Physica C 241 (1995) 319-322

ELSEVIER

Phase stability in the La-Ba-Cu-O system at 980C

and 200 bar oxygen pressure
M.R. Chandrachood, K.K. Singh, D.E. Morris *, A.P.B. Sinha
Morris Research Inc., 1918 University Avenue, Berkeley, CA 94704, USA

Received 18 December 1992; revisedmanuscript received 27 September 1994

Abstract

The LaOLs-BaO-CuO pseudo-ternary phase diagram at 200 bar oxygen pressure was explored by a solid-state reaction at
980"C of numerous compositions. The phases which formed have been identified by X-ray diffraction. Significant differences
from phases formed in air are noticed. BaCuO2 and Ba2CuO3arc absent, Ba2Cu3Os+~is stabilized. La2CuO4remains stable, in
addition LaCuOa is formed in high pressure. Both La2CuO4and LaCuO3 show an extended solubility with Ba2+ replacing La3+.
The following phases do not form in a high P(O2): LaBa2Cu3OT,LaBa2Cu4Os,La4BaCusO~3,LaaBaaCu6Oio,La2BaCu206and
La2BaCuOs. This is possibly because LaCuO3 is a highly oxidized phase (FCV~ 3.0), which is therefore strongly favored at
elevated P(O2) of 200 bar. Tie-lines have been worked out and a tentative phase diagram is presented.

1. Introduction

The discovery of superconductivity in La-Ba-Cu

oxide [ 1 ] created a great deal of interest in this system and many investigators started looking for different compounds that could be synthesized from
these oxides. Klibanow et al. [2 ] were the first to
publish the complete phase diagram of the LaO~.5BaO-CuO pseudo-ternary system. Seven stable compounds were found to be formed at 980C in air.
Although all of them had been known previously
(see the respective references cited below), Klibanow et al. determined their approximate tie-lines and
solid-solution regions. The compounds are: La2BaO4
(2:1:0 [3] ), BaCuO2 (0:1 : 1 [4] ), La4BaCusOl3+6
(4:1:5
[5,6]),
La2CuO4
(2:0:1
[7,8]),
La3Ba3Cu6014 (3:3:6 [9,10] ), LazBaCu206 (2:1:2
[ 11 ], isomorphous with the Ca, Sr compound), and
La2BaCuO5 (2:1 : 1 [ 12] ). In case of the last four
* Corresponding author.

compounds, the single-phase region extends towards

higher Ba content, with Ba 2+ replacing part of the
La 3 in the formula. Other stable compounds are also
known in this system but they are formed under different experimental conditions from those of Ref.
[2]. They are LaBa2Cu307 [13], Ba2CuO3 (lower
temperature [14]), Ba2Cu305+a (higher oxygen
pressure [15,16]) and LaCuO3_~ (higher oxygen
pressure [ 17,18 ] ). It can be seen that the stability of
the various phases is quite sensitive to the preparation conditions and it was anticipated that synthesis
in higher P(O2) may result in the appearance of new
highly oxidized phases.
The application of a high P(O2) in superconductor
synthesis has indeed been quite rewarding. The earlier examples of 1 : 2: 4 and 2: 4: 7 are well known [ 1921 ]. La2SrCu206 was rendered superconducting by
the use of a high P(O2) [22 ]. Tang et al. [23 ] showed
that (Pb, C u ) - 1 : 2 : 1 : 2 compounds could be made
superconductive by annealing in a high P(O2 ).
We therefore felt that a systematic investigation of

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320

M.R. Chandrachood et al. /Physica C 241 (1995) 319- 322

the complete L a - B a - C u - O phase diagram in higher

P(O2) was called for. We carried out the synthesis of
about 100 compositions at 980C in 200 bar oxygen
pressure. The phases formed have been identified by
X-ray diffraction. The results are presented below.

2. Experimental procedure

La203, BaO2 and CuO were used as the starting

material. In each case, the metal-wise purity was better than 99.9%. La203 was prefired at 950C for 2 h
to remove volatiles. BaO2 and CuO were dried at l 10120"C in a hot air oven. Appropriate amounts were
weighed and well-mixed using agate mortar and pestle. The mixture was pressed into pellets (6 m m
d i a 1-2 m m thickness) using a hydraulic laboratory press. The samples were individually wrapped in
gold foil, then 6-7 of such pellets were placed in a
gold roll and placed in a commercial high-pressure
furnace [ 24], filled with pure oxygen and sealed. The
furnace temperature was raised to 980"C at which
point the pressure attained was 200 bar. The heating
was continued for 15 h, then the furnace was switched
off. When the furnace had reached room temperature, the pressure was released and the sample taken
out. The pellet was ground to a fine powder and
pressed inside a glove box in an atmosphere of dry
N 2 and retired once more under the same conditions
to ensure that the sample received adequate opportunity to react and reach equilibrium. The pellet was
then ground to better than 200 mesh and spread on a
zero-reflection plate. The X-ray powder diffraction
was carried out on a Scintag PAD-V diffractometer
using Cu K a radiation and an intrinsic Ge solid-state
detector with 200 eV energy resolution. The phases
present could be identified by comparing the observed patterns with the standard patterns. Based on
the results of the first set of experiments, several additional compositions needed to settle the tie-lines
and solubility limits had to be analyzed. These were
prepared and investigated following the same procedures as described above.

3. Results and discussion

A tentative phase diagram for LaOL5-BaO2-CuO

at 980C and 200 bar oxygen pressure was prepared

on the basis of the above results, and is shown in Fig.

1. For comparison, the previously published phase
diagram at P(O2) = 1 bar [2] is given in Fig. 2. Significant differences are seen:
(1) Ba2Cu3Os+~ is the only phase found to be
formed on the BaO-CuO binary in high pressure oxygen. BaCuO2 and Ba2CuOa phases are absent.
Ba2CuO3 is unstable at 980"C at 200 bar as well as at
1 bar, while BaCuO2 gets destabilized at high oxygen
pressure.
(2) On the LaOLs-CuO binary, La2CuO4 continues to be stable at 200 bar P(O2) just as it is at one
bar. A new feature is the appearance of the LaCuO3
phase at this pressure. This phase was first reported
by Demazeau et al. [ 17 ] and has recently been studied in detail by Bringley et al. [ 18 ].
(3) Both La2CuO4 and LaCuO3 phases show a region of solid stability, where Ba 2 replaces a part of
the La 3+ ion while the Cu proportion remains unchanged. There is a homogeneous single-phase region
from La2CuO4+ J to Lal.7Bao.3CuO3.s5+6 and LaCuO3_6 to Lao.TBao.3CuO2.ss_ 6. Fig. 3 shows the Xray diffraction patterns of La~_xBaxCuOy for x = 0.1,

CuO
0.00

1.00

.... %O2cu3os+

o4o//.1#

,_aC,,03

o.6o.~'//~.7J/

0.00

La01.5

020

0 40

o\

0.60

~0.40

0.80

1.00

Ba02

Fig. 1. Phase diagram of LaOl.s-BaO2-CuO at 980C and

P(O2) = 200 bar. The followingphasesare present: Ba2Cu3Os+~,
LaCuO3_~and La2CuO4+6.The tie-lines are shown. Solid-solution regions are shown by heavy lines. The regions between the
lines have the following m i x e d phases: ( A )
Ba2Cu305+6+ CuO+ LaCuO3, (B) LaCuO3+ CuO, (C)
LaCuO3+La2CuO4, (D) La2CuO4+LaCuO3+BaOx, (E)
LaCuO3+Ba2Cu3Os+~+BaOx, (F) La2CuO4+LaOl.~, (G)
La2CuO4+ LaOL5+ BaOx. The compositionsprepared for phase
analysisare marked by small open circles.

M.R. Chandrachood et al. / Physica C 241 (1995) 319-322

321

CuO
loo

loo

G.8o

0.80

Y /
o.8o ~
Z" '
.'

/ oCuO
I "

6.~

ii1!

.~/." ./.4.' \ / ~ 2 /
\
" q)~'7
l/_~ rg~\

%
~.0.~0

o ~o

////

Lo

7~

G.O0

0.00

o. o

BaLo O

[00!5

2 ,,

\j;

Fig. 2. Phase diagram of LaO0.~5-BaO-CuO at 950C at P(O2 ) = 1 bar in air (after Klibanow et al. [ 2 ] ).

t[ .

:A

,, _

_.<...

* = CuO

~D

a
i,a
i

80

A~/'L,',,

25

80

35

o
i

O, ~ 1~
I

40

.45

,~ 0
i

~ o ~,

IV
{ '1

5.0

~ ~

o
I

i-7'

55

2(9
Fig. 3. X-ray diffraction pattern for La~ _xBaxCuOs-a with (a) x = 0.1, (b) x = 0.2 and x = 0.3. The patterns indicate that a single-phase
compound isomorphous to monoclinic LaCuO3 (see Ref. [ 18 ] ) has been formed. There are no lines due to any separate barium compound. Very weak CuO lines, marked (*), are observed.
0.2 and 0.3. T h e pattern clearly s h o w s a single-phase
i s o m o r p h o u s w i t h m o n o c l i n i c LaCuO3. At higher
values o f x lines d u e to Ba2Cu3Os+a start s h o w i n g up.

( 4 ) N o c o m p o u n d is f o r m e d on the L a O l . 5 - B a O
binary at high P ( O 2 ) . Higher P(O2) destabilizes the
LaEBaO4 phase w h i c h is reported to be f o r m e d in air

322

M.R. Chandrachood et al. / Physica C 241 (1995) 319-322

[ 3 ], possibly by favoring the formation of BaO2. Since

the formation of BaO2 will take up oxygen from the
high pressure gas, it is favored by the entropy term in
the free energy.
(5) In the L a O i . 5 - B a O - C u O ternary region, no
single-phase c o m p o u n d is formed. The compounds
which were found at P ( O 2 ) = 1 bar are destabilized
in a high P(O2). These include LaBa2Cu307 ( 1 : 2: 3),
La4BaCusOl3 ( 4 : 1 : 5 ) , La3BaaCu6Ol4 ( 3 : 3 : 6 ) ,
La2BaCu206 ( 2 : 1 : 2 ) and La2BaCuO5 (2: 1: I ). The
reason for this seems to be the existence of the highly
oxidized cuprate LaCuO3 with FACV as high as 3, in
contrast to the above mentioned compounds in which
FACV ranges from 2.00-2.43. These compounds
therefore give way to LaCuO3 u n d e r high pressure.

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