Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies

Guo, Peijun; Xia, Yi; Gong, Jue; Stoumpos, Constantinos C.; McCall, Kyle M.; Alexander, Grant C. B.; Ma, Zhiyuan; Zhou, Hua; Gosztola, David J.; Ketterson, John B.; Kanatzidis, Mercouri G.; Xu, Tao; Chan, Maria K. Y.; Schaller, Richard D.

doi:10.1021/acsenergylett.7b00790

Title: Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies

Journal Article · Thu Sep 28 00:00:00 EDT 2017 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.7b00790· OSTI ID:1402074

^[1]; Xia, Yi ^[1]; Gong, Jue ^[2];

^[3];

^[3]; Alexander, Grant C. B. ^[3]; Ma, Zhiyuan ^[1]; Zhou, Hua ^[1]; Gosztola, David J. ^[1]; Ketterson, John B. ^[3];

^[3];

^[2];

^[1];

^[4]

Argonne National Lab. (ANL), Lemont, IL (United States)
Northern Illinois Univ., DeKalb, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)

Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures. Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1402074

Journal Information:: ACS Energy Letters, Vol. 2, Issue 10; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 38 works

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References (48)

From soft harmonic phonons to fast relaxational dynamics in ${CH}_{3} {NH}_{3} {PbBr}_{3}$ Swainson, I. P.; Stock, C.; Parker, S. F. Physical Review B, Vol. 92, Issue 10 https://doi.org/10.1103/PhysRevB.92.100303	journal	September 2015
Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells Frost, Jarvist M.; Butler, Keith T.; Walsh, Aron APL Materials, Vol. 2, Issue 8 https://doi.org/10.1063/1.4890246	journal	August 2014
Excitonic emissions and above-band-gap luminescence in the single-crystal perovskite semiconductors $CsPbB r_{3}$ and $CsPbC l_{3}$ Sebastian, M.; Peters, J. A.; Stoumpos, C. C. Physical Review B, Vol. 92, Issue 23 https://doi.org/10.1103/PhysRevB.92.235210	journal	December 2015
Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide Whitfield, P. S.; Herron, N.; Guise, W. E. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep35685	journal	October 2016
Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals Shi, D.; Adinolfi, V.; Comin, R. Science, Vol. 347, Issue 6221 https://doi.org/10.1126/science.aaa2725	journal	January 2015
Metal halide perovskites for energy applications Zhang, Wei; Eperon, Giles E.; Snaith, Henry J. Nature Energy, Vol. 1, Issue 6 https://doi.org/10.1038/nenergy.2016.48	journal	May 2016
Switchable S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide perovskites Kim, M.; Im, J.; Freeman, A. J. Proceedings of the National Academy of Sciences, Vol. 111, Issue 19 https://doi.org/10.1073/pnas.1405780111	journal	April 2014
Role of Ferroelectric Nanodomains in the Transport Properties of Perovskite Solar Cells Pecchia, Alessandro; Gentilini, Desirée; Rossi, Daniele Nano Letters, Vol. 16, Issue 2 https://doi.org/10.1021/acs.nanolett.5b03957	journal	January 2016
Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites Liu, Shi; Zheng, Fan; Koocher, Nathan Z. The Journal of Physical Chemistry Letters, Vol. 6, Issue 4 https://doi.org/10.1021/jz502666j	journal	February 2015
Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite Beecher, Alexander N.; Semonin, Octavi E.; Skelton, Jonathan M. ACS Energy Letters, Vol. 1, Issue 4 https://doi.org/10.1021/acsenergylett.6b00381	journal	October 2016
Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH ₃ NH ₃ PbI ₃ Zheng, Fan; Tan, Liang Z.; Liu, Shi Nano Letters, Vol. 15, Issue 12 https://doi.org/10.1021/acs.nanolett.5b01854	journal	November 2015
Direct Observation of Ferroelectric Domains in Solution-Processed CH ₃ NH ₃ PbI ₃ Perovskite Thin Films Kutes, Yasemin; Ye, Linghan; Zhou, Yuanyuan The Journal of Physical Chemistry Letters, Vol. 5, Issue 19 https://doi.org/10.1021/jz501697b	journal	September 2014
High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization Saidaminov, Makhsud I.; Abdelhady, Ahmed L.; Murali, Banavoth Nature Communications, Vol. 6, Article No. 7586 https://doi.org/10.1038/ncomms8586	journal	July 2015
Crystal Growth of the Perovskite Semiconductor CsPbBr ₃ : A New Material for High-Energy Radiation Detection Stoumpos, Constantinos C.; Malliakas, Christos D.; Peters, John A. Crystal Growth & Design, Vol. 13, Issue 7 https://doi.org/10.1021/cg400645t	journal	June 2013
Photoexcitation dynamics in solution-processed formamidinium lead iodide perovskite thin films for solar cell applications Fang, Hong-Hua; Wang, Feng; Adjokatse, Sampson Light: Science & Applications, Vol. 5, Issue 4 https://doi.org/10.1038/lsa.2016.56	journal	December 2015
Experimental and theoretical optical properties of methylammonium lead halide perovskites Leguy, Aurélien M. A.; Azarhoosh, Pooya; Alonso, M. Isabel Nanoscale, Vol. 8, Issue 12 https://doi.org/10.1039/C5NR05435D	journal	January 2016
Chemical tuning of dynamic cation off-centering in the cubic phases of hybrid tin and lead halide perovskites Laurita, Geneva; Fabini, Douglas H.; Stoumpos, Constantinos C. Chemical Science, Vol. 8, Issue 8 https://doi.org/10.1039/C7SC01429E	journal	January 2017
Phonon modes and central peaks in an $A$ -site relaxor: A low-frequency Raman study of sodium bismuth titanate Jackson, Daniel K.; Toulouse, Jean; Luo, Haosu Physical Review B, Vol. 90, Issue 5 https://doi.org/10.1103/PhysRevB.90.054108	journal	August 2014
Surface generation and detection of phonons by picosecond light pulses Thomsen, C.; Grahn, H. T.; Maris, H. J. Physical Review B, Vol. 34, Issue 6 https://doi.org/10.1103/PhysRevB.34.4129	journal	September 1986
Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl500390f	journal	April 2014
Two-Inch-Sized Perovskite CH ₃ NH ₃ PbX ₃ (X = Cl, Br, I) Crystals: Growth and Characterization Liu, Yucheng; Yang, Zhou; Cui, Dong Advanced Materials, Vol. 27, Issue 35 https://doi.org/10.1002/adma.201502597	journal	August 2015
Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite Chen, Tianran; Foley, Benjamin J.; Park, Changwon Science Advances, Vol. 2, Issue 10 https://doi.org/10.1126/sciadv.1601650	journal	October 2016
Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination Fang, Yanjun; Dong, Qingfeng; Shao, Yuchuan Nature Photonics, Vol. 9, Issue 10 https://doi.org/10.1038/nphoton.2015.156	journal	August 2015
Elastic softening and central peaks in BaTiO3 single crystals above the cubic-tetragonal phase-transition temperature Ko, J. -H.; Kojima, S.; Koo, T. -Y. Applied Physics Letters, Vol. 93, Issue 10 https://doi.org/10.1063/1.2980444	journal	September 2008
Low-temperature solution-processed wavelength-tunable perovskites for lasing Xing, Guichuan; Mathews, Nripan; Lim, Swee Sien Nature Materials, Vol. 13, Issue 5 https://doi.org/10.1038/nmat3911	journal	March 2014
Direct–indirect character of the bandgap in methylammonium lead iodide perovskite Hutter, Eline M.; Gélvez-Rueda, María C.; Osherov, Anna Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4765	journal	October 2016
Elastic Constants and Thermal Expansion of CsPbCl ₃ Hirotsu, Shunsuke; Suzuki, Tomonobu Journal of the Physical Society of Japan, Vol. 44, Issue 5 https://doi.org/10.1143/JPSJ.44.1604	journal	May 1978
Low-Temperature Solution-Grown CsPbBr ₃ Single Crystals and Their Characterization Rakita, Yevgeny; Kedem, Nir; Gupta, Satyajit Crystal Growth & Design, Vol. 16, Issue 10 https://doi.org/10.1021/acs.cgd.6b00764	journal	September 2016
Electron–acoustic phonon coupling in single crystal CH3NH3PbI3 perovskites revealed by coherent acoustic phonons Mante, Pierre-Adrien; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14398	journal	February 2017
Spatially resolved studies of the phases and morphology of methylammonium and formamidinium lead tri-halide perovskites Galkowski, K.; Mitioglu, A. A.; Surrente, A. Nanoscale, Vol. 9, Issue 9 https://doi.org/10.1039/C7NR00355B	journal	January 2017
Research Update: Relativistic origin of slow electron-hole recombination in hybrid halide perovskite solar cells Azarhoosh, Pooya; McKechnie, Scott; Frost, Jarvist M. APL Materials, Vol. 4, Issue 9 https://doi.org/10.1063/1.4955028	journal	September 2016
Formamidinium Lead Halide Perovskite Crystals with Unprecedented Long Carrier Dynamics and Diffusion Length Zhumekenov, Ayan A.; Saidaminov, Makhsud I.; Haque, Md Azimul ACS Energy Letters, Vol. 1, Issue 1 https://doi.org/10.1021/acsenergylett.6b00002	journal	April 2016
Dielectric Response: Answer to Many Questions in the Methylammonium Lead Halide Solar Cell Absorbers Anusca, Irina; Balčiūnas, Sergejus; Gemeiner, Pascale Advanced Energy Materials, Vol. 7, Issue 19 https://doi.org/10.1002/aenm.201700600	journal	May 2017
CH ₃ NH ₃ PbCl ₃ Single Crystals: Inverse Temperature Crystallization and Visible-Blind UV-Photodetector Maculan, Giacomo; Sheikh, Arif D.; Abdelhady, Ahmed L. The Journal of Physical Chemistry Letters, Vol. 6, Issue 19 https://doi.org/10.1021/acs.jpclett.5b01666	journal	September 2015
Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)† Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi Journal of Physics and Chemistry of Solids, Vol. 51, Issue 12 https://doi.org/10.1016/0022-3697(90)90021-7	journal	January 1990
Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH ₃ NH ₃ PbI ₃ Pisoni, Andrea; Jaćimović, Jaćim; Barišić, Osor S. The Journal of Physical Chemistry Letters, Vol. 5, Issue 14 https://doi.org/10.1021/jz5012109	journal	July 2014
Ferroelectric Polarization in CH ₃ NH ₃ PbI ₃ Perovskite Kim, Hui-Seon; Kim, Sung Kyun; Kim, Byeong Jo The Journal of Physical Chemistry Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acs.jpclett.5b00695	journal	April 2015
Tetragonal CH ₃ NH ₃ PbI ₃ is ferroelectric Rakita, Yevgeny; Bar-Elli, Omri; Meirzadeh, Elena Proceedings of the National Academy of Sciences, Vol. 114, Issue 28 https://doi.org/10.1073/pnas.1702429114	journal	June 2017
The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8124	journal	May 2015
Photon recycling in lead iodide perovskite solar cells Pazos-Outon, L. M.; Szumilo, M.; Lamboll, R. Science, Vol. 351, Issue 6280 https://doi.org/10.1126/science.aaf1168	journal	March 2016
Relaxing with relaxors: a review of relaxor ferroelectrics Cowley, R. A.; Gvasaliya, S. N.; Lushnikov, S. G. Advances in Physics, Vol. 60, Issue 2 https://doi.org/10.1080/00018732.2011.555385	journal	April 2011
The study of structural phase transitions by means of ultrasonic experiments Rehwald, Walther Advances in Physics, Vol. 22, Issue 6 https://doi.org/10.1080/00018737300101379	journal	November 1973
Ferroelectric domains in methylammonium lead iodide perovskite thin-films Röhm, Holger; Leonhard, Tobias; Hoffmann, Michael J. Energy & Environmental Science, Vol. 10, Issue 4 https://doi.org/10.1039/C7EE00420F	journal	January 2017
CH ₃ NH ₃ PbI ₃ perovskites: Ferroelasticity revealed Strelcov, Evgheni; Dong, Qingfeng; Li, Tao Science Advances, Vol. 3, Issue 4 https://doi.org/10.1126/sciadv.1602165	journal	April 2017
CH3NH3PbBr3 is not pyroelectric, excluding ferroelectric-enhanced photovoltaic performance Rakita, Yevgeny; Meirzadeh, Elena; Bendikov, Tatyana APL Materials, Vol. 4, Issue 5 https://doi.org/10.1063/1.4949760	journal	May 2016
Lattice dynamics and the nature of structural transitions in organolead halide perovskites Comin, Riccardo; Crawford, Michael K.; Said, Ayman H. Physical Review B, Vol. 94, Issue 9 https://doi.org/10.1103/PhysRevB.94.094301	journal	September 2016
Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy Guo, Zhi; Wan, Yan; Yang, Mengjin Science, Vol. 356, Issue 6333 https://doi.org/10.1126/science.aam7744	journal	April 2017
Ferroelectricity of CH ₃ NH ₃ PbI ₃ Perovskite Fan, Zhen; Xiao, Juanxiu; Sun, Kuan The Journal of Physical Chemistry Letters, Vol. 6, Issue 7 https://doi.org/10.1021/acs.jpclett.5b00389	journal	March 2015

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Carrier recombination mechanism in $CsPbB r_{3}$ revealed by time-resolved photoluminescence spectroscopy Peters, J. A.; Liu, Zhifu; Yu, Ruihan Physical Review B, Vol. 100, Issue 23 https://doi.org/10.1103/physrevb.100.235305	journal	December 2019
Dynamic symmetry breaking and spin splitting in metal halide perovskites McKechnie, Scott; Frost, Jarvist M.; Pashov, Dimitar Physical Review B, Vol. 98, Issue 8 https://doi.org/10.1103/physrevb.98.085108	journal	August 2018
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