Trial of the Synthesis of Superconducting Bulk Samples of T-La2-yYyCuO4
Azhar Isti Hanifah (B6TJ1037)
Academic Advisor : Prof. Yoji Koike (Koike Lab)
Dept. of Electrical, Information and Physics Engineering, School of Engineering, Tohoku University
Introduction
Superconductivity appears through hole and electron doping into
insulating mother compounds Ln2CuO4 (Ln: lanthanide element) with the
K2NiF4-type (so-called T-type) and Nd2CuO4 type (so called T-type)
structures, respectively. In adequately reduced thin films of T-Nd2-
xCexCuO4, however, it has been reported that superconductivity appears
in a wide range of x and even in the undoped mother compound of x = 0
[1]. Moreover, Takamatsu et al. have succeeded in synthesizing undoped
and hole-doped bulk samples of T-La1.8-xEu0.2MxCuO4 (M = Sr, Ca; x =
0, 0.05, 0.10) by the low-temperature synthesis method [2,3]. These
surprising results suggest a new phase diagram of superconductivity and
attract great interest on the mechanism of emerging superconductivity in
T-Ln2CuO4.
The hole and electron doping are usually achieved by the partial
substitution of Sr2+ and Ce4+ for Ln3+, respectively. In the T-
La1.8Eu0.2CuO4 (T-LECO) system, however, it has been known that Ce
cannot be substituted for La because of the production of a stable second
phase of T-Eu2-xCexCuO4. Therefore, in order to investigate both hole
and electron doping dependences of the superconductivity around x = 0
using the same T-Ln2CuO4 system, I have chosen T-La2-x-yYyMxCuO4
(M = Sr, Ce), in which Y is used instead of Eu. In the present work,
accordingly, I have tried to prepare superconducting bulk samples of the
undoped mother compound of T-La2-yYyCuO4 (T-LYCO).
Experiment
First, samples of -LYCO with y = 0.05, 0.10, 0.15 were prepared
by the conventional solid-state reaction method as follows. The raw
materials were mixed using a ball mill and prefired in O2 flow at 800 C
for 24 h. Then, the prefired product was sintered in O2 at 1050 oC for 24h.
Next, the samples of T-LYCO were mixed with reductant CaH2 in
a molar ratio of T-LYCO : CaH2 = 1 : 2 in an argon-filled glove box. Then,
the mixtures were sealed in an evacuated Pyrex tube, heated at 275 oC for
24 h, and washed with saturated NH4Cl in anhydrous ethanol. So that
samples of La2-yYyCuO3.5 with the Nd4Cu2O7-type (so-called N-type)
structure were prepared. Then, the obtained samples of N-La2-yYyCuO3.5
were oxidized on various conditions to obtain samples of T-LYCO. Since
the obtained samples of T-LYCO included excess oxygen, they were
reduced on various conditions to remove the excess oxygen. All the
samples were characterized by the powder x-ray diffraction (XRD)
analysis at room temperature. Magnetic susceptibility measurements
were carried out using a superconducting quantum interference device
(SQUID) magnetometer.
Results and Discussion
From the XRD analysis, it has been found that single-phase
samples of T-LYCO with y = 0.05 and 0.10 are obtained by the
conventional solid-state reaction method, while there remains a small
amount of Y2O3 for y = 0.15. After the reduction using CaH2, it has been
found that single-phase samples of N-La2-yYyCuO3.5 with y = 0.05 are
obtained, while there remains a small amount of Y2O3 for y = 0.10 and
0.15. By the oxidation at 200 - 400 oC, it has been found that samples of
T-LYCO are obtained. After the reduction annealing at various
temperatures in vacuum for 24 h for the removal of excess oxygen, it has
been found that single-phase samples of T-LYCO are obtained only by
the reduction annealing at 500 oC and 550 oC. For y = 0.05, both T-LYCO
and a small amount of La2O3 have been found to appear together
with T-LYCO by the reduction annealing above 600 oC. This may be due
to the decomposition on the surface of crystalline grains. For y = 0.10 and
0.15, T-LYCO has been found to be broken by the reduction annealing
above 650 oC, indicating that the T-type structure is unstable at high
temperatures on account of the removal of indispensable oxygen by the
strong reduction. Accordingly, it has been concluded that single-phase
samples of T-LYCO are obtained only by the reduction annealing below
600 oC. This is consistent with the former report [4], where it has been
described that T-La2CuO4 is stable only below 600 oC.
The magnetic susceptibility measurements have revealed that
no superconductivity appears in any reduced samples. It is known that
undoped superconductivity is observed in samples with little excess
oxygen whose c-axis length is not too large. Figure 1 shows the
reduction-annealing-temperature dependence of the c-axis length for
reduced samples of T-LYCO (y = 0.05, 0.10, 0.15) together with that of
superconducting T-La1.8Eu0.2CuO4. It is found that the c-axis length in
T-LYCO is longer than that in T-LECO, suggesting that there remains
excess oxygen yet in T-LYCO and that the excess oxygen suppresses the
appearance of superconductivity. Accordingly, it is concluded that the
conditions of the oxidation and reduction process should be optimized for
the appearance of superconductivity.
12,56
T'-La2-yYyCuO4
12,54
12,52
c-axis ()
12,50
y = 0.05
12,48
y = 0.10
y = 0.15
La1.8Eu0.2CuO4
12,46
500 550 600
o
Reduction-annealing-temperature ( C)
Figure 1. Reduction-annealing-temperature dependence of the c-axis
length in samples of T-La2-yYyCuO4 (y = 0.05, 0.10, 0.15), which were
obtained after the oxidation at 300 oC for 12 h and the succeeding
reduction. The data of T-La1.8Eu0.2CuO4 are also plotted for reference.
Conclusions
I have succeeded in obtaining bulk samples of T-LYCO by the
low-temperature synthesis method, namely, the oxidation at 300 oC for
12 h and the succeeding reduction annealing at a temperature as low as
500 oC and 550 oC in vacuum for 24 h. However, no superconductivity
could be observed. The forthcoming issue is to optimize both conditions
of the oxidation and reduction processes for the appearance of
superconductivity.
References
[1] O. Matsumoto et al., Physica C 469, 924 (2009).
[2] T. Takamatsu et al., Appl. Phys. Express 5, 073101 (2012).
[3] T. Takamatsu et al., Phys. Procedia 58, 46 (2014).
[4] F. C. Chou et al.,Phys. Rev. B 42 6172 (1990).