Solution‐Processed 1D Wurtzite ZnS Nanostructures with Controlled Crystallographic Orientation and Tunable Band‐Edge Emission

Abstract 1D compound semiconductor nanomaterials possess unique physicochemical properties that strongly depend on their size, composition, and structures. ZnS has been widely investigated as one of the most important semiconductors, and the control of crystallographic orientation of 1D ZnS nanostructures is still challenging and crucial to exploring their anisotropic properties. Herein, a solution‐processed strategy is developed to synthesize 1D wurtzite (w‐)ZnS nanostructures with the specific <002> and <210> orientations by co‐decomposing the copper dibutyldithiocarbamate {[(C₄H₉)₂NCS₂]₂Cu, i.e., R₂Cu} and zinc dibutyldithiocarbamate (R₂Zn) precursors in the mixed solvents of oleylamine and 1‐dodecanethoil. A solution–solid–solid (SSS)‐Oriented growth mechanism is proposed, which includes oriented nucleation dominated and SSS growth dominated stages. The crystallographic orientation mainly depends on the interfacial energy and ligand effect. The 1D w‐ZnS nanostructures with controlled crystallographic orientation display unique morphologies, i.e., <002>‐oriented w‐ZnS nanorod enclosed with {110} facets while <210>‐oriented w‐ZnS nanobelt enclosed with wide (002) and narrow (110) facets. The bandgap of 1D w‐ZnS nanostructures can be tuned from 3.94 to 3.82 eV with the crystallographic growth direction varied from <002> to <210>, thus leading to the tunable band‐edge emission from ≈338 to ≈345 nm.