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Preparation of Unlead BSCCO Superconductor with Critical Temperature 110K

N.A.Prytkova and Zh.M.Tomilo

Institute of Solid State and Semiconductor Physics, Acad. of Science, Minsk 220072, Belarus.

Abstract-The results of the synthesis and superconducting superconductors at partial substitution of cooper oxide
properties and phase composition investigation of high-Tc commonly employed in the synthesis for copper. The choice
superconductors obtained in the BiSrCaCuO (BSCCO system) of the Bi-1112 composition is governed by the presence of
when partially substituting copper oxide for cooper are excess of calcium and copper, as compared with the
presented. Synthesized under special conditions samples of
concentration in the Bi2Sr2CaCu2Oy stoichiometric
BiSrCa((1-x) CuO+xCu))2Oy with x=(0.2-0.3) revealed
Tc(R=0)=(102-107)K and consisted of the single superconducting compound, resulting in improvement of superconducting
phase Bi2Sr2CaCu2Oy. The other impurity phases were not parameters of the Bi-2212 materials obtained [16-18]. Our
superconductors. experience with high-Tc superconductors also demonstrates
the advantage of using the Bi-1112 compound in synthesizing
the samples with higher values of Tc (=90-92K) by the
technique of quenching from the melt with subsequent
annealing [19]. We have employed this composition
The complexities of BiSrCaCuO phase diagrams as repeatedly in preparing BSCCO coatings on several
evidenced by difficulties associated with preparing substrates [20].
single phase superconducting Bi2Sr2CuOy (Bi-2201),
Bi2Sr2CaCu2Oy (Bi-2212) and Bi2Sr2Ca2Cu3Oy (Bi-2223) II. EXPERIMENTAL
samples with superconducting transition temperatures (10-15)
K, 85K and 110K, respectively, have been reported The samples were prepared from SrCO3, CaCO3 carbonates,
repeatedly [1-7]. Bi2O3, CuO oxides and fine grained copper. The copper oxide
The phase Bi-2212 is thermodynamic stability only. The was substituted for copper in a Bi3+: Sr2+: Ca2+: Cu2+:
phase Bi-2223 have been prepared by lead doped usually Cu=1:1:1:2(1-x):2x cation ratio where x=0.0, 0.1, 0.2, 0.3,
[2,5-7]. The preparation of Pb free Bi-2223 superconductors 0.4. The synthesis was carried out in three steps: the first -
are presented in some papers [1,8,9] using a layer-by-layer short time exposure (1-10 min) at relatively high
electrodeposition technique [8] and optimum reaction temperatures (900-980)0C; the second and third steps
between different precursors [9]. consisted in annealing at temperatures (860±15)0C and
Recently, amongst a great number of works dealing with 8100C, respectively, for from one to several days. Upon
properties of superconducting phases in the BSCCO system completion of each synthesis step the materials were ground
these have appeared some papers communicating a very and pressed into a pellet 1-2 mm in thickness and about 10
interesting experimental fact in our opinion, namely, the mm in diameter. The phase composition was checked by the
synthesis of superconducting phase with the 2212 crystal X-ray diffraction (Co Kα radiation) and microstructural
structure and Tc(R=0) above 100K [10-12]. analysis. The superconducting phases Bi-2212 and Bi-2223
The data obtained are rather difficult to interpret so far, were identified according to the literature data [21, 22]. The
since, first, these have been taken from the samples with superconducting transition temperatures were determined
various atom concentrations and different additives, second, from the resistivity and magnetic measurements. The samples
the like results are few. The role of the copper in the were synthesized in air, the synthesis parameters varied
appearance of high Tc superconductivity has always aroused within the above mentioned temperature and time.
keen interest among the researchers. The copper properties
show a broad variety of chemical states copper atoms in III. RESULTS AND DISCUSSION
compounds even within the same oxidation [13] . Some
researchers explained the experimentally observed Tc First, we shall point out the general tendency for the change
increase to 110-120K in Bi-2212 superconductors doped with of superconducting transition temperature Tc against the
Hg [12] or Ag [14] to the change of copper oxidation state. amount of copper (x) residing in the enhancement of the Tc
Notice, that the doping in these experiments was carried out value by several degrees with x=(0.1-0.3) as opposed to those
by substituting for strontium rather than cooper. The for basic compositions (x=0.0). Further increase in the
maximum value of Tc for oxide superconductors, as observed concentration of copper substituting the copper oxide is
in [15], is to be expected for the copper valence state close to accompanied by the Tc decrease. This is just for all
+2.2. synthesized conditions almost. However, under certain
In this paper we report the results of investigation of phase synthesis conditions some series of samples with x=(0.2-0.3)
composition and superconducting properties of BiSrCaCu2Oy
demonstrate a dramatic rise of Tc values above 100 K. Fig. 1 The phase composition of samples with the
shows the resistivity against temperature with x=0.3 (sample superconducting transition temperature above 100 K was
673) with Tc onset=120 K and Tc zero=107 K synthesized under studied fairly extensively. The X-ray diffraction pattern of
the following conditions: first step - (9000C - 10 min), the the surface of sample 673 (x=0.3, Tc zero=107 K) in the form
second step - (8600C - 24 hrs) and third step - (8100C - 24 of a pellet "0.3 mm thick is presented on Fig.2a.
hrs). Fig. 1 (inset) gives the induction measurement data
indicating that the values of Tc zero, as determined from the
resistive and induction measurements, are equal and reach
107-108 K. Repeated synthesis runs of some series of
samples at partial substitution of cooper oxide were carried
out under the synthesis conditions for sample 673. The Tc
values for samples with x=(0.2-0.3) in each series appeared
to exceed 100 K. By way of example the table lists the values
Tc zero for the sample series 734-738.


Sample 734 735 736 737 738

X 0.0 0.1 0.2 0.3 0.4
Tc zero 75.45 74.4 102.4 77.4 74.4

The temperature dependence of resistivity for sample 736

with x=0.2 and for sample 734 with x=0.0, revealing Tc zero
equal to 102.4 K and 75.45 K, respectively, are also shown in
Fig. 1.
Fig. 2. The surface X-ray patterns of the sample 673 (x=0.3) (a) and the
sample 674 (x=0.0) (b): (• - Bi2Sr2CaCu2Oy [21]; (¬- the "yellow phase"
[23, 24].

The analysis showed that this sample consisted of the small

size grey particles representing the superconducting Bi-2212
phase and equally arranged dark areas representing of pores.
A very small amount of the "yellow phase" is presented at
the surface. For comparison Fig. 2b illustrates the X-ray
diffraction pattern of the sample with x=0.0 synthesized
under the same conditions as sample 673.

The presence of the Bi-2223 superconducting phase in the

samples with Tc zero > 100 K has been elaborately analyzed.
Fig. 3 represents X-ray diffraction pattern of powdered
sample 734 and insert gives fragments of the X-ray
Fig. 1. R(T) curves of BSCCO samples: (•- sample 673 (x=0.3, Tc zero=107 diffraction pattern in the reflection angle range (4-8)0. The
K); x - sample 736 (x=0.02, Tc zero=102.4 K); o - sample 734 (x=0.00, Tc reflection angles (4-8)0, (27-28)0 and (30-31)0 have been used
zero=75.45 K). χ(T) of the sample 673 is shown on insert.
for identification of the Bi-2223 phase [22].
Examination of the phase composition of the BiSrCa((1-
x)CuO+xCu)2Oy system demonstrated predominant From the phase composition analysis performed one may
concentration of the Bi-2212 superconducting phase in suggest that the amount of the Bi-2223 phase in this sample
samples with x=0.0, 0.1, 0.2 and 0.3. Non-superconducting should be small if any, and is obviously, inadequate to cause
compound referring to the Bi-Sr-Ca-O group ("yellow Tc zero=107 K [25]. The lattice parameters as determined by
phase") [23, 24] was noted in the samples as an impurity X-ray diffraction are a≈b=5.396 Å , c=30.735Å for sample
phase, whose amount increase as x rose. Along with the 734 (x=0.0, Tc zero=75.45 K) and a≈b=5.412 Å, c=31.337 Å
"yellow phase" other impurities like CuO for large x values for sample 637 (x=0.3, Tc zero=107 K).
were found in the synthesized samples.
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