Preparation of Single Crystal Molybdenum Bronzes and Polycrystalline Rubidium Molybdenum Oxide
Lithium purple bronze (LiPB) Li0.9Mo6O17 was studied extensively in the 1980’s and has recently regained interest in the research community. The mechanism for the metal-insulator (M/I) transition at ∼25 K and superconductivity at ∼2 K is still unknown. The temperature gradient flux technique has been used to grow single crystal LiPB. A large superconducting LiPB single crystal was grown (di- mensions: 4.7×3.0×1.2 mm3) and characterized and will be referred to throughout this work as ‘I33sc2’. For the non-superconducting single crystal oriented along the b-crystallographic axis, we found the maximum value of the energy gap to be 2 meV±0.1 meV at 9.16 K, which is different from the accepted literature value of ∼1 meV at 5-6 K [1,2]. Furthermore, heavier alkali metals (Na, K and Rb) were used in the temperature gradient flux technique. Small lilac brown single crystals were found in all three growths. In particular, the rubidium growth yielded polyhedral (denoted as ‘POLY’, having approximate dimensions: 0.5 × 0.3 × 0.3 mm3) and small bar shaped (denoted as ‘SBAR’, having approximate dimensions: 1×0.1×0.1 mm3) lilac brown single crystals which exhibited anomalous properties in the re- sistivity and specific heat. The anomalous properties include a M/I transition at 250 K and a small phase transition in the resistivity at 94 K. These lilac brown single crystals were studied with powder X-ray diffraction (XRD) and match very closely with molybdenum dioxide MoO2, however with slightly larger ‘a’ and ‘b’ lattice parameters. These lilac brown crystals are being further characterized with single crystal XRD. Polycrystalline rubidium molybdenum dioxide Rb0.03MoO2−δ was then grown to further understand what rubidium doping (if any) these lilac brown single crystals have. The resistivity of polycrystalline Rb0.03MoO2−δ has a M/I transition at 250 K, similar to the lilac brown single crystals, but lacks a phase transition at 94 K. Unlike the lilac brown single crystals, the slope of the M/I transition at 250 K is strongly affected by thermal cycling. Furthermore, poly- crystalline Rb0.03MoO2−δ shows signs of a small superconducting volume fraction. This material is under further investigation.