Sl. Stoll et al., SINGLE-CRYSTAL GROWTH, ALKALI-METAL ORDERING, AND SUPERCONDUCTIVITY IN LA2-XMXCUO4 (M = NA, K), Inorganic chemistry, 33(13), 1994, pp. 2761-2765
Single crystals of La2-xMxCuO4, where M is Na or K, have been prepared
by precipitation from molten NaOH at 320-degrees-C or from molten KOH
at 450-degrees-C. The composition of several individual crystals as d
etermined by wavelength-dispersive X-ray fluorescence analysis average
d to La1.88Na0.12CuO4 and La1.79K0.21CuO4. Iodometric titrations on po
lycrystalline samples with identical compositions showed that the form
al oxidation states for the Cu atoms are +2.19 and +2.31, respectively
. On the basis of the analysis of single-crystal X-ray diffraction dat
a, it has been determined that the alkali metal doped lanthanum copper
oxides crystallize in a new structure type that is distinct from the
analogous phases containing alkaline earth metal ions. The space group
is P4/nmm, and lattice parameters are a = 3.766(1) angstrom, c = 13.2
16(5) angstrom for the Na-doped material and a = 3.7708(7) angstrom, c
= 13.321(2) angstrom for the K-doped material. In these phases, the a
lkali metal ions are ordered in the rock-salt blocks, and the Cu atoms
are displaced out of the plane toward the alkali metal ions. Despite
this distortion of the CuO2 planes, both phases exhibit superconductiv
ity, near 26 and 6 K, respectively.