Long range ordering between chromium and thallium has been evidenced for the first
time in copper oxychromate Tl3(CrO4)Sr8Cu4O16 using HREM, XRD and ND. This compound,
which crystallizes in an orthorhombic cell with a = 3.7803(1) Å,
b = 15.2573(2) Å and c = 17.6737(3) Å
derives from the "1201" TlSr2CuO5 structure by replacing one
thallium oxygen polyhedra out of
four by one CrO4 group in an ordered way. The Mayn features that
characterize this original
structure deal with the waving character of the [CuO2]∞ layers,
and the absolute planar character of
the [(Tl,Cr)O]∞ layers. In the [(Tl,Cr)O]∞ layers, the thallium and oxygen
atoms form triple
ribbons of edge-sharing TlO4 tetrahedra and TlO6 octahedra running
along a, whereas the CrO4
tetrahedra are displayed in rows running along a, but are disconnected
from each other and from the
other polyhedra in the layer. Two kinds of CuO6 octahedra are observed,
whose distortions originate
from their connection with different polyhedra along c.
This superconductor, whose Tc can be raised
to 34 K after argon-hydrogen annealing, exhibits a rather high
superconducting volume fraction (> 40%) compared to other "1201"
thallium cuprates.