Modeling the Photoelectrochemical Evolution of Lead-Based, Mixed-Halide Perovskites Due to Photosegregation

Ruth, Anthony; Kuno, Masaru

doi:10.1021/acsnano.3c07165

Modeling the Photoelectrochemical Evolution of Lead-Based, Mixed-Halide Perovskites Due to Photosegregation

Journal Article · Tue Oct 10 00:00:00 EDT 2023 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.3c07165· OSTI ID:2338290

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University of Notre Dame, IN (United States); University of Notre Dame
University of Notre Dame, IN (United States)

Lead-based, mixed-halide perovskites such as methylammonium lead iodide-bromide [MAPb(I_1-xBr_x)₃] undergo anion photosegregation under illumination. This is observed as low band gap photoluminescence from photogenerated iodine-rich domains due to favorable band offsets that induce carrier funneling into them. Unfortunately, theoretical rationalizations of mixed-halide photosegregation are complicated by biases inherent to photoluminescence-based observations. Recent compositionally-weighted X-ray diffraction (XRD) measurements now reveal broad distributions of photosegregated stoichiometries not captured by existing photosegregation models. To better bridge experiment and theory, we perform kinetic Monte Carlo (KMC) simulations of photosegregation within the context of a band gap-based thermodynamic model, which has previously accounted for numerous experimental observations. Our KMC simulations are modified to consider high carrier density Fermi-Dirac statistics that result from carrier funneling and accumulation within photosegregated I-rich domains. Obtained KMC results reproduce broad x_terminal distributions seen experimentally and illustrate how they are characterized by a central, heavily I-enriched stoichiometry. I-rich domain “drifting” during photosegregation rationalizes the long photosegregation timescales seen experimentally with drifting simultaneously producing a wake of variable stoichiometry I-rich inclusions that form the lion’s share of stoichiometric heterogeneities seen in compositionally-weighted XRD measurements. These simulations and accompanying rationalizations further reveal a general criterion for realizing favorable free energies to induce demixing. Central to the criterion is the statistical occupation of low gap inclusions in the parent alloy by excitations. Furthermore, the resulting model thus provides a general framework for conceptualizing mixed-halide perovskite light and temperature sensitivities, mediated by photocarriers.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0014334

OSTI ID:: 2338290

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 20 Vol. 17; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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