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
properties and phase composition investigation of high-Tc
superconductors obtained in the BiSrCaCuO (BSCCO system)
when partially substituting copper oxide for cooper are
presented. Synthesized under special conditions samples of
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
phase Bi2Sr2CaCu2Oy. The other impurity phases were not
superconductors.
I. INTRODUCTION
The complexities of BiSrCaCuO phase diagrams as
evidenced by difficulties associated with preparing
single phase superconducting Bi2Sr2CuOy (Bi-2201),
Bi2Sr2CaCu2Oy (Bi-2212) and Bi2Sr2Ca2Cu3Oy (Bi-2223)
samples with superconducting transition temperatures (10-15)
K, 85K and 110K, respectively, have been reported
repeatedly [1-7].
The phase Bi-2212 is thermodynamic stability only. The
phase Bi-2223 have been prepared by lead doped usually
[2,5-7]. The preparation of Pb free Bi-2223 superconductors
are presented in some papers [1,8,9] using a layer-by-layer
electrodeposition technique [8] and optimum reaction
between different precursors [9].
Recently, amongst a great number of works dealing with
properties of superconducting phases in the BSCCO system
these have appeared some papers communicating a very
interesting experimental fact in our opinion, namely, the
synthesis of superconducting phase with the 2212 crystal
structure and Tc(R=0) above 100K [10-12].
The data obtained are rather difficult to interpret so far,
since, first, these have been taken from the samples with
various atom concentrations and different additives, second,
the like results are few. The role of the copper in the
appearance of high Tc superconductivity has always aroused
keen interest among the researchers. The copper properties
show a broad variety of chemical states copper atoms in
compounds even within the same oxidation [13] . Some
researchers explained the experimentally observed Tc
increase to 110-120K in Bi-2212 superconductors doped with
Hg [12] or Ag [14] to the change of copper oxidation state.
Notice, that the doping in these experiments was carried out
by substituting for strontium rather than cooper. The
maximum value of Tc for oxide superconductors, as observed
in [15], is to be expected for the copper valence state close to
+2.2.
In this paper we report the results of investigation of phase
composition and superconducting properties of BiSrCaCu2Oy
superconductors at partial substitution of cooper oxide
commonly employed in the synthesis for copper. The choice
of the Bi-1112 composition is governed by the presence of
excess of calcium and copper, as compared with the
concentration in the Bi2Sr2CaCu2Oy stoichiometric
compound, resulting in improvement of superconducting
parameters of the Bi-2212 materials obtained [16-18]. Our
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
repeatedly in preparing BSCCO coatings on several
substrates [20].
II. EXPERIMENTAL
The samples were prepared from SrCO3, CaCO3 carbonates,
Bi2O3, CuO oxides and fine grained copper. The copper oxide
was substituted for copper in a Bi3+: Sr2+: Ca2+: Cu2+:
Cu=1:1:1:2(1-x):2x cation ratio where x=0.0, 0.1, 0.2, 0.3,
0.4. The synthesis was carried out in three steps: the first -
short time exposure (1-10 min) at relatively high
temperatures (900-980)0C; the second and third steps
consisted in annealing at temperatures (860±15)0C and
8100C, respectively, for from one to several days. Upon
completion of each synthesis step the materials were ground
and pressed into a pellet 1-2 mm in thickness and about 10
mm in diameter. The phase composition was checked by the
X-ray diffraction (Co Kα radiation) and microstructural
analysis. The superconducting phases Bi-2212 and Bi-2223
were identified according to the literature data [21, 22]. The
superconducting transition temperatures were determined
from the resistivity and magnetic measurements. The samples
were synthesized in air, the synthesis parameters varied
within the above mentioned temperature and time.
III. RESULTS AND DISCUSSION
First, we shall point out the general tendency for the change
of superconducting transition temperature Tc against the
amount of copper (x) residing in the enhancement of the Tc
value by several degrees with x=(0.1-0.3) as opposed to those
for basic compositions (x=0.0). Further increase in the
concentration of copper substituting the copper oxide is
accompanied by the Tc decrease. This is just for all
synthesized conditions almost. However, under certain
synthesis conditions some series of samples with x=(0.2-0.3)
demonstrate a dramatic rise of Tc values above 100 K. Fig. 1
shows the resistivity against temperature with x=0.3 (sample
673) with Tc onset=120 K and Tc zero=107 K synthesized under
the following conditions: first step - (9000C - 10 min), the
second step - (8600C - 24 hrs) and third step - (8100C - 24
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.
TABLE I
Tc zero FOR THE SAMPLE SERIES 734-738 IN WHICH THE COPPER OXIDE WAS
SUBSTITUTED FOR COOPER PARTIALLY (X)
Sample 734 735 736 737
X 0.0 0.1 0.2 0.3
Tc zero 75.45 74.4 102.4 77.4
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. 1. R(T) curves of BSCCO samples: (•- sample 673 (x=0.3, Tc zero=107
K); x - sample 736 (x=0.02, Tc zero=102.4 K); o - sample 734 (x=0.00, Tc
zero=75.45 K). χ(T) of the sample 673 is shown on insert.
Examination of the phase composition of the BiSrCa((1-
x)CuO+xCu)2Oy system demonstrated predominant
concentration of the Bi-2212 superconducting phase in
samples with x=0.0, 0.1, 0.2 and 0.3. Non-superconducting
compound referring to the Bi-Sr-Ca-O group ("yellow
phase") [23, 24] was noted in the samples as an impurity
phase, whose amount increase as x rose. Along with the
"yellow phase" other impurities like CuO for large x values
were found in the synthesized samples.
The phase composition of samples with the
superconducting transition temperature above 100 K was
studied fairly extensively. The X-ray diffraction pattern of
the surface of sample 673 (x=0.3, Tc zero=107 K) in the form
of a pellet "0.3 mm thick is presented on Fig.2a.
738
0.4
74.4
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
diffraction pattern in the reflection angle range (4-8)0. The
reflection angles (4-8)0, (27-28)0 and (30-31)0 have been used
for identification of the Bi-2223 phase [22].
From the phase composition analysis performed one may
suggest that the amount of the Bi-2223 phase in this sample
should be small if any, and is obviously, inadequate to cause
Tc zero=107 K [25]. The lattice parameters as determined by
X-ray diffraction are a≈b=5.396 Å , c=30.735Å for sample
734 (x=0.0, Tc zero=75.45 K) and a≈b=5.412 Å, c=31.337 Å
for sample 637 (x=0.3, Tc zero=107 K).

Fig. 3. The powder X-ray of the sample 673 (x=0.3, Tc zero=107 K):
(• - Bi2Sr2CaCu2Oy [21]; (¬ - the "yellow phase" [23, 24].
Our investigation showed that the sample 673 prepared
using the initial component mixture corresponding cation
ratio Bi 3+: Sr2+: Ca2+: Cu2+: Cu=1:1:1:2(1-x):2x (x=0.3)
under mentioned above conditions contained only one
superconducting phase Bi2Sr2CaCu2Oy. Moreover this sample
and other samples prepared without using lead under the
same conditions had superconducting temperatures Tc zero
above 100 K.
IV. SUMMARY
Thus, we have demonstrated that it is possible for the
BSCCO system, while partially substituting copper oxide for
copper under certain synthesis conditions, to synthesize
unlead superconducting samples with superconducting
transition temperature Tc≈110 K and Bi2Sr2CaCu2Oy phase
crystal structure. Similar results have been reported in [10-
12] at other cation substitutes. The discrepancy between Tc
and phase composition of the synthesized materials has been
observed also for the Bi-2201 phase [26-28].
The authors gratefully acknowledge the assistance of
L.A.Kurochkin in carrying out the magnetic measurements.
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