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Title: Anisotropic carrier diffusion in single MAPbI 3 grains correlates to their twin domains

Abstract

Polycrystalline thin films and single crystals of hybrid perovskites – a material group successfully used for photovoltaic and optoelectronic applications – reportedly display heterogeneous charge carrier dynamics often attributed to grain boundaries or crystalline strain. Here, we locally resolved the carrier diffusion in large, isolated methylammonium lead iodide (MAPbI3) grains via spatial- and time-resolved photoluminescence microscopy. We found that the anisotropic carrier dynamics directly correlate with the arrangement of ferroelastic twin domains. Comparing diffusion constants parallel and perpendicular to the domains showed carriers diffuse around 50–60% faster along the parallel direction. Extensive piezoresponse force microscopy experiments on the nature of the domain pattern suggest that the diffusion anisotropy most likely originates from structural and electrical anomalies at ferroelastic domain walls. We believe that the domain walls act as shallow energetic barriers, which delay the transversal diffusion of carriers. Furthermore, we demonstrate a rearrangement of the domains via heat treatment above the cubic-tetragnal phase transition. Together with the previously reported strain engineering via external stress, our findings promise additional routes to tailor the directionality of the charge carrier diffusion in MAPbI3-based photovoltaics and optoelectronics as well as other ferroelastic materials for optoelectronic applications.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [2];  [4]; ORCiD logo [1];  [3];  [1]; ORCiD logo [2]
  1. Max Planck Institute for Polymer Research, 55128 Mainz, Germany
  2. Max Planck Institute for Polymer Research, 55128 Mainz, Germany, Institute of Physics, Johannes Gutenberg University Mainz
  3. Department of Chemistry, University of Washington, Seattle, USA
  4. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, USA
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1633130
Alternate Identifier(s):
OSTI ID: 1661240
Grant/Contract Number:  
AC05-00OR22725; SC0013957; ECC-1542101
Resource Type:
Published Article
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Name: Energy & Environmental Science; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Hermes, Ilka M., Best, Andreas, Winkelmann, Leonard, Mars, Julian, Vorpahl, Sarah M., Mezger, Markus, Collins, Liam, Butt, Hans-Jürgen, Ginger, David S., Koynov, Kaloian, and Weber, Stefan A. L. Anisotropic carrier diffusion in single MAPbI 3 grains correlates to their twin domains. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0EE01016B.
Hermes, Ilka M., Best, Andreas, Winkelmann, Leonard, Mars, Julian, Vorpahl, Sarah M., Mezger, Markus, Collins, Liam, Butt, Hans-Jürgen, Ginger, David S., Koynov, Kaloian, & Weber, Stefan A. L. Anisotropic carrier diffusion in single MAPbI 3 grains correlates to their twin domains. United Kingdom. https://doi.org/10.1039/D0EE01016B
Hermes, Ilka M., Best, Andreas, Winkelmann, Leonard, Mars, Julian, Vorpahl, Sarah M., Mezger, Markus, Collins, Liam, Butt, Hans-Jürgen, Ginger, David S., Koynov, Kaloian, and Weber, Stefan A. L. Wed . "Anisotropic carrier diffusion in single MAPbI 3 grains correlates to their twin domains". United Kingdom. https://doi.org/10.1039/D0EE01016B.
@article{osti_1633130,
title = {Anisotropic carrier diffusion in single MAPbI 3 grains correlates to their twin domains},
author = {Hermes, Ilka M. and Best, Andreas and Winkelmann, Leonard and Mars, Julian and Vorpahl, Sarah M. and Mezger, Markus and Collins, Liam and Butt, Hans-Jürgen and Ginger, David S. and Koynov, Kaloian and Weber, Stefan A. L.},
abstractNote = {Polycrystalline thin films and single crystals of hybrid perovskites – a material group successfully used for photovoltaic and optoelectronic applications – reportedly display heterogeneous charge carrier dynamics often attributed to grain boundaries or crystalline strain. Here, we locally resolved the carrier diffusion in large, isolated methylammonium lead iodide (MAPbI3) grains via spatial- and time-resolved photoluminescence microscopy. We found that the anisotropic carrier dynamics directly correlate with the arrangement of ferroelastic twin domains. Comparing diffusion constants parallel and perpendicular to the domains showed carriers diffuse around 50–60% faster along the parallel direction. Extensive piezoresponse force microscopy experiments on the nature of the domain pattern suggest that the diffusion anisotropy most likely originates from structural and electrical anomalies at ferroelastic domain walls. We believe that the domain walls act as shallow energetic barriers, which delay the transversal diffusion of carriers. Furthermore, we demonstrate a rearrangement of the domains via heat treatment above the cubic-tetragnal phase transition. Together with the previously reported strain engineering via external stress, our findings promise additional routes to tailor the directionality of the charge carrier diffusion in MAPbI3-based photovoltaics and optoelectronics as well as other ferroelastic materials for optoelectronic applications.},
doi = {10.1039/D0EE01016B},
journal = {Energy & Environmental Science},
number = ,
volume = ,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/D0EE01016B

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