Excitons competition regulation via organic cation-site and halogen-site co-halogenation of (X-p-PEA)Pb(Cl/Br) perovskites.

In this work, we report a family of co-halogenated two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead halogen ((PEA)Pb(Cl/Br)) in which the organic cation-site (PEA) is substituted with halogen at the para-site, namely the formation of 4-halophenethylamine (X-p-PEA) (X = Cl, Br; p: para-site). The organic cations are regulated by introducing halogen ions at the para-site of the benzene ring to promote the structural distortion of the lead halide octahedral inorganic layer. Furthermore, (X-p-PEA) causes a shift in the energy band distribution of 2DHPs. In this case, the photoluminescence competition of free excitons (FEs) and self-trapped excitons (STEs) changes the microscopic relaxation process of excitons. In addition, we found that (Br-p-PEA) can increase the photoluminescence quantum yield (PLQY). At the same time, we regulate the halogen-site of perovskites from lead-chloride perovskites (LCPs) to lead bromine perovskites (LBPs), achieving emission from white light to blue light. Therefore, the co-halogenation regulation strategy of organic cation-site and halogen-site can effectively regulate the photoluminescence wavelength and improve the PLQY. This is of great significance for the development of perovskite materials with specific optoelectronic applications.