Fabrication of YBa2Cu3O7-x thin films and

Analysis.

Goutam Debnath
ICFAI University, Tripura.
ID: 18IUT0050014

Guide: Prof. K. Maiti

Department of Condensed Matter Physics & Materials Science
Tata Institute of Fundamental Research, Mumbai.
 ACKNOWLEDGEMENT

First of all, I would like to extend my sincere gratitude and thanks to Dr. Ganesh Adhikary
for helping to get the project position at TIFR and Dr. Priyankshu Rana Borthakur,
Coordinator, F.S.T, ICFAI University, Tripura for showing keen interest in students
internship program and motivating in every possible way.

It was my greatest privilege in having the opportunity for doing my summer internship under
the supervision of Dr. K. Maiti, Dean, Natural Science Faculty, TIFR.
I express my thanks to him for his continuous guidance and helping out in all possible way
during this internship.

I also express my thanks to Dr. Abhishek Singh, post-Doctoral, dept. of condensed matter
physics and material science, Dr. Anup, Ram, Arindam, Sawani for guiding me in the
experiments and in different analytical methods involved in it.

Goutam Debnath
18IUT0050014
B.Sc. Physics 4th semester.
Faculty of Science and Technology.
ICFAI University, Tripura.
 List of contents

1. Introduction.
1.1 Superconductivity.
1.2 Crystal structure of YBCO and its superconducting nature.
2. Sample preparation technique.
3. Characterization.
4. Results and discussion.
5. Conclusion.
6. Reference.
 1.
INTRODUCTION
1.1 Superconductivity.
Superconductivity was first discovered by Heike Kamerlingh Onnes, who was studying the
resistance of nearly pure mercury at low temperature. He observed that when the solid mercury
was cooled below a certain temperature near liquid helium, its resistance abruptly vanishes out.

Onnes also showed that other elementals materials such as Al, Sn, Pb along with Hg goes through
a phase transition where the resistance of the materials gets zero, when cooled below a particular
temperature known as TC (critical or superconducting transition temperature).

Till 1980s many elements and complexes were found which show superconducting transition
however, the transition temperature was well below the liquid nitrogen temperature. In 1986, J. G.
Bednorz and K. A. Muller discovered the first high TC superconducting material comprising La,
Ba, Cu, O. After a while, M. K. Wu found another superconducting material by replacing La with
Y, making YBa2Cu3O7 (YBCO) of TC = 92 K, which was economically important because the
cheap and easily available liquid nitrogen could also be used as a refrigerant (at atmospheric
pressure, the boiling point of liquid nitrogen is 77 K).

1.2 Crystal structure of YBCO and its superconducting nature.

Crystallographers defined the structure of YBCO as of perovskite type in which the CuO2 planes
are lying perpendicularly to the crystallographic c-axis. This is a common feature of these
materials; hence they are called cuprates. YBa2Cu3O7-x (YBCO) is the most well-known high
temperature superconductor, sometimes called the 1-2-3 compound. The lattice structure is an
orthorhombic with lattice parameters, a = 3.82 Å, b = 3.89 Å and c = 11.68 Å. It has always been
observed that the fabricated YBCO usually has oxygen deficiency, therefore it is always referred
as in the form YBa2Cu3O7-x (0<x<1). When x is 0 or very small, it is ortho-rhombic and
superconducting whereas in case of x =1 it adopts tetragonal crystal structure and doesn’t
superconducting transition down to 2 K sample temperature.

Similar to other high TC cuprate superconductors, YBCO also belongs to the type-II
superconductors as it shows two magnetic transitions which are characterized by their ability to
maintain its superconductivity at high magnetic fields.
 2.
SAMPLE PREPARATION TECHNIQUE
Pulsed Laser Deposition (PLD).
A thin film of YBCO is fabricated on a SrTiO3 (usually abbreviated as STO) substrate using PLD
technique. Choosing of substrate depends on the matching of physical and chemical parameters of
the substrate with the deposited compound (YBCO). SrTiO3 is one of the most widely used
substrates for growing high TC superconducting thin films. It possesses a perovskite structure and
a good lattice match with YBCO. Good thermal conduction and lattice match are important since
stress and strain will arise from the thermal mismatch between the substrate and grown materials.
Since the unit cell edge parameters of SrTiO3 (a = 3.905 Å, b = 3.905 Å, c = 3.905 Å, α = 90°, β
= 90°, γ = 90°) matches with the edge parameters of YBa2Cu3O7-x (a = 3.820 Å, b = 3.875 Å, c =
11.700 Å, α = 90°, β = 90°, γ = 90°) leading to lower induced strain in the film, the STO substrate
was chosen for epitaxial growth of YBCO thin films.

Fig. 1.: PLD system used for YBCO film deposition on STO (left).
Schematic diagram of PLD deposition (right).
PLD is a physical vapor deposition technique where a high-powered laser beam (here KrF excimer
laser is used which has a wavelength peak of about 248 nm) is focused on a target material which
is to be deposited (YBCO) on an atomically clean substrate inside an evacuated or filled with
desired gas chamber. The process is divided into three steps;
1. Laser absorption on the target surface and formation of the plasma: The electronic
excitation of the molecules by the energy from the laser results into evaporation and
plasma formation.
 2. Dynamic of the plasma: The excited state charged particles coming out from the target
material also known as plasma, expands in the surrounding medium known as plasma
plume.
3. Deposition of the ablated material on the substrate: This step determines the quality of the
film growth. The highly energized particles ejected from the target bombards the substrate.
The species from the target form a collision region, which serves as a source for
condensation of particles. High condensation rate leads to the thermal equilibrium and the
growth of the film.

The whole process is worked under the presence of oxygen gas in the evacuated chamber to
encounter the oxygen deficiency during fabrication of YBCO in order to get the superconducting
YBCO thin film (fully oxygenated YBa2Cu3O7)
 3.
CHARACTERIZATION
In order to confirm the phase of fabricated thin films, we have performed X-ray diffraction (XRD).
Scanning electron microscopy (SEM) and Energy dispersive analysis of X-ray spectroscopy
(EDAX) have been utilized to analyze the morphology and elemental composition of the surface
or thin film deposited on the substrate surface.

3.1 X-ray Diffraction (XRD):

This technique mainly focuses on the determination of the atomic arrangement inside a crystal.
When x-ray beam falls on the crystalline structure, it scatters the incident x-ray into different
directions. However, due to certain repetitive arrangement of atoms in crystalline solid, the
scattering intensity in different directions varies with the scattering angle 2𝜃. The technique is
governed by the Bragg’s law (2𝑑 sin 𝜃 = 𝑛𝜆) which is based upon the constructive interference
of the diffracted x-rays from the crystal planes. Whenever there is constructive interference, we
get a peak in XRD spectrum which is basically variation of measured intensity vs. 2𝜃. If we index
the peaks obtained in intensity vs. 2𝜃 with miller indices, it will give the information about the
arrangement of the atoms in different planes in the crystal.

Fig 2.: Schematic diagram of x-ray diffraction from a solid formed by periodic arrangement
atoms at fixed distance (Bragg’s law).
3.2 Scanning Electron Microscopy (SEM):
This technique is based on the measurement of amplified electronic signals generated by the
emission of secondary electrons from the surface atoms when the electrons from a source are
bombarded on the sample surface, displaying digital image signals depending on the angles and
intensities of the secondary electron emission detected by an electron detector.

Fig. 3.: Schematic diagram of SEM.

3.3 Energy Dispersive X-ray Spectroscopy (EDAX):

This analytical technique is used to find the elemental composition inside a compound. In
this technique, a photon detector detects x-rays emitted from the sample during bombardment by
an electron beam to characterize the elemental composition of the analyzed volume. This technique
basically involves an interaction of highly energized electron from an electron source and the
electrons tightly bounded with positively charge nucleus of atoms in the solid which leads to
stimulating excitation of electrons of the sample atoms to the vacuum level. Removing these
electrons from the system will leave behind a hole that a higher energy electron can fill in.
Transition of higher-level electrons to the hole state relaxes the system by producing a photon of
energy exactly equal to the binding energy difference between two levels. The EDAX
measurement involves the detection of characteristic x-ray produced from the sample as shown in
Fig. 4. The energy of the photon released during this relaxation process is unique to each element
in the periodic table.

Fig 4.: All possible outcomes of scattering of highly energized beam of electron from a solid.

3.4 Sample Preparation:

To grow epitaxial film, we have different conditions for different samples which is given below:

1st preparation:
Laser energy: 510 mJ Laser energy density: 25 mJ/cm2 Laser Shots: 45000
Step 1. First, we have evacuated the chamber down to 10-6 mbar and heated the substrate up to
800 °C in 1 hour from room temperature and maintained the same temperature for 2-hours 30
mins for thermal equilibrium.
Step 2. Reducing the temperature from 800 °C to 750 °C in 30 mins.
Step 3. Deposition occurs at this temperature for 3 hours in O2 environment of 0.3 mbar pressure.
Step 4. Reducing the temperature of the chamber from 750 °C to 550 °C at the rate of 15 °C/hr.
Step 5. Keeping the substrate at 550 °C for 1 hour (0.5 mbar pressure), it is then cooled to room
temperature at the rate of 20 °C/min.
2nd preparation:
Laser energy: 540 mJ Laser energy density: 25 mJ/cm2 Shots: 15000
Step 1. First, we have evacuated the chamber down to 10-6 mbar and heated the substrate up to
800 °C in 1 hour and maintained the same temperature for 2-hour 30 mins.
Step 2. Deposition occurs at this temperature for an about 71 mins at O2 pressure of 0.26 mbar
and then kept the substrate as it is for 2 hrs and 30 mins.
Step 3. Reducing the temperature from 200 °C to room temperature at the rate of 12 °C/min.

3rd preparation:
Laser energy: 275 mJ Laser energy density: 1.64 mJ/cm 2 Shots: 5000
Step 1. First, we have evacuated the chamber down to 10-6 mbar then heating of the substrate has
been done up to 750 °C for 2 hours.
Step 2. Deposition occurs at this temperature for 18 mins with O2 pressure 0.3 mbar and then
kept the system for 1 hour at O2 pressure of 0.5 mbar.
Step 3. Reducing the temperature to 40 °C at the rate of 5 °C/min.
 4.
RESULTS AND DISCUSSION

Fig. 5: XRD peaks of 1st,2nd,3rd and pure sample.

The above graphs are the XRD patterns showing variation of intensity vs. 2𝜃 for different samples.
Peaks result due to the constructive interference of the x-rays diffracting from any crystal plane of
the sample. It is clear from the XRD spectra of as prepared samples (1st, 2nd and 3rd) that the as
prepared samples are not epitaxial one and have polycrystalline nature as there are many intense
peaks which are multiple of any other peak.
We have also shown the XRD pattern of YBa2Cu3O6.9 sample (which is target) as a reference.
When we compared the XRD spectra of the three samples with the reference spectrum, we found
that 2nd sample is fabricated quite well because the XRD pattern of this sample is very similar to
the reference sample. In 3rd preparation, we got peaks which correspond to only STO, since we
have used only 5000 shots so low thickness of film might be a possible reason that thickness of
film is too low for diffraction.

The red marked indices shown in thin film XRD spectra are the peaks of STO which is present
because of the x-rays penetration to the STO substrate and causing strong x-ray reflection from
STO atom planes instead of thin film plane.

Fig. 6.: SEM images of 1st preparation.

Fig. 7.: SEM images of 2nd preparation.

In Fig. 6 and 7, we are showing SEM image of 1st and 2nd preparation giving information about
the surface morphology of the deposited films. It is clear from these figures that the large size
particulates have been found in 1st prep which was absent in 2nd prep. In 2nd preparation image it
is quite clear that the film is homogeneous.

Table 1: EDAX data of 1st preparation.

Table 2.: EDAX data of 2nd preparation.

It is clear from the EDAX data collected on three samples that all of the element Y, Ba, Cu and O
are present in the prepared thin film. Due to very thin layer of deposited layers, signals of Sr and
Ti have also been found, which originate due to the substrate.
 5.
CONCLUSIONS
Thin films of high temperature superconducting compound, YBCO, are fabricated on the
atomically clean STO substrate using pulsed laser deposition technique. The detail analysis of
XRD spectra measured on thin films, shows that YBCO is being deposited and it is in
polycrystalline form. The SEM images show the polycrystalline nature of the sample where
different crystals are arranged with grain boundaries separating them. The EDX data also confirms
the chemical composition of deposited YBCO. Further studies such as magnetic and resistive
measurements as a function of temperature of these samples, are required to find the
superconducting transition temperature of these samples.
 6.
REFERENCE

1. Pulsed Laser Deposition of Thin Films, edited by Douglas B. Chrisey and Graham K.
Hubler, John Wiley & Sons, 1994 ISBN 0-471-59218-8
2. FABRICATION OF YBCO THIN FILMS BY PULSED LASER DEPOSITION
TECHNIQUE AND THEIR CHARACTERISATION thesis; Şerife TOZAN
3. Joseph Goldstein (2003). Scanning Electron Microscopy and X-Ray Microanalysis.
Springer. ISBN 978-0-306-47292-3. Retrieved 26 May 2012.