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Title: Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites

Abstract

Abstract A fundamental understanding of the interplay between the microscopic structure and macroscopic optoelectronic properties of organic‐inorganic hybrid perovskite materials is essential to design new materials and improve device performance. However, how exactly the organic cations affect the structural phase transition and optoelectronic properties of the materials is not well understood. Here, real‐time, in situ temperature‐dependent neutron/X‐ray diffraction and photoluminescence (PL) measurements reveal a transformation of the organic cation CH 3 NH 3 + from order to disorder with increasing temperature in CH 3 NH 3 PbBr 3 perovskites. The molecular‐level order‐to‐disorder transformation of CH 3 NH 3 + not only leads to an anomalous increase in PL intensity, but also results in a multidomain to single‐domain structural transition. This discovery establishes the important role that organic cation ordering has in dictating structural order and anomalous optoelectronic phenomenon in hybrid perovskites.

Authors:
 [1];  [2];  [2];  [3];  [4];  [4];  [5];  [4];  [6];  [4]
+ Show Author Affiliations
  1. Hunan Univ., Changsha (China). College of Materials Science and Engineering, Key Lab. for Micro-Nano Physics and Technology of Hunan Province; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  5. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Mechanical and Materials Engineering
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1458381
Alternate Identifier(s):
OSTI ID: 1433297
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 22; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; optoelectronic properties; organohalide perovskites; phase transitions; single crystal neutron diffraction; solar cells

Citation Formats

Yang, Bin, Ming, Wenmei, Du, Mao-Hua, Keum, Jong K., Puretzky, Alexander A., Rouleau, Christopher M., Huang, Jinsong, Geohegan, David B., Wang, Xiaoping, and Xiao, Kai. Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites. United States: N. p., 2018. Web. doi:10.1002/adma.201705801.
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Yang, Bin, Ming, Wenmei, Du, Mao-Hua, Keum, Jong K., Puretzky, Alexander A., Rouleau, Christopher M., Huang, Jinsong, Geohegan, David B., Wang, Xiaoping, & Xiao, Kai. Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites. United States. https://doi.org/10.1002/adma.201705801
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Yang, Bin, Ming, Wenmei, Du, Mao-Hua, Keum, Jong K., Puretzky, Alexander A., Rouleau, Christopher M., Huang, Jinsong, Geohegan, David B., Wang, Xiaoping, and Xiao, Kai. Mon . "Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites". United States. https://doi.org/10.1002/adma.201705801. https://www.osti.gov/servlets/purl/1458381.
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@article{osti_1458381,
title = {Real-Time Observation of Order-Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites},
author = {Yang, Bin and Ming, Wenmei and Du, Mao-Hua and Keum, Jong K. and Puretzky, Alexander A. and Rouleau, Christopher M. and Huang, Jinsong and Geohegan, David B. and Wang, Xiaoping and Xiao, Kai},
abstractNote = {Abstract A fundamental understanding of the interplay between the microscopic structure and macroscopic optoelectronic properties of organic‐inorganic hybrid perovskite materials is essential to design new materials and improve device performance. However, how exactly the organic cations affect the structural phase transition and optoelectronic properties of the materials is not well understood. Here, real‐time, in situ temperature‐dependent neutron/X‐ray diffraction and photoluminescence (PL) measurements reveal a transformation of the organic cation CH 3 NH 3 + from order to disorder with increasing temperature in CH 3 NH 3 PbBr 3 perovskites. The molecular‐level order‐to‐disorder transformation of CH 3 NH 3 + not only leads to an anomalous increase in PL intensity, but also results in a multidomain to single‐domain structural transition. This discovery establishes the important role that organic cation ordering has in dictating structural order and anomalous optoelectronic phenomenon in hybrid perovskites.},
doi = {10.1002/adma.201705801},
journal = {Advanced Materials},
number = 22,
volume = 30,
place = {United States},
year = {Mon Apr 16 00:00:00 EDT 2018},
month = {Mon Apr 16 00:00:00 EDT 2018}
}
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https://doi.org/10.1002/adma.201705801
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Figures / Tables:

Figure 1 Figure 1: Neutron diffraction of MAPbBr3 single crystals at different temperatures spanning the orthorhombic to tetragonal to cubic phase transition. a) Variable temperature plot showing the change of the (200)C peak during continuous heating from 95 to 295 K at the rate of 1 K min−1. The (200)C peak ismore » indexed as the (220)T peak in the tetragonal I4/$mcm$ phase between 230 and 153 K and the (202)O peak in the orthorhombic $Pnma$ phase at temperatures below 153 K, respectively. The fluctuation of the (200)C peak between ≈140 and 155 K is most likely due to the coexistence of the tetragonal and orthorhombic phase. The inset shows a millimeter‐size crystal that was used for neutron single crystal diffraction measurements. b–d) 2D scattering profiles of the (200) peak in the (H, K, 0) RLP along the [0, 0, L] direction measured at 95, 180, and 295 K, respectively.« less
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