Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements
Abstract
Solution-processed mixed halide perovskites are excellent materials for multijunction solar cells. Unfortunately, light-induced halide phase segregation has prevented their effective integration into working devices. In this study, we rationalize and quantify anion photosegregation in stoichiometric and halide-deficient MAPb(I1–xBrx)3 thin films through kinetic Monte Carlo simulations and complementary optical measurements. Our study reveals that segregation rates are dictated by halide vacancy hopping barriers and are modulated by vacancy concentrations. The simulations further suggest that near-ubiquitous emission energies, which converge on that for MAPb(I0.8Br0.2)3 (i.e., x ≈ 0.2) following photosegregation, arise from the existence of kinetically trapped Br– within nucleated I-rich domains. An established photosegregation excitation intensity threshold is independent of the number of vacancies and instead depends critically on parameters such as carrier diffusion length, lifetime, and bandgap tunability. The study thus sheds new light on important parameters that define halide photosegregation and presents opportunities for controlling the phenomenon.
- Authors:
-
[3];
[4]
- Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Physics
- Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
- Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Div.
- Univ. of Notre Dame, Notre Dame, IN (United States). Dept. pf Physics and Dept. of Chemistry and Biochemistry
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States); University of Notre Dame, IN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1489373
- Alternate Identifier(s):
- OSTI ID: 1657799
- Grant/Contract Number:
- AC02-06CH11357; SC0014334
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 10; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ruth, Anthony, Brennan, Michael C., Draguta, Sergiu, Morozov, Yurii V., Zhukovskyi, Maksym, Janko, Boldizsar, Zapol, Peter, and Kuno, Masaru. Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements. United States: N. p., 2018.
Web. doi:10.1021/acsenergylett.8b01369.
Ruth, Anthony, Brennan, Michael C., Draguta, Sergiu, Morozov, Yurii V., Zhukovskyi, Maksym, Janko, Boldizsar, Zapol, Peter, & Kuno, Masaru. Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements. United States. https://doi.org/10.1021/acsenergylett.8b01369
Ruth, Anthony, Brennan, Michael C., Draguta, Sergiu, Morozov, Yurii V., Zhukovskyi, Maksym, Janko, Boldizsar, Zapol, Peter, and Kuno, Masaru. Wed .
"Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements". United States. https://doi.org/10.1021/acsenergylett.8b01369. https://www.osti.gov/servlets/purl/1489373.
@article{osti_1489373,
title = {Vacancy-Mediated Anion Photosegregation Kinetics in Mixed Halide Hybrid Perovskites: Coupled Kinetic Monte Carlo and Optical Measurements},
author = {Ruth, Anthony and Brennan, Michael C. and Draguta, Sergiu and Morozov, Yurii V. and Zhukovskyi, Maksym and Janko, Boldizsar and Zapol, Peter and Kuno, Masaru},
abstractNote = {Solution-processed mixed halide perovskites are excellent materials for multijunction solar cells. Unfortunately, light-induced halide phase segregation has prevented their effective integration into working devices. In this study, we rationalize and quantify anion photosegregation in stoichiometric and halide-deficient MAPb(I1–xBrx)3 thin films through kinetic Monte Carlo simulations and complementary optical measurements. Our study reveals that segregation rates are dictated by halide vacancy hopping barriers and are modulated by vacancy concentrations. The simulations further suggest that near-ubiquitous emission energies, which converge on that for MAPb(I0.8Br0.2)3 (i.e., x ≈ 0.2) following photosegregation, arise from the existence of kinetically trapped Br– within nucleated I-rich domains. An established photosegregation excitation intensity threshold is independent of the number of vacancies and instead depends critically on parameters such as carrier diffusion length, lifetime, and bandgap tunability. The study thus sheds new light on important parameters that define halide photosegregation and presents opportunities for controlling the phenomenon.},
doi = {10.1021/acsenergylett.8b01369},
journal = {ACS Energy Letters},
number = 10,
volume = 3,
place = {United States},
year = {Wed Sep 05 00:00:00 EDT 2018},
month = {Wed Sep 05 00:00:00 EDT 2018}
}
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