A size-dependent structural evolution of ZnS nanoparticles

Recently, ZnS quantum dots have attracted a lot of attention since they can be a suitable alternative for cadmium-based quantum dots, which are known to be highly carcinogenic for living systems. However, the structural stability of nanocrystalline ZnS seems to be a challenging issue since ZnS nanoparticles have the potential to undergo uncontrolled structural change at room temperature. Using the molecular dynamics technique, we have studied the structural evolution of 1 to 5 nm freestanding ZnS nanoparticles with zinc-blende and wurtzite crystal structures. Simulation results revealed that relaxed configurations of ZnS nanoparticles larger than 3 nm consist of three regions: a) a crystalline core, b) a distorted network of 4-coordinated atoms environing the crystalline core, and c) a surface structure made entirely of 3-coordinated atoms. Decreasing the size of ZnS nanoparticle to 2 nm will cause the crystalline core to disappear. Further reducing the size will cause all of the atoms to become 3-coordinated. Dipole moments of zinc-blende and wurtzite nanoparticles are in the same range when the nanoparticles are smaller than 3 nm. Increasing the size makes dipole moments converge to the bulk values. This makes zinc-blende and wurtzite nanoparticles less and more polar, respectively.