Deterministic Two-Dimensional Polymorphism Growth of Hexagonal n-Type SnS₂ and Orthorhombic p-Type SnS Crystals

van der Waals layered materials have large crystal anisotropy and crystallize spontaneously into two-dimensional (2D) morphologies. Two-dimensional materials with hexagonal lattices are emerging 2D confined electronic systems at the limit of one or three atom thickness. Often these 2D lattices also form orthorhombic symmetries, but these materials have not been extensively investigated, mainly due to thermodynamic instability during crystal growth. Here, we show controlled polymorphic growth of 2D tin-sulfide crystals of either hexagonal SnS₂ or orthorhombic SnS. Addition of H₂ during the growth reaction enables selective determination of either n-type SnS₂ or p-type SnS 2D crystal of dissimilar energy band gap of 2.77 eV (SnS₂) or 1.26 eV (SnS) as a final product. Based on this synthetic 2D polymorphism of p-n crystals, we also demonstrate p-n heterojunctions for rectifiers and photovoltaic cells, and complementary inverters. (Chemical Equation Presented).