Ultrafast Imaging of Carrier Transport across Grain Boundaries in Hybrid Perovskite Thin Films

Snaider, Jordan M.; Guo, Zhi; Wang, Ti; Yang, Mengjin; Yuan, Long; Zhu, Kai; Huang, Libai

doi:10.1021/acsenergylett.8b00560

Title: Ultrafast Imaging of Carrier Transport across Grain Boundaries in Hybrid Perovskite Thin Films

Journal Article · 21 May 2018 · ACS Energy Letters

DOI: https://doi.org/10.1021/acsenergylett.8b00560 · OSTI ID:1468735

^[1]; Guo, Zhi ^[1]; Wang, Ti ^[1]; Yang, Mengjin ^[2]; Yuan, Long ^[1];

^[2];

^[1]

Purdue Univ., West Lafayette, IN (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

For optoelectronic devices based on polycrystalline semiconducting thin films, carrier transport across grain boundaries is an important process in defining efficiency. Here we employ transient absorption microscopy (TAM) to directly measure carrier transport within and across the boundaries in hybrid organic-inorganic perovskite thin films for solar cell applications with 50 nm spatial precision and 300 fs temporal resolution. By selectively imaging sub-bandgap states, our results show that lateral carrier transport is slowed down by these states at the grain boundaries. However, the long carrier lifetimes allow for efficient transport across the grain boundaries. The carrier diffusion constant is reduced by about a factor of 2 for micron-sized grain samples by the grain boundaries. For grain sizes on the order of ~200 nm, carrier transport over multiple grains has been observed within a time window of 5 ns. These observations explain both the shortened photoluminescence lifetimes at the boundaries as well as the seemingly benign nature of the grain boundaries in carrier generation.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1468735

Report Number(s):: NREL/JA-5900-71299

Journal Information:: ACS Energy Letters, Vol. 3, Issue 6; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 49 works

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References (52)

Carrier transport through grain boundaries in semiconductors Blatter, G.; Greuter, F. Physical Review B, Vol. 33, Issue 6 https://doi.org/10.1103/PhysRevB.33.3952	journal	March 1986
Charged Grain Boundaries and Carrier Recombination in Polycrystalline Thin-Film Solar Cells Gaury, Benoit; Haney, Paul M. Physical Review Applied, Vol. 8, Issue 5 https://doi.org/10.1103/PhysRevApplied.8.054026	journal	November 2017
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites Lee, M. M.; Teuscher, J.; Miyasaka, T. Science, Vol. 338, Issue 6107, p. 643-647 https://doi.org/10.1126/science.1228604	journal	October 2012
Sequential deposition as a route to high-performance perovskite-sensitized solar cells Burschka, Julian; Pellet, Norman; Moon, Soo-Jin Nature, Vol. 499, Issue 7458, p. 316-319 https://doi.org/10.1038/nature12340	journal	July 2013
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
Compositional engineering of perovskite materials for high-performance solar cells Jeon, Nam Joong; Noh, Jun Hong; Yang, Woon Seok Nature, Vol. 517, Issue 7535 https://doi.org/10.1038/nature14133	journal	January 2015
High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe Nature, Vol. 536, Issue 7616 https://doi.org/10.1038/nature18306	journal	July 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
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
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
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
Effect of Carrier Thermalization Dynamics on Light Emission and Amplification in Organometal Halide Perovskites Chen, Kai; Barker, Alex J.; Morgan, Francis L. C. The Journal of Physical Chemistry Letters, Vol. 6, Issue 1 https://doi.org/10.1021/jz502528c	journal	December 2014
Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements Chen, Y.; Yi, H. T.; Wu, X. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12253	journal	August 2016
Charge-Carrier Dynamics in Organic-Inorganic Metal Halide Perovskites Herz, Laura M. Annual Review of Physical Chemistry, Vol. 67, Issue 1 https://doi.org/10.1146/annurev-physchem-040215-112222	journal	May 2016
Origin of long lifetime of band-edge charge carriers in organic–inorganic lead iodide perovskites Chen, Tianran; Chen, Wei-Liang; Foley, Benjamin J. Proceedings of the National Academy of Sciences, Vol. 114, Issue 29 https://doi.org/10.1073/pnas.1704421114	journal	July 2017
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
High-efficiency solution-processed perovskite solar cells with millimeter-scale grains Nie, W.; Tsai, H.; Asadpour, R. Science, Vol. 347, Issue 6221, p. 522-525 https://doi.org/10.1126/science.aaa0472	journal	January 2015
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
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
Spatial and temporal imaging of long-range charge transport in perovskite thin films by ultrafast microscopy Guo, Zhi; Manser, Joseph S.; Wan, Yan Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8471	journal	June 2015
Imaging the Long Transport Lengths of Photo-generated Carriers in Oriented Perovskite Films Liu, Shuhao; Wang, Lili; Lin, Wei-Chun Nano Letters, Vol. 16, Issue 12 https://doi.org/10.1021/acs.nanolett.6b04235	journal	December 2016
Carrier trapping and recombination: the role of defect physics in enhancing the open circuit voltage of metal halide perovskite solar cells Leijtens, Tomas; Eperon, Giles E.; Barker, Alex J. Energy & Environmental Science, Vol. 9, Issue 11 https://doi.org/10.1039/C6EE01729K	journal	January 2016
Intrinsic Charge Transport across Phase Transitions in Hybrid Organo-Inorganic Perovskites Yi, Hee Taek; Wu, Xiaoxi; Zhu, Xiaoyang Advanced Materials, Vol. 28, Issue 30 https://doi.org/10.1002/adma.201600011	journal	May 2016
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
The role of grain boundaries in perovskite solar cells Lee, Jin-Wook; Bae, Sang-Hoon; De Marco, Nicholas Materials Today Energy, Vol. 7 https://doi.org/10.1016/j.mtener.2017.07.014	journal	March 2018
Quantum Dynamics of Photogenerated Charge Carriers in Hybrid Perovskites: Dopants, Grain Boundaries, Electric Order, and Other Realistic Aspects Jankowska, Joanna; Long, Run; Prezhdo, Oleg V. ACS Energy Letters, Vol. 2, Issue 7 https://doi.org/10.1021/acsenergylett.7b00198	journal	June 2017
Band Tailing and Deep Defect States in CH ₃ NH ₃ Pb(I _{1– x} Br _x ) ₃ Perovskites As Revealed by Sub-Bandgap Photocurrent Sutter-Fella, Carolin M.; Miller, D. Westley; Ngo, Quynh P. ACS Energy Letters, Vol. 2, Issue 3 https://doi.org/10.1021/acsenergylett.6b00727	journal	February 2017
Impact of grain boundaries on efficiency and stability of organic-inorganic trihalide perovskites Chu, Zhaodong; Yang, Mengjin; Schulz, Philip Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02331-4	journal	December 2017
Recombination in Perovskite Solar Cells: Significance of Grain Boundaries, Interface Traps, and Defect Ions Sherkar, Tejas S.; Momblona, Cristina; Gil-Escrig, Lidón ACS Energy Letters, Vol. 2, Issue 5 https://doi.org/10.1021/acsenergylett.7b00236	journal	April 2017
Spatially Resolved Imaging on Photocarrier Generations and Band Alignments at Perovskite/PbI ₂ Heterointerfaces of Perovskite Solar Cells by Light-Modulated Scanning Tunneling Microscopy Shih, Min-Chuan; Li, Shao-Sian; Hsieh, Cheng-Hua Nano Letters, Vol. 17, Issue 2 https://doi.org/10.1021/acs.nanolett.6b04803	journal	January 2017
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
Imaging Electronic Trap States in Perovskite Thin Films with Combined Fluorescence and Femtosecond Transient Absorption Microscopy Simpson, Mary Jane; Doughty, Benjamin; Yang, Bin The Journal of Physical Chemistry Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acs.jpclett.6b00715	journal	April 2016
Spatially Non-uniform Trap State Densities in Solution-Processed Hybrid Perovskite Thin Films Draguta, Sergiu; Thakur, Siddharatha; Morozov, Yurii V. The Journal of Physical Chemistry Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acs.jpclett.5b02888	journal	February 2016
Limiting Perovskite Solar Cell Performance by Heterogeneous Carrier Extraction Tian, Wenming; Cui, Rongrong; Leng, Jing Angewandte Chemie, Vol. 128, Issue 42 https://doi.org/10.1002/ange.201606574	journal	October 2016
Tracking Photoexcited Carriers in Hybrid Perovskite Semiconductors: Trap-Dominated Spatial Heterogeneity and Diffusion deQuilettes, Dane W.; Jariwala, Sarthak; Burke, Sven ACS Nano, Vol. 11, Issue 11 https://doi.org/10.1021/acsnano.7b06242	journal	September 2017
A quantitative and spatially resolved analysis of the performance-bottleneck in high efficiency, planar hybrid perovskite solar cells Draguta, Sergiu; Christians, Jeffrey A.; Morozov, Yurii V. Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03654J	journal	January 2018
Transient Sub-bandgap States in Halide Perovskite Thin Films Nah, S.; Spokoyny, B.; Jiang, X. Nano Letters, Vol. 18, Issue 2 https://doi.org/10.1021/acs.nanolett.7b04078	journal	January 2018
Hole Trapping by Iodine Interstitial Defects Decreases Free Carrier Losses in Perovskite Solar Cells: A Time-Domain Ab Initio Study Li, Wei; Liu, Jin; Bai, Fu-Quan ACS Energy Letters, Vol. 2, Issue 6 https://doi.org/10.1021/acsenergylett.7b00183	journal	May 2017
Do grain boundaries dominate non-radiative recombination in CH ₃ NH ₃ PbI ₃ perovskite thin films? Yang, Mengjin; Zeng, Yining; Li, Zhen Physical Chemistry Chemical Physics, Vol. 19, Issue 7 https://doi.org/10.1039/C6CP08770A	journal	January 2017
The role of PbI ₂ in CH ₃ NH ₃ PbI ₃ perovskite stability, solar cell parameters and device degradation Gujar, Tanaji P.; Unger, Thomas; Schönleber, Andreas Physical Chemistry Chemical Physics, Vol. 20, Issue 1 https://doi.org/10.1039/C7CP04749E	journal	January 2018
Perovskite Solar Cells: From the Atomic Level to Film Quality and Device Performance Saliba, Michael; Correa-Baena, Juan-Pablo; Grätzel, Michael Angewandte Chemie International Edition, Vol. 57, Issue 10 https://doi.org/10.1002/anie.201703226	journal	February 2018
Determination of the True Lateral Grain Size in Organic–Inorganic Halide Perovskite Thin Films MacDonald, Gordon A.; Heveran, Chelsea M.; Yang, Mengjin ACS Applied Materials & Interfaces, Vol. 9, Issue 39 https://doi.org/10.1021/acsami.7b11434	journal	April 2017
Unreacted PbI ₂ as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells Jacobsson, T. Jesper; Correa-Baena, Juan-Pablo; Halvani Anaraki, Elham Journal of the American Chemical Society, Vol. 138, Issue 32 https://doi.org/10.1021/jacs.6b06320	journal	August 2016
Methylammonium lead iodide grain boundaries exhibit depth-dependent electrical properties MacDonald, Gordon A.; Yang, Mengjin; Berweger, Samuel Energy & Environmental Science, Vol. 9, Issue 12 https://doi.org/10.1039/C6EE01889K	journal	January 2016
Formation, location and beneficial role of PbI ₂ in lead halide perovskite solar cells Du, Tian; Burgess, Claire H.; Kim, Jinhyun Sustainable Energy & Fuels, Vol. 1, Issue 1 https://doi.org/10.1039/C6SE00029K	journal	January 2017
Measuring long-range carrier diffusion across multiple grains in polycrystalline semiconductors by photoluminescence imaging Alberi, K.; Fluegel, B.; Moutinho, H. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3699	journal	October 2013
Square-Centimeter Solution-Processed Planar CH ₃ NH ₃ PbI ₃ Perovskite Solar Cells with Efficiency Exceeding 15% Yang, Mengjin; Zhou, Yuanyuan; Zeng, Yining Advanced Materials, Vol. 27, Issue 41 https://doi.org/10.1002/adma.201502586	journal	September 2015
Refractive index and extinction coefficient of CH_3NH_3PbI_3 studied by spectroscopic ellipsometry Ziang, Xie; Shifeng, Liu; Laixiang, Qin Optical Materials Express, Vol. 5, Issue 1 https://doi.org/10.1364/OME.5.000029	journal	December 2014
Tuning the Light Emission Properties by Band Gap Engineering in Hybrid Lead Halide Perovskite D’Innocenzo, Valerio; Srimath Kandada, Ajay Ram; De Bastiani, Michele Journal of the American Chemical Society, Vol. 136, Issue 51 https://doi.org/10.1021/ja511198f	journal	December 2014
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
Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites Miyata, Atsuhiko; Mitioglu, Anatolie; Plochocka, Paulina Nature Physics, Vol. 11, Issue 7 https://doi.org/10.1038/nphys3357	journal	June 2015
Calculating polaron mobility in halide perovskites Frost, Jarvist Moore Physical Review B, Vol. 96, Issue 19 https://doi.org/10.1103/PhysRevB.96.195202	journal	November 2017

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