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Effect of Mn doping on the specific heat of the high Tc superconductor Y1-xPrxBa2Cu3Oy

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2006 J. Phys.: Conf. Ser. 43 531

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Institute of Physics Publishing Journal of Physics: Conference Series 43 (2006) 531534
doi:10.1088/1742-6596/43/1/131 7th European Conference on Applied Superconductivity

Effect of Mn doping on the specific heat of the high Tc

superconductor Y1-x Prx Ba2Cu3Oy

Ashok Rao1, Radhe Shyam1, Anirban Das1, Rajeev Rawat2, Bhasker

Gahtori3, Vikram Sen3, Neeraj Panwar3, S K Agarwal3
1
Department of Physics, Sikkim Manipal Institute of Technology, Majitar, Rangpo, Sikkim-
737132, India.
2
Inter-University Consortium for DAE Facilities, University Campus, Khandwa Road, Indore-
452017, MP, India.
3
National Physical Laboratory, K.S. Krishnan Marg, New Delhi-1100012, India.

Abstracts: In the present work specific heat measurements have been carried out for the Mn-
substituted compounds Y0.95 Pr 0.05 Ba2 (Cu1-xMnx)3Oy (0 x 2%) using the semi adiabatic
heat pulse method. Resistivity measurements indicate that resistivity increases with Mn
concentration. In the present setup, we could get absolute accuracy in specific heat of about
0.5% for samples of about few hundred mg. The present results show that specific heat jump of
3.8J/mol K, was observed only for pure Y-123 sample. However no jump was observed in
other samples.

1. Introduction:

It is well known that superconductivity is strongly suppressed by the substitution of Pr for Y in

Y1Ba2Cu3Oy . The study of YPrBaCuO has attracted lot of attention and several investigators have
carried out the substitution effects in these high Tc superconductors [1-7]. The YPr system is
isostructural with Y1Ba2Cu3Oy system but the transition temperature decreases monotonically with
increase in Pr concentration. Little attention has been paid on specific heat studies of such system
[8,9]. The behaviour of Y1Ba2Cu3Oy under Cu site doping, on the other hand has also attracted lot of
attention [10-14] which is of prime importance in understanding the mechanism of superconductivity
and to improve the magnetic properties, like flux pinning etc., in order to enhance the applicability of
these materials. In particular Mn doping is important as the transition temperature of Y1Ba2Cu3Oy is
slightly affected by the Mn content [15-16]. In addition to this Mn behaves like Fe or Co [17] in as
much as the occupancy of copper plane site is concerned. However it behaves like Zn or Ni as far as
the retention of orthorhomicity is concerned [18]. Because of structural changes, doping affects not
only the properties associated with the super conducting state of YBaCuO but also properties like
thermal expansion and specific heat [8, 9, 13, 14]. No work seems to have been done on substitution of
Mn for Cu in YPrBaCuO system possibly because of their small solubility.
It was therefore evidently desirable to carry out specific heat measurements in such systems.
This paper reports some preliminary results obtained on the effect Mn content on the specific heat of
Y0.95 Pr 0.05 Ba2 (Cu1-xMnx)3Oy (0 x 2%) in the temperature range 2.2-300 K. All the samples were
prepared using the solid-state reaction technique. Specific heat measurements were carried out using
the semi adiabatic heat pulse method, described elsewhere [19]. For samples of about few hundred mg,
the absolute accuracy of about 0.5% could be obtained.

2006 IOP Publishing Ltd 531

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2. Experimental Techniques:

All the samples were prepared using the well-known solid-state reaction technique. Appropriate
amounts of Y2O3, BaCO3 CuO, Pr6O11 and MnO were thoroughly mixed in an agate mortar and then
calcined at 930C in air for 12 h. The mixing and calcination was repeated three times to improve the
homogeneity. The power was cold pressed into pellets and sintering was at 930C in flowing oxygen
for 72h, this was followed by slow cooling to 450oC and then slowly cooled to room temperature. The
transition temperature determination was done using the standard four-probe technique. The X-ray
diffraction technique was used to determine the atomic spacing of super conducting compounds and to
see if any impurity phases are present. The specific heat of the samples was determined using semi
adiabatic pulse method. In this one passes a small amount of heat to the sample whose specific heat is
to be measured and it kept under adiabatic conditions. The change in temperature is measured and the
ratio of the two gives the heat capacity of the sample. In the present arrangement, vacuum of the order
of 10-6 Torr could be achieved.

3. Results and Discussion:

Figure 1 shows the temperature variation of resistivity for Mn substituted compounds Y0.95 Pr 0.05 Ba2
(Cu1-xMnx)3Oy (0 x 2%). For comparison, the resistivity of pure Y-123 compound is also depicted
in the figure. The normal state resistivity of Y0.95 Pr 0.05 Ba2 Cu3Oy sample is less than that of Y-123
sample. The normal state resistivity of Mn doped compounds increases monotonically with the dopant
concentration. However sample with Mn=0.5% exhibits a departure from this and in fact its resistivity
is closer to the sample with Mn=2%. The possible reason for this is that the transition temperature for
x=0.5% is governed mainly due to the electronic effect when the electron transfer from Mn causes
changes in the nature of excitations of the system by affecting the spectral weight transfer and
chemical potential shift. This effect possibly weakens as x is increased. All the super conducting
samples show a metallic behaviour in the normal state. It is observed that the transition temperature of
Pr-doped samples decreases with Mn concentration. For comparison, resistivity measurements were
also done on pure sample of Y-123. The resistivity of Y-123 sample in the present studies is in good
agreement with that in literature [20]

2 .2

2 .0 P r5 % ,M n 2 %

1 .8
P r 5 % ,M n 0 .5 %

1 .6

1 .4 P r 5 % ,M n 1 %
Resistivity (mohm-cm)

1 .2 P r5 % ,M n 0 .7 5 %

1 .0 Y 1 2 3

P r5 %
0 .8

0 .6

0 .4

0 .2

0 .0
5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0
T e m p e ra tu re (K )

Figure 1 Resistivity as a function of temperature for the series of samples of pure Y-123 and
Mn doped Y0.95 Pr 0.05 Ba2 (Cu1-xMnx)3Oy with different values of x
 533

XRD patterns of all the samples prepared in the present investigations indicate that they were
single-phased. The lattice parameters determined from the XRD patterns show that the samples remain
orthorhombic which is in good agreement with that observed by other investigators [18]. Figure 2
shows the temperature dependent specific heat of Y0.95 Pr 0.05 Ba2 (Cu1-xMnx)3Oy (0 x 2%). For
comparison we have also prepared a pure Y-123 sample and measurements of specific heat were also
carried out for this sample. It is evident from figure 2 that the normal state specific heat increases with
Mn concentration. Specific heat jump was calculated using the method of equal area construction. We
could observe jump in the pure sample. However no jump in specific heat is observed in other samples
within experimental limits. To ensure that the anomaly in specific heat is only due to super conducting
transition and not due to fluctuations, specific heat measurements on the pure sample of Y-123 were
carried out thrice and we could observe jump in all the cases. In figure 3, the data are presented in a
way to enlarge the anomaly at Tc.

0 .6 5

0 .6 0
P r 5 % M n 0 .7 5 %
0 .5 5
P r 5 % M n 1 .0 0 %
0 .5 0 P r 5 % M n 0 .0 0 %
0 .4 5 Y 123
0 .4 0
C (J/gm K)

0 .3 5

0 .3 0
p

0 .2 5

0 .2 0

0 .1 5

0 .1 0

0 .0 5

0 .0 0
0 50 100 150 200 250
T e m p e ra tu re (K )

Figure 2 Specific heat behaviour as a function of temperature for Y-123 and Mn doped samples of
Y0.95 Pr 0.05 Ba2 (Cu1-xMnx)3Oy with x=0,0.75 and 1%

0 .2 4
P r 5% M n 0.75%
P r 5% M n 1.00%
0 .2 2 P r 5% M n 0.00%
Y 12 3
Cp(J/gm K)

0 .2 0

0 .1 8

0 .1 6

0 .1 4

70 80 90 100
T em perature (K )

Figure 3 Specific heat behaviour of Y-123 and Mn doped samples of Y0.95 Pr 0.05 Ba2 (Cu1-xMnx)3Oy
with x=0, 0.75 and 1% in the vicinity of Tc
534

We could observe a jump in specific heat only in the pure Y-123 sample of 3.8J/mol K, which is in
good agreement with those reported in literature [21]. The anomalies observed are not like the
traditional BCS superconductors; in fact we observed a broadening in the specific heat, which is
essentially because of the broad transitions observed in high temperature superconductors. Similar
broadening is also observed in thermal expansion of high temperature superconductors [13,14].

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