Tracking carrier and exciton dynamics in mixed-cation lead mixed-halide perovskite thin films

Chang, Qing; Bao, Di; Chen, Bingbing; Hu, Hongwei; Chen, Xiaoxuan; Sun, Handong; Lam, Yeng Ming; Zhu, Jian-Xin; Zhao, Daming; Chia, Elbert E. M.

doi:10.1038/s42005-022-00966-4

Tracking carrier and exciton dynamics in mixed-cation lead mixed-halide perovskite thin films

Journal Article · Tue Jul 19 00:00:00 EDT 2022 · Communications Physics

DOI:https://doi.org/10.1038/s42005-022-00966-4· OSTI ID:1922771

Chang, Qing ^[1]; Bao, Di ^[1]; Chen, Bingbing ^[2]; Hu, Hongwei ^[3]; Chen, Xiaoxuan ^[1]; ^[1]; Lam, Yeng Ming ^[2]; ^[4]; ^[1]; ^[1]

Nanyang Technological Univ. (Singapore)
Nanyang Technological Univ. (Singapore). School of Materials Science and Engineering
Nanyang Technological Univ. (Singapore). School of Materials Science and Engineering; Jiangnan Univ., Zhenjiang (China)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Mixed-cation lead mixed-halide perovskites simultaneously possess structural stability and high power conversion efficiency. A thorough study of both carrier and exciton dynamics is needed to understand the photophysical properties that underpin its superior photovoltaic performance. By utilizing a broadband transient absorption spectroscopy, we observe the carrier and exciton dynamics in a FA_0.85Cs_0.15Pb(I_0.97Br_0.03)₃ (FCPIB) perovskite by simultaneously resolving the carrier and exciton contribution to the transient change of the absorption spectra, from which the carrier density and exciton oscillator strength can be determined. Our data reveal a quick and significant conversion of the photogenerated carriers to excitons, on top of the usual carrier recombination process. Moreover, the decay of carrier density shows a change of kinetics from a second-order recombination at high pump fluence to a third-order recombination at low pump fluence. Our analysis utilizes band anharmonicity, presents an independent determination of electronic temperature and quasi-Fermi energy, and reveals an interesting interplay among the processes of carrier cooling, exciton formation/decay and carrier recombination, all as a function of time after photoexcitation. Our work demonstrates the use of pump fluence as a knob to tune the relative populations of carriers and excitons in halide perovskite materials.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: Singapore Ministry of Education (MOE); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1922771

Report Number(s):: LA-UR-21-30751

Journal Information:: Communications Physics, Journal Name: Communications Physics Journal Issue: 1 Vol. 5; ISSN 2399-3650

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

CH ₃ NH ₃ PbI ₃ Perovskite/Fullerene Planar-Heterojunction Hybrid Solar Cells Jeng, Jun-Yuan; Chiang, Yi-Fang; Lee, Mu-Huan Advanced Materials, Vol. 25, Issue 27 https://doi.org/10.1002/adma.201301327	journal	June 2013
High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B. Advanced Materials, Vol. 26, Issue 10 https://doi.org/10.1002/adma.201305172	journal	December 2013
From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives Xiao, Zewen; Song, Zhaoning; Yan, Yanfa Advanced Materials, Vol. 31, Issue 47 https://doi.org/10.1002/adma.201803792	journal	January 2019
Formamidinium and Cesium Hybridization for Photo- and Moisture-Stable Perovskite Solar Cell Lee, Jin-Wook; Kim, Deok-Hwan; Kim, Hui-Seon Advanced Energy Materials, Vol. 5, Issue 20 https://doi.org/10.1002/aenm.201501310	journal	September 2015
Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite Jiang, Shaojie; Fang, Yanan; Li, Ruipeng Angewandte Chemie, Vol. 128, Issue 22 https://doi.org/10.1002/ange.201601788	journal	April 2016
Solar cell efficiency tables (version 49): Solar cell efficiency tables (version 49) Green, Martin A.; Emery, Keith; Hishikawa, Yoshihiro Progress in Photovoltaics: Research and Applications, Vol. 25, Issue 1 https://doi.org/10.1002/pip.2855	journal	November 2016
Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys Li, Zhen; Yang, Mengjin; Park, Ji-Sang Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04107	journal	December 2015
Absorption F-Sum Rule for the Exciton Binding Energy in Methylammonium Lead Halide Perovskites Sestu, Nicola; Cadelano, Michele; Sarritzu, Valerio The Journal of Physical Chemistry Letters, Vol. 6, Issue 22 https://doi.org/10.1021/acs.jpclett.5b02099	journal	October 2015
Comparison of Recombination Dynamics in CH ₃ NH ₃ PbBr ₃ and CH ₃ NH ₃ PbI ₃ Perovskite Films: Influence of Exciton Binding Energy Yang, Ye; Yang, Mengjin; Li, Zhen The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02290	journal	November 2015
Equal Footing of Thermal Expansion and Electron–Phonon Interaction in the Temperature Dependence of Lead Halide Perovskite Band Gaps Francisco-López, Adrián; Charles, Bethan; Weber, Oliver J. The Journal of Physical Chemistry Letters, Vol. 10, Issue 11 https://doi.org/10.1021/acs.jpclett.9b00876	journal	May 2019
Color-Pure Violet-Light-Emitting Diodes Based on Layered Lead Halide Perovskite Nanoplates Liang, Dong; Peng, Yuelin; Fu, Yongping ACS Nano, Vol. 10, Issue 7 https://doi.org/10.1021/acsnano.6b02683	journal	June 2016
Highly Efficient Light-Emitting Diodes of Colloidal Metal–Halide Perovskite Nanocrystals beyond Quantum Size Kim, Young-Hoon; Wolf, Christoph; Kim, Young-Tae ACS Nano, Vol. 11, Issue 7 https://doi.org/10.1021/acsnano.6b07617	journal	June 2017
Monitoring Electron–Phonon Interactions in Lead Halide Perovskites Using Time-Resolved THz Spectroscopy Zhao, Daming; Hu, Hongwei; Haselsberger, Reinhard ACS Nano, Vol. 13, Issue 8 https://doi.org/10.1021/acsnano.9b02049	journal	July 2019
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
Bandgap Modulation in ZnO by Size, Pressure, and Temperature Li, J. W.; Yang, L. W.; Zhou, Z. F. The Journal of Physical Chemistry C, Vol. 114, Issue 31 https://doi.org/10.1021/jp104204y	journal	July 2010
Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin The Journal of Physical Chemistry Letters, Vol. 5, Issue 6 https://doi.org/10.1021/jz500279b	journal	March 2014
Excitons versus free charges in organo-lead tri-halide perovskites D’Innocenzo, Valerio; Grancini, Giulia; Alcocer, Marcelo J. P. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4586	journal	April 2014
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
Elucidating the role of disorder and free-carrier recombination kinetics in CH3NH3PbI3 perovskite films La-o-vorakiat, Chan; Salim, Teddy; Kadro, Jeannette Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8903	journal	July 2015
Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9420	journal	September 2015
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
Band filling with free charge carriers in organometal halide perovskites Manser, Joseph S.; Kamat, Prashant V. Nature Photonics, Vol. 8, Issue 9 https://doi.org/10.1038/nphoton.2014.171	journal	August 2014
Observation of a hot-phonon bottleneck in lead-iodide perovskites Yang, Ye; Ostrowski, David P.; France, Ryan M. Nature Photonics, Vol. 10, Issue 1 https://doi.org/10.1038/nphoton.2015.213	journal	October 2015
Hot carrier cooling mechanisms in halide perovskites Fu, Jianhui; Xu, Qiang; Han, Guifang Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01360-3	journal	November 2017
The origin of high efficiency in low-temperature solution-processable bilayer organometal halide hybrid solar cells Sun, Shuangyong; Salim, Teddy; Mathews, Nripan Energy Environ. Sci., Vol. 7, Issue 1 https://doi.org/10.1039/C3EE43161D	journal	January 2014
Entropic stabilization of mixed A-cation ABX ₃ metal halide perovskites for high performance perovskite solar cells Yi, Chenyi; Luo, Jingshan; Meloni, Simone Energy & Environmental Science, Vol. 9, Issue 2 https://doi.org/10.1039/C5EE03255E	journal	January 2016
Temperature dependent energy levels of methylammonium lead iodide perovskite Foley, Benjamin J.; Marlowe, Daniel L.; Sun, Keye Applied Physics Letters, Vol. 106, Issue 24 https://doi.org/10.1063/1.4922804	journal	June 2015
Intensity of Optical Absorption by Excitons Elliott, R. J. Physical Review, Vol. 108, Issue 6 https://doi.org/10.1103/PhysRev.108.1384	journal	December 1957
Band-gap narrowing in heavily doped many-valley semiconductors Berggren, K. -F.; Sernelius, B. E. Physical Review B, Vol. 24, Issue 4 https://doi.org/10.1103/PhysRevB.24.1971	journal	August 1981
Band-gap widening in heavily Sn-doped In 2 O 3 Hamberg, I.; Granqvist, C. G.; Berggren, K. -F. Physical Review B, Vol. 30, Issue 6 https://doi.org/10.1103/PhysRevB.30.3240	journal	September 1984
Carrier effects on the excitonic absorption in GaAs quantum-well structures: Phase-space filling Huang, Daming; Chyi, Jen-Inn; Morkoç, Hadis Physical Review B, Vol. 42, Issue 8 https://doi.org/10.1103/PhysRevB.42.5147	journal	September 1990
Origins of band-gap renormalization in degenerately doped semiconductors Walsh, Aron; Da Silva, Juarez L. F.; Wei, Su-Huai Physical Review B, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevB.78.075211	journal	August 2008
Ultrafast exciton many-body interactions and hot-phonon bottleneck in colloidal cesium lead halide perovskite nanocrystals Mondal, Anirban; Aneesh, J.; Kumar Ravi, Vikash Physical Review B, Vol. 98, Issue 11 https://doi.org/10.1103/PhysRevB.98.115418	journal	September 2018
Ultrafast THz Probe of Photoinduced Polarons in Lead-Halide Perovskites Cinquanta, Eugenio; Meggiolaro, Daniele; Motti, Silvia G. Physical Review Letters, Vol. 122, Issue 16 https://doi.org/10.1103/PhysRevLett.122.166601	journal	April 2019
Lead halide perovskites: Crystal-liquid duality, phonon glass electron crystals, and large polaron formation Miyata, Kiyoshi; Atallah, Timothy L.; Zhu, X. -Y. Science Advances, Vol. 3, Issue 10 https://doi.org/10.1126/sciadv.1701469	journal	October 2017
Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH₃NH₃PbI₃ Xing, G.; Mathews, N.; Sun, S. Science, Vol. 342, Issue 6156, p. 344-347 https://doi.org/10.1126/science.1243167	journal	October 2013
A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells McMeekin, D. P.; Sadoughi, G.; Rehman, W. Science, Vol. 351, Issue 6269 https://doi.org/10.1126/science.aad5845	journal	January 2016
Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance Saliba, M.; Matsui, T.; Domanski, K. Science, Vol. 354, Issue 6309 https://doi.org/10.1126/science.aah5557	journal	September 2016
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells Yang, Woon Seok; Park, Byung-Wook; Jung, Eui Hyuk Science, Vol. 356, Issue 6345 https://doi.org/10.1126/science.aan2301	journal	June 2017
A piperidinium salt stabilizes efficient metal-halide perovskite solar cells Lin, Yen-Hung; Sakai, Nobuya; Da, Peimei Science, Vol. 369, Issue 6499 https://doi.org/10.1126/science.aba1628	journal	July 2020

Similar Records

Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites

Journal Article · Sun Jul 12 20:00:00 EDT 2020 · Journal of Physical Chemistry Letters · OSTI ID:1674972

Reducing Surface Recombination Velocity of Methylammonium-Free Mixed-Cation Mixed-Halide Perovskites via Surface Passivation

Journal Article · Tue Jun 15 20:00:00 EDT 2021 · Chemistry of Materials · OSTI ID:1806288

Related Subjects

36 MATERIALS SCIENCE
optical physics
ultrafast photonics

Tracking carrier and exciton dynamics in mixed-cation lead mixed-halide perovskite thin films

Citation Formats

References (40)

Similar Records

Related Subjects