Synthesis of Pure Metastable Wurtzite CZTS Nanocrystals by Facile One-Pot Method

In this article, pure phase metastable wurtzite Cu2ZnSnS4 (CZTS) nanocrystals (NCs) were synthesized by a facile one-pot method. When pure 1-dodecanethiol (DDT) was used as the solvent, two coexisting CZTS phases (wurtzite and kesterite) were found. When an increased amount of oleylamine (OAm) was added to DDT, kesterite CZTS disappeared gradually, and the as-obtained CZTS NCs became smaller and more uniform. When 0.5 mL of OAm was added, rice-like pure phase metastable wurtzite CZTS NCs were obtained. The factors, including amount of OAm, reaction temperature, reaction time, and concentration of precursors, which influence the morphology, size, and monodispersity of CZTS NCs, were studied in detail. The results showed OAm played an important role in the formation of the final pure phase metastable wurtzite NCs. Time-dependent experiments were performed to observe the growth of CZTS NCs. The final CZTS NCs evolved from spherical-like Cu2S NCs through rhombus-like intermediate shaped NCs to rice-like pure wurtzite CZTS NCs. On the basis of the detailed time-dependent shape and elemental composition evolutions, a possible asynchronous doping growth and formation mechanism was proposed. The optical and electrical properties of the pure wurtzite CZTS NCs were also investigated. The band gap of the rice-like CZTS is about 1.49 eV, which approaches the optimum value for solar photoelectric conversion. Meanwhile, the current-voltage characteristics and Hall effect measurement of the wurtzite CZTS NCs films indicated that rice-like CZTS NCs favored the electronic transmission and thus may induce the generation of photocurrent. Thus, the obtained wurtzite CZTS NCs are more suitable for using as absorber layer in low cost solar cells.