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Halyna Okrepka

Publications and source records attributed to Halyna Okrepka.

2 recordsLinked to original sources

Ionic-instability induced color tuning in lead-based, mixed-halide perovskites

Contrary to conventional wisdom, intermediate photoluminescence energies can be stabilized in mixed-halide lead perovskites during photosegregation. These intermediate energies reside between those of the parent, mixed-halide alloy and fully photosegregated specimens. This demonstrates rudimentary color tuning and has practical implications for potential uses of mixed-halide perovskites in lighting applications. More fundamentally, such color tuning begs the question of how intermediate photosegregation energies arise and how they are kinetically stabilized. What follows is a study of the kinetics of terminal photosegregation energies under pulsed laser excitation. Through concerted continuous wave and pulsed laser photosegregation measurements, we develop a kinetic rationalization for how photosegregations repetition rate or duty cycle and peak fluence dependencies lead to intermediate, terminal photoluminescence energies. The developed model, in turn, explains prior observations of pulsed illumination photosegregation and offers potential insights into other, yet to be explained, phenomena such as spectral blueshifting under high intensity, pulsed illumination.

cond-mat.mtrl-sci

A thermodynamic band gap model for photoinduced phase segregation in mixed-halide perovskites

Provided is a comprehensive description of a band gap thermodynamic model, which predicts and explains key features of photosegregation in lead-based, mixed-halide perovskites. The model provides a prescription for illustrating halide migration driven by photocarrier energies. Where possible, model predictions are compared to experimental results. Free energy derivations are provided for three assumptions: (1) halide mixing in the dark, (2) a fixed number of photogenerated carriers funneling to and localizing in low band gap inclusions of the alloy, and (3) the statistical occupancy of said inclusions from a bath of thermalized photocarriers in the parent material. Model predictions include: excitation intensity ($I_{\textrm{exc}}$)-dependent terminal halide stoichiometries ($x_{\textrm{terminal}}$), excitation intensity thresholds ($I_{\textrm{exc,threshold}}$) below which photosegregation is suppressed, reduced segregation in nanocrystals as compared to thin films, the possibility to kinetically manipulate photosegregation rates via control of underlying mediators, asymmetries in forward and reverse photosegregation rate constants/activation energies, and a preference for high band gap products to recombine with the parent phase. What emerges is a cohesive framework for understanding ubiquitous photosegregation in mixed-halide perovskites and a rational basis by which to manage the phenomenon.

cond-mat.mtrl-sci