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Superconductors with a van der Waals (vdW) structure have attracted a considerable interest because of the possibility for truly two-dimensional (2D) superconducting systems. We recently reported NaSn 2 As 2  as a novel vdW-type superconductor with transition temperature ( T  c ) of 1.3 K. Herein, we present the crystal structure and superconductivity of new material Na 1− x  Sn 2 P 2  with  T  c  = 2.0 K. Its crystal structure consists of two layers of a buckled honeycomb network of SnP, bound by the vdW forces and separated by Na ions, as similar to that of NaSn 2 As 2 . Amount of Na deficiency ( x ) was estimated to be 0.074(18) using synchrotron X-ray diffraction. Bulk nature of superconductivity was confirmed by the measurements of electrical resistivity, magnetic susceptibility, and specific heat. First-principles calculation using density functional theory shows that Na 1− x  Sn 2 P 2  and NaSn 2 As 2  have comparable electronic structure, suggesting higher  T  c  of Na 1− x  Sn 2 P 2  resulted from increased density of states at the Fermi level due to Na deficiency. Because there are various structural analogues with tin-pnictide (SnPn) conducting layers, our results indicate that SnPn-based layered compounds can be categorized into a novel family of vdW-type superconductors, providing a new platform for studies on physics and chemistry of low-dimensional superconductors.

Na1−xSn2P2 as a new member of van der Waals-type layered tin pnictide superconductors