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0.06 oO 0.020
show strong Jahn-Teller (J.T.) effects [13]. While
SrFe(VI)O3 is distorted perovskite insulator, o 9~
~o x* 9
9 0%o o e~ 9 1 4 9 1 4x 9
line of the metal-insulator transition in mixed perovs- 99 ooo~ o 9149 x x
99 .9 ,x 0.012
kites, a subject on which we have recently carried
out a series of investigations [15]. Here, we report o xx o
0.03 xx
on the synthesis and electrical measurements of com-
Q.
pounds within the B a - L a - C u - O system. This sys- o x~'~Kxxxxxxxxxxxxx~'~ 0 . 0 0 8 o..
tem exhibits a number of oxygen-deficient phases x
x o 0.25 A/cm 2
with mixed-valent copper constituents [16], i.e., with 0.02 Ox
~,~ 9 0.50 A/cm 2
itinerant electronic states between the non-J.T. Cu a + ,x x 0.50 A/cm 2
and the J.T. Cu z+ ions, and thus was expected to
~. 0.004
have considerable electron-phonon coupling and me- OOl -~:
tallic conductivity.
t I I I o
0 100 200 30(
T (K)
lI. Experimental
Fig. 1. Temperature dependence ofresistivityin Ba~Las _=Cu505 (a y)
for samples with x ( B a ) = 1 (upper curves, left scale) and x ( B a ) =
1. Sample Preparation and Characterization 0.75 (lower curve, right scale). The first two cases also show the
influence of current density
Samples were prepared by a coprecipitation method
from aqueous solutions [17] of Ba-, La- and Cu-ni-
trate (SPECPURE JMC) in their appropriate ratios. 3. Conductivity Measurements
When added to an aqueous solution of oxalic acid
as the precipitant, an intimate mixture of the corre- The dc conductivity was measured by the four-point
sponding oxalates was formed. The decomposition method. Rectangular-shaped samples, cut from the
of the precipitate and the solid-state reaction were sintered pellets, were provided with gold electrodes
performed by heating at 900 ~ for 5 h. The product and contacted by In wires. Our measurements be-
was pressed into pellets at 4 kbar, and reheated to tween 300 and 4.2 K were performed in a continuous-
900 ~ for sintering. flow cryostat (Leybold-Hereaus) incorporated in a
computer-controlled (IBM-PC) fully-automatic sys-
tem for temperature variation, data acquisition and
2. X-Ray Analysis processing.
For samples with x(Ba)_<l.0, the conductivity
X-ray powder diffract 9 (System D 500 SIE- measurements, involving typical current densities of
MENS) revealed three individual crystallographic 0.5 A/cm 2, generally exhibit a high-temperature me-
phases. Within a range of 10~ to 80 ~ (20), 17 lines tallic behaviour with an increase in resistivity at low
could be identified to correspond to a layer-type per- temperatures (Fig. 1). At still lower temperatures, a
ovskite-like phase, related to the K2NiF, structure sharp drop in resistivity (>90%) occurs, which for
( a = 3 . 7 9 ~ and c=13.21 ~) [16]. The second phase higher currents becomes partially suppressed (Fig. 1 :
is most probably a cubic one, whose presence depends upper curves, left scale), This characteristic drop has
on the Ba concentration, as the line intensity de- been studied as a function of annealing conditions,
creases for smaller x(Ba). The amount of the third i.e., temperature and 02 partial pressure (Fig. 2). For
phase (volume fraction > 30% from the x-ray intensi- samples annealed in air, the transition from itinerant
ties) seems to be independent of the starting composi- to localized behaviour, as indicated by the minimum
tion, and shows thermal stability up to 1,000 ~ For in resistivity in the 80 K range, is not very pro-
higher temperatures, this phase disappears progres- nounced. Annealing in a slightly reducing atmo-
sively, giving rise to the formation of an oxygen-defi- sphere, however, leads to an increase in resistivity
cient perovskite (La3Ba3Cu601,) as described by Mi- and a more pronounced localization effect. At the
chel and Raveau [16]. same time, the onset of the resistivity drop is shifted
J.G. Bednorz and K.A. Mfiller: B a - L a - C u - O System 191
| 900~ 2 h
| 540~ 15 min
| 630~ 12 h
| 900~ 15 rain 0.010
| 900~ 1h
| 950~ 1h
L~ 104s ~ 15 min
o x9 ~
0.05 - e •
0.008 - xs
•
o
•149
0.04 _ , . _
~
O 0.006
x*
Q. O
0.03
Q.
0.004
x
x9 o 7.5 A / c m 2
0.02 --
9 * 2.5 A / c m 2
•215
9 0.5 A/cm 2
0,002
0.01 -
o .7
oL__
0 10 20 30 40 50 60 0 10 20 30 40 50 60
T (K) T (K)
Fig. 2. Low-temperature resistivity of samples with x (Ba)= 1.0, an- Fig. 3. Low-temperature resistivity of a sample with x ( B a ) = 0 . 7 5 ,
nealed at O2 partial pressure of 0 . 2 b a r (curve O ) and recorded for different current densities
0.2 x 10 -4 bar (curves (~) to @)
towards the 30 K region. Curves @ and @, recorded BaPbl-xBixO3 polycrystalline thin films [5, 18].
for samples treated at 900 ~ show the occurrence Upon cooling from room temperature, the latter ex-
of a shoulder at still lower temperature, more pro- hibit a nearly linear metallic decrease of p(T), then
nounced in curve | At annealing temperatures of a logarithmic type of increase, before undergoing the
1,040 ~ the highly conducting phase has almost transition to superconductivity. One could, of course,
vanished. As mentioned in the Introduction, the speculate that in our samples a metal-to-metal struc-
mixed-valent state of copper is of importance for elec- tural phase transition occurs in one of the phases.
tron-phonon coupling. Therefore, the concentration The shift in the drop in p (T) with increasing current
of electrons was varied by the Ba/La ratio. A typical density (Fig. 3), however, would be hard to explain
curve for a sample with a lower Ba concentration with such an assumption, while it supports our inter-
of 0.75 is shown in Fig. 1 (right scale). Its resistivity pretation that we observe the onset of superconducti-
decreases by at least three orders of magnitude, giving vity of percolative nature, as discussed below. In
evidence for the bulk being superconducting below BaPbl-xBixO3, the onset of superconductivity has
13 K with an onset around 35 K, as shown in Fig. 3, been taken at the resistivity peak [18]. This assump-
on an expanded temperature scale. The latter figure tion appears to be valid in percolative systems, i.e.,
also shows the influence of the current density, typical in the thin films [18] consisting of polycrystals with
for granular compounds. grain boundaries, or when different crystalline phases
with interpenetrating grains are present, as found in
the L i - T i - O [5] or in our B a - L a - C u - - O system.
III. Discussion The onset can also be due to fluctuations in the super-
conducting wave functions. We assume one of the
The resistivity behaviour of our samples, Fig. 1, Ba-La-Cu-O phases exhibits this behaviour.
is qualitatively very similar to the one reported in Therefore, under the above premises, the peak in p(T)
the L i - T i - O system, and in superconducting at 35 K, observed for an x(Ba)=0.75 (Fig. 1), has
192 J.G. Bednorz and K.A. Miiller: Ba--La--Cu--O System
to be identified as the start to superconductive coop- nents and the high reactivity of the oxalates owing
erative p h e n o m e n a in the isolated grains. It should to the evolution o f large amounts of H 2 0 and CO2
be noted that in granular A1, Cooper pairs in coupled during decomposition.
grains have been shown to exist already at a point
where p (T) upon cooling has decreased by only 20%
o f its highest value. This has been proven qualitative- IV. Conclusion
ly [19] and more recently also quantitatively [20] by
the negative frequency shift occurring in a microwave In the concentration range investigated, compounds
cavity. In 100 ~ films, a shoulder in the frequency of the B a - L a - C u - O system are metallic at high
shift owing to 2 D fluctuations was observed above temperatures, and exhibit a tendency towards local-
the Tc o f the grains. In our B a - L a - C u - O system, ization upon cooling. Samples annealed near 900 ~
a series of layer-like phases with considerable variety under reducing conditions show features associated
in compositions are known to exist [16, 21], and with an onset of granular superconductivity near
therefore 2 D correlations can be present. 30 K. The system consists o f three phases, one of
The granularity of our system can be justified them having a metallic perovskite-type layer-like
f r o m the structural information, and more quantita- structure. The characterization o f the new, apparently
tively from the normal conductivity behaviour. F r o m superconducting, phase is in progress. An identifica-
the former, we k n o w that more than one phase is tion o f that phase m a y allow growing o f single crys-
present and the question arises how large are the tals for studying the Meissner effect, and collecting
grains. This can be inferred f r o m the logarithmic specific-heat data to prove the presence o f high Tc
fingerprint in resistivity. Such logarithmic increases bulk superconductivity.
are usually associated with beginning o f localization.
A m o s t recent example is the Anderson transition The authors would like to thank H.E. Weibel for his help in getting
in granular Sn films [22]. C o m m o n for the granular familiar with the conductivity measurement system, E. Courtens
and H. Thomas for discussions and a critical reading of the manu-
Sn and our samples is also the resistivity at 300 K, script.
lying in the range o f 0.06 to 0.02 ~ c m , which is near
the microscopic critical resistivity o f p c = 1 0 L o h / e z
for localization. F r o m the latter formula, an inter-
atomic distance Lo in the range o f 100 ~ is computed, References
thus a size of superconducting grains of this order
1. Tinkham, M., Beasley, M.R., Larbalestier, D.C., Clark, A.F.,
o f magnitude must be present. U p o n cooling below Finnemore, D.K. : Workshop on Problems in Superconductiv-
To, Josephson junctions between the grains phase- ity, Copper Mountain, Colorado, August 1983, p. 12
lock progressively [23] and the bulk resistivity gradu- 2. Beasley, M.R., Geballe, T.H. : Phys. Today 36 (10), 60 (1984)
ally drops to zero by three orders o f magnitude, for 3. Miiller, J. : Rep. Prog. Phys. 43, 663 (1980)
4. Ott, H.R.: Unconventional Superconductivity. Z/irich Phys.
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J.L. : In: Superconductivity in d- and f-Band Metals, Proceed-
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The way the samples have been prepared seems zentrum Karlsruhe 1982
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Lett. 45, 1352 (1980)
tained a single-phase perovskite by mixing the oxides 8. Sleight, A.W., Gillson, J.L., Bierstedt, F.E.: Solid State Com-
o f La and Cu and BaCOa in an appropriate ratio mun. 17, 27 (1975)
and subsequent annealing at 1,000 ~ in air. We also Batlogg, B. : Physica 126 B, 275 (1984)
applied this annealing condition to one of our sam- 9. Thanh, T.D., Korea, A., Tanaka, S. : Appl. Phys. 22, 205 (1980)
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ibid. 28, 4227 (1983)
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Thus, the preparation from the oxalates and anneal- 1351 (1981)
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ovskite-type phase with a limited temperature range 237 (1983)
13. Englmann, R.: In: The Jahn-Teller Effect in Molecules and
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is favoured by the intimate mixture o f the compo- of oxide and related compounds. In: Landolt-Boernstein New
J.G. Bednorz and K.A. Mfilter: B a - L a - Cu--O System 193
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(in Japanese) J.G. Bednorz
Enomoto, Y., Suzuki, M., Murakami, T., Inukai, T., Inamura, K.A. Mfiller
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