Large Thermal Motion in Halide Perovskites
Abstract
Solar cells based on hybrid perovskites have shown high efficiency while possessing simple processing methods. To gain a fundamental understanding of their properties on an atomic level, we investigate single crystals of CH3NH3PbI3 with a narrow transition (~5 K) near 327 K. Temperature dependent structural measurements reveal a persistent tetragonal structure with smooth changes in the atomic displacement parameters (ADPs) on crossing T*. We show that the ADPs for I ions yield extended flat regions in the potential wells consistent with the measured large thermal expansion parameter. Molecular dynamics simulations reveal that this material exhibits significant asymmetries in the Pb-I pair distribution functions. We also show that the intrinsically enhanced freedom of motion of the iodine atoms enables large deformations. This flexibility (softness) of the atomic structure results in highly localized atomic relaxation about defects and hence accounts for both the high carrier mobility as well as the structural instability.
- Authors:
-
[2];
- New Jersey Inst. of Technology, Newark, NJ (United States)
- Univ. of South Florida, Tampa, FL (United States)
- Univ. of Chicago, IL (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1413908
- Report Number(s):
- BNL-114284-2017-JA
Journal ID: ISSN 2045-2322
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Tyson, T. A., Gao, W., Chen, Y. -S., Ghose, S., and Yan, Y. Large Thermal Motion in Halide Perovskites. United States: N. p., 2017.
Web. doi:10.1038/s41598-017-09220-2.
Tyson, T. A., Gao, W., Chen, Y. -S., Ghose, S., & Yan, Y. Large Thermal Motion in Halide Perovskites. United States. https://doi.org/10.1038/s41598-017-09220-2
Tyson, T. A., Gao, W., Chen, Y. -S., Ghose, S., and Yan, Y. Thu .
"Large Thermal Motion in Halide Perovskites". United States. https://doi.org/10.1038/s41598-017-09220-2. https://www.osti.gov/servlets/purl/1413908.
@article{osti_1413908,
title = {Large Thermal Motion in Halide Perovskites},
author = {Tyson, T. A. and Gao, W. and Chen, Y. -S. and Ghose, S. and Yan, Y.},
abstractNote = {Solar cells based on hybrid perovskites have shown high efficiency while possessing simple processing methods. To gain a fundamental understanding of their properties on an atomic level, we investigate single crystals of CH3NH3PbI3 with a narrow transition (~5 K) near 327 K. Temperature dependent structural measurements reveal a persistent tetragonal structure with smooth changes in the atomic displacement parameters (ADPs) on crossing T*. We show that the ADPs for I ions yield extended flat regions in the potential wells consistent with the measured large thermal expansion parameter. Molecular dynamics simulations reveal that this material exhibits significant asymmetries in the Pb-I pair distribution functions. We also show that the intrinsically enhanced freedom of motion of the iodine atoms enables large deformations. This flexibility (softness) of the atomic structure results in highly localized atomic relaxation about defects and hence accounts for both the high carrier mobility as well as the structural instability.},
doi = {10.1038/s41598-017-09220-2},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = {Thu Aug 24 00:00:00 EDT 2017},
month = {Thu Aug 24 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 19 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Impact of Processing Temperature and Composition on the Formation of Methylammonium Lead Iodide Perovskites
journal, June 2015
- Song, Zhaoning; Watthage, Suneth C.; Phillips, Adam B.
- Chemistry of Materials, Vol. 27, Issue 13
Impact of Processing Temperature and Composition on the Formation of Methylammonium Lead Iodide Perovskites
journal, June 2015
- Song, Zhaoning; Watthage, Suneth C.; Phillips, Adam B.
- Chemistry of Materials, Vol. 27, Issue 13
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
Exceptionally large positive and negative anisotropic thermal expansion of an organic crystalline material
journal, November 2009
- Das, Dinabandhu; Jacobs, Tia; Barbour, Leonard J.
- Nature Materials, Vol. 9, Issue 1
Observation of a low-symmetry crystal structure for superconducting by Ni K -edge x-ray absorption measurements
journal, February 2003
- Ignatov, A. Yu.; Dieng, L. M.; Tyson, T. A.
- Physical Review B, Vol. 67, Issue 6
Compositional effects on the structure and magnetotransport properties of lacunar La1-xMnO3-δ films (x>0) grown by MOCVD
journal, December 2004
- Bosak, A.; Dubourdieu, C.; Audier, M.
- Applied Physics A, Vol. 79, Issue 8
Structural Evolution in Methylammonium Lead Iodide CH 3 NH 3 PbI 3
journal, October 2015
- Ong, Khuong P.; Goh, Teck Wee; Xu, Qiang
- The Journal of Physical Chemistry A, Vol. 119, Issue 44
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016
- Saparov, Bayrammurad; Mitzi, David B.
- Chemical Reviews, Vol. 116, Issue 7
Effect of charged impurity scattering on the electron diffusivity and mobility in graphene
journal, October 2015
- Rengel, R.; Iglesias, J. M.; Pascual, E.
- Journal of Physics: Conference Series, Vol. 647
Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†
journal, January 1990
- Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi
- Journal of Physics and Chemistry of Solids, Vol. 51, Issue 12
Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite
journal, October 2016
- Beecher, Alexander N.; Semonin, Octavi E.; Skelton, Jonathan M.
- ACS Energy Letters, Vol. 1, Issue 4
Perovskites: transforming photovoltaics, a mini-review
journal, January 2015
- Chilvery, Ashwith Kumar; Batra, Ashok K.; Yang, Bin
- Journal of Photonics for Energy, Vol. 5, Issue 1
Entropy and specific heat of the 3D ising model as functions of temperature and microscopic parameters of the system
journal, May 1994
- Kozlovskii, M. P.; Pylyuk, I. V.
- physica status solidi (b), Vol. 183, Issue 1
A combined single crystal neutron/X-ray diffraction and solid-state nuclear magnetic resonance study of the hybrid perovskites CH 3 NH 3 PbX 3 (X = I, Br and Cl)
journal, January 2015
- Baikie, Tom; Barrow, Nathan S.; Fang, Yanan
- Journal of Materials Chemistry A, Vol. 3, Issue 17
Entropy and specific heat of the 3D ising model as functions of temperature and microscopic parameters of the system
journal, May 1994
- Kozlovskii, M. P.; Pylyuk, I. V.
- physica status solidi (b), Vol. 183, Issue 1
A neutron diffraction study of anharmonic thermal vibrations in cubic CsPb X 3
journal, January 1980
- Sakata, M.; Harada, J.; Cooper, M. J.
- Acta Crystallographica Section A, Vol. 36, Issue 1
Orientation of Organic Cations in Hybrid Inorganic–Organic Perovskite CH 3 NH 3 PbI 3 from Subatomic Resolution Single Crystal Neutron Diffraction Structural Studies
journal, April 2016
- Ren, Yixin; Oswald, Iain W. H.; Wang, Xiaoping
- Crystal Growth & Design, Vol. 16, Issue 5
Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation
journal, February 2017
- Zhao, Xin-Gang; Yang, Ji-Hui; Fu, Yuhao
- Journal of the American Chemical Society, Vol. 139, Issue 7
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
Structural Study on Cubic–Tetragonal Transition of CH 3 NH 3 PbI 3
journal, July 2002
- Kawamura, Yukihiko; Mashiyama, Hiroyuki; Hasebe, Katsuhiko
- Journal of the Physical Society of Japan, Vol. 71, Issue 7
Room-temperature multiferroic magnetoelectrics
journal, November 2013
- Scott, James F.
- NPG Asia Materials, Vol. 5, Issue 11
Recent advances in perovskites: Processing and properties
journal, December 2015
- Moure, Carlos; Peña, Octavio
- Progress in Solid State Chemistry, Vol. 43, Issue 4
Vibrational Properties of the Organic–Inorganic Halide Perovskite CH 3 NH 3 PbI 3 from Theory and Experiment: Factor Group Analysis, First-Principles Calculations, and Low-Temperature Infrared Spectra
journal, November 2015
- Pérez-Osorio, Miguel A.; Milot, Rebecca L.; Filip, Marina R.
- The Journal of Physical Chemistry C, Vol. 119, Issue 46
Mixed-valence manganites
journal, March 1999
- Coey, J. M. D.; Viret, M.; von Molnár, S.
- Advances in Physics, Vol. 48, Issue 2
Orientation of Organic Cations in Hybrid Inorganic–Organic Perovskite CH 3 NH 3 PbI 3 from Subatomic Resolution Single Crystal Neutron Diffraction Structural Studies
journal, April 2016
- Ren, Yixin; Oswald, Iain W. H.; Wang, Xiaoping
- Crystal Growth & Design, Vol. 16, Issue 5
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016
- Saparov, Bayrammurad; Mitzi, David B.
- Chemical Reviews, Vol. 116, Issue 7
Role of complex energy landscapes and strains in multiscale inhomogeneities in perovskite manganites
journal, October 2013
- Ahn, K. H.; Seman, T. F.; Lookman, T.
- Physical Review B, Vol. 88, Issue 14
Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation
journal, February 2017
- Zhao, Xin-Gang; Yang, Ji-Hui; Fu, Yuhao
- Journal of the American Chemical Society, Vol. 139, Issue 7
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
The heat capacity of matter beyond the Dulong–Petit value
journal, May 2013
- Andritsos, E. I.; Zarkadoula, E.; Phillips, A. E.
- Journal of Physics: Condensed Matter, Vol. 25, Issue 23
Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015
- Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan
- Science, Vol. 347, Issue 6225
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
Anharmonic lattice dynamics of studied by inelastic neutron scattering and first-principles molecular dynamics simulations
journal, February 2014
- Lan, Tian; Li, Chen W.; Niedziela, J. L.
- Physical Review B, Vol. 89, Issue 5
Recent advancements in perovskite solar cells: flexibility, stability and large scale
journal, January 2016
- Ye, Meidan; Hong, Xiaodan; Zhang, Fayin
- Journal of Materials Chemistry A, Vol. 4, Issue 18
Polarization and Dielectric Study of Methylammonium Lead Iodide Thin Film to Reveal its Nonferroelectric Nature under Solar Cell Operating Conditions
journal, May 2016
- Hoque, Md Nadim Ferdous; Yang, Mengjin; Li, Zhen
- ACS Energy Letters, Vol. 1, Issue 1
Organic-inorganic electronics
journal, January 2001
- Mitzi, D. B.; Chondroudis, K.; Kagan, C. R.
- IBM Journal of Research and Development, Vol. 45, 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
Room-temperature multiferroic magnetoelectrics
journal, November 2013
- Scott, James F.
- NPG Asia Materials, Vol. 5, Issue 11
Compositional effects on the structure and magnetotransport properties of lacunar La1-xMnO3-δ films (x>0) grown by MOCVD
journal, December 2004
- Bosak, A.; Dubourdieu, C.; Audier, M.
- Applied Physics A, Vol. 79, Issue 8
Structural Evolution in Methylammonium Lead Iodide CH 3 NH 3 PbI 3
journal, October 2015
- Ong, Khuong P.; Goh, Teck Wee; Xu, Qiang
- The Journal of Physical Chemistry A, Vol. 119, Issue 44
What Is Moving in Hybrid Halide Perovskite Solar Cells?
journal, February 2016
- Frost, Jarvist M.; Walsh, Aron
- Accounts of Chemical Research, Vol. 49, Issue 3
Exceptionally large positive and negative anisotropic thermal expansion of an organic crystalline material
journal, November 2009
- Das, Dinabandhu; Jacobs, Tia; Barbour, Leonard J.
- Nature Materials, Vol. 9, Issue 1
Works referencing / citing this record:
Lead halide perovskites for photocatalytic organic synthesis
journal, June 2019
- Zhu, Xiaolin; Lin, Yixiong; San Martin, Jovan
- Nature Communications, Vol. 10, Issue 1
Effect of Thermal Cycling on the Structural Evolution of Methylammonium Lead Iodide Monitored around the Phase Transition Temperatures
journal, May 2019
- Glushkova, Anastasiia; Mantulnikovs, Konstantins; Giriat, Gaétan
- Solar RRL, Vol. 3, Issue 7
Lead halide perovskites for photocatalytic organic synthesis
journal, June 2019
- Zhu, Xiaolin; Lin, Yixiong; San Martin, Jovan
- Nature Communications, Vol. 10, Issue 1
Low-temperature processed non-TiO 2 electron selective layers for perovskite solar cells
journal, January 2018
- Guo, Zhanglin; Gao, Liguo; Zhang, Chu
- Journal of Materials Chemistry A, Vol. 6, Issue 11