Generalized and Facile Synthesis of Semiconducting Metal Sulfide Nanocrystals

Abstract

We report on the synthesis of semiconductor nanocrystals of PbS, ZnS, CdS, and MnS through a facile and inexpensive synthetic process. Metal−oleylamine complexes, which were obtained from the reaction of metal chloride and oleylamine, were mixed with sulfur. The reaction mixture was heated under appropriate experimental conditions to produce metal sulfide nanocrystals. Uniform cube-shaped PbS nanocrystals with particle sizes of 6, 8, 9, and 13 nm were synthesized. The particle size was controlled by changing the relative amount of PbCl₂ and sulfur. Uniform 11 nm sized spherical ZnS nanocrystals were synthesized from the reaction of zinc chloride and sulfur, followed by one cycle of size-selective precipitation. CdS nanocrystals that consist of rods, bipods, and tripods were synthesized from a reaction mixture containing a 1:6 molar ratio of cadmium to sulfur. Spherical CdS nanocrystals (5.1 nm sized) were obtained from a reaction mixture with a cadmium to sulfur molar ratio of 2:1. MnS nanocrystals with various sizes and shapes were synthesized from the reaction of MnCl₂ and sulfur in oleylamine. Rod-shaped MnS nanocrystals with an average size of 20 nm (thickness) × 37 nm (length) were synthesized from a 1:1 molar ratio of MnCl₂ and sulfur at 240 °C. Novel bullet-shaped MnS nanocrystals with an average size of 17 nm (thickness) × 44 nm (length) were synthesized from the reaction of 4 mmol of MnCl₂ and 2 mmol of sulfur at 280 °C for 2 h. Shorter bullet-shaped MnS nanocrystals were synthesized from a 3:1 molar ratio of MnCl₂ and sulfur. Hexagon-shaped MnS nanocrystals were also obtained. All of the synthesized nanocrystals were highly crystalline.