Em. Kopnin et al., SUPPRESSION OF SUPERCONDUCTIVITY IN HG-1223 AND HG-1234 BY PARTIAL REPLACEMENT OF HG BY CARBON, Physica. C, Superconductivity, 243(3-4), 1995, pp. 222-232
Hg based 1223 and 1234 phases were prepared by a high-pressure high-te
mperature technique using precursors obtained by the decomposition of
BaO2, CaCO3 and CuO in oxygen flow at 925 degrees C. These phases were
found to exhibit much lower T-c's (64 K for 1223 phase, and no superc
onductivity for the 1234 phase) than the corresponding Hg based sample
s prepared by different precursors and this even after heat treatments
in oxygen flow. The structural refinement of this 1223 phase carried
out by using synchrotron X-ray powder data revealed a large deficiency
on the Hg site; the occupancy factor for this site was found to be 0.
69(1). This may be due to the replacement of some of the Hg cations by
C. By IR spectroscopy the characteristic frequencies corresponding to
the vibrations of the CO3-2 group were found in these samples. Large
amounts of intergrowth defects were detected by electron microscopy an
d no superstructure spots were found in the diffraction patterns. The
replacement of Hg by C in the structures of the Hg based superconducto
rs induces a decrease of the concentration of the extra oxygen in the
(Hg, C) layer bonded to the Hg atoms. Since it is this oxygen which ox
idizes the (CuO2) layers, its decrease causes a reduction of these lay
ers, which is responsible for the decrease of the superconducting tran
sition temperatures.