Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites

Neukirch, Amanda J.; Abate, Iwnetim I.; Zhou, Liujiang; Nie, Wanyi; Tsai, Hsinhan; Pedesseau, Laurent; Even, Jacky; Crochet, Jared J.; Mohite, Aditya D.; Katan, Claudine; Tretiak, Sergei

doi:10.1021/acs.jpclett.8b03343

Title: Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites

Journal Article · 07 December 2018 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.8b03343 · OSTI ID:1487363

^[1]; Abate, Iwnetim I. ^[2];

^[1]; Nie, Wanyi ^[1]; Tsai, Hsinhan ^[1];

^[3];

^[3]; Crochet, Jared J. ^[1];

^[4];

^[3];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. Rennes (France)
Rice Univ., Houston, TX (United States)

Halide perovskites have demonstrated remarkable performance in optoelectronic applications. Despite extraordinary progress, questions remain about device stability. We report an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies of several experimentally relevant halide perovskites using isolated clusters. Local lattice symmetry, electronic structure, and electron-phonon coupling are interrelated in polaron formation in these materials. To illustrate this, first principles calculations are performed on (MA/Cs/FA)Pb(I/Br)₃ and MASnI₃. Across the materials studied, electron small polaron formation is manifested by Jahn-Teller like distortions in the central octahedron, with apical PbI bonds expanding significantly more than the equatorial bonds. In contrast, hole polarons cause the central octahedron to uniformly contract. This difference in manifestation of electron and hole polaron formation can be a tool to determine what is taking place in individual systems to systematically control performance. Other trends as the anion and cations are changed, are established for optimization in specific optoelectronic applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Los Alamos National Laboratory (LANL)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1487363

Report Number(s):: LA-UR-18-30565

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 24 Vol. 9; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Interfacial Control Toward Efficient and Low-Voltage Perovskite Light-Emitting Diodes Wang, Jianpu; Wang, Nana; Jin, Yizheng Advanced Materials, Vol. 27, Issue 14 https://doi.org/10.1002/adma.201405217	journal	February 2015
Photostriction of CH ₃ NH ₃ PbBr ₃ Perovskite Crystals Wei, Tzu-Chiao; Wang, Hsin-Ping; Li, Ting-You Advanced Materials, Vol. 29, Issue 35 https://doi.org/10.1002/adma.201701789	journal	July 2017
Electron Transfer Reactions in Chemistry: Theory and Experiment (Nobel Lecture) Marcus, Rudolph A. Angewandte Chemie International Edition in English, Vol. 32, Issue 8 https://doi.org/10.1002/anie.199311113	journal	August 1993
Exciton-phonon interactions in the Cs ₃ Bi ₂ I ₉ crystal structure revealed by Raman spectroscopic studies : Exciton-phonon interactions in Cs Nilă, Andreea; Baibarac, Mihaela; Matea, Adelina physica status solidi (b), Vol. 254, Issue 4 https://doi.org/10.1002/pssb.201552805	journal	October 2016
Studies of polaron motion Holstein, T. Annals of Physics, Vol. 8, Issue 3 https://doi.org/10.1016/0003-4916(59)90003-X	journal	November 1959
Polaron formation and symmetry breaking Zuppiroli, L.; Bieber, A.; Michoud, D. Chemical Physics Letters, Vol. 374, Issue 1-2 https://doi.org/10.1016/S0009-2614(03)00646-8	journal	June 2003
Phase transitions in the perovskite methylammonium lead bromide, CH3ND3PbBr3 Swainson, I. P.; Hammond, R. P.; Soullière, C. Journal of Solid State Chemistry, Vol. 176, Issue 1 https://doi.org/10.1016/S0022-4596(03)00352-9	journal	November 2003
High-temperature structural evolution of caesium and rubidium triiodoplumbates Trots, D. M.; Myagkota, S. V. Journal of Physics and Chemistry of Solids, Vol. 69, Issue 10, p. 2520-2526 https://doi.org/10.1016/j.jpcs.2008.05.007	journal	October 2008
First principle study of the structural and optoelectronic properties of cubic perovskites CsPbM3 (M=Cl, Br, I) Murtaza, G.; Ahmad, Iftikhar Physica B: Condensed Matter, Vol. 406, Issue 17 https://doi.org/10.1016/j.physb.2011.05.028	journal	September 2011
Strong Electron–Phonon Coupling and Self-Trapped Excitons in the Defect Halide Perovskites A ₃ M ₂ I ₉ (A = Cs, Rb; M = Bi, Sb) McCall, Kyle M.; Stoumpos, Constantinos C.; Kostina, Svetlana S. Chemistry of Materials, Vol. 29, Issue 9 https://doi.org/10.1021/acs.chemmater.7b01184	journal	April 2017
Ultrafast Exciton Dynamics in Shape-Controlled Methylammonium Lead Bromide Perovskite Nanostructures: Effect of Quantum Confinement on Charge Carrier Recombination Telfah, Hamzeh; Jamhawi, Abdelqader; Teunis, Meghan B. The Journal of Physical Chemistry C, Vol. 121, Issue 51 https://doi.org/10.1021/acs.jpcc.7b10377	journal	December 2017
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
Thermodynamic Origin of Photoinstability in the CH ₃ NH ₃ Pb(I _{1– x} Br _x ) ₃ Hybrid Halide Perovskite Alloy Brivio, Federico; Caetano, Clovis; Walsh, Aron The Journal of Physical Chemistry Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acs.jpclett.6b00226	journal	March 2016
Direct Experimental Evidence for Photoinduced Strong-Coupling Polarons in Organolead Halide Perovskite Nanoparticles Zheng, Kaibo; Abdellah, Mohamed; Zhu, Qiushi The Journal of Physical Chemistry Letters, Vol. 7, Issue 22 https://doi.org/10.1021/acs.jpclett.6b02046	journal	November 2016
Narrow Linewidth Excitonic Emission in Organic–Inorganic Lead Iodide Perovskite Single Crystals Diab, Hiba; Trippé-Allard, Gaëlle; Lédée, Ferdinand The Journal of Physical Chemistry Letters, Vol. 7, Issue 24 https://doi.org/10.1021/acs.jpclett.6b02261	journal	November 2016
Pressure-Induced Polymorphic, Optical, and Electronic Transitions of Formamidinium Lead Iodide Perovskite Wang, Pan; Guan, Jiwen; Galeschuk, Draven T. K. The Journal of Physical Chemistry Letters, Vol. 8, Issue 10 https://doi.org/10.1021/acs.jpclett.7b00665	journal	April 2017
Long-Lived Photoinduced Polarons in Organohalide Perovskites Ivanovska, Tanja; Dionigi, Chiara; Mosconi, Edoardo The Journal of Physical Chemistry Letters, Vol. 8, Issue 13 https://doi.org/10.1021/acs.jpclett.7b01156	journal	June 2017
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
Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites Bischak, Connor G.; Hetherington, Craig L.; Wu, Hao Nano Letters, Vol. 17, Issue 2 https://doi.org/10.1021/acs.nanolett.6b04453	journal	January 2017
Concept of Lattice Mismatch and Emergence of Surface States in Two-dimensional Hybrid Perovskite Quantum Wells Kepenekian, Mikaël; Traore, Boubacar; Blancon, Jean-Christophe Nano Letters, Vol. 18, Issue 9 https://doi.org/10.1021/acs.nanolett.8b02078	journal	August 2018
Excitonic and Polaronic Properties of 2D Hybrid Organic–Inorganic Perovskites Yin, Jun; Li, Hong; Cortecchia, Daniele ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00659	journal	January 2017
Rashba and Dresselhaus Effects in Hybrid Organic–Inorganic Perovskites: From Basics to Devices Kepenekian, Mikaël; Robles, Roberto; Katan, Claudine ACS Nano, Vol. 9, Issue 12 https://doi.org/10.1021/acsnano.5b04409	journal	September 2015
Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors Pedesseau, Laurent; Sapori, Daniel; Traore, Boubacar ACS Nano, Vol. 10, Issue 11 https://doi.org/10.1021/acsnano.6b05944	journal	October 2016
Composite Nature of Layered Hybrid Perovskites: Assessment on Quantum and Dielectric Confinements and Band Alignment Traore, Boubacar; Pedesseau, Laurent; Assam, Linda ACS Nano, Vol. 12, Issue 4 https://doi.org/10.1021/acsnano.7b08202	journal	February 2018
Anomalous Dielectric Behavior of a Pb/Sn Perovskite: Effect of Trapped Charges on Complex Photoconductivity Yamada, Kento; Nishikubo, Ryosuke; Oga, Hikaru ACS Photonics, Vol. 5, Issue 8 https://doi.org/10.1021/acsphotonics.8b00422	journal	June 2018
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
Pressure Response of an Organic−Inorganic Perovskite: Methylammonium Lead Bromide Swainson, I. P.; Tucker, M. G.; Wilson, D. J. Chemistry of Materials, Vol. 19, Issue 10 https://doi.org/10.1021/cm0621601	journal	May 2007
Tuning the Band Gap in Hybrid Tin Iodide Perovskite Semiconductors Using Structural Templating Knutson, Jeremy L.; Martin, James D.; Mitzi, David B. Inorganic Chemistry, Vol. 44, Issue 13 https://doi.org/10.1021/ic050244q	journal	June 2005
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
Modeling of Lead Halide Perovskites for Photovoltaic Applications Jishi, Radi A.; Ta, Oliver B.; Sharif, Adel A. The Journal of Physical Chemistry C, Vol. 118, Issue 49 https://doi.org/10.1021/jp5050145	journal	November 2014
Light-activated photocurrent degradation and self-healing in perovskite solar cells Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda J. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11574	journal	May 2016
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
Steric engineering of metal-halide perovskites with tunable optical band gaps Filip, Marina R.; Eperon, Giles E.; Snaith, Henry J. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6757	journal	December 2014
Perovskite energy funnels for efficient light-emitting diodes Yuan, Mingjian; Quan, Li Na; Comin, Riccardo Nature Nanotechnology, Vol. 11, Issue 10 https://doi.org/10.1038/nnano.2016.110	journal	June 2016
Detection of X-ray photons by solution-processed lead halide perovskites Yakunin, Sergii; Sytnyk, Mykhailo; Kriegner, Dominik Nature Photonics, Vol. 9, Issue 7 https://doi.org/10.1038/nphoton.2015.82	journal	May 2015
Detection of gamma photons using solution-grown single crystals of hybrid lead halide perovskites Yakunin, Sergii; Dirin, Dmitry N.; Shynkarenko, Yevhen Nature Photonics, Vol. 10, Issue 9 https://doi.org/10.1038/nphoton.2016.139	journal	July 2016
Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00284-2	journal	August 2017
Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite Park, Myeongkee; Neukirch, Amanda J.; Reyes-Lillo, Sebastian E. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04946-7	journal	June 2018
Large tunable photoeffect on ion conduction in halide perovskites and implications for photodecomposition Kim, Gee Yeong; Senocrate, Alessandro; Yang, Tae-Youl Nature Materials, Vol. 17, Issue 5 https://doi.org/10.1038/s41563-018-0038-0	journal	March 2018
Entropy in halide perovskites Katan, Claudine; Mohite, Aditya D.; Even, Jacky Nature Materials, Vol. 17, Issue 5 https://doi.org/10.1038/s41563-018-0070-0	journal	April 2018
Ultrafast zero-bias photocurrent and terahertz emission in hybrid perovskites Obraztsov, Petr A.; Lyashenko, Dmitry; Chizhov, Pavel A. Communications Physics, Vol. 1, Issue 1 https://doi.org/10.1038/s42005-018-0013-8	journal	April 2018
Luminescent hybrid perovskite nanoparticles as a new platform for selective detection of 2,4,6-trinitrophenol Muthu, Chinnadurai; Nagamma, Sunena R.; Nair, Vijayakumar C. RSC Adv., Vol. 4, Issue 99 https://doi.org/10.1039/C4RA07884E	journal	January 2014
Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC03141E	journal	January 2015
Interplay of spin–orbit coupling and lattice distortion in metal substituted 3D tri-chloride hybrid perovskites Katan, C.; Pedesseau, L.; Kepenekian, M. Journal of Materials Chemistry A, Vol. 3, Issue 17 https://doi.org/10.1039/C4TA06418F	journal	January 2015
Polaron self-localization in white-light emitting hybrid perovskites Cortecchia, Daniele; Yin, Jun; Bruno, Annalisa Journal of Materials Chemistry C, Vol. 5, Issue 11 https://doi.org/10.1039/C7TC00366H	journal	January 2017
Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications Baikie, Tom; Fang, Yanan; Kadro, Jeannette M. Journal of Materials Chemistry A, Vol. 1, Issue 18 https://doi.org/10.1039/c3ta10518k	journal	January 2013
Polaronic exciton binding energy in iodide and bromide organic-inorganic lead halide perovskites Soufiani, Arman Mahboubi; Huang, Fuzhi; Reece, Peter Applied Physics Letters, Vol. 107, Issue 23 https://doi.org/10.1063/1.4936418	journal	December 2015
Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy Santomauro, Fabio G.; Grilj, Jakob; Mewes, Lars Structural Dynamics, Vol. 4, Issue 4 https://doi.org/10.1063/1.4971999	journal	July 2017
Density functional theory + U modeling of polarons in organohalide lead perovskites Welch, Eric; Scolfaro, Luisa; Zakhidov, Alex AIP Advances, Vol. 6, Issue 12 https://doi.org/10.1063/1.4972341	journal	December 2016
Electric Field Control of Jahn-Teller Distortions in Bulk Perovskites Varignon, Julien; Bristowe, Nicholas C.; Ghosez, Philippe Physical Review Letters, Vol. 116, Issue 5 https://doi.org/10.1103/PhysRevLett.116.057602	journal	February 2016
Elastic Softness of Hybrid Lead Halide Perovskites Ferreira, A. C.; Létoublon, A.; Paofai, S. Physical Review Letters, Vol. 121, Issue 8 https://doi.org/10.1103/PhysRevLett.121.085502	journal	August 2018
Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts Luo, J.; Im, J. -H.; Mayer, M. T. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1258307	journal	September 2014
Jahn-Teller Phenomena in Solids Goodenough, J. B. Annual Review of Materials Science, Vol. 28, Issue 1 https://doi.org/10.1146/annurev.matsci.28.1.1	journal	August 1998

Cited By (4)

Perspective: Exciton polarons in two-dimensional hybrid metal-halide perovskites Kandada, Ajay Ram Srimath; Silva, Carlos arXiv https://doi.org/10.48550/arxiv.1908.03909	text	January 2019
Polarons in Metal Halide Perovskites Meggiolaro, Daniele; Ambrosio, Francesco; Mosconi, Edoardo Advanced Energy Materials, Vol. 10, Issue 13 https://doi.org/10.1002/aenm.201902748	journal	April 2020
Optical deformation potential and self-trapped excitons in 2D hybrid perovskites Yu, Zhi-Gang Physical Chemistry Chemical Physics, Vol. 21, Issue 40 https://doi.org/10.1039/c9cp03080h	journal	January 2019
Resonant free-carrier absorption in 2D hybrid organic-inorganic perovskites: The Rashba effect or small polarons? Yu, Zhi-Gang The Journal of Chemical Physics, Vol. 151, Issue 20 https://doi.org/10.1063/1.5127459	journal	November 2019

Similar Records

Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials

Journal Article · 2016 · Nano Letters · OSTI ID:1336128

Neukirch, Amanda J.; Nie, Wanyi; Blancon, Jean-Christophe; +10 more

Topological polarons in halide perovskites

Journal Article · 2024 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:2352332

Lafuente-Bartolome, Jon; Lian, Chao; Giustino, Feliciano

Visualization of dynamic polaronic strain fields in hybrid lead halide perovskites

Journal Article · 2021 · Nature Materials · OSTI ID:1767932

Guzelturk, Burak; Winkler, Thomas; Van de Goor, Tim J.; +14 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Material Science

Title: Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites

Citation Formats

References (53)

Cited By (4)

Similar Records

Related Subjects