Materials Chemistry and Physics 193 (2017) 496e500

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Improving superconducting properties of YBCO high temperature

superconductor by Graphene Oxide doping
S. Dadras*, S. Dehghani, M. Davoudiniya, S. Falahati
Department of Physics, Alzahra University, Tehran, 1993893973, Iran

h i g h l i g h t s

Graphene Oxide doping increased the YBCO critical current density.

Graphene Oxide creates a better connection between the YBCO grains.

The normal resistivity of samples were decreased by GO doping to YBCO compounds.

Graphene Oxide doping has a positive effect on the critical transition temperature.

a r t i c l e i n f o a b s t r a c t

Article history: In this research, we report the synthesis and characterization of YBa2Cu3O7-d (YBCO) high temperature
Received 3 January 2017 superconductor prepared by sol-gel method and doped with Graphene Oxide (GO) in different weight
Received in revised form percentages, 0, 0.1, 0.7 and 1 % wt. The x-ray diffraction (XRD) analysis confirms the formation of
15 February 2017
orthorhombic phase of superconductivity for all the prepared samples. We found that GO doping reduces
Accepted 1 March 2017
Available online 2 March 2017
the crystalline size of the samples. We evaluated the effects of GO doping on the normal state resistivity
(r), superconducting transition temperature (Tc) and critical current density (Jc). The results show that
the GO doping has a positive effect on these properties. Also, the highest Jc is obtained for the 0.7 %wt GO
Keywords:
High temperature superconductor
doped YBCO compound that its critical current density is about 15 times more than the Jc of pure one in
Graphene Oxide 0.4 T magnetic field. The scanning electron microscope (SEM) analysis shows that there are better
YBCO connections between the grains of GO doped samples.
Critical current density © 2017 Elsevier B.V. All rights reserved.
Transition temperature

1. Introduction
Graphene oxide is known as a satisfactory candidate material for
the next generation of electronics [1,2], optoelectronics [3], energy
conversion and storage technologies [4e7]. As the discovery of
Graphene (G) [8e10], many efforts have been focused on GO [11,12].
GO can be visualized as individual sheets of Graphene decorated
with oxygen functional groups on both basal planes and edges. The
presence of oxygen makes GO capable to do more chemical activ-
ities. Nevertheless, it disturbs the extended sp2 network of the
Graphene hexagonal lattice.
The effects of different nanostructures doping in MgB2 were
investigated and also it is reported that doping G and GO to MgB2
superconductor creates additional flux pinning energy and thus
* Corresponding author.
E-mail address: dadras@alzahra.ac.ir (S. Dadras).
increases the critical current density [13e15]. Since the discovery of
superconductivity in YBCO at 93 K (Tc) [16], a lot of attempts has
been made to enhance its superconducting properties. YBCO high
temperature superconductor is a kind of ceramic superconductor
which is very considerable because of its numerous applications
[17e19]. It is a layered cuprate with short coherence length. So, the
supercurrent couldn’t pass easily through the grain boundary [20].
It has reported that nanostructure materials and carbon base
compounds doping in high temperature superconductor create
high Jc at high magnetic fields [21,22]. Impurity phases and defects
present at grain boundaries can act as a weak-link [23]. Also,
nanoparticles as a dopant in high temperature superconductors
behave as flux pinning centers. They localize between grains and
increase the grains boundary connections. Therefore, nanoparticles
doping increases the pinning energy Uj and critical current density
Jc in compounds [21,22].
In this paper, we are investigating the influences of GO doping
on the properties of YBCO high temperature superconductor.

http://dx.doi.org/10.1016/j.matchemphys.2017.03.003
0254-0584/© 2017 Elsevier B.V. All rights reserved.
 S. Dadras et al. / Materials Chemistry and Physics 193 (2017) 496e500
2. Materials and methods
We used sol-gel method to synthesize the YBCO samples. First,
0.5 M solutions of Y(NO3)3$6H2O, Ba(NO3)2 and Cu(NO3)2$3H2O
were separately prepared and then the solutions were mixed
together. A light blue solution was obtained and the pH was raised
to 7 by addition of Ethylenediamine to the mixture as a complexing
agent. By heating the solution at 85  C, the water removed from the
solution and a violet gel was created. Since the firing process occurs
in the 520  C, we heated the samples in this temperature for 2 h. In
this time, the brown NO2 gasses were released and a black powder
was produced. Then the powder was calcined at 900  C. We added
GO with different weight percentages to the YBCO powder and
mixed well to prepare samples of 0% wt, 0.1 wt%, 0.7 wt% and 1 wt%
GO doped YBCO. The powder samples were pressed into circular
pellets and sintered at 930  C for 19 h by Oxygen flow, cooled down
to 630  C, and kept in this temperature for 2 h [24].
3. Results and discussions
The YBCO samples were analyzed by XRD pattern to indicate
phase match and the data were analyzed by X’Pert High Score
software. Fig. 1 shows the XRD spectrum of GO powder used in our
samples. Based on Debby-Scherrer equation, the crystalline size of
the GO added in YBCO compounds is about 40 nm that is calculated
and the main peak at 2q ¼ 12.85 .The XRD patterns of all YBCO
samples are shown in Fig. 2. The orthorhombic structure is main-
tained to have the highest peak at 2q ¼ 38.3 with (103) planes for
all the samples. In addition, there are other reflections of ortho-
rhombic phase at (003), (112), (104), (113), (200), (220), (123), and
(130). The lattice parameters computed by MAUD software are
a ¼ 3.8364 Å, b ¼ 3.8873 Å, and c ¼ 11.6719 Å. Furthermore, the
peak at 2q ¼ 26.53 can also indicate Reduced Graphene Oxide
(RGO). The crystalline size of the samples was calculated by using of
Debby-Scherrer equation. These values for all the prepared samples
are tabulated at Table 1. It is clearly observed a decreasing trend in
the values of crystalline size with addition of GO in YBCO
compound.
We cut the samples to rectangular form and attached copper
wires on them. We measured the electrical resistivity versus tem-
perature (reT) through four-probe method to find the values of
critical temperature (Tc). Fig. 3 shows the resistivity versus
Fig. 1. XRD pattern of the GO used as a dopant in our research.
497
temperature of the pure and GO doped YBCO samples. It demon-
strates that all of the samples (above the transition temperature
onset (Tcon)) have a linear metallic behavior in the normal state. We
found that the samples’ normal resistivity reduces by adding GO to
the YBCO compound. Furthermore, it is observed that the transition
width DT of the doped samples is less than the pure one that in-
dicates positive effect of GO doping in the compounds. Table 1 also
shows calculated values of critical transition temperatures (Tcon,
Tcmid, Tcoff), transition width DT and normal resistivity of the pure
and doped samples. Also, we found that the values of Tc increases
by GO doping. It seems that in the sintering process; the oxygen in
the functional groups of GO is removed from it and entered in the
CuO chains in the YBCO structure, and caused to increase the
transition temperature. It is reported that the values of oxygen
content would have a severe influence on the superconducting
properties such as the critical temperature [25]. The values of the
oxygen that is measured by iodometry are shown in the Table 1.
Iodometry, also known as iodometric titration, is a method of
volumetric chemical analysis to find the values of the oxygen in the
compound [26]. As it is clear, there is a good agreement between
the values of oxygen and the increasing trend of temperature
transition in the compounds.
To measure the currentevoltages (IeV) values of the samples,
we used a four probe setup in the 0.4 T magnetic fields at a tem-
perature of 77 K. By E ¼ V/d and J ¼ I/A equations, we calculated the
electrical field versus current density (EeJ) curve, where d and A
are the length and surface area of the samples. Fig. 4 shows the EeJ
diagram in 0.4 T magnetic field for pure and GO doped samples. It is
obvious that adding GO in the YBCO compound, increases the value
of critical current density. According to the models of J dependence
of the Uj, a logarithmic barrier has been proposed by Zeldov et al.
for high temperature superconductors [27,28]. Our data are actually
stable with this model for all samples, which implies a potential
logarithmic barrier for the flux pinning as follow:
 
J
Ueff ðT; H; JÞ ¼ Uj ðT; HÞLn C (1)
J
where Uj is the characteristic pinning potential energy in the con-
stant current density [29]. We obtained the relation between E and
J as in Eq. (3) by substitution of Ueff from the model in Ref. [27] into
Eq. (2)
 
Ueff
E ¼ E0 exp  (2)
KB T
  
Uj J
E ¼ E0 exp  Ln C (3)
KB T J
Logarithm of this equation is
 
Uj Uj
LnðEÞ ¼ LnðE0 Þ  LnJC þ LnJ (4)
KB T KB T
So, by the slope of Ln E versus Ln J curves we can compute the Uj.
The inset of Fig. 4 shows the linear behavior of Ln E versus Ln J for all
the samples in 0.4 T magnetic field. The Jc values increase with
addition of GO to the YBCO compounds in a constant magnetic field.
The 0.7%wt GO doped sample shows the highest Jc value. We ob-
tained Uj and Jc values, by considering Zeldov model and fitting the
curves with Eq. (3). The values of Jc and Uj for all the samples in 0.4 T
magnetic field are tabulated at Table 2. Fig. 5 shows the Jc versus the
GO doping in 0.4 T magnetic field for all the samples at 77 K. Since
the values of Uj and Jc for all the doped samples are increased with
respect to the pure one, we can conclude that GO doping has caused
498 S. Dadras et al. / Materials Chemistry and Physics 193 (2017) 496e500

Fig. 2. XRD patterns of pure and GO doped YBCO compounds.

Table 1
Values of Crystalline size, transition temperatures, Transition width, normal resistivity and calculated Values of oxygen through iodometry for pure and GO doped YBCO
samples.

sample Pure 0.1%wt 0.7%wt 1%wt

YBCO GO doped GO doped GO doped

crystalline size (nm) 83 62 42 20

Ton
c (K) 93 99 101 102
Tmid
c (K) 87 94 96 97
Toff
c (K) 82 89 92 92
DT(K) 5.5 5 4.5 5
Normal resistivity (in 200 K) 4211 1688 2057 1542
calculated Values of oxygen through idometery 6.62 6.60 6.93 6.69

vortices to be pinned and has increased the Jc values.

Fig. 6 shows the SEM images of pure and 0.7%wt GO doped YBCO
samples that has the higher Jc value in the prepared samples. It
seems that GO doping created more homogeneity and better
connection among the superconducting grains, and the porosity
between them is reduced. It could be a reason for increasing Jc in
the GO doped samples. Also, it is possible that in sintering process
in temperatures more than 650  C, the oxygens in the functional
groups of GO is removed into RGO [30]. So they are acting as con-
ductors and they can improve the grains boundary connections of
YBCO compound and transmit the electrical current easily [31]. We
can conclude that, GO is changed to RGO which it is a good
conductor and it is possible that removed oxygens enter to CuO
chains and cause increasing the transition temperature [25].

4. Conclusions

Overall, we have investigated the effects of GO doping on the

properties of YBCO high temperature superconductor. Through
XRD and SEM analysis, we found that the structure of all the
Fig. 3. Resistivity vs temperature of the pure and doped YBCO samples. samples has the Y-123 orthorhombic phase. The results of r(T)
 S. Dadras et al. / Materials Chemistry and Physics 193 (2017) 496e500 499

Fig. 4. Electrical field versus current density for pure and GO doped YBCO samples. in 0.4 T magnetic field. The inset shows the EeJ curve in logarithmic scale.

Table 2
Values of Ujand Jc in 0.4 T magnetic field for all the samples at 77 K.

sample Pure 0.1%wt 0.7%wt 1%wt

YBCO GO doped GO doped GO doped

Uj (mev) 4.96 6.79 9.35 6.31

Jc (A/cm2) 0.44 3.88 6.75 1.86

measurements show that GO has acted in an effective manner and

increased the critical transition temperature. It also showed that
Fig. 6. SEM images of (a) pure and (b) 0.7 wt% GO doped YBCO samples.

the normal resistivity of GO doped samples were decreased by

doping GO to YBCO compounds. Besides, the GO doped YBCO
samples display higher Jc values, compared to the pure sample. So
an enhancement can be beneficial in both Tc and Jc of GO doped
YBCO compounds for the practical applications of these high tem-
perature superconducting materials.

Acknowledgment

The authors would like to acknowledge the financial support by

Alzahra University.

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Fig. 5. The critical current density versus GO doping in 0.4 T magnetic field for all the
samples at 77 K.
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