LAUSR

Metal intercalation using a solvent has produced significant advances in the development of Fe-chalcogenide superconducting materials. Recently, the superconducting transition temperature (TC) of metal-intercalated FeSe has been raised to 46 K using ammonia as the solvent for the alkali-metal atom. However, multiple superconducting phases have been found, which may arise from different concentrations of intercalants, further complicating the situation. Here, we report the synthesis of single-crystals of metal-intercalated FeSe superconductors using liquid ammonia, and their physical properties. Particularly, utilization of single-crystals allows us to investigate the resistivity in these ammoniated metal-intercalated FeSe superconductors, Ax(NH3)yFe2-δSe2, for the first time. Firstly, we compared with their TC s and the interlayer distance between the FeSe layers (dI) as a function of ionic radius (r) of the exchangeable intercalant. We found that both TC and dI show weak dependence on the r, if the r is smaller than the effective size of another intercalant, i.e., NH3 molecule. Besides the enhancement of the dI by the insertion of NH3 molecule, one expects that the charge-transfer due to the intercalation of cation would leads to the shift of the Fermi energy. The intercalants (Ba and K) have similar rs, but different valences (Ba2+ and K+), which may throw light on the significance of charge transfer. When the metal concentrations were investigated on the cleaved surfaces of these single crystals, clear differences were found between the two compounds, with the K-concentration about double the Ba-concentration, which may imply the identical charge-transfer. This was also supported for the investigation of the Li-concentration. These results suggest not only the local environment within the conductive FeSe layers but also the significance of the number of electronic charges supplied to the FeSe layers by the intercalated metal and/or ammonia molecules.