Fully Inorganic Ruddlesden–Popper Double Cl–I and Triple Cl–Br–I Lead Halide Perovskite Nanocrystals

The vast majority of lead halide perovskite (LHP) nanocrystals (NCs) are currently based on either a single halide composition (CsPbCl₃, CsPbBr₃, and CsPbI₃) or an alloyed mixture of bromide with either Cl^– or I^– [i.e., CsPb(Br:Cl)₃ or CsPb(Br:I)₃]. In this work, we present the synthesis as well as a detailed optical and structural study of two halide alloying cases that have not previously been reported for LHP NCs: Cs₂PbI₂Cl₂ NCs and triple halide CsPb(Cl:Br:I)₃ NCs. In the case of Cs₂PbI₂Cl₂, we observe for the first time NCs with a fully inorganic Ruddlesden–Popper phase (RPP) crystal structure. Unlike the well-explored organic–inorganic RPP, here, the RPP formation is triggered by the size difference between the halide ions. These NCs exhibit a strong excitonic absorption, albeit with a weak photoluminescence quantum yield (PLQY). In the case of the triple halide CsPb(Cl:Br:I)₃ composition, the NCs comprise a CsPbBr₂Cl perovskite crystal lattice with only a small amount of incorporated iodide, which segregates at RPP planes’ interfaces within the CsPb(Cl:Br:I)₃ NCs. Supported by density functional theory calculations and postsynthetic surface treatments to enhance the PLQY, we show that the combination of iodide segregation and defective RPP interfaces are most likely linked to the strong PL quenching observed in these nanostructures. In summary, this work demonstrates the limits of halide alloying in LHP NCs because a mixture that contains halide ions of very different sizes leads to the formation of defective RPP interfaces and a severe quenching of LHP NC’s optical properties.