Electron–acoustic phonon coupling in single crystal CH3NH3PbI3 perovskites revealed by coherent acoustic phonons

Mante, Pierre-Adrien; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.; Yartsev, Arkady

doi:10.1038/ncomms14398

Electron–acoustic phonon coupling in single crystal CH₃NH₃PbI₃ perovskites revealed by coherent acoustic phonons

Journal Article · Wed Feb 08 00:00:00 EST 2017 · Nature Communications

DOI:https://doi.org/10.1038/ncomms14398· OSTI ID:1347386

Mante, Pierre-Adrien ^[1]; ^[2]; Kanatzidis, Mercouri G. ^[2]; Yartsev, Arkady ^[3]

Lund Univ. (Sweden). Dept. of Chemistry and NanoLund; Lund University, Sweden
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Lund Univ. (Sweden). Dept. of Chemistry and NanoLund

The intrinsic properties of CH₃NH₃PbI₃ are still largely unknown in spite of the great amount of attention it has received for its solar cell application. Mobility of charges is a quintessential property in this aspect; however, there is still no clear understanding of electron transport, as reported values span over three orders of magnitude. Here we develop a method to measure the electron and hole deformation potentials using coherent acoustic phonons generated by femtosecond laser pulses. Furthermore, we apply this method to characterize a CH₃NH₃PbI₃ single crystal.We measure the acoustic phonon properties and characterize electron-acoustic phonon scattering. Then, using the deformation potential theory, we calculate the carrier intrinsic mobility and compare it to the reported experimental and theoretical values. These results reveal high electron and hole mobilities of 2,800 and 9,400 cm²V^-1 s ^-1 , respectively. Comparison with literature values of mobility demonstrates the potential role played by polarons in charge transport in CH₃NH₃PbI₃.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0012541

OSTI ID:: 1347386

Journal Information:: Nature Communications, Journal Name: Nature Communications Vol. 8; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Temperature-Dependent Charge-Carrier Dynamics in CH ₃ NH ₃ PbI ₃ Perovskite Thin Films Milot, Rebecca L.; Eperon, Giles E.; Snaith, Henry J. Advanced Functional Materials, Vol. 25, Issue 39 https://doi.org/10.1002/adfm.201502340	journal	September 2015
Donor states and deformation around impurity atoms in semiconductors Shinohara, S. Il Nuovo Cimento, Vol. 22, Issue 1 https://doi.org/10.1007/BF02828991	journal	October 1961
Physical mechanisms of coherent acoustic phonons generation by ultrafast laser action Ruello, Pascal; Gusev, Vitalyi E. Ultrasonics, Vol. 56 https://doi.org/10.1016/j.ultras.2014.06.004	journal	February 2015
THz acoustic phonon spectroscopy and nanoscopy by using piezoelectric semiconductor heterostructures Mante, Pierre-Adrien; Huang, Yu-Ru; Yang, Szu-Chi Ultrasonics, Vol. 56 https://doi.org/10.1016/j.ultras.2014.09.020	journal	February 2015
Charge Carriers in Planar and Meso-Structured Organic–Inorganic Perovskites: Mobilities, Lifetimes, and Concentrations of Trap States Hutter, Eline M.; Eperon, Giles E.; Stranks, Samuel D. The Journal of Physical Chemistry Letters, Vol. 6, Issue 15 https://doi.org/10.1021/acs.jpclett.5b01361	journal	July 2015
Are Mobilities in Hybrid Organic–Inorganic Halide Perovskites Actually “High”? Brenner, Thomas M.; Egger, David A.; Rappe, Andrew M. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02390	journal	November 2015
Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons Zhu, X. -Y.; Podzorov, V. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02462	journal	November 2015
Phonon–Electron Scattering Limits Free Charge Mobility in Methylammonium Lead Iodide Perovskites Karakus, Melike; Jensen, Søren A.; D’Angelo, Francesco The Journal of Physical Chemistry Letters, Vol. 6, Issue 24 https://doi.org/10.1021/acs.jpclett.5b02485	journal	December 2015
Photoferroelectric and Photopiezoelectric Properties of Organometal Halide Perovskites Liu, Shi; Zheng, Fan; Grinberg, Ilya The Journal of Physical Chemistry Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acs.jpclett.6b00527	journal	April 2016
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
Perovskites for Solar Thermoelectric Applications: A First Principle Study of CH ₃ NH ₃ AI ₃ (A = Pb and Sn) He, Yuping; Galli, Giulia Chemistry of Materials, Vol. 26, Issue 18 https://doi.org/10.1021/cm5026766	journal	August 2014
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038 https://doi.org/10.1021/ic401215x	journal	July 2013
Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination Ponseca, Carlito S.; Savenije, Tom J.; Abdellah, Mohamed Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja412583t	journal	February 2014
Improved Understanding of the Electronic and Energetic Landscapes of Perovskite Solar Cells: High Local Charge Carrier Mobility, Reduced Recombination, and Extremely Shallow Traps Oga, Hikaru; Saeki, Akinori; Ogomi, Yuhei Journal of the American Chemical Society, Vol. 136, Issue 39 https://doi.org/10.1021/ja506936f	journal	September 2014
Trap States in Lead Iodide Perovskites Wu, Xiaoxi; Trinh, M. Tuan; Niesner, Daniel Journal of the American Chemical Society, Vol. 137, Issue 5 https://doi.org/10.1021/ja512833n	journal	January 2015
Perovskites: The Emergence of a New Era for Low-Cost, High-Efficiency Solar Cells Snaith, Henry J. The Journal of Physical Chemistry Letters, Vol. 4, Issue 21, p. 3623-3630 https://doi.org/10.1021/jz4020162	journal	October 2013
Thermally Activated Exciton Dissociation and Recombination Control the Carrier Dynamics in Organometal Halide Perovskite Savenije, Tom J.; Ponseca, Carlito S.; Kunneman, Lucas The Journal of Physical Chemistry Letters, Vol. 5, Issue 13 https://doi.org/10.1021/jz500858a	journal	June 2014
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
Graphene-to-Substrate Energy Transfer through Out-of-Plane Longitudinal Acoustic Phonons Chen, I-Ju; Mante, Pierre-Adrien; Chang, Cheng-Kai Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl404297r	journal	February 2014
Hybrid organic—inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties Brenner, Thomas M.; Egger, David A.; Kronik, Leeor Nature Reviews Materials, Vol. 1, Issue 1 https://doi.org/10.1038/natrevmats.2015.7	journal	January 2016
Efficient planar heterojunction perovskite solar cells by vapour deposition Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J. Nature, Vol. 501, Issue 7467, p. 395-398 https://doi.org/10.1038/nature12509	journal	September 2013
Electron–phonon coupling in hybrid lead halide perovskites Wright, Adam D.; Verdi, Carla; Milot, Rebecca L. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11755	journal	May 2016
Correlated electron–hole plasma in organometal perovskites Saba, Michele; Cadelano, Michele; Marongiu, Daniela Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6049	journal	September 2014
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
Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors Zhu, Haiming; Fu, Yongping; Meng, Fei Nature Materials, Vol. 14, Issue 6 https://doi.org/10.1038/nmat4271	journal	April 2015
Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques Liu, Dianyi; Kelly, Timothy L. Nature Photonics, Vol. 8, Issue 2, p. 133-138 https://doi.org/10.1038/nphoton.2013.342	journal	December 2013
Charge carrier mobility in hybrid halide perovskites Motta, Carlo; El-Mellouhi, Fedwa; Sanvito, Stefano Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep12746	journal	August 2015
Intrinsic and Extrinsic Charge Transport in CH3NH3PbI3 Perovskites Predicted from First-Principles Zhao, Tianqi; Shi, Wen; Xi, Jinyang Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep19968	journal	January 2016
Bulk crystal growth of hybrid perovskite material CH ₃ NH ₃ PbI ₃ Dang, Yangyang; Liu, Yang; Sun, Youxuan CrystEngComm, Vol. 17, Issue 3 https://doi.org/10.1039/C4CE02106A	journal	January 2015
Band alignment of the hybrid halide perovskites CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbBr ₃ and CH ₃ NH ₃ PbI ₃ Butler, Keith T.; Frost, Jarvist M.; Walsh, Aron Materials Horizons, Vol. 2, Issue 2 https://doi.org/10.1039/C4MH00174E	journal	January 2015
High intrinsic carrier mobility and photon absorption in the perovskite CH ₃ NH ₃ PbI ₃ Wang, Youwei; Zhang, Yubo; Zhang, Peihong Physical Chemistry Chemical Physics, Vol. 17, Issue 17 https://doi.org/10.1039/C5CP00448A	journal	January 2015
Intrinsic femtosecond charge generation dynamics in single crystal CH ₃ NH ₃ PbI ₃ Valverde-Chávez, David A.; Ponseca, Carlito S.; Stoumpos, Constantinos C. Energy & Environmental Science, Vol. 8, Issue 12 https://doi.org/10.1039/C5EE02503F	journal	January 2015
Mechanical properties of hybrid organic-inorganic CH ₃ NH ₃ BX ₃ (B = Sn, Pb; X = Br, I) perovskites for solar cell absorbers Feng, Jing APL Materials, Vol. 2, Issue 8 https://doi.org/10.1063/1.4885256	journal	August 2014
Qualifying composition dependent p and n self-doping in CH ₃ NH ₃ PbI ₃ Wang, Qi; Shao, Yuchuan; Xie, Haipeng Applied Physics Letters, Vol. 105, Issue 16 https://doi.org/10.1063/1.4899051	journal	October 2014
The elastic constants of GaAs from 2 K to 320 K Cottam, R. I.; Saunders, G. A. Journal of Physics C: Solid State Physics, Vol. 6, Issue 13 https://doi.org/10.1088/0022-3719/6/13/011	journal	July 1973
Deformation Potentials and Mobilities in Non-Polar Crystals Bardeen, J.; Shockley, W. Physical Review, Vol. 80, Issue 1 https://doi.org/10.1103/PhysRev.80.72	journal	October 1950
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
Laser-induced coherent acoustical phonons mechanisms in the metal-insulator transition compound NdNiO 3 : Thermal and nonthermal processes Ruello, P.; Zhang, S.; Laffez, P. Physical Review B, Vol. 79, Issue 9 https://doi.org/10.1103/PhysRevB.79.094303	journal	March 2009
Thermal Boundary Resistance between GaN and Cubic Ice and THz Acoustic Attenuation Spectrum of Cubic Ice from Complex Acoustic Impedance Measurements Mante, Pierre-Adrien; Chen, Chien-Cheng; Wen, Yu-Chieh Physical Review Letters, Vol. 111, Issue 22 https://doi.org/10.1103/PhysRevLett.111.225901	journal	November 2013
Observation of Hot-Electron Pressure in the Vibration Dynamics of Metal Nanoparticles Perner, M.; Gresillon, S.; März, J. Physical Review Letters, Vol. 85, Issue 4 https://doi.org/10.1103/PhysRevLett.85.792	journal	July 2000
Interface engineering of highly efficient perovskite solar cells Zhou, H.; Chen, Q.; Li, G. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1254050	journal	July 2014
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
Electron-hole diffusion lengths > 175 μm in solution-grown CH ₃ NH ₃ PbI ₃ single crystals Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan Science, Vol. 347, Issue 6225 https://doi.org/10.1126/science.aaa5760	journal	January 2015

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