Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CH3NH3PbI3) Perovskite Photochemistry

Park, Myeongkee; Kornienko, Nikolay; Reyes-Lillo, Sebastian E.; Lai, Minliang; Neaton, Jeffrey B.; Yang, Peidong; Mathies, Richard A.

doi:10.1021/acs.nanolett.7b00919

Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CH₃NH₃PbI₃) Perovskite Photochemistry

Journal Article · Wed Jun 07 04:00:00 EDT 2017 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.7b00919· OSTI ID:1601643

^[1]; Kornienko, Nikolay ^[1]; Reyes-Lillo, Sebastian E. ^[2]; Lai, Minliang ^[1]; Neaton, Jeffrey B. ^[3]; ^[4]; Mathies, Richard A. ^[1]

Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States). Kavli Energy NanoSciences Inst.
Univ. of California, Berkeley, CA (United States). Kavli Energy NanoSciences Inst.

Raman and photoluminescence (PL) spectroscopy are used to investigate dynamic structure-function relationships in methylammonium lead iodide (MAPbI₃) perovskite. The intensity of the 150 cm^-1 methylammonium (MA) librational Raman mode is found to be correlated with PL intensities in microstructures of MAPbI3. Because of the strong hydrogen bond between hydrogens in MA and iodine in the PbI6 perovskite octahedra, the Raman activity of MA is very sensitive to structural distortions of the inorganic framework. The structural distortions directly influence PL intensities, which in turn have been correlated with microstructure quality. Our measurements, supported with first-principles calculations, indicate how excited-state MA librational displacements mechanistically control PL efficiency and lifetime in MAPbI₃-material parameters that are likely important for efficient photovoltaic devices.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Mathies Royalty Fund

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1601643

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 7 Vol. 17; ISSN 1530-6984

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

References (57)

Raman Spectroscopy of Organic–Inorganic Halide Perovskites Ledinský, Martin; Löper, Philipp; Niesen, Bjoern The Journal of Physical Chemistry Letters, Vol. 6, Issue 3 https://doi.org/10.1021/jz5026323	journal	January 2015
Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Advanced Materials, Vol. 26, Issue 27 https://doi.org/10.1002/adma.201306281	journal	May 2014
Uncovering the Veil of the Degradation in Perovskite CH ₃ NH ₃ PbI ₃ upon Humidity Exposure: A First-Principles Study Tong, Chuan-Jia; Geng, Wei; Tang, Zhen-Kun The Journal of Physical Chemistry Letters, Vol. 6, Issue 16 https://doi.org/10.1021/acs.jpclett.5b01544	journal	July 2015
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
Perovskites for photovoltaics: a combined review of organic–inorganic halide perovskites and ferroelectric oxide perovskites Fan, Zhen; Sun, Kuan; Wang, John Journal of Materials Chemistry A, Vol. 3, Issue 37 https://doi.org/10.1039/C5TA04235F	journal	January 2015
The Impact of the Crystallization Processes on the Structural and Optical Properties of Hybrid Perovskite Films for Photovoltaics Grancini, Giulia; Marras, Sergio; Prato, Mirko The Journal of Physical Chemistry Letters, Vol. 5, Issue 21 https://doi.org/10.1021/jz501877h	journal	October 2014
Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials Neukirch, Amanda J.; Nie, Wanyi; Blancon, Jean-Christophe Nano Letters, Vol. 16, Issue 6 https://doi.org/10.1021/acs.nanolett.6b01218	journal	May 2016
Under the spotlight: The organic–inorganic hybrid halide perovskite for optoelectronic applications Chen, Qi; De Marco, Nicholas; Yang, Yang (Michael) Nano Today, Vol. 10, Issue 3 https://doi.org/10.1016/j.nantod.2015.04.009	journal	June 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
Review of recent progress in chemical stability of perovskite solar cells Niu, Guangda; Guo, Xudong; Wang, Liduo Journal of Materials Chemistry A, Vol. 3, Issue 17, p. 8970-8980 https://doi.org/10.1039/C4TA04994B	journal	December 2014
General Working Principles of CH ₃ NH ₃ PbX ₃ Perovskite Solar Cells Gonzalez-Pedro, Victoria; Juarez-Perez, Emilio J.; Arsyad, Waode-Sukmawati Nano Letters, Vol. 14, Issue 2 https://doi.org/10.1021/nl404252e	journal	January 2014
Methylammonium Rotational Dynamics in Lead Halide Perovskite by Classical Molecular Dynamics: The Role of Temperature Mattoni, A.; Filippetti, A.; Saba, M. I. The Journal of Physical Chemistry C, Vol. 119, Issue 30 https://doi.org/10.1021/acs.jpcc.5b04283	journal	July 2015
Atomically thin two-dimensional organic-inorganic hybrid perovskites Dou, L.; Wong, A. B.; Yu, Y. Science, Vol. 349, Issue 6255 https://doi.org/10.1126/science.aac7660	journal	September 2015
Post-synthetic halide conversion and selective halogen capture in hybrid perovskites Solis-Ibarra, D.; Smith, I. C.; Karunadasa, H. I. Chemical Science, Vol. 6, Issue 7 https://doi.org/10.1039/C5SC01135C	journal	January 2015
Size-Dependent Exciton–Phonon Coupling in CdSe Nanocrystals through Resonance Raman Excitation Profile Analysis Lin, Chen; Gong, Ke; Kelley, David F. The Journal of Physical Chemistry C, Vol. 119, Issue 13 https://doi.org/10.1021/acs.jpcc.5b00774	journal	March 2015
Impact of microstructure on local carrier lifetime in perovskite solar cells de Quilettes, D. W.; Vorpahl, S. M.; Stranks, S. D. Science, Vol. 348, Issue 6235 https://doi.org/10.1126/science.aaa5333	journal	April 2015
Engineering of CH ₃ NH ₃ PbI ₃ Perovskite Crystals by Alloying Large Organic Cations for Enhanced Thermal Stability and Transport Properties Peng, Wei; Miao, Xiaohe; Adinolfi, Valerio Angewandte Chemie International Edition, Vol. 55, Issue 36 https://doi.org/10.1002/anie.201604880	journal	July 2016
Unusual defect physics in CH ₃ NH ₃ PbI ₃ perovskite solar cell absorber Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Applied Physics Letters, Vol. 104, Issue 6 https://doi.org/10.1063/1.4864778	journal	February 2014
Interplay of Orientational Order and Electronic Structure in Methylammonium Lead Iodide: Implications for Solar Cell Operation Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo Chemistry of Materials, Vol. 26, Issue 22 https://doi.org/10.1021/cm5032046	journal	November 2014
Revealing the role of organic cations in hybrid halide perovskite CH3NH3PbI3 Motta, Carlo; El-Mellouhi, Fedwa; Kais, Sabre Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8026	journal	April 2015
Decreasing Radiative Recombination Coefficients via an Indirect Band Gap in Lead Halide Perovskites Kirchartz, Thomas; Rau, Uwe The Journal of Physical Chemistry Letters, Vol. 8, Issue 6 https://doi.org/10.1021/acs.jpclett.7b00236	journal	March 2017
Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites Bakulin, Artem A.; Selig, Oleg; Bakker, Huib J. The Journal of Physical Chemistry Letters, Vol. 6, Issue 18 https://doi.org/10.1021/acs.jpclett.5b01555	journal	August 2015
Quantum-dot-in-perovskite solids Ning, Zhijun; Gong, Xiwen; Comin, Riccardo Nature, Vol. 523, Issue 7560 https://doi.org/10.1038/nature14563	journal	July 2015
A Layered Hybrid Perovskite Solar-Cell Absorber with Enhanced Moisture Stability Smith, Ian C.; Hoke, Eric T.; Solis-Ibarra, Diego Angewandte Chemie International Edition, Vol. 53, Issue 42 https://doi.org/10.1002/anie.201406466	journal	September 2014
Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites Gélvez-Rueda, María C.; Cao, Duyen H.; Patwardhan, Sameer The Journal of Physical Chemistry C, Vol. 120, Issue 30 https://doi.org/10.1021/acs.jpcc.6b06722	journal	July 2016
High-performance photovoltaic perovskite layers fabricated through intramolecular exchange Yang, W. S.; Noh, J. H.; Jeon, N. J. Science, Vol. 348, Issue 6240 https://doi.org/10.1126/science.aaa9272	journal	May 2015
Role of hydrogen-bonding and its interplay with octahedral tilting in CH ₃ NH ₃ PbI ₃ Lee, Jung-Hoon; Bristowe, Nicholas C.; Bristowe, Paul D. Chemical Communications, Vol. 51, Issue 29 https://doi.org/10.1039/C5CC00979K	journal	January 2015
Structural and optical properties of methylammonium lead iodide across the tetragonal to cubic phase transition: implications for perovskite solar cells Quarti, Claudio; Mosconi, Edoardo; Ball, James M. Energy & Environmental Science, Vol. 9, Issue 1 https://doi.org/10.1039/C5EE02925B	journal	January 2016
Chemical Approaches to Addressing the Instability and Toxicity of Lead–Halide Perovskite Absorbers Slavney, Adam H.; Smaha, Rebecca W.; Smith, Ian C. Inorganic Chemistry, Vol. 56, Issue 1 https://doi.org/10.1021/acs.inorgchem.6b01336	journal	August 2016
Advancements in perovskite solar cells: photophysics behind the photovoltaics Sum, Tze Chien; Mathews, Nripan Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE00673A	journal	January 2014
What Is Moving in Hybrid Halide Perovskite Solar Cells? Frost, Jarvist M.; Walsh, Aron Accounts of Chemical Research, Vol. 49, Issue 3 https://doi.org/10.1021/acs.accounts.5b00431	journal	February 2016
Screening in crystalline liquids protects energetic carriers in hybrid perovskites Zhu, H.; Miyata, K.; Fu, Y. Science, Vol. 353, Issue 6306 https://doi.org/10.1126/science.aaf9570	journal	September 2016
Extremely Slow Photoconductivity Response of CH ₃ NH ₃ PbI ₃ Perovskites Suggesting Structural Changes under Working Conditions Gottesman, Ronen; Haltzi, Eynav; Gouda, Laxman The Journal of Physical Chemistry Letters, Vol. 5, Issue 15 https://doi.org/10.1021/jz501373f	journal	July 2014
An extended Tolerance Factor approach for organic–inorganic perovskites Kieslich, Gregor; Sun, Shijing; Cheetham, Anthony K. Chemical Science, Vol. 6, Issue 6 https://doi.org/10.1039/C5SC00961H	journal	January 2015
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
Resolving the Physical Origin of Octahedral Tilting in Halide Perovskites Lee, Jung-Hoon; Bristowe, Nicholas C.; Lee, June Ho Chemistry of Materials, Vol. 28, Issue 12 https://doi.org/10.1021/acs.chemmater.6b00968	journal	June 2016
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 Pérez-Osorio, Miguel A.; Milot, Rebecca L.; Filip, Marina R. The Journal of Physical Chemistry C, Vol. 119, Issue 46 https://doi.org/10.1021/acs.jpcc.5b07432	journal	November 2015
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
Structural and electronic properties of hybrid perovskites for high-efficiency thin-film photovoltaics from first-principles Brivio, Federico; Walker, Alison B.; Walsh, Aron APL Materials, Vol. 1, Issue 4 https://doi.org/10.1063/1.4824147	journal	October 2013
Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal, and cubic phases of methylammonium lead iodide Brivio, Federico; Frost, Jarvist M.; Skelton, Jonathan M. Physical Review B, Vol. 92, Issue 14 https://doi.org/10.1103/PhysRevB.92.144308	journal	October 2015
Time-dependent theory of Raman scattering Lee, Soo-Y.; Heller, E. J. The Journal of Chemical Physics, Vol. 71, Issue 12 https://doi.org/10.1063/1.438316	journal	January 1979
Transformation of the Excited State and Photovoltaic Efficiency of CH ₃ NH ₃ PbI ₃ Perovskite upon Controlled Exposure to Humidified Air Christians, Jeffrey A.; Miranda Herrera, Pierre A.; Kamat, Prashant V. Journal of the American Chemical Society, Vol. 137, Issue 4 https://doi.org/10.1021/ja511132a	journal	January 2015
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber Stranks, S. D.; Eperon, G. E.; Grancini, G. Science, Vol. 342, Issue 6156, p. 341-344 https://doi.org/10.1126/science.1243982	journal	October 2013
Identification of the symmetry of phonon modes in CsPbCl3 in phase IV by Raman and resonance-Raman scattering Calistru, Dana M.; Mihut, L.; Lefrant, S. Journal of Applied Physics, Vol. 82, Issue 11 https://doi.org/10.1063/1.366307	journal	December 1997
Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite Leblebici, Sibel Y.; Leppert, Linn; Li, Yanbo Nature Energy, Vol. 1, Issue 8 https://doi.org/10.1038/nenergy.2016.93	journal	July 2016
Raman scattering in PbI2 Capozzi, V.; Fontana, A.; Fontana, M. P. Il Nuovo Cimento B Series 11, Vol. 39, Issue 2 https://doi.org/10.1007/BF02725793	journal	June 1977
Mechanical properties of organic–inorganic halide perovskites, CH ₃ NH ₃ PbX ₃ (X = I, Br and Cl), by nanoindentation Sun, Shijing; Fang, Yanan; Kieslich, Gregor Journal of Materials Chemistry A, Vol. 3, Issue 36 https://doi.org/10.1039/C5TA03331D	journal	January 2015
Ab Initio Molecular Dynamics Simulations of Methylammonium Lead Iodide Perovskite Degradation by Water Mosconi, Edoardo; Azpiroz, Jon M.; De Angelis, Filippo Chemistry of Materials, Vol. 27, Issue 13 https://doi.org/10.1021/acs.chemmater.5b01991	journal	June 2015
Degradation observations of encapsulated planar CH ₃ NH ₃ PbI ₃ perovskite solar cells at high temperatures and humidity Han, Yu; Meyer, Steffen; Dkhissi, Yasmina Journal of Materials Chemistry A, Vol. 3, Issue 15 https://doi.org/10.1039/C5TA00358J	journal	January 2015
Resonance Raman and Excitation Energy Dependent Charge Transfer Mechanism in Halide-Substituted Hybrid Perovskite Solar Cells Park, Byung-wook; Jain, Sagar M.; Zhang, Xiaoliang ACS Nano, Vol. 9, Issue 2 https://doi.org/10.1021/nn507345e	journal	January 2015
Photoinduced Reversible Structural Transformations in Free-Standing CH ₃ NH ₃ PbI ₃ Perovskite Films Gottesman, Ronen; Gouda, Laxman; Kalanoor, Basanth S. The Journal of Physical Chemistry Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acs.jpclett.5b00994	journal	June 2015
Reversible Hydration of CH ₃ NH ₃ PbI ₃ in Films, Single Crystals, and Solar Cells Leguy, Aurélien M. A.; Hu, Yinghong; Campoy-Quiles, Mariano Chemistry of Materials, Vol. 27, Issue 9 https://doi.org/10.1021/acs.chemmater.5b00660	journal	April 2015
Dynamical Origin of the Rashba Effect in Organohalide Lead Perovskites: A Key to Suppressed Carrier Recombination in Perovskite Solar Cells? Etienne, Thibaud; Mosconi, Edoardo; De Angelis, Filippo The Journal of Physical Chemistry Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acs.jpclett.6b00564	journal	April 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
Perovskite Solar Cells: From Materials to Devices Jung, Hyun Suk; Park, Nam-Gyu Small, Vol. 11, Issue 1 https://doi.org/10.1002/smll.201402767	journal	October 2014
Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides Li, Xiong; Ibrahim Dar, M.; Yi, Chenyi Nature Chemistry, Vol. 7, Issue 9 https://doi.org/10.1038/nchem.2324	journal	August 2015
Investigation of CH ₃ NH ₃ PbI ₃ Degradation Rates and Mechanisms in Controlled Humidity Environments Using in Situ Techniques Yang, Jinli; Siempelkamp, Braden D.; Liu, Dianyi ACS Nano, Vol. 9, Issue 2 https://doi.org/10.1021/nn506864k	journal	January 2015

Similar Records

Mapping the Photoresponse of CH₃NH₃PbI₃ Hybrid Perovskite Thin Films at the Nanoscale

Journal Article · Thu May 26 00:00:00 EDT 2016 · Nano Letters · OSTI ID:1418561

Related Subjects

DFT
MAPbI3
Methylammonium lead iodide perovskite
Raman microscopy
photoluminescence microscopy
photovoltaics

Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CH3NH3PbI3) Perovskite Photochemistry

Citation Formats

References (57)

Similar Records

Related Subjects

Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CH₃NH₃PbI₃) Perovskite Photochemistry