Physiea C 235-240 (1994) 755-756
North-Holland
PHYSICA
Infrared and Transport Properties of the Layered Perovskite Related Oxide BasNb40~s
and its Oxygen Deficient Phases
S. Pagola ", N.E. Massa b, G. Polla °, G. Leyva °, and R.E. Carbonio"
" INFIQC, Dpto. de Fisicoquimica, Fac. Cs. Quimicas, U.N.C., CC 61, 5016, C6rdoba, Argentina.
b LANAIS en Espectroscopia 6ptica and QUINOR - Dpto. de Quimica and Dpto. de Fisica, U.N.L.P., CC 962,
1900, La Plata, Argentina.
° CNEA, Dpto. de Fisica, Av. del Libertador 8250, 1429, Buenos Aires, Argentina.
BasNb40~., oxides were studied by infrared, electrical resistivity and thermogravimmetric analysis (TGA).
FIR reflectivity, measurementsreveal a strong ionic compound that has well defined features in groups that we
assign to oxygen stretching, bending and lattice phonons splitted by the lower symmetry of this layered
compound. For the sample with x = 0.56, oxygen vacancies do not affect phonon b~ld profiles, indicating that
carriers are not free enough to interact with longitudinal modes. Electrical resistivity vs. temperature
measurements show that the oxygen deficient compounds, for low values of x, are small band gap
semiconductors.
Since the discovery of high-temperature
superconductivity, perovskite related oxides have
0een extensively studied in order to understand its
mechanism and search for new materials. Among
these, the non copper ones are growing in interest.
Cations with and ~ (n=3, 4, 5) configuration such as
Ti(III), Nb(IV) or Ta(IV) all having s=l/2 spin state,
are of particular interest. Among the niobium
oxides, Li,,NbO2 and (Sq.x P-,, )NbzO6 where R is a
lantanide, were reported to be superconducting [1,2].
BasNb40~5 is a layered perovskite related oxide [3L
that can be prepared with Nb(IV) as BasNb40~3. /dl
these characteristics make this compound a good
candidate to search for new superconductors.
BasNb40~s was obtained by heat treatment of the
stoichiomellic mixture of BaCO3 and Nb205 at
1000°C in air. The oxygen deficient phases were
prepared by reduction of BasNb40~5 in a 95% Ar +
5% H: atmosphere by changing the temperature
between 1300 and 1500°C and the time of reduction
betwee md 54 hours.
Ele~. ,a~ resistivity measuremenls have been
done by he four probe method, between 80 and 300
K. The samples were characterized by TGA on a
Mettler TG 50 equipment, x values were determined
by the mass gain measured in flowing O~ at 600 °C.
X ray powder diffraction measurements were
done in a Philips PW 3710 Diffractometer, ,and
temperature dependent reflective measurements have
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SSDI 0921-4534(94)00941-4
been done with and interferometer Bruker 113V
from 5,000 to 30 cm 4 , the samples were mounted
on an Oxford DN 1754 cryostat.
Figure 1 shows our preliminary reflectivity
spectra of BasNb4Ol5 and BasN~4014.44 at 80 K.
X-ray diffraction powder patterns correspond to the
Ba~Nb4Ot5 phase [3].
i00 ..............................
"~ 60
40 /~
0 ~ . . . . .
1500 1000 500 0
Frequency (cm -1)
Figure 1. IR reflectivity spectra in the phonon region of
Ba~Nb4Ots (solid line) and BasNb4Ot4.44(dashed line), at
80 K.
The oxidized sample has a typical white ionic
insulator color, while in contrast, a lead like shine is
the characteristic for the one treated in the reducing
atmosphere. Our spectra confirms earlier X-ray data
showing that this layered compo,md has a
perovskite distorted lattice. Unscreened pi~onon
features from 800 to 30 cm ~ are found in g~oups at
four, at the same frequency positions of the room
temperature three infrared active reflection bands of