Increase in Tc upon reduction of doping in LixZrNCl superconductors.

We revealed a detailed phase diagram of the very lightly doped regime in Li-intercalated superconductors, LixZrNCl, to which previous studies have never gained access owing to the difficulty in synthesizing single-phase samples. A continuous and uniform Li intercalation without any indication of phase separation was carefully confirmed by means of synchrotron x-ray diffraction and Raman scattering experiments. Upon reducing the carrier density below x=0.12, we found a rapid increase in the superconducting transition temperature (Tc) immediately followed by the superconductor-to-insulator transition (SIT). Such an increase in Tc on the verge of SIT seems to be difficult to explain by the conventional theory, but may be indicative of the charge fluctuation contribution to superconductivity in low-carrier-density systems.