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:
-
[1];
[1];
[2];
[1];
[2]
- Max Planck Institute for Polymer Research, 55128 Mainz, Germany
- Max Planck Institute for Polymer Research, 55128 Mainz, Germany, Institute of Physics, Johannes Gutenberg University Mainz
- Department of Chemistry, University of Washington, Seattle, USA
- Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, USA
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (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. doi: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 = {Wed Jan 01 00:00:00 EST 2020},
month = {Wed Jan 01 00:00:00 EST 2020}
}
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Works referenced in this record:
Bulk crystal growth of hybrid perovskite material CH 3 NH 3 PbI 3
journal, January 2015
- Dang, Yangyang; Liu, Yang; Sun, Youxuan
- CrystEngComm, Vol. 17, Issue 3
Grain Boundaries Act as Solid Walls for Charge Carrier Diffusion in Large Crystal MAPI Thin Films
journal, February 2018
- Ciesielski, Richard; Schäfer, Frank; Hartmann, Nicolai F.
- ACS Applied Materials & Interfaces, Vol. 10, Issue 9
The Role of Grain Boundaries in Perovskite Solar Cells
journal, August 2019
- Castro‐Méndez, Andrés‐Felipe; Hidalgo, Juanita; Correa‐Baena, Juan‐Pablo
- Advanced Energy Materials, Vol. 9, Issue 38
Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals
journal, January 2015
- Shi, D.; Adinolfi, V.; Comin, R.
- Science, Vol. 347, Issue 6221
Observation of Dirac-like energy band and ring-torus Fermi surface associated with the nodal line in topological insulator CaAgAs
journal, January 2018
- Takane, Daichi; Nakayama, Kosuke; Souma, Seigo
- npj Quantum Materials, Vol. 3, Issue 1
Domains in Ferroic Crystals and Thin Films
book, January 2010
- Tagantsev, Alexander K.; Cross, L. Eric; Fousek, Jan
First-Principles Study of Ferroelastic Twins in Halide Perovskites
journal, February 2019
- Warwick, Andrew R.; Íñiguez, Jorge; Haynes, Peter D.
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 6
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009
- Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
- Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
Impact of Photon Recycling on the Open-Circuit Voltage of Metal Halide Perovskite Solar Cells
journal, September 2016
- Kirchartz, Thomas; Staub, Florian; Rau, Uwe
- ACS Energy Letters, Vol. 1, Issue 4
Dual-frequency resonance-tracking atomic force microscopy
journal, October 2007
- Rodriguez, Brian J.; Callahan, Clint; Kalinin, Sergei V.
- Nanotechnology, Vol. 18, Issue 47, Article No. 475504
Local Crystal Misorientation Influences Non-radiative Recombination in Halide Perovskites
journal, December 2019
- Jariwala, Sarthak; Sun, Hongyu; Adhyaksa, Gede W. P.
- Joule, Vol. 3, Issue 12
The existence and impact of persistent ferroelectric domains in MAPbI 3
journal, January 2019
- Garten, Lauren M.; Moore, David T.; Nanayakkara, Sanjini U.
- Science Advances, Vol. 5, Issue 1
Role of Ferroelectric Nanodomains in the Transport Properties of Perovskite Solar Cells
journal, January 2016
- Pecchia, Alessandro; Gentilini, Desirée; Rossi, Daniele
- Nano Letters, Vol. 16, Issue 2
Quantitative measurements of electromechanical response with a combined optical beam and interferometric atomic force microscope
journal, June 2015
- Labuda, Aleksander; Proksch, Roger
- Applied Physics Letters, Vol. 106, Issue 25
Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites
journal, February 2015
- Liu, Shi; Zheng, Fan; Koocher, Nathan Z.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 4
Visualizing Buried Local Carrier Diffusion in Halide Perovskite Crystals via Two-Photon Microscopy
journal, November 2019
- Stavrakas, Camille; Delport, Géraud; Zhumekenov, Ayan A.
- ACS Energy Letters, Vol. 5, Issue 1
Visualizing Carrier Diffusion in Individual Single-Crystal Organolead Halide Perovskite Nanowires and Nanoplates
journal, September 2015
- Tian, Wenming; Zhao, Chunyi; Leng, Jing
- Journal of the American Chemical Society, Vol. 137, Issue 39
Limiting Perovskite Solar Cell Performance by Heterogeneous Carrier Extraction
journal, October 2016
- Tian, Wenming; Cui, Rongrong; Leng, Jing
- Angewandte Chemie International Edition, Vol. 55, Issue 42
Solvent Annealing of Perovskite-Induced Crystal Growth for Photovoltaic-Device Efficiency Enhancement
journal, August 2014
- Xiao, Zhengguo; Dong, Qingfeng; Bi, Cheng
- Advanced Materials, Vol. 26, Issue 37
Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
journal, April 2014
- Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico
- Nano Letters, Vol. 14, Issue 5
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013
- Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
- Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
Physics and applications of charged domain walls
journal, November 2018
- Bednyakov, Petr S.; Sturman, Boris I.; Sluka, Tomas
- npj Computational Materials, Vol. 4, Issue 1
Ferroelastic Materials
journal, August 2012
- Salje, Ekhard K. H.
- Annual Review of Materials Research, Vol. 42, Issue 1
Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K
journal, January 2015
- Weller, Mark T.; Weber, Oliver J.; Henry, Paul F.
- Chemical Communications, Vol. 51, Issue 20
Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%
journal, August 2012
- Kim, Hui-Seon; Lee, Chang-Ryul; Im, Jeong-Hyeok
- Scientific Reports, Vol. 2, Issue 1
Quantitative Electromechanical Atomic Force Microscopy
journal, July 2019
- Collins, Liam; Liu, Yongtao; Ovchinnikova, Olga S.
- ACS Nano, Vol. 13, Issue 7
Spatial and temporal imaging of long-range charge transport in perovskite thin films by ultrafast microscopy
journal, June 2015
- Guo, Zhi; Manser, Joseph S.; Wan, Yan
- Nature Communications, Vol. 6, Issue 1
On the importance of ferroelectric domains for the performance of perovskite solar cells
journal, June 2018
- Rossi, Daniele; Pecchia, Alessandro; Maur, Matthias Auf der
- Nano Energy, Vol. 48
Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells
journal, January 2016
- Jesper Jacobsson, T.; Correa-Baena, Juan-Pablo; Pazoki, Meysam
- Energy & Environmental Science, Vol. 9, Issue 5
Screened Charge Carrier Transport in Methylammonium Lead Iodide Perovskite Thin Films
journal, February 2017
- Hill, Andrew H.; Smyser, Kori E.; Kennedy, Casey L.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 5
Dynamic behavior of CH 3 NH 3 PbI 3 perovskite twin domains
journal, August 2018
- Liu, Yongtao; Collins, Liam; Belianinov, Alex
- Applied Physics Letters, Vol. 113, Issue 7
Scanning Probe Microscopy
book, January 2007
- Kalinin, Sergei; Gruverman, Alexei
- Springer New York, NY
Direct Mapping of Phase Separation across the Metal–Insulator Transition of NdNiO 3
journal, March 2018
- Preziosi, Daniele; Lopez-Mir, Laura; Li, Xiaoyan
- Nano Letters, Vol. 18, Issue 4
Grain-Size-Limited Mobility in Methylammonium Lead Iodide Perovskite Thin Films
journal, August 2016
- Reid, Obadiah G.; Yang, Mengjin; Kopidakis, Nikos
- ACS Energy Letters, Vol. 1, Issue 3
Subgrain Special Boundaries in Halide Perovskite Thin Films Restrict Carrier Diffusion
journal, October 2018
- Li, Wenhao; Yadavalli, Srinivas K.; Lizarazo-Ferro, David
- ACS Energy Letters, Vol. 3, Issue 11
Piezoresponse force microscopy (PFM)
journal, November 2011
- Soergel, Elisabeth
- Journal of Physics D: Applied Physics, Vol. 44, Issue 46, Article No. 464003
Enhancing photoluminescence yields in lead halide perovskites by photon recycling and light out-coupling
journal, December 2016
- Richter, Johannes M.; Abdi-Jalebi, Mojtaba; Sadhanala, Aditya
- Nature Communications, Vol. 7, Issue 1
Dielectric Response: Answer to Many Questions in the Methylammonium Lead Halide Solar Cell Absorbers
journal, May 2017
- Anusca, Irina; Balčiūnas, Sergejus; Gemeiner, Pascale
- Advanced Energy Materials, Vol. 7, Issue 19
Bright Visible-Infrared Light Emitting Diodes Based on Hybrid Halide Perovskite with Spiro-OMeTAD as a Hole-Injecting Layer
journal, May 2015
- Jaramillo-Quintero, Oscar A.; Sanchez, Rafael S.; Rincon, Marina
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 10
Charge-Carrier Dynamics in Organic-Inorganic Metal Halide Perovskites
journal, May 2016
- Herz, Laura M.
- Annual Review of Physical Chemistry, Vol. 67, Issue 1
Orientation of Ferroelectric Domains and Disappearance upon Heating Methylammonium Lead Triiodide Perovskite from Tetragonal to Cubic Phase
journal, March 2018
- Vorpahl, Sarah M.; Giridharagopal, Rajiv; Eperon, Giles E.
- ACS Applied Energy Materials, Vol. 1, Issue 4
Ferroelastic Fingerprints in Methylammonium Lead Iodide Perovskite
journal, January 2016
- Hermes, Ilka M.; Bretschneider, Simon A.; Bergmann, Victor W.
- The Journal of Physical Chemistry C, Vol. 120, Issue 10
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013
- Stranks, S. D.; Eperon, G. E.; Grancini, G.
- Science, Vol. 342, Issue 6156, p. 341-344
Hybrid Perovskites for Photovoltaics: Charge-Carrier Recombination, Diffusion, and Radiative Efficiencies
journal, December 2015
- Johnston, Michael B.; Herz, Laura M.
- Accounts of Chemical Research, Vol. 49, Issue 1
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012
- Lee, M. M.; Teuscher, J.; Miyasaka, T.
- Science, Vol. 338, Issue 6107, p. 643-647
Understanding the Implication of Carrier Diffusion Length in Photovoltaic Cells
journal, September 2015
- Hodes, Gary; Kamat, Prashant V.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 20
Tracking Photoexcited Carriers in Hybrid Perovskite Semiconductors: Trap-Dominated Spatial Heterogeneity and Diffusion
journal, September 2017
- deQuilettes, Dane W.; Jariwala, Sarthak; Burke, Sven
- ACS Nano, Vol. 11, Issue 11
Chemical nature of ferroelastic twin domains in CH3NH3PbI3 perovskite
journal, August 2018
- Liu, Yongtao; Collins, Liam; Proksch, Roger
- Nature Materials, Vol. 17, Issue 11
Ferroelastic domains drive charge separation and suppress electron–hole recombination in all-inorganic halide perovskites: time-domain ab initio analysis
journal, January 2020
- Shi, Ran; Zhang, Zhaosheng; Fang, Wei-hai
- Nanoscale Horizons, Vol. 5, Issue 4
Piezoresponse force microscopy and recent advances in nanoscale studies of ferroelectrics
journal, January 2006
- Gruverman, A.; Kalinin, S. V.
- Journal of Materials Science, Vol. 41, Issue 1
Probing the Microstructure of Methylammonium Lead Iodide Perovskite Solar Cells
journal, March 2019
- Leonhard, Tobias; Schulz, Alexander D.; Röhm, Holger
- Energy Technology, Vol. 7, Issue 3
Photon recycling in lead iodide perovskite solar cells
journal, March 2016
- Pazos-Outon, L. M.; Szumilo, M.; Lamboll, R.
- Science, Vol. 351, Issue 6280
Photon Reabsorption Masks Intrinsic Bimolecular Charge-Carrier Recombination in CH 3 NH 3 PbI 3 Perovskite
journal, August 2017
- Crothers, Timothy W.; Milot, Rebecca L.; Patel, Jay B.
- Nano Letters, Vol. 17, Issue 9
Ferroelectric domains in methylammonium lead iodide perovskite thin-films
journal, January 2017
- Röhm, Holger; Leonhard, Tobias; Hoffmann, Michael J.
- Energy & Environmental Science, Vol. 10, Issue 4
Insight into Photon Recycling in Perovskite Semiconductors from the Concept of Photon Diffusion
journal, September 2018
- Ansari-Rad, Mehdi; Bisquert, Juan
- Physical Review Applied, Vol. 10, Issue 3
Direct observation of intrinsic twin domains in tetragonal CH3NH3PbI3
journal, February 2017
- Rothmann, Mathias Uller; Li, Wei; Zhu, Ye
- Nature Communications, Vol. 8, Issue 1
CH 3 NH 3 PbI 3 perovskites: Ferroelasticity revealed
journal, April 2017
- Strelcov, Evgheni; Dong, Qingfeng; Li, Tao
- Science Advances, Vol. 3, Issue 4
Dynamic Optical Properties of CH 3 NH 3 PbI 3 Single Crystals As Revealed by One- and Two-Photon Excited Photoluminescence Measurements
journal, August 2015
- Yamada, Yasuhiro; Yamada, Takumi; Phuong, Le Quang
- Journal of the American Chemical Society, Vol. 137, Issue 33
Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites
journal, April 2015
- Coll, Mariona; Gomez, Andrés; Mas-Marza, Elena
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 8
Ferroelectricity-free lead halide perovskites
journal, January 2019
- Gómez, Andrés; Wang, Qiong; Goñi, Alejandro R.
- Energy & Environmental Science, Vol. 12, Issue 8
An interface stabilized perovskite solar cell with high stabilized efficiency and low voltage loss
journal, January 2019
- Yoo, Jason J.; Wieghold, Sarah; Sponseller, Melany C.
- Energy & Environmental Science, Vol. 12, Issue 7
Defect Tolerance in Methylammonium Lead Triiodide Perovskite
journal, July 2016
- Steirer, K. Xerxes; Schulz, Philip; Teeter, Glenn
- ACS Energy Letters, Vol. 1, Issue 2
Local Versus Long-Range Diffusion Effects of Photoexcited States on Radiative Recombination in Organic-Inorganic Lead Halide Perovskites
journal, July 2015
- Vrućinić, Milan; Matthiesen, Clemens; Sadhanala, Aditya
- Advanced Science, Vol. 2, Issue 9
Hybrid Perovskite-Based Position-Sensitive Detectors
journal, December 2017
- Ashar, A. Z.; Ganesh, N.; Narayan, K. S.
- Advanced Electronic Materials, Vol. 4, Issue 2
Contactless Visualization of Fast Charge Carrier Diffusion in Hybrid Halide Perovskite Thin Films
journal, January 2016
- Handloser, Kathrin; Giesbrecht, Nadja; Bein, Thomas
- ACS Photonics, Vol. 3, Issue 2