Nanocrystals Heterostructures based on Halide Perovskites and Metal Sulfides

Abstract: We report the synthesis of nanocrystal heterostructures composed of CsPbCl3 and PbS domains sharing an epitaxial interface. We were able to promote the growth of a PbS domain (in competition with the more commonly observed Pb4S3Cl2 one) on top of the CsPbCl3 domain by employing Mn2$^+$ ions, the latter acting most likely as scavengers of Cl$^-$ ions. Complete suppression of the Pb4S3Cl2 domain growth was then achieved by additionally selecting an appropriate sulfur source (bis(trimethylsilyl)sulfide, which also acted as scavenger of Cl$^-$ ions), and reaction temperature. In the heterostructures, emission from the perovskite domain was quenched, while emission from the PbS domain was observed, pointing to a type-I band alignment, as confirmed by calculations. These heterostructures in turn could be exploited to prepare second-generation heterostructures through selective ion exchange on the individual domains (halide ion exchange on CsPbCl3, cation exchange on PbS). We demonstrate the cases of Cl$^-$ to Br$^-$ and Pb2$^+$ to Cu$^+$ exchanges, which deliver CsPbBr3@PbS and CsPbCl3@Cu2-xS epitaxial heterostructures, respectively.