Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide
Abstract
The temperature-dependent structure evolution of the hybrid halide perovskite compounds, formamidinium tin iodide (FASnI3, FA+ = CH[NH2]2+) and formamidinium lead bromide (FAPbBr3), has been monitored using high-resolution synchrotron X-ray powder diffraction between 300 and 100 K. The data are consistent with a transition from cubic Pm$$\bar{3}$$m (No. 221) to tetragonal P4/mbm (No. 127) for both materials upon cooling; this occurs for FAPbBr3 between 275 and 250 K, and for FASnI3 between 250 and 225 K. Upon further cooling, between 150 and 125 K, both materials undergo a transition to an orthorhombic Pnma (No. 62) structure. The transitions are confirmed by calorimetry and dielectric measurements. In the tetragonal regime, the coefficients of volumetric thermal expansion of FASnI3 and FAPbBr3 are among the highest recorded for any extended inorganic crystalline solid, reaching 219 ppm K–1 for FASnI3 at 225 K. Atomic displacement parameters of all atoms for both materials suggest dynamic motion is occurring in the inorganic sublattice due to the flexibility of the inorganic network and dynamic lone pair stereochemical activity on the B-site. Unusual pseudocubic behavior is displayed in the tetragonal phase of the FAPbBr3, similar to that previously observed in FAPbI3.
- Authors:
-
[2];
[1];
[3];
[3];
[1]
- Univ. of California, Santa Barbara, CA (United States)
- Bates College, Lewiston, ME (United States)
- Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Santa Barbara, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1599741
- Grant/Contract Number:
- SC0012541; AC02-06CH11357; DMR-1720256; DGE-1144085
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 2; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Schueller, Emily C., Laurita, Geneva, Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., and Seshadri, Ram. Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide. United States: N. p., 2017.
Web. doi:10.1021/acs.inorgchem.7b02576.
Schueller, Emily C., Laurita, Geneva, Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., & Seshadri, Ram. Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide. United States. https://doi.org/10.1021/acs.inorgchem.7b02576
Schueller, Emily C., Laurita, Geneva, Fabini, Douglas H., Stoumpos, Constantinos C., Kanatzidis, Mercouri G., and Seshadri, Ram. Tue .
"Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide". United States. https://doi.org/10.1021/acs.inorgchem.7b02576. https://www.osti.gov/servlets/purl/1599741.
@article{osti_1599741,
title = {Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide},
author = {Schueller, Emily C. and Laurita, Geneva and Fabini, Douglas H. and Stoumpos, Constantinos C. and Kanatzidis, Mercouri G. and Seshadri, Ram},
abstractNote = {The temperature-dependent structure evolution of the hybrid halide perovskite compounds, formamidinium tin iodide (FASnI3, FA+ = CH[NH2]2+) and formamidinium lead bromide (FAPbBr3), has been monitored using high-resolution synchrotron X-ray powder diffraction between 300 and 100 K. The data are consistent with a transition from cubic Pm$\bar{3}$m (No. 221) to tetragonal P4/mbm (No. 127) for both materials upon cooling; this occurs for FAPbBr3 between 275 and 250 K, and for FASnI3 between 250 and 225 K. Upon further cooling, between 150 and 125 K, both materials undergo a transition to an orthorhombic Pnma (No. 62) structure. The transitions are confirmed by calorimetry and dielectric measurements. In the tetragonal regime, the coefficients of volumetric thermal expansion of FASnI3 and FAPbBr3 are among the highest recorded for any extended inorganic crystalline solid, reaching 219 ppm K–1 for FASnI3 at 225 K. Atomic displacement parameters of all atoms for both materials suggest dynamic motion is occurring in the inorganic sublattice due to the flexibility of the inorganic network and dynamic lone pair stereochemical activity on the B-site. Unusual pseudocubic behavior is displayed in the tetragonal phase of the FAPbBr3, similar to that previously observed in FAPbI3.},
doi = {10.1021/acs.inorgchem.7b02576},
journal = {Inorganic Chemistry},
number = 2,
volume = 57,
place = {United States},
year = {Tue Dec 26 00:00:00 EST 2017},
month = {Tue Dec 26 00:00:00 EST 2017}
}
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Works referenced in this record:
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
High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors
journal, March 2014
- Deschler, Felix; Price, Michael; Pathak, Sandeep
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
Bright light-emitting diodes based on organometal halide perovskite
journal, August 2014
- Tan, Zhi-Kuang; Moghaddam, Reza Saberi; Lai, May Ling
- Nature Nanotechnology, Vol. 9, Issue 9
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
Efficient luminescent solar cells based on tailored mixed-cation perovskites
journal, January 2016
- Bi, Dongqin; Tress, Wolfgang; Dar, M. Ibrahim
- Science Advances, Vol. 2, Issue 1
High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites
journal, December 2013
- Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B.
- Advanced Materials, Vol. 26, Issue 10
Improved Understanding of the Electronic and Energetic Landscapes of Perovskite Solar Cells: High Local Charge Carrier Mobility, Reduced Recombination, and Extremely Shallow Traps
journal, September 2014
- Oga, Hikaru; Saeki, Akinori; Ogomi, Yuhei
- Journal of the American Chemical Society, Vol. 136, Issue 39
Trap States in Lead Iodide Perovskites
journal, January 2015
- Wu, Xiaoxi; Trinh, M. Tuan; Niesner, Daniel
- Journal of the American Chemical Society, Vol. 137, Issue 5
Trap-Assisted Non-Radiative Recombination in Organic-Inorganic Perovskite Solar Cells
journal, February 2015
- Wetzelaer, Gert-Jan A. H.; Scheepers, Max; Sempere, Araceli Miquel
- Advanced Materials, Vol. 27, Issue 11
Group-Theoretical Analysis of Octahedral Tilting in Perovskites
journal, December 1998
- Howard, C. J.; Stokes, H. T.
- Acta Crystallographica Section B Structural Science, Vol. 54, Issue 6, p. 782-789
CsSnI3 : Semiconductor or Metal? High Electrical Conductivity and Strong Near-Infrared Photoluminescence from a Single Material. High Hole Mobility and Phase-Transitions
journal, May 2012
- Chung, In; Song, Jung-Hwan; Im, Jino
- Journal of the American Chemical Society, Vol. 134, Issue 20, p. 8579-8587
Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
journal, January 2013
- Baikie, Tom; Fang, Yanan; Kadro, Jeannette M.
- Journal of Materials Chemistry A, Vol. 1, Issue 18
The ordered phase of methylammonium lead chloride CH3ND3PbCl3
journal, May 2005
- Chi, Lisheng; Swainson, Ian; Cranswick, Lachlan
- Journal of Solid State Chemistry, Vol. 178, Issue 5
Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide
journal, November 2016
- Fabini, Douglas H.; Stoumpos, Constantinos C.; Laurita, Geneva
- Angewandte Chemie International Edition, Vol. 55, Issue 49
Study of Local Structure in Selected Organic–Inorganic Perovskites in the Pm 3̅ m Phase
journal, February 2008
- Worhatch, Richard J.; Kim, HyunJeong; Swainson, Ian P.
- Chemistry of Materials, Vol. 20, Issue 4
Chemical tuning of dynamic cation off-centering in the cubic phases of hybrid tin and lead halide perovskites
journal, January 2017
- Laurita, Geneva; Fabini, Douglas H.; Stoumpos, Constantinos C.
- Chemical Science, Vol. 8, Issue 8
Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3
journal, September 2016
- Fabini, Douglas H.; Laurita, Geneva; Bechtel, Jonathon S.
- Journal of the American Chemical Society, Vol. 138, Issue 36
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
Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites
journal, July 2017
- Wu, Xiaoxi; Tan, Liang Z.; Shen, Xiaozhe
- Science Advances, Vol. 3, Issue 7
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
EXPGUI , a graphical user interface for GSAS
journal, April 2001
- Toby, Brian H.
- Journal of Applied Crystallography, Vol. 34, Issue 2
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Synthesis, Resistivity, and Thermal Properties of the Cubic Perovskite NH2CH=NH2SnI3 and Related Systems
journal, December 1997
- Mitzi, D. B.; Liang, K.
- Journal of Solid State Chemistry, Vol. 134, Issue 2, p. 376-381
Formation of Hybrid Perovskite Tin Iodide Single Crystals by Top-Seeded Solution Growth
journal, February 2016
- Dang, Yangyang; Zhou, Yian; Liu, Xiaolong
- Angewandte Chemie International Edition, Vol. 55, Issue 10
Efficient Planar Heterojunction Perovskite Solar Cells Based on Formamidinium Lead Bromide
journal, August 2014
- Hanusch, Fabian C.; Wiesenmayer, Erwin; Mankel, Eric
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 16
Formamidinium Lead Halide Perovskite Crystals with Unprecedented Long Carrier Dynamics and Diffusion Length
journal, April 2016
- Zhumekenov, Ayan A.; Saidaminov, Makhsud I.; Haque, Md Azimul
- ACS Energy Letters, Vol. 1, Issue 1
Formamidinium tin-based perovskite with low E g for photovoltaic applications
journal, January 2015
- Koh, Teck Ming; Krishnamoorthy, Thirumal; Yantara, Natalia
- Journal of Materials Chemistry A, Vol. 3, Issue 29
Fabrication of Efficient Formamidinium Tin Iodide Perovskite Solar Cells through SnF 2 –Pyrazine Complex
journal, March 2016
- Lee, Seon Joo; Shin, Seong Sik; Kim, Young Chan
- Journal of the American Chemical Society, Vol. 138, Issue 12
Tunable ferroelectric polarization and its interplay with spin–orbit coupling in tin iodide perovskites
journal, December 2014
- Stroppa, Alessandro; Di Sante, Domenico; Barone, Paolo
- Nature Communications, Vol. 5, Issue 1
First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb
journal, March 2003
- Waghmare, U. V.; Spaldin, N. A.; Kandpal, H. C.
- Physical Review B, Vol. 67, Issue 12
Entropically Stabilized Local Dipole Formation in Lead Chalcogenides
journal, December 2010
- Bozin, E. S.; Malliakas, C. D.; Souvatzis, P.
- Science, Vol. 330, Issue 6011
Lattice dynamics reveals a local symmetry breaking in the emergent dipole phase of PbTe
journal, August 2012
- Jensen, Kirsten M. Ø.; Božin, Emil S.; Malliakas, Christos D.
- Physical Review B, Vol. 86, Issue 8
Local off-centering symmetry breaking in the high-temperature regime of SnTe
journal, January 2014
- Knox, K. R.; Bozin, E. S.; Malliakas, C. D.
- Physical Review B, Vol. 89, Issue 1
Local Polar Fluctuations in Lead Halide Perovskite Crystals
journal, March 2017
- Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.
- Physical Review Letters, Vol. 118, Issue 13
Structural origins of broadband emission from layered Pb–Br hybrid perovskites
journal, January 2017
- Smith, Matthew D.; Jaffe, Adam; Dohner, Emma R.
- Chemical Science, Vol. 8, Issue 6
Dielectric and Thermodynamic Signatures of Low-Temperature Glassy Dynamics in the Hybrid Perovskites CH 3 NH 3 PbI 3 and HC(NH 2 ) 2 PbI 3
journal, January 2016
- Fabini, Douglas H.; Hogan, Tom; Evans, Hayden A.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
Dielectric study of CH3NH3PbX3 (X = Cl, Br, I)
journal, July 1992
- Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi
- Journal of Physics and Chemistry of Solids, Vol. 53, Issue 7
Works referencing / citing this record:
Quasicubic model for metal halide perovskite nanocrystals
journal, December 2019
- Sercel, Peter C.; Lyons, John L.; Bernstein, Noam
- The Journal of Chemical Physics, Vol. 151, Issue 23
Interplay of Structural and Optoelectronic Properties in Formamidinium Mixed Tin-Lead Triiodide Perovskites
journal, June 2018
- Parrott, Elizabeth S.; Green, Thomas; Milot, Rebecca L.
- Advanced Functional Materials, Vol. 28, Issue 33
Lead-free hybrid ferroelectric material based on formamidine: [NH 2 CHNH 2 ] 3 Bi 2 I 9
journal, January 2019
- Szklarz, Przemysław; Gągor, Anna; Jakubas, Ryszard
- Journal of Materials Chemistry C, Vol. 7, Issue 10
The phase diagram of a mixed halide (Br, I) hybrid perovskite obtained by synchrotron X-ray diffraction
journal, January 2019
- Lehmann, Frederike; Franz, Alexandra; Többens, Daniel M.
- RSC Advances, Vol. 9, Issue 20
Robust Tin-Based Perovskite Solar Cells with Hybrid Organic Cations to Attain Efficiency Approaching 10%
journal, November 2018
- Jokar, Efat; Chien, Cheng-Hsun; Tsai, Cheng-Min
- Advanced Materials, Vol. 31, Issue 2
The Effects of Doping Density and Temperature on the Optoelectronic Properties of Formamidinium Tin Triiodide Thin Films
journal, September 2018
- Milot, Rebecca L.; Klug, Matthew T.; Davies, Christopher L.
- Advanced Materials, Vol. 30, Issue 44
The ground exciton state of formamidinium lead bromide perovskite nanocrystals is a singlet dark state
journal, May 2019
- Tamarat, Philippe; Bodnarchuk, Maryna I.; Trebbia, Jean-Baptiste
- Nature Materials, Vol. 18, Issue 7
Enhancing exciton binding energy and photoluminescence of formamidinium lead bromide by reducing its dimensions to 2D nanoplates for producing efficient light emitting diodes
journal, January 2018
- Li, Feiming; Yang, Lan; Cai, Zhixiong
- Nanoscale, Vol. 10, Issue 44
Tracking Structural Phase Transitions in Lead‐Halide Perovskites by Means of Thermal Expansion
journal, April 2019
- Keshavarz, Masoumeh; Ottesen, Martin; Wiedmann, Steffen
- Advanced Materials
Stable Cesium Formamidinium Lead Halide Perovskites: A Comparison of Photophysics and Phase Purity in Thin Films and Single Crystals
journal, April 2020
- Groeneveld, Bart G. H. M.; Adjokatse, Sampson; Nazarenko, Olga
- Energy Technology, Vol. 8, Issue 4
The distinctive phase stability and defect physics in CsPbI 2 Br perovskite
journal, January 2019
- Chen, Yuxuan; Shi, Tingting; Liu, Pengyi
- Journal of Materials Chemistry A, Vol. 7, Issue 35
Tracking Structural Phase Transitions in Lead‐Halide Perovskites by Means of Thermal Expansion
text, January 2019
- Keshavarz, Masoumeh; Ottesen, Martin; Wiedmann, Steffen
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Stable Cesium Formamidinium Lead Halide Perovskites: A Comparison of Photophysics and Phase Purity in Thin Films and Single Crystals
text, January 2020
- Groeneveld, Bart G. H. M.; Adjokatse, Sampson; Nazarenko, Olga
- ETH Zurich
Exploration of Near-Infrared-Emissive Colloidal Multinary Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform
journal, May 2018
- Lignos, Ioannis; Morad, Viktoriia; Shynkarenko, Yevhen
- ACS Nano, Vol. 12, Issue 6
Direct evidence of weakly dispersed and strongly anharmonic optical phonons in hybrid perovskites
text, January 2020
- Ferreira, A. C.; Paofai, S.; Létoublon, A.
- arXiv