Nanocrystal Heterostructures Based on Halide Perovskites and Metal Sulfides

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 Pb4S(3)Cl(2) one) on top of the CsPbCl3 domain by employing Mn2+ ions, the latter most likely acting 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 a 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 and cation exchange on PbS). We demonstrate the cases of Cl- -> Br- and Pb2+ -> Cu+ exchanges, which deliver CsPbBr3-PbS and CsPbCl3-Cu2-xS epitaxial heterostructures, respectively.