High-Pressure Synthesis of Fully Occupied Tetragonal and Cubic Tungsten Bronze Oxides.

A high-pressure reaction yielded the fully occupied tetragonal tungsten bronze K3 W5 O15 (K0.6 WO3 ). The terminal phase shows an unusual transport property featuring slightly negative temperature-dependence in resistivity (dρ/dT<0) and a large Wilson ratio of RW =3.2. Such anomalous metallic behavior possibly arises from the low-dimensional electronic structure with a van Hove singularity at the Fermi level and/or from enhanced magnetic fluctuations by geometrical frustration of the tungsten sublattice. The asymmetric nature of the tetragonal tungsten bronze Kx WO3 -K0.6-y Bay WO3 phase diagram implies that superconductivity for x≤0.45 originates from the lattice instability because of potassium deficiency. A cubic perovskite KWO3 phase was also identified as a line phase-in marked contrast to Nax WO3 and Lix WO3 with varying quantities of x (<1). This study presents a versatile method by which the solubility limit of tungsten bronze oxides can be extended.