Experimental Phonon Dispersion and Lifetimes of Tetragonal CH3NH3PbI3 Perovskite Crystals
Abstract
Hybrid organic–inorganic perovskites were reported to have ultralow thermal conductivity in recent studies. In this Letter, we report the first experimental phonon dispersion and lifetimes of tetragonal CH3NH3PbI3 single crystals at both 200 and 300 K by high-energy resolution inelastic X-ray scattering, which enables a thorough understanding of the underlying mechanisms for the ultralow thermal conductivity. Notably, we observed unusual and significant phonon dips along the [100] and [110] directions at both temperatures. The ultralow thermal conductivity can be attributed to small group velocities due to ultrasoft acoustic modes and short phonon lifetimes originating from the strong acoustic-optical coupling. We further provided the structural origins for these peculiar phonon features. Moreover, our results and interpretation are consistent with the reported temperature-dependent trend for thermal conductivity of CH3NH3PbI3. Lastly, our work offers critical guidelines for accelerating the design and discovery of novel hybrid materials for energy applications including photovoltaics and thermoelectrics.
- Authors:
-
[1];
[5];
- Cornell Univ., Ithaca, NY (United States)
- Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Illinois Inst. of Technology, Chicago, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1491239
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ma, Hao, Ma, Yunwei, Wang, Heng, Slebodnick, Carla, Alatas, Ahmet, Urban, Jeffrey J., and Tian, Zhiting. Experimental Phonon Dispersion and Lifetimes of Tetragonal CH3NH3PbI3 Perovskite Crystals. United States: N. p., 2018.
Web. doi:10.1021/acs.jpclett.8b03419.
Ma, Hao, Ma, Yunwei, Wang, Heng, Slebodnick, Carla, Alatas, Ahmet, Urban, Jeffrey J., & Tian, Zhiting. Experimental Phonon Dispersion and Lifetimes of Tetragonal CH3NH3PbI3 Perovskite Crystals. United States. https://doi.org/10.1021/acs.jpclett.8b03419
Ma, Hao, Ma, Yunwei, Wang, Heng, Slebodnick, Carla, Alatas, Ahmet, Urban, Jeffrey J., and Tian, Zhiting. Sun .
"Experimental Phonon Dispersion and Lifetimes of Tetragonal CH3NH3PbI3 Perovskite Crystals". United States. https://doi.org/10.1021/acs.jpclett.8b03419. https://www.osti.gov/servlets/purl/1491239.
@article{osti_1491239,
title = {Experimental Phonon Dispersion and Lifetimes of Tetragonal CH3NH3PbI3 Perovskite Crystals},
author = {Ma, Hao and Ma, Yunwei and Wang, Heng and Slebodnick, Carla and Alatas, Ahmet and Urban, Jeffrey J. and Tian, Zhiting},
abstractNote = {Hybrid organic–inorganic perovskites were reported to have ultralow thermal conductivity in recent studies. In this Letter, we report the first experimental phonon dispersion and lifetimes of tetragonal CH3NH3PbI3 single crystals at both 200 and 300 K by high-energy resolution inelastic X-ray scattering, which enables a thorough understanding of the underlying mechanisms for the ultralow thermal conductivity. Notably, we observed unusual and significant phonon dips along the [100] and [110] directions at both temperatures. The ultralow thermal conductivity can be attributed to small group velocities due to ultrasoft acoustic modes and short phonon lifetimes originating from the strong acoustic-optical coupling. We further provided the structural origins for these peculiar phonon features. Moreover, our results and interpretation are consistent with the reported temperature-dependent trend for thermal conductivity of CH3NH3PbI3. Lastly, our work offers critical guidelines for accelerating the design and discovery of novel hybrid materials for energy applications including photovoltaics and thermoelectrics.},
doi = {10.1021/acs.jpclett.8b03419},
journal = {Journal of Physical Chemistry Letters},
number = 1,
volume = 10,
place = {United States},
year = {2018},
month = {12}
}
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:
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 emergence of perovskite solar cells
journal, July 2014
- Green, Martin A.; Ho-Baillie, Anita; Snaith, Henry J.
- Nature Photonics, Vol. 8, Issue 7, p. 506-514
The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors
journal, September 2015
- Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.
- Accounts of Chemical Research, Vol. 48, 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
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
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
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
Recent Progress of Innovative Perovskite Hybrid Solar Cells
journal, April 2015
- Heo, Jin Hyuck; Song, Dae Ho; Patil, Basavaraj Rudragouda
- Israel Journal of Chemistry, Vol. 55, Issue 9
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
Piezoelectric properties of CH 3 NH 3 PbI 3 perovskite thin films and their applications in piezoelectric generators
journal, January 2016
- Kim, Yun-Jeong; Dang, Tran-Van; Choi, Hyung-Jin
- Journal of Materials Chemistry A, Vol. 4, Issue 3
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
Visible light response, electrical transport, and amorphization in compressed organolead iodine perovskites
journal, January 2016
- Ou, Tianji; Yan, Jiejuan; Xiao, Chuanhai
- Nanoscale, Vol. 8, Issue 22
Phonon–Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites
journal, December 2015
- Karakus, Melike; Jensen, Søren A.; D’Angelo, Francesco
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 24
Electron–phonon coupling in hybrid lead halide perovskites
journal, May 2016
- Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.
- Nature Communications, Vol. 7, Issue 1
Homogeneous Emission Line Broadening in the Organo Lead Halide Perovskite CH 3 NH 3 PbI 3– x Cl x
journal, March 2014
- Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
Organic–inorganic hybrid perovskites ABI 3 (A = CH 3 NH 3 , NH 2 CHNH 2 ; B = Sn, Pb) as potential thermoelectric materials: a density functional evaluation
journal, January 2015
- Lee, Changhoon; Hong, Jisook; Stroppa, Alessandro
- RSC Advances, Vol. 5, Issue 96
Perovskites for Solar Thermoelectric Applications: A First Principle Study of CH 3 NH 3 AI 3 (A = Pb and Sn)
journal, August 2014
- He, Yuping; Galli, Giulia
- Chemistry of Materials, Vol. 26, Issue 18
Tuning of the Thermoelectric Figure of Merit of CH 3 NH 3 MI 3 (M═Pb,Sn) Photovoltaic Perovskites
journal, May 2015
- Mettan, Xavier; Pisoni, Riccardo; Matus, Péter
- The Journal of Physical Chemistry C, Vol. 119, Issue 21
Ultra-high Seebeck coefficient and low thermal conductivity of a centimeter-sized perovskite single crystal acquired by a modified fast growth method
journal, January 2017
- Ye, Tao; Wang, Xizu; Li, Xianqiang
- Journal of Materials Chemistry C, Vol. 5, Issue 5
Towards high-performance polymer-based thermoelectric materials
journal, January 2013
- He, Ming; Qiu, Feng; Lin, Zhiqun
- Energy & Environmental Science, Vol. 6, Issue 5
Towards polymer-based organic thermoelectric generators
journal, January 2012
- Bubnova, Olga; Crispin, Xavier
- Energy & Environmental Science, Vol. 5, Issue 11
Anisotropic and Ultralow Phonon Thermal Transport in Organic-Inorganic Hybrid Perovskites: Atomistic Insights into Solar Cell Thermal Management and Thermoelectric Energy Conversion Efficiency
journal, May 2016
- Wang, Mingchao; Lin, Shangchao
- Advanced Functional Materials, Vol. 26, Issue 29
The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells
journal, May 2015
- Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P.
- Nature Communications, Vol. 6, 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
Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH 3 NH 3 PbI 3
journal, July 2014
- Pisoni, Andrea; Jaćimović, Jaćim; Barišić, Osor S.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 14
Phonon Speed, Not Scattering, Differentiates Thermal Transport in Lead Halide Perovskites
journal, August 2017
- Elbaz, Giselle A.; Ong, Wee-Liat; Doud, Evan A.
- Nano Letters, Vol. 17, Issue 9
Thermal Conductivity of Methylammonium Lead Halide Perovskite Single Crystals and Thin Films: A Comparative Study
journal, December 2017
- Heiderhoff, Ralf; Haeger, Tobias; Pourdavoud, Neda
- The Journal of Physical Chemistry C, Vol. 121, Issue 51
Phonon-Mediated Thermal Conductivity in Ionic Solids by Lattice Dynamics-Based Methods
journal, July 2011
- Chernatynskiy, Aleksandr; Turney, Joseph E.; McGaughey, Alan J. H.
- Journal of the American Ceramic Society, Vol. 94, Issue 10
Structural and electronic properties of organo-halide lead perovskites: a combined IR-spectroscopy and ab initio molecular dynamics investigation
journal, January 2014
- Mosconi, Edoardo; Quarti, Claudio; Ivanovska, Tanja
- Phys. Chem. Chem. Phys., Vol. 16, Issue 30
Infrared Spectroscopic Study of Vibrational Modes in Methylammonium Lead Halide Perovskites
journal, July 2015
- Glaser, Tobias; Müller, Christian; Sendner, Michael
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 15
The Raman Spectrum of the CH 3 NH 3 PbI 3 Hybrid Perovskite: Interplay of Theory and Experiment
journal, December 2013
- Quarti, Claudio; Grancini, Giulia; Mosconi, Edoardo
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 2
Raman Spectroscopy of Organic–Inorganic Halide Perovskites
journal, January 2015
- Ledinský, Martin; Löper, Philipp; Niesen, Bjoern
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 3
Cation rotation in methylammonium lead halides
journal, November 1985
- Wasylishen, R. E.; Knop, Osvald; Macdonald, J. B.
- Solid State Communications, Vol. 56, Issue 7
Erratum: Corrigendum: The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells
journal, July 2015
- Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P.
- Nature Communications, Vol. 6, Issue 1
Polar rotor scattering as atomic-level origin of low mobility and thermal conductivity of perovskite CH3NH3PbI3
journal, June 2017
- Li, Bing; Kawakita, Yukinobu; Liu, Yucheng
- Nature Communications, Vol. 8, Issue 1
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
Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal, and cubic phases of methylammonium lead iodide
journal, October 2015
- Brivio, Federico; Frost, Jarvist M.; Skelton, Jonathan M.
- Physical Review B, Vol. 92, Issue 14
Lattice thermal conductivity of organic-inorganic hybrid perovskite CH 3 NH 3 PbI 3
journal, February 2016
- Qian, Xin; Gu, Xiaokun; Yang, Ronggui
- Applied Physics Letters, Vol. 108, Issue 6
An inelastic X-ray spectrometer with 2.2meV energy resolution
journal, July 2001
- Sinn, H.; Alp, E. E.; Alatas, A.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 467-468
Six-reflection meV-monochromator for synchrotron radiation
journal, May 2011
- Toellner, T. S.; Alatas, A.; Said, A. H.
- Journal of Synchrotron Radiation, Vol. 18, Issue 4
Improved focusing capability for inelastic X-ray spectrometer at 3-ID of the APS: A combination of toroidal and Kirkpatrick-Baez (KB) mirrors
journal, September 2011
- Alatas, A.; Leu, B. M.; Zhao, J.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 649, Issue 1
Inelastic x-ray scattering measurements of phonon dispersion and lifetimes in PbTe 1− x Se x alloys
journal, September 2015
- Tian, Zhiting; Li, Mingda; Ren, Zhensong
- Journal of Physics: Condensed Matter, Vol. 27, Issue 37
Boron arsenide phonon dispersion from inelastic x-ray scattering: Potential for ultrahigh thermal conductivity
journal, December 2016
- Ma, Hao; Li, Chen; Tang, Shixiong
- Physical Review B, Vol. 94, Issue 22
Gated tuned superconductivity and phonon softening in monolayer and bilayer MoS2
journal, September 2017
- Fu, Yajun; Liu, Erfu; Yuan, Hongtao
- npj Quantum Materials, Vol. 2, Issue 1
Phonon conduction in PbSe, PbTe, and PbTe Se from first-principles calculations
journal, May 2012
- Tian, Zhiting; Garg, Jivtesh; Esfarjani, Keivan
- Physical Review B, Vol. 85, Issue 18
Probing Phonons in Plutonium
journal, January 2003
- Wong, Joe; Krisch, Michael; Farber, Daniel L.
- MRS Proceedings, Vol. 802
Temperature Evolution of Methylammonium Trihalide Vibrations at the Atomic Scale
journal, January 2016
- Mattoni, A.; Filippetti, A.; Saba, M. I.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 3
Why Are There So Few Perovskite Ferroelectrics?
journal, May 2013
- Benedek, Nicole A.; Fennie, Craig J.
- The Journal of Physical Chemistry C, Vol. 117, Issue 26
Pressure dependence of the phonon spectrum in BaTiO polytypes studied by ab initio calculations
journal, July 2013
- Seo, Yu-Seong; Ahn, Jai Seok
- Physical Review B, Vol. 88, Issue 1
Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013
- Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J.
- Nature, Vol. 501, Issue 7467, p. 395-398
Heat transport in silicon from first-principles calculations
journal, August 2011
- Esfarjani, Keivan; Chen, Gang; Stokes, Harold T.
- Physical Review B, Vol. 84, Issue 8
Cation Dynamics Governed Thermal Properties of Lead Halide Perovskite Nanowires
journal, April 2018
- Wang, Yuxi; Lin, Renxing; Zhu, Pengchen
- Nano Letters, Vol. 18, Issue 5