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Title: Humidity-Induced Photoluminescence Hysteresis in Variable Cs/Br Ratio Hybrid Perovskites

Abstract

Hybrid organic–inorganic perovskites containing Cs are a promising new material for light-absorbing and light-emitting optoelectronics. However, the impact of environmental conditions on their optical properties is not fully understood. In this paper, we elucidate and quantify the influence of distinct humidity levels on the charge carrier recombination in CsxFA1–xPb(IyBr1–y)3 perovskites. Using in situ environmental photoluminescence (PL), we temporally and spectrally resolve light emission within a loop of critical relative humidity (rH) levels. Our measurements show that exposure up to 35% rH increases the PL emission for all Cs (10–17%) and Br (17–38%) concentrations investigated here. Spectrally, samples with larger Br concentrations exhibit PL redshift at higher humidity levels, revealing water-driven halide segregation. The compositions considered present hysteresis in their PL intensity upon returning to a low-moisture environment due to partially reversible hydration of the perovskites. Our findings demonstrate that the Cs/Br ratio strongly influences both the spectral stability and extent of light emission hysteresis. Finally, we expect our method to become standard when testing the stability of emerging perovskites, including lead-free options, and to be combined with other parameters known for affecting material degradation, e.g., oxygen and temperature.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [1]
  1. Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering. Inst. for Research in Electronics and Applied Physics
  2. Univ. of Maryland, College Park, MD (United States). Inst. for Research in Electronics and Applied Physics. Dept. of Physics
  3. Univ. of Campinas (Brazil). Inst. of Chemistry
  4. Univ. of Maryland, College Park, MD (United States). Inst. for Research in Electronics and Applied Physics. Dept. of Electrical and Computer Engineering
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource; Univ. of Campinas (Brazil). Inst. of Chemistry
  7. Univ. of Maryland, College Park, MD (United States). Inst. for Research in Electronics and Applied Physics; Federal Univ. of Minas Gerais, Belo Horizonte (Brazil). Dept. of Physics
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Maryland, College Park, MD (United States); Univ. of Campinas (Brazil)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); São Paulo Research Foundation (FAPESP) (Brazil)
OSTI Identifier:
1469619
Grant/Contract Number:  
AC02-76SF00515; 16-10833; 2017/12582-5; 2015/50450-8
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Howard, John M., Tennyson, Elizabeth M., Barik, Sabyasachi, Szostak, Rodrigo, Waks, Edo, Toney, Michael F., Nogueira, Ana F., Neves, Bernardo R. A., and Leite, Marina S. Humidity-Induced Photoluminescence Hysteresis in Variable Cs/Br Ratio Hybrid Perovskites. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b01357.
Howard, John M., Tennyson, Elizabeth M., Barik, Sabyasachi, Szostak, Rodrigo, Waks, Edo, Toney, Michael F., Nogueira, Ana F., Neves, Bernardo R. A., & Leite, Marina S. Humidity-Induced Photoluminescence Hysteresis in Variable Cs/Br Ratio Hybrid Perovskites. United States. https://doi.org/10.1021/acs.jpclett.8b01357
Howard, John M., Tennyson, Elizabeth M., Barik, Sabyasachi, Szostak, Rodrigo, Waks, Edo, Toney, Michael F., Nogueira, Ana F., Neves, Bernardo R. A., and Leite, Marina S. Fri . "Humidity-Induced Photoluminescence Hysteresis in Variable Cs/Br Ratio Hybrid Perovskites". United States. https://doi.org/10.1021/acs.jpclett.8b01357. https://www.osti.gov/servlets/purl/1469619.
@article{osti_1469619,
title = {Humidity-Induced Photoluminescence Hysteresis in Variable Cs/Br Ratio Hybrid Perovskites},
author = {Howard, John M. and Tennyson, Elizabeth M. and Barik, Sabyasachi and Szostak, Rodrigo and Waks, Edo and Toney, Michael F. and Nogueira, Ana F. and Neves, Bernardo R. A. and Leite, Marina S.},
abstractNote = {Hybrid organic–inorganic perovskites containing Cs are a promising new material for light-absorbing and light-emitting optoelectronics. However, the impact of environmental conditions on their optical properties is not fully understood. In this paper, we elucidate and quantify the influence of distinct humidity levels on the charge carrier recombination in CsxFA1–xPb(IyBr1–y)3 perovskites. Using in situ environmental photoluminescence (PL), we temporally and spectrally resolve light emission within a loop of critical relative humidity (rH) levels. Our measurements show that exposure up to 35% rH increases the PL emission for all Cs (10–17%) and Br (17–38%) concentrations investigated here. Spectrally, samples with larger Br concentrations exhibit PL redshift at higher humidity levels, revealing water-driven halide segregation. The compositions considered present hysteresis in their PL intensity upon returning to a low-moisture environment due to partially reversible hydration of the perovskites. Our findings demonstrate that the Cs/Br ratio strongly influences both the spectral stability and extent of light emission hysteresis. Finally, we expect our method to become standard when testing the stability of emerging perovskites, including lead-free options, and to be combined with other parameters known for affecting material degradation, e.g., oxygen and temperature.},
doi = {10.1021/acs.jpclett.8b01357},
journal = {Journal of Physical Chemistry Letters},
number = 12,
volume = 9,
place = {United States},
year = {Fri Jun 08 00:00:00 EDT 2018},
month = {Fri Jun 08 00:00:00 EDT 2018}
}

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Figures / Tables:

Figure 1 Figure 1: Morphology and humidity-dependent PL imaging of different composition perovskites. (a-d) SEM micrographs and (e-h) normalized PL images at < 5% rH for Cs-10%/Br-17%, Cs-17%/Br-17%, Cs-17%/38%-Br, and 10%-Cs/38%-Br, respectively. All PL images are independently normalized by their individual minimum and maximum values.

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.