Rapid Synthesis of Core/Shell ZnS:Mn/Si Nanotetrapods by a Catalyst-Free Thermal Evaporation Route

We report the fabrication of a hybrid all semiconductor core/shell nanotetrapod structure consisting of crystalline ZnS:Mn core and amorphous Si shell for the first time. The nanostructures were produced via a catalyst-free rapid thermal evaporation technique. Core/shell nanotetrapods were formed in two steps: (i) formation of the crystalline ZnS:Mn tetrapods and (ii) simultaneous surface adsorption of the in situ formed Si vapor species providing the amorphous shell. Crystalline tetrapod formation was guided by the formation of cubic structured ZnS octahedrons with four active (111) polar growth planes, which served as the favored growth site for the four wurtzite structured legs of the tetrapods. Choice of chloride salt as the source of dopant ion was crucial for the in situ generation of Si vapor. At elevated temperature, chloride salt reacted with the sulfur vapor to produce S2Cl2 gas that etched the Si wafers, generating Si vapor. Suppression of the surface-state-related blue emission was observed in the core/shell structures that clearly supported the formation of a shell layer. Elimination of the surface states ensured efficient energy transfer to the dopant Mn ionic state, resulting in the strong orange emission via (4)T(1)-(6)A(1) electronic transition.