Stabilization and superconductivity of AlB2-type nonstoichiometric molybdenum diboride by Sc doping

Molybdenum diboride is unique among transition metal diborides because it exists in both hexagonal (AlB₂-type) and rhombohedral structures. However, it is difficult to stabilize the superconducting AlB₂-type phase, which requires either extreme synthesis condition or suitable chemical doping. Here we report the structural and physical properties of Sc-doped nonstoichiometric molybdenum diborides (Mo_0.95Sc_0.05)_1-xB₂ and (Mo_1-ySc_y)_0.71B₂ prepared by the common arc melting method. The AlB₂-type phase is found to form over wide ranges of 0 ≤ x ≤ 0.29 and 0.025 ≤ y ≤ 0.30 for the first time, and bulk superconductivity with T_c up to 7.9 K is observed. T_c increases with increasing x in the (Mo_0.95Sc_0.05)_1-xB₂ series, but evolves nonmonotonically with varying y in the (Mo_1-ySc_y)_0.71B₂ series. Despite this contrast, T_c of both borides follows nearly the same linear dependence on the electron-phonon coupling constant, suggesting that it is mainly controlled by the electron-phonon interaction. In addition, the stabilization of AlB₂-type structure is attributed to the decrease in the number of d electrons as a consequence of Sc doping, which suggests that a similar effect may be achieved by substituting Mo with other d electron-poorer metal elements.