectively. The fluctuation amplitude A for one, two, and three
dimensional fluctuations is given by [35]

{
where e is the electron charge,

is the zero-temperature coherence length along c-axis, is

the reduced Planks constant, d is the effective layer thickness of the 2D system, and s is the
cross-sectional area of the 1D system.

69

The physical microscopic parameters calculated from FIC analysis depend strongly on the dimensionality of the fluctuations. LD introduced the concept of interlayer coupling
via Josephson coupling of adjacent layers close to the critical temperature. According to the LD
model for layered superconductors, the excess conductivity LD due to superconducting fluctuations is

where ,
[

is a dimensionless coupling parameter. The cross-over from 2D to 3D is mainly found

above the critical temperature known as cross-over temperature (To). The system has 3D fluctuations below this temperature and 2D fluctuations above this temperature, and the expression for
To according to the LD model is
*

) +

The second term is the inter-layer coupling strength, which is related to the reduced temperature
by J=/4. In layered superconductors at very low temperature close to zero resistivity temperature

, where

is the distance between the conducting layers of adjacent unit cells ( is

approximately equal to the c-axis lattice parameter of the unit cell). The advantage of LD model
is that it reduces to 2D AL model for large values where the coupling constant J is quite small
and to 3D AL model for small values where in some cases the coupling constant J is quite
strong. The above theoretical AL and LD models are based on direct contribution to the excess
conductivity.
There is one more region of fluctuations close to critical temperature for which =1/3 and is
known as critical region [36]. Some authors have observed a cross-over to 0D fluctuations with
critical exponent 2. In high Tc superconductors, the MT contribution, which is due to the interac-

70

tion of fluctuating Cooper pairs with normal electrons, is not easily observable. Since the MT
contribution is negligible in cuprate superconductors [37]. This indirect contribution to the excess conductivity was calculated by Maki [38] and later on modified by Thompson [39]. For layered superconductors, Hikami and Larkin [40] derived the indirect contribution to the excess
conductivity independently by Maki and Thompson [41, 42].

*( ) (

)+

where
*(

) (

)+

is the pair-breaking parameter, which was introduced by Thompson [39] and is related to inelastic scattering processes that limit the phase relaxation time of the quasi-particles involved in
MT process [43] and kB is the Boltzmann constant. In s-wave BCS superconductor, nonmagnetic
impurities neither change Tc nor affect AL and MT terms, while on the other hand in p or d-wave
superconductor these impurities may act pair-breaking and are supposed to suppress the MT contribution [43].

The cross-over from 2D AL to 0D MT fluctuation contribution occurs at a temperature where

, which gives [44]

]
(

)(

71

When the mean free path l of the Cooper pairs approaches to ab at a particular temperature then
they (Cooper pairs) are broken to Fermions and at that temperature the phase relaxation time can
be estimated as
[

Fermi velocity of the carriers can also be estimated by

[

where K 0.12 is a co-efficient of proportionality [45]. Fermi energy of the carriers can also be
calculated by

where m* =10mo is the effective mass of the carrier and mo is the carrier free mass [46].
Ginzburg and Landau observed the existence of two types of superconductors depending
upon the energy of the interface between the normal and superconducting states. In1957, Alexei
Abrikosov used GinzburgLandau theory to explain the experimental data of superconducting
alloys and thin films. He found that high magnetic field in a type-II superconductor penetrates in
the form of magnetic flux quanta o. The thermodynamics magnetic field Bc(0) can be estimated
from Ginzburg number NG, which is given by [46, 47]
|

} {

where = ab(0)/c(0) is anisotropy and TG is the cross-over temperature from critical to 3D regime. We can estimate penetration depth p.d, lower critical magnetic field Bc1(0), upper critical
magnetic field Bc2(0), and the critical current density Jc(0) after determination of Bc(0) as follows: [48-51]

72

where o = /2e is the flux quantum and j is the GL parameter, which is the ratio of penetration
depth to coherence length.

4.2.2. Nano-superconductor (Ni)x/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt. %)

composites
The x-ray diffraction scans of Ni-nano-particles are shown in Fig.1. These nano-particles
are grown in cubic crystal structure with cell parameters of side length 4.324 and unit cell volume 643.

Figure 4.1: X-ray diffraction scans for Ni nano-particles

The x-ray diffraction scans of Ni-nano-particles added (Ni)x/CuTl-1223, x = 0, 3, 5, 7, 10 wt. %,

nano-superconductor composites are shown in Fig. 2(a,b,c,d,e).

73

74

Figure.4.2. X-rays diffraction scans of Nix/CuTl-1223 (x=0, 3, 5, 7, 10 wt%)

75

The planar reflections peaks are best fitted to the orthorhombic crystal structure following
PMMM space group. The addition of first few percentages of Ni-nano-particles suppresses
whereas the further addition of nano-particles enhances the c-axis length and hence the volume
of the unit cell. The increases in the volume of the unit cell suggested that Ni-nano particles not
only fill the inter-grain voids but Ni is also incorporated into the unit cell of the final compound.
It is therefore expected that superconducting properties will also be altered with the various percentage additions of Ni-nano-particles. The variation of a-axis and b-axis because of Ni-contents
is shown in Fig.4.2a while the variation of c-axis because of Ni-contents is shown in Fig.4.2b.

Figure 4.2(a): Variation in a,b-axis length because of Ni-contents. (b) variation in caxis with Ni-contents

76

The resistivity measurements of Nix/(Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors are

shown in Fig.3. All the samples have shown metallic variations of the resistivity from room temperature down to onset of superconductivity.

Figure 4.3: Combined resistivitys for Nix/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) nanosuperconducting composites.

These samples have shown onset of superconductivity around 113, 101, 103, 105, 103 K
and the zero resistivity around 95, 90, 92, 93, 92 K. Both the onset temperature and the zero resistivity critical temperature of superconductivity suppressed with the increased additive percentage of Nix nano-particles. The resistivity measurements also complimented the XRD data that
some of the Nix from the inter-grain sites is incorporated into the unit cell that may change the
superconducting properties of the final compound.
The Ac-susceptibility measurements of Nix/(Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors
are displayed in Fig.4.

77

Figure 4.4: AC-susceptibility measurements for Nix/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) nanosuperconducting composites

These samples have shown onset of superconductivity around 93, 94, 93, 94, 94 K. The
magnitude of the diamagnetism suppresses for first few Nix additions but it increases for 7 and
10% addition. Increase in the magnitude of diamagnetism shows that despite incorporation of Nix
into the unit cell of the final compound formation of the pinning centers at the inter-grain and
intra-grain sites initiated by Ni atoms is most probable route cause of enhancement of magnitude
of diamagnetism.
The FTIR absorption measurements of (Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors samples are displayed in Fig. 5. In pristine (Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors four absorption modes related to the vibrations of apical oxygen atoms and CuO2 planar oxygen atoms. These modes are observed at 423-487, 540 and 609cm-1. The former two modes are related to the
vibrations of apical oxygen atoms of type Tl-OA-Cu(2) and Cu(1)-OA-Cu(2) atoms whereas the
phonon mode around 606cm-1 is related to the vibration of CuO2 planar oxygen atoms.

78

Figure 4.5: F.T.I.R spectrum for Nix/CuTl-1223 (x = 0, 3, 5, 7 and 10 wt%) nano-superconducting

composites.

The peak position of the planar oxygen mode is not significantly alter with the increase in additive concentration of Ni-nano-particles. However, the apical oxygen mode of type Cu(1)-OACu(2) is softened at a higher additive concentration; the Tl-OA-Cu(2) phonon mode around 423-

79

487 is not appreciably altered with increase addition of Ni in the final compound. The softening
of apical oxygen mode of type Cu(1)-OA-Cu(2) shows that there is some doping of Ni at the
Cu(1) site of the charge reservoir layer from the inter-grain sites in the unit cells.
The excess conductivity analyses of (Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors have
shown that the width of the 3D conductivity regime, mean field critical temperature Tcmf are
shifted to the lower temperatures, Table 1. Moreover, the coherence length along the c-axis, the
inter-layer coupling and the Fermi-velocity of the carriers are suppressed with the addition of NiNano-particles in the final compound. The suppression of these parameters also supported the
XRD and FTIR absorption measurements that Ni in most probably incorporated into the unit cell
of (Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors. However, the

the

, the

are en-

hanced with the addition of Ni-nano-particles. The London penetration depth also suppresses
with the addition of Ni-nano-particles, table 2.

Sample

3D

2D

SW

TCR-3D=TG

T3D-2D

T2D-SW

Tcmf

T*

=n(0K)

W=Tc

(K)

(K)

(K)

(K)

(K)

(-cm)

(K)

Ni 0 %

0.52

1.05

1.97

104.4

108.4

117.4

103.4

142.5

0.077

5.14

Ni 3 %

0.50

1.04

1.96

93.3

94.3

104.4

92.4

137.5

0.060

4.59

Ni 5 %

0.51

1.01

2.0

96.3

97.4

128.5

95.3

164.6

0.103

5.40

Ni 7 %

0.48

0.98

2.05

95.3

97.4

124.5

94.4

162.6

0.079

1.85

Ni 10 %

0.50

0.97

1.99

94.4

95.3

112.4

93.3

149.5

0.069

4.72

Table 1: Parameters estimated from

80

Sample

c(0)

NG

()

p.d

Bc(0)

Bc1

Bc2

()

(T)

(T)

(T)

Jc(0)*103

VF*107

EBreak

(A/cm2)

(m/s)

(eV)

* 10-14

Ni 0 %

1.65

0.05

0.09

714.3

2.03

0.12

128.7

44.6

1.55

1.34

0.04

11.1

Ni 3 %

1.10

0.02

0.03

309.4

4.70

0.50

128.7

19.3

8.27

0.85

0.02

18.5

Ni 5 %

1.08

0.02

0.04

319.2

4.56

0.48

128.7

19.9

7.76

0.86

0.07

5.9

Ni 7 %

1.33

0.03

0.02

362.1

4.02

0.39

128.7

22.6

6.03

1.07

0.06

7.2

Ni 10 %

1.09

0.02

0.02

277.7

5.24

0.61

128.7

17.4

10.26

0.87

0.03

12.2

Table 2: Superconducting parameters estimated from excess conductivity

Figure 4.6(a): ln() vs ln() of Nix/CuTl-1223 x = 0 wt% nano-superconducting composites

81

Figure 4.6(b): ln() vs ln() of Nix/CuTl-1223 x = 3 wt% nano-superconducting composites.

Figure 4.6(c): ln() vs ln() of Nix/CuTl-1223 x = 5 wt% nano-superconducting composites.

82

Figure 4.6(d): ln() vs ln() of Nix/CuTl-1223 x = 7 wt% nano-superconducting composites.

Figure 4.6(e): ln() vs ln() of Nix/CuTl-1223 x = 10 wt% nano-superconducting composites.

83

4.3. Conclusions
(Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors samples added with Ni-nano-particles have
been synthesized at normal pressure by two step solid state reaction method at 860oC. The samples have shown orthorhombic crystal structure in which axes length increases with the increase
in the added concentration of Ni-nano-particles. The analyses of XRD data have shown that Ni
nano-particle added at the inter-grain sites partially diffuse into the (Cu0.5Tl0.5)Ba2Ca2Cu3O10-
unit cell thereby inducing increases in the cell parameters and volume of the unit cell. All the
samples have shown a metallic variation of resistivity from room temperature down to the onset
of superconductivity with a small suppression in the Tc(R=0) in Ni-nano-particle added samples.
The magnitude of diamagnetism is suppressed in 3 and 5% Ni-nano-particles addition, whereas
magnitude of diamagnetism is significantly enhanced in 7 and 10% nano-particle added samples.
The diffusion of Ni from the inter-grain sites in the unit cell is also noted in the softening of apical oxygen modes of type Cu(1)-OA-Cu(2). The FIC analyses of conductivity data have shown
enhancement in the values of Bc(0), Bc1 and Jc with the addition of Ni-nano-particles. The increase in the values of these parameters suggests that added Ni-nano-particles diffuse at intergrain sites not only act as a cementing agent but also as efficient pinning centers. This also is
shown in shown in the suppression of suppression of the London penetration depth of the field.
This unequivocally proves that Ni-nano-particles act as efficient pinning centers in the solid state
matrix of (Cu0.5Tl0.5)Ba2Ca2Cu3O10- superconductors and their addition in the final compound is
useful from application point of view.

84

4.4.

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