PHYSICA Physica C 180 (1991) 4 6 - 4 9

North-Holland

EFFECT OF Ba, Ca AND Pb ON THE C-LATTICE PARAMETER OF BSCCO FILMS

G. Balestrino*, M. Marinelli, E. Milani, A. Paoletti, P. Paroli ÷

Dipartimento di Ingegneria Meccanica, II Universit& di Roma Via O. Raimondo 8, 1-00173 Roma, Italy
* Dipartimento di Fisica, Universit& di Salerno, 1-84100 Salerno, Italy
+ Dipartimento di Fisica, Universit& della Calabria, Arcavacata di Rende, 1-87036 Cosenza, Italy

The Liquid Phase Epitaxy (LPE) technique has been used to grow epitaxial, single-phase BSCCO films of
both the 2201 and the 2212 phase. The possibility to introduce in the BSCCO structure ions different from
the basic constituent ones by simply adding new elements to the melt has been explored. The effects on the
c-lattice parameter of Ba and Pb doping in the 2212 BSCCO structure, and of Ca doping in the 2201
structure have been determined.

1. INTRODUCTION constituent ones, simply by adding these elements in

Liquid Phase Epitaxy (LPE) has been recently
used 1'2 to grow high quality films of the high-To
BSCCO superconductor with nominal composition
Bi2Sr2Cal.xCU2.xOy ( x = 0, 1). With the choice of a
suitable substrate 1-3'4, the films obtained are truly
epitaxial. The mosaic spread is about 0.1" and the
thickness of about 1-2 lam.
In a recent paper5 we reported on the effects on
the film stoichiometry and c-lattice constant of
varying the molar ratios of the BSCCO constituent
oxides in the LPE growth melt. We showed that it is
possible to change the relative content of the 2201,
2212 and 2223 BSCCO phases in the film by
increasing or decreasing the relative content of Ca
and Cu in the melt. In particular, suitable melt
compositions lead to the growth of single-phase
2201 or 2212 BSCCO films. It is also possible, within
the 2212 phase, to vary the ratio of Ca to Sr content;
these changes of stoichiometry affect the c-lattice
parameter of the film, which was found to decrease
linearly with Ca content.
In this paper we report on the possibility to grow
dooed BSCCO films with the LPE technique. We will
show that it is possible to incorporate in the BSCCO
structure other elements than the standard
the growth melt. In particular, Ca ions have been
substituted in the 2201 phase of BSCCO, and
doping of the 2212 phase has been achieved with
both lead and barium. The c-lattice parameter
changes due to these substitutions have been
analyzed.
2. EXPERIMENTAL
The film growth has been performed following the
guidelines reported in Ref. 5. The melt composition
was varied to change the film stoichiometry. The
substrate used was NdGaO3. The films were
characterized from the structural, electrical and
chemical point of view. A Bragg-Brentano X-ray
diffractometer in 0 - 20 geometry was used (Cu K,,
radiation) to check the phase, orientation and
c-lattice constant of the films, while a standard
4-point technique was employed to measure the
resistivity vs temperature curves. Scanning electron
microscopy (SEM) and energy dispersive
microprobe analysis (EDS) were used to check the
surface quality and the composition of the films. The
latter was normalized to a five- or seven-cation
composition for the 2201 and 2212 phases
respectively. The error on the amount of each cation

0921-4534/91/$03.50 © 1991 - Elsevier Science Publishers B.V. All rights reserved.

 G. Balestrino et aL / Effect of Ba, Ca and Pb on the C-lattice parameter 47

is about 0.05 atoms per formula unit (afu).
3. RESULTS AND DISCUSSION
The substitution of barium in BSCCO should have
important structural effects because of the large
ionic radius of Ba. This means, of course, that it
could be difficult to incorporate large amounts of Ba
in the BSCCO structure. To our knowledge, no
Ba-doped single crystals of BSCCO have been
obtained up to now.
The starting point to grow Ba:BSCCO films by LPE
was simply to add 0.4 afu of Ba to the standard melt
for the growth of 2212 BSCCO films. The EDS
measurements of the films obtained in this way
showed however that only a minimal amount of Ba
entered in the film, whose composition was checked
to be Bi2.~sSrl.F2Bao.o3Cal.o2Cu2.osOy. The zero
resistance temperature is To = 84.5 K. Both the
composition and the critical temperature are similar
to the ones of films obtained from Ba-free standard
melts. In Tab. I the melt composition, film
composition, c-lattice parameter, growth temperature
and superconducting transition temperature are
reported for the films used in this experiment.
Since this result was probably due to the fact that
Ba is not easily accepted in the BSCCO lattice cell
because of its large ionic radius, we tried to force Ba
substitution in Sr sites by increasing the Ba content
in the melt to 1 afu and by strongly decreasing the Sr
content, in the hope to "make room" for Ba. The
films grown under these conditions were either
extremely thin, or contained the 2201 phase. To
overcome this last problem we put in the melt an
excess of both Ca and Cu and finally obtained a film
with no 2201 phase content, and composition
Bi2.17Sq.48Bao2oCa~.14Cu2.olOy. The quality of the film
was however not very good, and the zero resistivity
temperature was as low as 53 K, thus confirming
that it is not possible to incorporate large amounts of
Ba in the BSCCO structure without modifying its
properties.
It is not straightforward to check the effects of a
dopant on the c-lattice parameter of BSCCO films
because they can be masked by a change in the

Tab. I. Melt composition, film composition, c-lattice parameter, critical temperature To and growth temperature T~
for some selected films

Sample N. Melt comp. Film composition c (A) To(K) T~('C)

SF43-1 2223 Bi22sSr189Cao.84Cu2

o2 30.95 82 830
S F48-2 2223 Bi2.16Sr184Cal .oTCu192 30.82 79 820
SF74-1 2146 + 1 Ba Bi2.17Srl.48Bao.2oCal.14Cu2.o~ 30.80 53 845
SF68-1 2223 + 0.4 Ba Bi2 leSr~ 72Bao.o3Cal.o2Cu2.os 30.81 84.5 810
S F51 - 1 2246 Bi2.26Srls4Ca1.200u 1.9e 30.75 80 810
SF51-2 2246 Bi213Sq.s2Ca126Cu2.oo 30.71 80 810
SF52-2 2246 Bi223Srl 56Cal.2,Cu195 30.69 79 830
SF51-3 2246 Bi2 ~sSq.s6Ca1.260u2.02 30.68 77 845
SF54-2 2269 Bi2.19Srl.s3Ca1.44Cul.es 30.60 60 820
SF30-1 (1.3,0.7)21 2 Bi2.osPbo19Sq.7oCao93Cu212 30.74 76 830
SF32-2 (1.3,0.7)21 2 Bil.82Pbo.38Srl 9oCao.9oCu2.oo 30.81 70 826
SF50-1 (1.3,0.7)246 Bil 8oPbo4oSrl.72Cal loCu196 30.73 69 800
48 G. Balestrino et al. / Effect of Ba, Ca and Pb on the C-lattice parameter

films lay well below the straight line which refers to

the undoped films. This shows that lead substitution
°< 30.9 decreases the c-lattice constant of BSCCO.
I-i However, due to the simultaneous effects of Ca and
Pb content on the c-lattice parameter, it is difficult to
30.8 give a quantitative connection between the lead
content alone and the decrease of the c-lattice
CA 30.7 parameter. Roughly, for the above mentioned range
of Pb concentration, the decrease in the c-lattice
parameter is 0.1 A.
30.6
Furthermore we have investigated the possibility of
0.'8 1.'0 l .'2 1.4' partially substituting Ca for Sr in the 2201 phase. We
x (a.f.u.) first grew a film of the 2201 phase from a melt
without Ca. The X-ray spectrum showed that the film
FIGURE 1
Behavior of the c-lattice parameter of the epitaxial is a single-phase one, with a lattice constant
films vs X (Ca afu) for non-substituted (open circles) c=24.51 A. Then we have grown another 2201 film
and Pb-doped (full circles) films.
from a melt containing Ca. Again, as shown in Fig. 2,
the film was single-phase 2201 phase. The EDS
measurement gave the following composition :
content of both Sr and Ca in the film (at least in the BizosSrl.76Cao 18Cu0.grOr The content of Ca cannot be
2212 phase). In a recent paper s we extensively explained with a contamination from the 2212 phase
studied the effect of the stoichiometry of the 2212
BSCCO phase on the c-lattice parameter, and found
(see Fig. 1) that the latter is linearly connected to the
0 o
Ca content in the film. According to these data, a -- 0
2212 BSCCO film with a Ca content of 1.14 afu (the
one of the Ba-doped film), should have a lattice 4
0
parameter c=30.77 A. The c-lattice parameter of the 0
Ba-doped film is c=30.80 A, only slightly larger than <3
v

the previous one, in spite of the large ionic radius of

Ba. The error on c is about 0.01 A. ~
C 2 O
A much simpler and more widely studied 6 o
substitution in BSCCO is the one of lead for bismuth O
I
in the 2212 phase. We have prepared lead
substituted BSCCO 2212 films starting from melts in
0
which 0.7 afu of Bi have been substituted with Pb
(see Tab. I). The resulting Pb content in the films I I I I I I
was measured by EDS and found to be between 0.2 2O 30 40
and 0.4 afu for all films. In Fig. 1 we report (full dots) 2 0 ( °)
the values of the c-lattice parameter for these films
FIGURE 2
as a function of their Ca content. It can be clearly X-ray spectrum of a Ca-substituted 2201, single
seen that the lattice parameter of all lead substituted phase BSCCO film.
 G. Balestrino et a L / Effect of Ba, Ca and Pb on the C-latticeparameter
which, according to the X-ray spectrum, must be
less than 1% of the sample in volume. The lattice
parameter was then measured to be c=24.24 A. This
shows that the effect of Ca substitution in the 2201
phase is to decrease the value of the c-lattice
parameter with respect to the undoped film. The
difference Ac=0.27 A between the two lattice
parameters is about twice the one expected for the
2212 phase when the calcium content varies of 0.18
afu.
4. CONCLUSIONS
We have shown that the LPE technique is suitable
for growing doped films of both the 2212 and the
2201 phase of BSCCO. Pb and Ba have been
substituted into the 2212 phase, and Ca in the 2201
49
phase. The effects of such substitutions on the
c-lattice parameter have been measured.
REFERENCES
1) G. Balestrino, M. Marinelli, E. Milani, A. Paoletti,
P. Paroli, Journ. Appl. Phys. 68 (1990) 361
2) G. Balestrino, V. Foglietti, M. Marinelli, E. Milani,
A. Paoletti, P. Paroli, G. Luce, Solid State Comm. 76
(1990) 503
3) G. Balestrino, V. Foglietti, M. Marinelli, E. Milani,
A. Paoletti, P. Paroli, submitted to Journ. Appl. Phys.
4) E.A. Giess et al., IBM Research Report, August
16, 1990
5) G. Balestrino, M. Marinelli, E. Milani, A. Paoletti
and P. Paroli, submitted to Journ. Appl. Phys.
6) S.A. Sunshine et al., Phys. Rev. t338 (1988) 893