Defect structure in quantum-cutting Yb³⁺-doped CsPbCl₃ perovskites probed by x-ray absorption and atomic pair distribution function analysis

Ytterbium doping in all-inorganic lead-halide perovskites [CsPb(Cl1-xBrx)(3)] generates interesting properties including quantum cutting and narrow line emission, making these materials attractive spectral down converters for solar photovoltaics. The relationship between this optical efficiency and the defect structure(s) associated with Yb3+ dopants within perovskites is not well understood. Various charge-neutral doping motifs have previously been proposed and studied computationally, including clusters involving two substitutional Yb3+ ions charge compensated by a single local Pb2+ vacancy. Near-band-edge defect states associated with such motifs are believed to play an important mechanistic role in quantum cutting itself. Here, we report the results of x-ray absorption and x-ray total-scattering measurements on ytterbium-doped CsPbCl3. XANES shows that the dopant oxidation state is exclusively Yb3+, and a combination of Yb L-3 and Pb L-3 extended x-ray absorption fine structure (EXAFS) shows that this Yb3+ substitutes exclusively at Pb2+ sites, where it adopts a pseudo-octahedral [YbCl6](3-) coordination environment. Shell-by-shell fits to the data show a short Yb-Cl bond distance of 2.58 angstrom compared to the Pb-Cl bond distance of 2.83 angstrom. We confirm this finding by x-ray pair distribution function analysis, which also shows evidence of additional Pb2+ vacancy formation induced by Yb3+ doping. We evaluate whether this is the primary mechanism of charge compensation using simulated EXAFS and pair distribution function data for several computed defect structures. Together, these results resolve the local dopant structures and charge-compensation mechanisms in lanthanide-doped all-inorganic lead-halide perovskites, and, as such, significantly advance the understanding of structure-function relationships in this important class of materials.