DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

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.

Save / Share:

Works referenced in this record:

Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites
journal, January 2017


The Bright Side of Perovskites
journal, October 2016

  • Colella, Silvia; Mazzeo, Marco; Rizzo, Aurora
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 21
  • DOI: 10.1021/acs.jpclett.6b01799

Perovskite energy funnels for efficient light-emitting diodes
journal, June 2016

  • Yuan, Mingjian; Quan, Li Na; Comin, Riccardo
  • Nature Nanotechnology, Vol. 11, Issue 10
  • DOI: 10.1038/nnano.2016.110

Stabilizing Cesium Lead Halide Perovskite Lattice through Mn(II) Substitution for Air-Stable Light-Emitting Diodes
journal, August 2017

  • Zou, Shenghan; Liu, Yongsheng; Li, Jianhai
  • Journal of the American Chemical Society, Vol. 139, Issue 33
  • DOI: 10.1021/jacs.7b04000

23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability
journal, February 2017

  • Bush, Kevin A.; Palmstrom, Axel F.; Yu, Zhengshan J.
  • Nature Energy, Vol. 2, Issue 4
  • DOI: 10.1038/nenergy.2017.9

A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016


Universal Approach toward Hysteresis-Free Perovskite Solar Cell via Defect Engineering
journal, January 2018

  • Son, Dae-Yong; Kim, Seul-Gi; Seo, Ja-Young
  • Journal of the American Chemical Society, Vol. 140, Issue 4
  • DOI: 10.1021/jacs.7b10430

Evolution of Chemical Composition, Morphology, and Photovoltaic Efficiency of CH 3 NH 3 PbI 3 Perovskite under Ambient Conditions
journal, December 2015


Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency
journal, January 2016

  • Saliba, Michael; Matsui, Taisuke; Seo, Ji-Youn
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C5EE03874J

Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys
journal, December 2015


Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability
journal, January 2018


Systematic investigation of the impact of operation conditions on the degradation behaviour of perovskite solar cells
journal, January 2018


Formamidinium and Cesium Hybridization for Photo- and Moisture-Stable Perovskite Solar Cell
journal, September 2015

  • Lee, Jin-Wook; Kim, Deok-Hwan; Kim, Hui-Seon
  • Advanced Energy Materials, Vol. 5, Issue 20
  • DOI: 10.1002/aenm.201501310

Imaging Energy Harvesting and Storage Systems at the Nanoscale
journal, November 2017


Mesoscale Functional Imaging of Materials for Photovoltaics
journal, July 2017


Real-Time Nanoscale Open-Circuit Voltage Dynamics of Perovskite Solar Cells
journal, March 2017


Anomalous photovoltaic effect in organic-inorganic hybrid perovskite solar cells
journal, March 2017


Nanoimaging of Open-Circuit Voltage in Photovoltaic Devices
journal, September 2015

  • Tennyson, Elizabeth M.; Garrett, Joseph L.; Frantz, Jesse A.
  • Advanced Energy Materials, Vol. 5, Issue 23
  • DOI: 10.1002/aenm.201501142

Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite
journal, July 2016


Mapping the Photoresponse of CH 3 NH 3 PbI 3 Hybrid Perovskite Thin Films at the Nanoscale
journal, May 2016


Anticorrelation between Local Photoluminescence and Photocurrent Suggests Variability in Contact to Active Layer in Perovskite Solar Cells
journal, October 2016


Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals
journal, September 2017


Photoinduced Emissive Trap States in Lead Halide Perovskite Semiconductors
journal, September 2016


Tracking Photoexcited Carriers in Hybrid Perovskite Semiconductors: Trap-Dominated Spatial Heterogeneity and Diffusion
journal, September 2017


Elucidation of Perovskite Film Micro-Orientations Using Two-Photon Total Internal Reflectance Fluorescence Microscopy
journal, July 2015

  • Watson, Brianna R.; Yang, Bin; Xiao, Kai
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 16
  • DOI: 10.1021/acs.jpclett.5b01474

Correlation between Photoluminescence and Carrier Transport and a Simple In Situ Passivation Method for High-Bandgap Hybrid Perovskites
journal, July 2017

  • Stoddard, Ryan J.; Eickemeyer, Felix T.; Katahara, John K.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 14
  • DOI: 10.1021/acs.jpclett.7b01185

Reversible Hydration of CH 3 NH 3 PbI 3 in Films, Single Crystals, and Solar Cells
journal, April 2015


Perovskite Solar Cell Stability in Humid Air: Partially Reversible Phase Transitions in the PbI 2 -CH 3 NH 3 I-H 2 O System
journal, July 2016

  • Song, Zhaoning; Abate, Antonio; Watthage, Suneth C.
  • Advanced Energy Materials, Vol. 6, Issue 19
  • DOI: 10.1002/aenm.201600846

Influence of water intercalation and hydration on chemical decomposition and ion transport in methylammonium lead halide perovskites
journal, January 2018

  • Jong, Un-Gi; Yu, Chol-Jun; Ri, Gum-Chol
  • Journal of Materials Chemistry A, Vol. 6, Issue 3
  • DOI: 10.1039/C7TA09112E

Shift Happens . How Halide Ion Defects Influence Photoinduced Segregation in Mixed Halide Perovskites
journal, June 2017


Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics
journal, January 2015

  • Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R.
  • Chemical Science, Vol. 6, Issue 1
  • DOI: 10.1039/C4SC03141E

Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells
journal, May 2017

  • Aristidou, Nicholas; Eames, Christopher; Sanchez-Molina, Irene
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15218

The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers
journal, May 2015

  • Aristidou, Nicholas; Sanchez-Molina, Irene; Chotchuangchutchaval, Thana
  • Angewandte Chemie International Edition, Vol. 54, Issue 28
  • DOI: 10.1002/anie.201503153

Improved environmental stability of organic lead trihalide perovskite-based photoactive-layers in the presence of mesoporous TiO 2
journal, January 2015

  • O'Mahony, Flannan T. F.; Lee, Yong Hui; Jellett, Cameron
  • Journal of Materials Chemistry A, Vol. 3, Issue 14
  • DOI: 10.1039/C5TA01221J

Impact of H 2 O on organic–inorganic hybrid perovskite solar cells
journal, January 2017

  • Huang, Jianbing; Tan, Shunquan; Lund, Peter D.
  • Energy & Environmental Science, Vol. 10, Issue 11
  • DOI: 10.1039/C7EE01674C

Transformation of the Excited State and Photovoltaic Efficiency of CH 3 NH 3 PbI 3 Perovskite upon Controlled Exposure to Humidified Air
journal, January 2015

  • Christians, Jeffrey A.; Miranda Herrera, Pierre A.; Kamat, Prashant V.
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja511132a

Surface Restructuring of Hybrid Perovskite Crystals
journal, November 2016


Controlled Humidity Study on the Formation of Higher Efficiency Formamidinium Lead Triiodide-Based Solar Cells
journal, June 2015


In Situ Monitoring the Uptake of Moisture into Hybrid Perovskite Thin Films
journal, April 2018

  • Schlipf, Johannes; Bießmann, Lorenz; Oesinghaus, Lukas
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 8
  • DOI: 10.1021/acs.jpclett.8b00687

Interaction of Organic Cation with Water Molecule in Perovskite MAPbI 3 : From Dynamic Orientational Disorder to Hydrogen Bonding
journal, October 2016


Photoluminescence Enhancement in Formamidinium Lead Iodide Thin Films
journal, April 2016

  • Fang, Hong-Hua; Wang, Feng; Adjokatse, Sampson
  • Advanced Functional Materials, Vol. 26, Issue 26
  • DOI: 10.1002/adfm.201600715

The Importance of Moisture in Hybrid Lead Halide Perovskite Thin Film Fabrication
journal, August 2015

  • Eperon, Giles E.; Habisreutinger, Severin N.; Leijtens, Tomas
  • ACS Nano, Vol. 9, Issue 9
  • DOI: 10.1021/acsnano.5b03626

Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells
journal, March 2013

  • Noh, Jun Hong; Im, Sang Hyuk; Heo, Jin Hyuck
  • Nano Letters, Vol. 13, Issue 4, p. 1764-1769
  • DOI: 10.1021/nl400349b

Works referencing / citing this record:

Imaging and Mapping Characterization Tools for Perovskite Solar Cells
journal, July 2019

  • Hidalgo, Juanita; Castro‐Méndez, Andrés‐Felipe; Correa‐Baena, Juan‐Pablo
  • Advanced Energy Materials, Vol. 9, Issue 30
  • DOI: 10.1002/aenm.201900444

Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures
journal, January 2020


Heterogeneity at multiple length scales in halide perovskite semiconductors
journal, July 2019

  • Tennyson, Elizabeth M.; Doherty, Tiarnan A. S.; Stranks, Samuel D.
  • Nature Reviews Materials, Vol. 4, Issue 9
  • DOI: 10.1038/s41578-019-0125-0

Bias‐Dependent Stability of Perovskite Solar Cells Studied Using Natural and Concentrated Sunlight
journal, August 2019

  • K. M., Anoop; Khenkin, Mark V.; Di Giacomo, Francesco
  • Solar RRL, Vol. 4, Issue 2
  • DOI: 10.1002/solr.201900335

Imaging Metal Halide Perovskites Material and Properties at the Nanoscale
journal, December 2019


In Situ 2D Perovskite Formation and the Impact of the 2D/3D Structures on Performance and Stability of Perovskite Solar Cells
journal, May 2019

  • de Holanda, Matheus S.; Szostak, Rodrigo; Marchezi, Paulo E.
  • Solar RRL, Vol. 3, Issue 9
  • DOI: 10.1002/solr.201900199

A Highly Emissive Surface Layer in Mixed‐Halide Multication Perovskites
journal, September 2019

  • Andaji‐Garmaroudi, Zahra; Abdi‐Jalebi, Mojtaba; Guo, Dengyang
  • Advanced Materials, Vol. 31, Issue 42
  • DOI: 10.1002/adma.201902374

In Situ 2D Perovskite Formation and the Impact of the 2D/3D Structures on Performance and Stability of Perovskite Solar Cells
journal, May 2019

  • de Holanda, Matheus S.; Szostak, Rodrigo; Marchezi, Paulo E.
  • Solar RRL, Vol. 3, Issue 9
  • DOI: 10.1002/solr.201970084

Heterogeneity at multiple length scales in halide perovskite semiconductors
text, January 2019

  • Tennyson, Beth; Doherty, Tas; Stranks, Samuel
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.41839

Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures
text, January 2020

  • Khenkin, Mark V.; Katz, Eugene A.; Abate, Antonio
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.63659

A Highly Emissive Surface Layer in Mixed-Halide Multication Perovskites.
text, January 2019

  • Andaji-Garmaroudi, Zahra; Abdi-Jalebi, Mojtaba; Guo, Dengyang
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.43272

Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures
text, January 2020

  • Khenkin, Mv; Katz, Ea; Abate, A.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.54194

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