Superconductor Bi-2212
SYNTHESIS OF COMPOUND Bi2Sr2CaCu2O8+δ AND STUDY OF IT’S 
NORMAL MODES THROUGH RAMAN SPECTROSCOPY 

BY: Bharti Mahendru | B.Sc. Physical Science | 2016‐2017 
UNDER: Dr. Alka Garg 
 
 
 
 
 
 CERTIFICATE: 
This is to certify that Bharti Mahendru of B.Sc. Physical
Science (3rd Year) of Gargi College, University of Delhi (India)
has successfully done project on SYNTHESIS OF COMPOUND 
Bi2Sr2CaCu2O8+δ AND STUDY OF IT’S NORMAL MODES THROUGH 
RAMAN SPECTROSCOPY under the guidance of Dr. Alka Garg in Gargi 
College Research Lab.  
 
 
 
 
Dr. Alka Garg 
(alkagargi67@yahoo.com) 

 
 

BHARTI MAHENDRU | PAGE 1 
 ACKNOWLEDGEMENT 
This project would be incomplete without the acknowledgement of my 
mentor who helped me from the very initial stage until the end. This 
golden opportunity helped me grow in the field of material science and 
provided me with the hands‐on experience. Heartfelt thanks to Dr. 
Alka Garg for providing all the facilities and her constant and 
continued support to carry out this work.  

Deep sense of gratitude to Delhi University Laboratory, 
Nanotechnology Lab at IIT, Delhi and Department of Physics, Gargi 
College for facilitating us in various stages of time during this work. 
Also, I would like to express my respect to all the teachers at Physics 
Department for giving me consequential insights throughout the work.  

BHARTI MAHENDRU | PAGE 2 
CONTENTS 
1) ABSTRACT 
2) INTRODUCTION  
a) Definition 
b) History and Uses 
c) Type I Superconductors 
d) Type II Superconductors 
3) THEORY   
a) BCS Theory 
b) Important Characteristics 
c) X‐Ray Diffraction 
d) UV‐VIS Spectroscopy 
e) Raman Spectroscopy 
4) PROCEDURE 
5) ANALYSIS, RESULTS AND DISCUSSIONS 
6) CONCLUSIONS 
7) APPLICATION AND SCOPE OF THE PRESENT WORK 
8) REFERENCE AND BIBLIOGRAPHY 
 
 

BHARTI MAHENDRU | PAGE 3 
 ABSTRACT: 
 
The high-temperature type- II superconducting
material BSSCO was synthesized by solid-state
reaction. Pure (AR Grade with purity > 99%) oxides
and carbonates powders were takes of Bi2O3, SrCO3,
CaCO3, CuO for the synthesis. Annealing of the pellet
was done at appropriate temperature. Further, the
phases, the size of crystal, lattice constants of the
sample were determined by X-Ray Diffraction, And the
results were verified by various research papers. UV-
Visible spectrum of the sample was taken to study the
conductivity and band-gap. Finally, Raman Spectra
were analyzed for normal modes’ characterization and
confirmation of sample grown.

BHARTI MAHENDRU | PAGE 4 
INTRODUCTION 
Definition:  

HISTORY AND USE: 
In 1911, Kammerlingh Onnes was first to observe zero resistivity in metal
mercury below temperature 4.2K (called the critical temperature, 𝑻_𝒄)
and named the phenomenon “superconductivity”. He also termed the
'critical magnetic field' (𝑯_𝒄), as the magnetic field above which a
superconductor changes from the superconducting state to normal state.

After about twenty years of the discovery of Onnes, Meissner and

Oschenfield, in 1933 observed the perfect diamagnetism (No magnetic
induction) of the superconductor, when a superconductor was cooled
below its critical temperature in a magnetic field. This expulsion of
magnetic field at superconducting state is called 'Meissner and
Oschenfield effect'.

Another important parameter of aforesaid phenomenon is ‘critical

current density’ (𝑱_𝒄), when a high current is applied to the material
(superconductor), its superconductivity behavior is lost. The current at
which the material is no more a superconductor is called critical current
density.

Based on the behavior of superconductors in magnetic fields they

are divided into two categories, 'Type I' and 'Type II'. In Type I
superconductors, above the thermodynamic critical field, Hc, perfect

BHARTI MAHENDRU | PAGE 5 
diamagnetism is destroyed, and the superconductor is reverted to the
normal state. But in Type II superconductors perfect diamagnetism is
observed only up to a limit called the 'lower critical field', Hc1. Above Hc1,
magnetic flux partially penetrates the material up to a field called the
upper critical field, Hc2. and above Hc2. the magnetic flux fully penetrates
the material and the material returns to the normal state. Between Hc1 and
Hc2, the material is said to exist in a 'mixed state' or 'intermediate state'.

Superconducting materials are very important in scientific and

technological prospective. Some technological innovations benefiting from
the discovery of superconductivity are
 Magnetic resonance imaging
 Sensitive magnetometer based on SQUIDS.
 Beam-steering magnets in particle accelerator.
 Microwave filters.
 Electronic power transmission cables.
 Magnetic levitation devices.

Figure 1 Three‐dimensional surface of superconductivity 

BHARTI MAHENDRU | PAGE 6 
TYPE I SUPERCONDUCTORS:  
The Type 1 category of superconductors is mainly comprised of metals
and metalloids that show some conductivity at room temperature. They require
incredible cold to slow down molecular vibrations sufficiently to facilitate
unimpeded electron flow in accordance with what is known as BCS theory.

There are mainly 27 pure metals in the periodic table listed as Type
Superconductors, namely: (Critical Temperature indicated in parentheses,
Kelvin) Rh (0.000325 K), W (0.015), Be** (0.026), Ir (0.1), Lu (0.1), Hf (0.1), Ru
(0.5), Os (0.7), Mo (0.92), Zr (0.546), Cd (0.56), U (0.2), Ti (0.39), Zn (0.85), Ga
(1.083), Gd* (1.1), Al (1.2), Pa (1.4), Th (1.4), Re (1.4), Tl (2.39), In (3.408), Sn
(3.722), Hg (4.153), Ta (4.47), La (6.00), Pb (7.193).

Type 1 superconductors - characterized as the "soft" superconductors – were

discovered first and require the coldest temperatures to become
superconductive. They exhibit a very sharp transition to a superconducting
state and "perfect" diamagnetism - the ability to repel a magnetic field
completely.

TYPE II SUPERCONDUCTORS: 
Except for the elements vanadium, technetium and niobium, the Type 2
category of superconductors is comprised of metallic compounds and alloys.
The recently-discovered superconducting "perovskites" (metal-oxide ceramics
that normally have a ratio of 2 metal atoms to every 3 oxygen atoms) belong to
this Type 2 group. They achieve higher Tc's than Type 1 superconductors by a
mechanism that is still not completely understood. Conventional wisdom holds
that it relates to the planar layering within the crystalline structure. Although,
other recent research suggests the holes of hypo-charged oxygen in the charge
reservoirs are responsible. (Holes are positively-charged vacancies within the
lattice.) The superconducting cuprates (copper-oxides) have achieved
astonishingly high Tc's when you consider that by 1985 known Tc's had only
reached 23 Kelvin. To date, the highest Tc attained at ambient pressure for a
material that will form stoichiometrically (by direct mixing) has been 147 Kelvin.
And the highest Tc overall is 216 Celsius for a material which does not form
stoichiometrically. It is almost certain that other, more-synergistic compounds
still await discovery among the high-temperature superconductors.

The first superconducting Type 2 compound, an alloy of lead and bismuth, was
fabricated in 1930 by W. de Haas and J. Voogd. But, was not recognized as
such until later, after the Meissner effect had been discovered. This new
category of superconductors was identified by L.V. Shubnikov at the Kharkov
Institute of Science and Technology in the Ukraine in 1936(1) when he found
two distinct critical magnetic fields (known as Hc1 and Hc2) in PbTl2. The first of
the oxide superconductors was created in 1973 by DuPont researcher Art

BHARTI MAHENDRU | PAGE 7 
Sleight when Ba(Pb,Bi)O3 was found to have a Tc of 13K. The superconducting
oxo-cuprates followed in 1986.

Type 2 superconductors - also known as the "hard" superconductors -

differ from Type 1 in that their transition from a normal to a superconducting
state is gradual across a region of "mixed state" behavior. Since a Type 2 will
allow some penetration by an external magnetic field into its surface, this
creates some rather novel mesoscopic phenomena like superconducting
"stripes" and "flux-lattice vortices". While there are far too many to list in
totality, some of the more interesting Type 2 superconductors are listed below
by similarity and with descending Tc's. Where available, the lattice structure of
the system is also noted.

Some examples (Critical Temperature are indicated in parentheses) are

Sn12SbTe11Ba2V2Mg24O50+ (216K), LBCO (Lanthanum Barium Copper Oxide)
(35K), LBCO (Lanthanum Barium Copper Oxide) (93K), BSCCO (Bismuth
Strontium Calcium Copper Oxide) It has general formula Bi2Sr2Can-1CunO2n+4+x
with specific transition temperature ranging from Tc=20K (n=1, 2201 phase),
85K (n=2, 2212 phase), 110K (n=3,2223 phase) and 104K (n=4,2224 phase),
TBCCO (Thallium Barium Calcium Copper Oxide) with general formula of
Ti2Ba2Can-1CunO2n+4+x with transition temperature ranging from Tc=85K (n=1,
2201 phase), 110K (n=2, 2212 phase) and 127K (n=3,2223 phase) where the
CuO2 layers are thicker and closer together in comparison to BSCCO system
and HBCCO (Mercury Barium Calcium Copper Oxide) having general formula of
Hg1Ba2Can-1CunO2n+4+x with specific transition temperature ranging from Tc=94K
(n=1, 1201 phase), 128K (n=2, 1212 phase) and 134K (n=3, 1223 phase). The Tc
of the Hg compound containing one CuO2 layer is much larger as compared to
the one CuO2 layer compounds of TBCCO.

BHARTI MAHENDRU | PAGE 8 
 THEORY 
BCS THEORY:  
The properties of Type I superconductors were modeled successfully by
the efforts of John Bardeen, Leon Cooper, and Robert Schrieffer in what is
commonly called the BCS theory. A key conceptual element in this theory is the
pairing of electrons close to the Fermi level into Cooper pairs through interaction
with the crystal lattice. This pairing results from a slight attraction between the
electrons related to lattice vibrations; the coupling to the lattice is called a phonon
interaction.

Pairs of electrons can behave very differently from single electrons which are
fermions and must obey the Pauli exclusion principle. The pairs of electrons act
more like bosons which can condense into the same energy level. The electron
pairs have a slightly lower energy and leave an energy gap above them on the
order of .001 eV which inhibits the kind of collision interactions which lead to
ordinary resistivity. For temperatures such that the thermal energy is less than
the band gap, the material exhibits zero resistivity.

Bardeen, Cooper, and Schrieffer received the Nobel Prize in 1972 for the
development of the theory of superconductivity.

COOPER PAIRS: The behavior of superconductors suggests that electron pairs

are coupling over a range of hundreds of nanometers, three orders of magnitude
larger than the lattice spacing. Called Cooper pairs, these coupled electrons can
take the character of a boson and condense into the ground state.

This pair condensation is the basis for the BCS theory of superconductivity. The
effective net attraction between the normally repulsive electrons produces a pair
binding energy on the order of milli-electron volts, enough to keep them paired
at extremely low temperatures.

The transition of a metal from the normal to the superconducting state has the
nature of a condensation of the electrons into a state which leaves a band gap
above them. This kind of condensation is seen with superfluid helium, but helium
is made up of bosons -- multiple electrons can't collect into a single state because
of the Pauli exclusion principle. Froehlich was first to suggest that the electrons
act as pairs coupled by lattice vibrations in the material. This coupling is viewed
as an exchange of phonons, phonons being the quanta of lattice vibration energy.
Experimental corroboration of an interaction with the lattice was provided by the
isotope effect on the superconducting transition temperature. The boson-like
behavior of such electron pairs was further investigated by Cooper and they are
called "Cooper pairs". The condensation of Cooper pairs is the foundation of the
c

BHARTI MAHENDRU | PAGE 9 
The BCS theory prediction of Cooper pair interaction with the crystal lattice has
been verified experimentally by the isotope effect. That is, the critical temperature
of a material depends on the mass of the nucleus of the atoms. If an isotope is
used (neutrons are added to make it more massive), the critical temperature
decreases. This effect is most evident in Type I and appears only weakly in Type
II.

This superconductivity of Cooper pairs is somewhat related to Bose-Einstein

Condensation. The Cooper pairs act somewhat like bosons, which condense into
their lowest energy level below the critical temperature and lose electrical
resistance.

The BCS theory does not account well for the high-Tc super conduction,
which is still not fully understood. The presence of positively charged holes within
the crystal lattice that would constantly want to reduce could be possible
explanation for the high-Tc phenomena.

Here we report the discovery and the characterization of the 2212 ceramic
sharing a two-dimensional layered (perovskite) structure in the Bi-Sr-Ca-Cu-O
system (BSCCO). In fact, it is very difficult to synthesize ceramic of quantity that
would satisfy in all respects the high resolution of modern experimental methods
and analysis of the data. The reasons lie in the poor knowledge of phase
diagrams, incongruency of melting, high toxicity of some chemical components,
high sensitivity to the profile of cooling, etc. Here, we describe the results of
synthesis of high-Tc Bi2Sr2CaCu2O8+x superconductor obtained by solid state
reaction method. The results of this work should not be considered as final
answer to the problem of synthesis of BSCCO-2212, but rather a set of
experimental results that indicate how particular parameters influence the
properties of the grown crystals. For the synthesis of monocrystalline, following
methods can be used: self-flux, sealed cavity method,

In Bi-, Hg-, Tl-based high-Tc superconductors it is very difficult to synthesize a

single-phase crystal because of the existence of three (or more) phases having
similar layered structure. Thus, syntactic inter-growth and stacking faults occur
during synthesis and it becomes difficult to isolate a single superconducting
phase. In BSCCO system, it is relatively simple to obtain 2212 single phase
compared to 2223. Although, the substitution of lead (Pb) in the BSCCO system
has been found to promote the growth of high-Tc phase, a long sintering time is
still required.

BHARTI MAHENDRU | PAGE 10 
FOUR IMPORTANT CHARATERSTICS:  
 ZERO RESITIVITY:
A material in its superconducting state offers no resistance to the flow of
direct electric current or in the other words superconductor is a perfect
conductor.
 MEISSNER EFFECT:
Another property of superconducting materials is the Meissner effect. It
was observed that as a magnet is brought near a superconductor the
magnet encounters a repulsive force. It can be said that the
superconductor completely expels the magnetic field and behave as
diamagnet.
Typically, a magnet is kept on a superconductive disk and is cooled by
liquid nitrogen, this causes the magnet to levitate. The floating magnet
induces a current, and therefore a magnetic field. In the presence of
superconductor, the two magnetic fields repel to levitate the magnet.
Meissner effect is discovered by Meissner and Ochsenfeld in 1933. This
effect tells that a superconductor expels the magnetic flux applied
externally, when it is cooled below critical temperature. Hence the
magnetic field inside a superconductor is zero
i.e. B = μ0(M + H) = 0
or, χ = M/H = –1
The susceptibility of superconductor is –1 which shows that the
superconductor is perfectly diamagnetic material.
 JOSEPHSON EFFECT:
One other properties of superconductors is that when two of them are
joint by a thin, insulating layer it is easier for the electron pairs to pass
from one superconductor to another without resistance, this is called the
Josephson Effect. And the junction is called Josephson junction. This
has a perfect implication for super-fast electrical switches that can be
used to make small, high speed computers.
The Josephson current flows only if no battery is connected across the
two superconductors. If a battery is inserted, the current oscillates very
rapidly so that no net current flows. The presence of magnetic fields near
the superconductors influences the Josephson effect, allowing it to be
used to measure very weak magnetic fields.
 QUANTIZATION OF MAGNETIC FIELD (FLUX QUANTIZATION):
The magnetic flux that passes through a superconducting ring may
assume only quantized value, integral quantum of the flux quantum
ℎ𝑐 𝑞, where q=-2e, the charge of an electron pair and h is Planck’s
constant and c is speed of light.

The last two properties are related to electric power applications and the first to
properties are related to microelectronic applications.

BHARTI MAHENDRU | PAGE 11 
 The Bi-Sr-Ca-Cu-O superconductor which was invented by Maeda et al.
is considered as one of the prospective materials for device applications owing
to its higher transition temperature. Several techniques have been employed to
prepare thin films of the BSCCO system which includes magnetron sputtering,
e-beam evaporation co-evaporation, laser ablation, etc. However, these
techniques require many elaborate peripheral accessories involving higher cost
of fabrication. The film deposited by these techniques have shown more or less
similar properties. Different methods however yields different film qualities, for
example sputtering technique may yield films having microwave quality surface
for application in microwave devices while films obtained by deposition methods
are typically off granule structure after heat treatment and are used in light
detectors devices etc. For application in device is it is very crucial to prepare
high quality thin films. In this project we report the preparation of good quality
superconducting BSCCO thin films using solid-state reaction method. Our
technique does not require sophisticated instruments for composition control.
The simplest method for preparing high-Tc superconductors is a solid state
thermo-chemical reaction involving mixing calcination and sintering. The
appropriate amount of precursor powders, usually oxides in carbonates, are
mixed thoroughly using a ball mill. Solution chemistry processes such as group
coprecipitation freeze drying and sol-gel methods are alternative ways of
preparing a homogeneous mixture. These powders are calculated in the
temperature range from 800 degrees Celsius to 950 degrees Celsius for several
hours. The pellets are cooled and calcined again. This process is repeated
several times to get homogeneous material. The sintering environment such as
temperature and annealing time, atmosphere and cooling rate play a very
important role in getting good high-Tc superconducting materials

X‐RAY DIFFRACTION: 
In a polycrystalline material or the powder of a crystalline material, the
crystals are randomly oriented. When an X-ray beam (~ 1A°) incident on such a
sample, there may be many planes which are oriented in such a way that Bragg's
law is satisfied, and we obtain a resultant diffraction pattern with peaks
corresponding to all such planes. For exposing a greater number of planes, the
sample is rotated by an angle θ on its own axis during exposure in such a way
that a scintillating counter, which acts as a detector and rotate by 2θ angle,
collect the entire diffracted beam. This output is fed to a recorder which records
the output (which is proportional to the intensity of the diffracted beam) versus
2θ.
The obtained diffraction pattern is expressed in terms of Bragg’s diffraction law:

𝟐𝒅𝐬𝐢 𝐧 𝜽 𝒏𝝀 (eq. 1)
where, λ is wavelength of the X-Ray beam, θ is the angle between plane of the
specimen and the X-Ray source, d is the interplanar distance.

BHARTI MAHENDRU | PAGE 12 
FWHM (Full Width Half Maximum) of the most intense peak of the XRD pattern
has been used for the particle size through Scherrer’s Formula.

𝑫 𝟎. 𝟗𝟒𝝀 / 𝜷 𝐜𝐨𝐬 𝜽 (eq. 2)

where, D is the crystallite size (in nm), λ is the wavelegth of the X-ray beam, θ is
the diffraction angle and β is the FWHM in radians.
 

UV‐VIS SPECTROSCOPY: 
Ultraviolet–visible spectroscopy or ultraviolet–visible spectrophotometry
(UV–Vis or UV/Vis) refers to absorption spectroscopy or reflectance
spectroscopy in the ultraviolet-visible spectral region. This means it uses light
in the visible and adjacent ranges. The absorption or reflectance in the visible
range directly affects the perceived color of the chemicals involved. In this
region of the electromagnetic spectrum, atoms and molecules undergo
electronic transitions. Absorption spectroscopy is complementary to
fluorescence spectroscopy, in that fluorescence deals with transitions from the
excited state to the ground state, while absorption measures transitions from
the ground state to the excited state. Generally, the most probable transition is
from highest occupied molecular orbital (HOMO) to lowest occupied molecular
orbital (LUMO).

We can use Lambert-Beer’s Law

𝐈𝐨 𝟏𝟎𝟎
𝑨 𝐥𝐨𝐠𝟏𝟎 𝐈 𝐥𝐨𝐠𝟏𝟎 𝑻 𝐤𝐜𝐋 (eq. 3)
where L is the length of the radiation path through the sample, c is the
concentration of absorbing molecules in that path, and k is the extinction
coefficient - a constant dependent only on the nature of the molecule and the
wavelength of the radiation, A is absorbance, T is Transmittance, I0 is initial
intensity of light and I is final intensity of light after passing through the
specimen.
The measurement of the band gap of materials is important in the
semiconductor, nanomaterial and solar industries. The term “band gap” refers
to the energy difference between the top of the valence band to the bottom of
the conduction band; electrons can jump from one band to another. For an
electron to jump from a valence band to a conduction band, it requires a
specific minimum amount of energy for the transition, the band gap energy.

Band gap can be calculated using Tauc method as given below:

𝜶 𝑨 𝒉𝝂 𝑬_𝒈 ^𝒏 /𝒉𝝂 (eq. 4)

where, 𝛼 ln 1 𝑇 /𝑥, absorption coefficient, T is transmittance, x is thickness,

Eg is band gap of the material, n=2,1 ⁄ 2, 2 ⁄ 3, 1 ⁄ 3 for direct allowed, indirect
allowed, direct forbidden, and indirect forbidden transitions respectively.

BHARTI MAHENDRU | PAGE 13 
RAMAN SPECTROSCOPY: 
When a beam of light is passed through a transparent substance, a small
amount of the radiation energy is scattered, the scattering persisting even if all
dust particles or other extraneous matter are rigorously excluded from the
substance. If monochromatic radiation or radiation of a very narrow frequency
band, is used, the scattered energy will consist almost entirely of radiation of
the incident frequency (the so-called Rayleigh scattering) but, in addition,
certain discreet frequencies above and below (almost 1%) that of the incident
beam will be scattered; it is this which is referred to as Raman scattering.

Similar to IR spectroscopy, Raman spectroscopy provides information regarding

the

vibrational motion of molecules, but the origin of Raman spectra is relatively

dissimilar to IR spectra. As, Raman spectra arises due to induced polarization
of the vibrating molecule and is based on scattering of light while IR spectra
induced due to permanent dipole moment and based upon absorption of
photons. Therefore, some peaks appear in Raman spectra may not detect in IR
spectra.

Raman spectroscopy is the study of the small fraction of light that is not
elastically (Rayleigh) scattered but inelastically scattered off a sample. The
energy shift can be generated by any type of excitation that couples to light and
does not require a large momentum transfer. Very commonly investigated are
for instance the creation and annihilation of optical phonons near the center of
the Brillouin zone. These phonons appear as sharp peaks in the Raman
spectra. An excitation typical for the cuprates is two-magnon scattering, which
produces an exchange of two neighboring spins on the antiferromagnetically
ordered copper sublattice. Since the antiferromagnetic order becomes short-
range for over-doped cuprates, the two-magnon peak softens and shifts to lower
energies.

Well, below the critical temperature of superconducting cuprates, the Raman

scattering from the quasiparticles is very small (→ clean limit). Here another
type of excitation is dominant, namely the breaking of Cooper pairs, which is
allowed thanks to their vanishing total momentum. Thus, the Raman spectra in
the superconducting state render information about the bonding strength of the
Cooper pairs in the condensate.

Here we limit the discussion to qualitative analysis up-to undergraduate level.

The scope of the Raman spectra shall be discussed after conclusion for further
analysis.

BHARTI MAHENDRU | PAGE 14 
STRUCTURE OF Bi2Sr2CaCu2O8+x: 

BHARTI MAHENDRU | PAGE 15 
STRUCTURE OF Bi‐2212: 
Bi-2212 system consists of a layered stacking of double Bi-O sheets and
perovskite like blocks containing CuO2 layers sandwiched between Sr and Ca
layers. The unit cell this phase has double Bi-O planes stacked in a way that
the Bi-atom of one plane sits below the oxygen atom of the next consecutive
plane. The bismuth atom is in octahedral co-ordination with oxygen whereas
copper-oxygen co-ordination is square pyramidal, which shares its apical
oxygen with bismuth octahedra. Calcium has a coordination of eight and has
no oxygen in its plane. The Ca-atom forms a layer within the interior of the
CuO2 layers. Bi-2212 has two CuO2 planes. The c-axis of this please increases
with the number of CuO2 planes. The Cu-atom is surrounded by five oxygen
atoms in a pyramidal arrangement. Bi-O layers in Bi-2212 are center of
controversy.

BHARTI MAHENDRU | PAGE 16 
PROCEDURE:  
SYNTHESIS:  
There exist a wide variety of methods for the synthesis of ceramic
materials. Out of them, the solid-state reaction method is the broadly
used method for the preparation of polycrystalline solids. In this method
reactants are mixed together in a powder form and heated for extended
periods at high temperature. High temperature provides a considerable
amount of energy for the reaction to occur. Hence, the final product
obtained from this method is thermodynamically stable. The major benefit
of this method is the formation of structurally pure product with desired
properties which depends on final sintering temperature.

Initially, powders of oxides and carbonates with Bi, Cu, Sr and Ca of AR

Grade (>99%) were weighed according to their stoichiometric formula
(2:2:1:2) of the composition in accordance with the following equation:

Bi2O3 + 2SrCO3 + CaCO3 + 2CuO → Bi2Sr2CaCu2O8+x + 3O2

The weights of the compounds used in the preparation are:

Compound Weight
Bi2O3 4.665g
SrCO3 2.9512g
CaCO3 1.0088g
CuO 1.5920g

Then the powders were mixed together in a clean mortar and pestle and for 12 hours 
to eliminate aggregates and reduce the particle size.  
And pellets of 12mm diameter were made from the mixture by applying hydraulic 
pressure.  The  pellet  was  calcined  at  700°C  for  five  hours  for  high  purity  phase 
synthesis.  Calcination  procedure  is  an  endothermic  decomposition  reaction.  It 
involves decomposition of carbonate, oxide and hydroxide to achieve a solid product 
in the form of oxides with liberation of gas. During calcinations process, the solid 
phase reaction takes place between the constituents by inter‐diffusion of its ions, 
resulting in the partial phase formation.  
Then again, the pellet was grinded for 3 hours made into pellet using hydraulic press 
and  sintered  for  740°C  for  5  hours  as  the  pellet  turns  black  and  shiny.  During 
sintering  process,  the  particles  grow  (through  lattice  diffusion)  at  the  region  of 
contact  which  results  in  densification  and  grain  growth.  The  sintering  process 
considerably affects grain boundaries and pores. Grinding is continued for 3 hours 
as the mixture gets hard.  

BHARTI MAHENDRU | PAGE 17 
Finally, the pellet was sintered at 830°C for 0.5 hours and calcined at 740°C for 5 
hours before natural cooling.  
 
The schematic flow chart is as follows:  
 
  Bi2O3, SrCO3, CaCO3,
  CuO Powders of AR
GRADE (in 2:2:!:2
stochiometric ratio)  

Mixing and 
Grinding 
(10h) 

Calcinating
at 700°C
(5h)
Grinding
(3h) and
Pelleting

Sintering at
740°C (5h)

Grinding
(3h) and
Pelleting
Sintering at
830°C (0.5h),
740°C (5h)

BSCCO 2212

BHARTI MAHENDRU | PAGE 18 
 830°C for
0.5 hour

300°C/hr. 740°C for

5 hours

Natural
Cooling

Room
Temperature
Figure 2 Final Scheme for Annealing 

UV‐VIS DOUBLE SPECTROSCOPY:  
The pellet appeared hard, shiny and reduced in size after complete synthesis process. A part 
of  pellet  was  crushed  from  one  edge  and  dissolved  in  acetone  to  take  its  UV‐Visible 
Spectrum.  

X‐RAY DIFFRACTION:  
The X‐Ray Diffraction Pattern was taken in Bruker High resolution X‐ray diffractometer of 
the pellet.  

RAMAN SPECTROSCOPY:  
The Raman Spectroscopy was taken in Micro Raman Spectrometer of the pellet.  

BHARTI MAHENDRU | PAGE 19 
 CHARACTERIZATION, RESULT AND DISCUSSION:  
STRUCTURAL CHARACTERISATION BY X‐RAY DIFFRACTION:  
X-Ray Diffractometer utilizing Cu-Kα radiation (40kV, 200mA) and with
wavelength, λ = 1.54A° has been used for the structural characterization of the
synthesized Bi-2212 pellet which confirms the synthesis of the material.

300000

BSSCO

FWHM = 0.1930417
Intensity (Counts)

200000
0010

008
100000

0012
1110 0020
002
0
0 30 60 90
Angle (2 theta)

Figure 3 Observed XRD Pattern of Bi2212 after final sintering. 

The pellet’s X-Ray Diffraction was taken ranging from 0° to 90° and indexing of
the peaks was done. Then, the data was matched with JCPDS card and various
research papers to confirm the phases observed in the crystal. These values were
then used to find particle size and lattice constants to finally determine the shape
of the polycrystal synthesized.

BHARTI MAHENDRU | PAGE 20 
X-Ray Analysis:
TABLE 1: Interplanar distance for lattice calculations of specimen:

2theta Theta Hkl d(A°)

7.4 3.7 002 11.932
21.98 10.99 008 4.03908
29.4 14.7 0010 3.03439
36.94 18.47 0012 2.43049
44.66 22.33 1110 2.02663
60.8 30.4 0020 1.52164
 

The dominant peaks observed have been identified as (pseudo)tetragonal

structure with lattice constants 𝒂 𝒃 𝟒. 𝟎𝟓 𝑨° and 𝒄 𝟐𝟗. 𝟕𝟓𝟒𝟗 𝑨°. The pattern
shows that the sample is c-axis oriented.

However, the sample shows a series of strong peaks at 0010, 008, 0012. The
peaks of the ceramics exhibit a mixed of 2212, 2201 (at 7.4°) and 2223 phase
whereas very small peaks to the other phases of Bi-Sr-Ca-Cu-O are not
significantly observed.

For a representative result of Bi2Sr2CaCu2O8+x peaks of 2θ values have been

used for calculating the crystallite size with FWHM as 3.36922×10-3 radians.
The crystallite size is calculated to be 44.42 nm for Bi-2212.

UV‐VISIBLE SPECTRUM ANALYSIS:  

UV-Visible light is used to analyze electronic transitions and study them as a UV-
Visible light is used to excite valence electrons to empty orbitals within the
sample. Here, we measure the relative change of transmittance of light when it
passes through a solution. Tungsten lamp is used for visible light source and
deuterium for UV.

UV-Visible spectrum of the sample in acetone was taken ranging from 200nm to
900nm (complete UV-Visible range) and was plotted against intensity to analyze
the data. Both absorbance and transmittance data were taken to see the
complementary spectra.

BHARTI MAHENDRU | PAGE 21 
 SYSTRONICS
DOUBLE BEAM UV‐VIS Spectrophotometer : 2212
Absorbance
Name of the Laboratary: Physics Dept. , Gargi College
4.5
Bandwidth: 2.0 nm                                    Sample: Bi‐2212         
4
3.5
3
2.5
ABS (%)

2
1.5  ABS
1
0.5
0
376.4

855.2
552.8

729.2
275.6

401.6

527.6

678.8
200

830

880.4
225.2
250.4

300.8

351.2

426.8
452
477.2
502.4

578

704

754.4

804.8
603.2
628.4
653.6
326

779.6
‐0.5
Wavelength (nm)
Figure 5 Absorbance UV‐Visible Spectra of Bi‐2212 dissolved in acetone solvent. 

  SYSTRONICS
DOUBLE BEAM UV‐VIS Spectrophotometer : 2212
Transmittance
Name of the Laboratary : Physics Dept. , Gargi College
 
120 Bandwidth: 2.0 nm Sample: Bi‐2212
 
100

80
%T

60

40  % T

20

0
376.4

855.2
552.8

729.2
275.6

401.6

527.6

678.8
200

830

880.4
225.2
250.4

300.8

351.2

426.8
452
477.2
502.4

578

704

754.4

804.8
603.2
628.4
653.6
326

779.6

Wavelength (nm)

Figure 4 Transmittance UV‐Visible Spectra of Bi‐2212 dissolved in acetone solvent. 

BHARTI MAHENDRU | PAGE 22 
UV‐Visible Analysis: 
As we see that no peaks are observed in the UV-Visible area (200nm-900nm),
we can say that the sample is conducting in the region. The prominent peak
observed near 200nm is due to machine setup and holds no significance in the
sample reading. One can see that the the band gap is overlapping the aforesaid
region. Also, the absorbance and transmittance graphs compliment each other
very well to confirm that no reflectance is taking place. Even though UV-Visible
spectra are not essential for the superconducting material, it has been done to
understand the underlying techniques of spectroscopy and analysis.

RAMAN SPECTROSCOPY: 
The Raman Spectra was taken to understand the various vibrational modes
present in the synthesized sample. The obtained plot is shown below for
frequency range. The results were compared to various research papers to
confirms the vibrational modes present.

The intense peaks were observed at 117cm-1 (Sr phonon), 291 cm-1 (B1g phonon),
458 cm-1 (OSr phonon), 629 cm-1 (OBi phonon).

T=300K
t10s p50p
11000 t10s p100p
t20s p50p
10000 t30s p50p
9000

8000
Intensity (Counts)

7000

6000

5000

4000

3000

2000

1000

0
100 200 300 400 500 600 700 800 900
-1
Frequency (cm )
Figure 6 Raman Spectra of Synthesized Bi‐2212 

BHARTI MAHENDRU | PAGE 23 
In the graph, “t10s p50p” represents the laser exposure time on the sample as
10 seconds and power of laser (in percentage) is 50. Different data of various
configurations were recorded to find the best quality in terms of intensity and
sharpness of peaks. These data with promising peaks were used to compare
with other research papers for analysis.

 
 

BHARTI MAHENDRU | PAGE 24 
CONCLUSION: 
The Bi-2212/2223 oxide superconducting phase has been synthesized using
solid state reaction method. The XRD pattern indicate that the ceramic was
grown in 2212 phase (majority) and with little impurity of 2223 phase. X-ray
diffraction data shows the ceramic to be c-axis oriented and unit cell to be of
(pseudo)tetragonal shape. Also, the pattern shows the sample to be practically
nearly crystalline of the size of 44.42 nm. The UV-Vis spectra show the sample
to be conducting at room temperature with no band gap present at 300K. While
the Raman Spectra show the various vibrational modes to support the structure
determined via XRD.

BHARTI MAHENDRU | PAGE 25 
APPLICATION AND SCOPE OF THE PRESENT WORK: 
BSSCO was the first High-Tc superconductor (HTS) material to be used for
making superconducting wires. All HTS have an extremely short coherence
length, of the order 1,6nm. This means that the grains in polycrystalline wire
must be extremely good contact – they must be automatically smooth. Further,
because the superconductivity resides substantially only in the copper-oxygen
planes, the grains must be crystallographically aligned. BSSCO is therefore a
good candidate because it’s grains can be aligned either by melting processing
or by mechanical deformation. The double bismuth oxide layer is only weakly
bonded by van der Waal forces, so like graphite or mica, deformation causes
slip on these BiO planes and grains tend to deform into aligned plates. Further,
because BSCCO has n = 1,2 and 3 members these naturally tend to
accommodate low angle grain boundaries so that indeed they remain
automatically smooth. Thus, first generation HTS wires (referred to as 1G) have
been manufactured for many years now by companies such as American
Superconductor Corporation in the USA, Innost in China and Sumitomo in
Japan - though ASC now abandoned BSSCO wire are in favor of 2G wire based
on YBCO. While scientists still face problem for fabrication of 3G based
superconductors.

Typically, precursor powders are packed into a silver tube, which is then
extruded down in diameter. These are then repacked as multiple tubes in a
silver tube and again extruded down in diameter, then drawn down further in
size and rolled into a flat tape. The last step ensures grain alignment. The tapes
are then reacted at high temperature to form dense, crystallographically aligned
Bi-2223 multifilamentary conducting tape suitable for winding cables or coils
for transformers, magnets, motors and generators. Typical tapes of 4 mm width
and 0.2 mm thickness support a current of 200 A at 77 K, giving a critical
current density in the Bi-2223 filaments of 5×105 A/cm2. This rises markedly
with decreasing temperature so that many applications are implemented at 30–
35 K, even though Tc is 108 K.

Substitutional studies in high-Tc superconductors have been found to be of

prime interest from theoretical and experimental point of view. Usually the
substation is made at the Cu site. 3d transition metals substitution is usually
seen in Bi-superconductors. This is because the Bi-system has three related
superconducting phases and it is difficult to prepare a single-phase
superconductor with a consistent Tc. There have been reports that were took
under study during the analysis of sample and reporting this project where
doping was done by Pd, Gd, Fe, La on Bi-2212 superconductor synthesized by
the conventional solid-state reaction and sol-gel methods. There is no good
agreement between the results reported by different groups presumably
because of the different preparation conditions used by different groups.

BHARTI MAHENDRU | PAGE 26 
Composite synthesis of Bi-superconductors along with others have also been
found in various reports.

With proper knowledge of group theory in quantum mechanics and tensors a

complete analysis of Raman data can be done to find the vibrational modes
present in the synthesized sample and is seen to be reported by various reports
available on google scholar but is beyond the scope of this project. SEM is also
usually taken after confirmation of sample that analyses the surface and gives
an insight to the ceramic’s tensile strength, load, etc.

Among the many high-temperature superconductors (HTS), bismuth-based

superconductors are state-of-the-art materials that have been implemented in
components and devices, such as HTS current leads, power cables, motors,
generators, transformers, fault current limiters, and magnets. Few reports now
claim the synthesis of Bi-superconductor based wires from few nanometers up
to 1 km and to analyze its power applications.

BHARTI MAHENDRU | PAGE 27 
REFERENCES AND BIBLIOGRAPHY 
 http://www.superconductors.org/
 Structural and transport properties of rare earth modified Bi Pb 2212
superconductors-
http://shodhganga.inflibnet.ac.in/handle/10603/99544
  STUDY  ON  Bi2Sr2CaCu2O8/CoFe2O4  COMPOSITES  –  Bamdev  Dass,  Dr. 
Prakash Nath Vishwakarma (Guide), NIT Rourkela, May 2012
 http://www.wikipedia.org/ 
 SYNTHESIS  AND  CHARACTERIZATION  OF  SUPERCONDUCTOR 
COMPOSITE  Bi2Sr2Ca1Cu2O8/La0.85Sr0.15MnO3  ‐  SHREELEKHA  MISHRA, 
Dr. Prakash Nath Vishwakarma (Guide), NIT Rourkela, May 2012 
 http://hoffman.physics.harvard.edu/materials/CuprateIntro.php 
 http://hyperphysics.phy‐astr.gsu.edu/hbase/Solids/supcon.html#c1 
 http://ffden‐2.phys.uaf.edu/212_fall2003.web.dir/T.J_Barry/bcstheory.html 
 https://www.britannica.com/science/quantum‐mechanics‐
physics/Applications‐of‐quantum‐mechanics#ref611938 
 Fundamentals of Molecular Spectroscopy – Colin N. Banwell and Elaine M. 
McCash (4th Edition, Indian) 
 https://www.wmi.badw.de/publications/theses/Munnikes_Diplomarbeit_20
08.pdf 

BHARTI MAHENDRU | PAGE 28