Structural Determination and Nonlinear Optical Properties of New 1T'''-Type MoS 2 Compound

Noncentrosymmetric MoS semiconductors (1H, 3R) possess not only novel electronic structures of spin-orbit coupling (SOC) and valley polarization but also remarkable nonlinear optical effects. A more interesting noncentrosymmetric struc-ture - the so-called 1T'''-MoS layers was predicted to be built up from [MoS6] octahedral motifs by theoreticians, but the bulk 1T''' MoS or its single crystal structure has not been reported yet. Here, we have successfully harvested 1T''' MoS single crystals by a topochemical method. The new layered structure is determined from single-crystal X-ray diffraction. The crystal crystallizes in space group P31m with a cell of a = b = 5.580(2) Å and c = 5.957(2) Å, which is a √3a × √3a superstructure of 1T MoS with corner-sharing Mo triangular trimers observed by the STEM. 1T''' MoS is verified to be semiconducting and possesses a band gap of 0.65 eV, different from metallic nature of 1T or 1T' MoS . More surprisingly, the 1T''' MoS does show strong optical second-harmonic generation signals. This work provides the first layered noncentrosymmetric semicon-ductor of edge-sharing MoS octahedra for the research of non-linear optics.