Raman study of colloidal Cu2ZnSnS4 nanocrystals obtained by “green” synthesis modified by seed nanocrystals or extra cations in the solution

The method of affordable colloidal synthesis of nanocrystalline Cu2ZnSnS4 (CZTS) is developed, which is suitable for obtaining bare CZTS nanocrystals (NCs), cation substituted CZTS NCs, and CZTS-based hetero-NCs. For the hetero-NCs, the synthesized in advance NCs of another material are introduced into the reaction solution so that the formation of CZTS takes place preferably on these "seed" NCs. Raman spectroscopy is used as the primary method of structural characterization of the NCs in this work because it is very sensitive to the CZTS structure and allows to probe NCs both in solutions and films. Raman data are corroborated by optical absorption measurements and transmission electron microscopy on selected samples. The CdTe and Ag NCs are found to be good seed NCs, resulting in a comparable or even better quality of the CZTS compound compared to bare CZTS NCs. For Au NCs, on the contrary, no hetero-NCs could be obtained under the given condition. Partial substitution of Zn for Ba during the synthesis of bare CZTS NCs results in a superior structural quality of NCs, while the introduction of Ag for partial substitution of Cu deteriorates the structural quality of the NCs.