Ion-Assisted Ligand Exchange for Efficient and Stable Inverted FAPbI3 Quantum Dot Solar Cells

Xu, Yuanze; Li, Hao; Ramakrishnan, Shripathi; Song, Donghoon; Zhang, Yugang; Cotlet, Mircea; Yu, Qiuming

doi:10.1021/acsaem.2c01565

Title: Ion-Assisted Ligand Exchange for Efficient and Stable Inverted FAPbI₃ Quantum Dot Solar Cells

Journal Article · 04 August 2022 · ACS Applied Energy Materials

DOI: https://doi.org/10.1021/acsaem.2c01565 · OSTI ID:1887816

^[1];

^[1]; Ramakrishnan, Shripathi ^[1];

^[1];

^[2]; Cotlet, Mircea ^[2];

^[1]

Cornell University, Ithaca, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Perovskite quantum dot (QD) has emerged as a promising material for photovoltaics with its superior stability compared to their three-dimensional bulk counterparts, owing to its thermodynamically stabilized photoactive phase. However, ligand management on perovskite QD surfaces is extremely difficult due to the ionic nature of the perovskite lattice, which often leads to either incomplete removal of the native insulating ligands or formation of trap states during the ligand-exchange process, greatly hampering the photovoltaic performances. In this work, we report an ion-assisted ligand-exchange method for FAPbI₃QDs using AOAc (A = formamidinium (FA⁺), guanidinium (GA⁺), and phenethylammonium (PEA⁺), OAc = acetate), with the A⁺ and OAC^- ions promoting the removal of native long-chain insulating ligands. Further, the more complete ligand exchange results in dense and well-oriented packing of QDs, together with the enhancement of electronic coupling and charge transport across QDs. In addition, the A⁺ and OAC^-ions can fill the surface A-/X-site vacancies, respectively, reducing the QD surface trap state density and hence suppressing charge recombination and iodide migration. The p-i-n inverted QD solar cells fabricated with this ligand-exchange method exhibit significant enhancement in shortcircuit current density (J_SC), reaching a PCE of 10.13%. Moreover, unencapsulated devices show impressive stabilities of more than 7300 h (10 months) storage time in a N₂-filled glovebox.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1887816

Report Number(s):: BNL--223379-2022-JAAM

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 8 Vol. 5; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (54)

A Small‐Molecule “Charge Driver” enables Perovskite Quantum Dot Solar Cells with Efficiency Approaching 13% Xue, Jingjing; Wang, Rui; Chen, Lan Advanced Materials, Vol. 31, Issue 37 https://doi.org/10.1002/adma.201900111	journal	July 2019
Surface Ligand Management Aided by a Secondary Amine Enables Increased Synthesis Yield of CsPbI ₃ Perovskite Quantum Dots and High Photovoltaic Performance Wang, Yao; Yuan, Jianyu; Zhang, Xuliang Advanced Materials, Vol. 32, Issue 32 https://doi.org/10.1002/adma.202000449	journal	July 2020
In Situ Grazing‐Incidence Wide‐Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films Hoffman, Justin M.; Strzalka, Joseph; Flanders, Nathan C. Advanced Materials, Vol. 32, Issue 33 https://doi.org/10.1002/adma.202002812	journal	July 2020
Surface Chemistry Engineering of Perovskite Quantum Dots: Strategies, Applications, and Perspectives Bai, Yang; Hao, Mengmeng; Ding, Shanshan Advanced Materials, Vol. 34, Issue 4 https://doi.org/10.1002/adma.202105958	journal	November 2021
Surface Ligand Management for Stable FAPbI3 Perovskite Quantum Dot Solar Cells Xue, Jingjing; Lee, Jin-Wook; Dai, Zhenghong Joule, Vol. 2, Issue 9 https://doi.org/10.1016/j.joule.2018.07.018	journal	September 2018
Tailoring solvent-mediated ligand exchange for CsPbI3 perovskite quantum dot solar cells with efficiency exceeding 16.5% Jia, Donglin; Chen, Jingxuan; Qiu, Junming Joule, Vol. 6, Issue 7 https://doi.org/10.1016/j.joule.2022.05.007	journal	July 2022
Tabulated values of the Shockley–Queisser limit for single junction solar cells Rühle, Sven Solar Energy, Vol. 130 https://doi.org/10.1016/j.solener.2016.02.015	journal	June 2016
Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan Accounts of Chemical Research, Vol. 49, Issue 2 https://doi.org/10.1021/acs.accounts.5b00433	journal	January 2016
High-Efficiency Perovskite Solar Cells Kim, Jin Young; Lee, Jin-Wook; Jung, Hyun Suk Chemical Reviews, Vol. 120, Issue 15 https://doi.org/10.1021/acs.chemrev.0c00107	journal	July 2020
Impedance Spectroscopy of Metal Halide Perovskite Solar Cells from the Perspective of Equivalent Circuits Guerrero, Antonio; Bisquert, Juan; Garcia-Belmonte, Germà Chemical Reviews, Vol. 121, Issue 23 https://doi.org/10.1021/acs.chemrev.1c00214	journal	November 2021
Intriguing Optoelectronic Properties of Metal Halide Perovskites Manser, Joseph S.; Christians, Jeffrey A.; Kamat, Prashant V. Chemical Reviews, Vol. 116, Issue 21 https://doi.org/10.1021/acs.chemrev.6b00136	journal	June 2016
Revealing Stability of Inverted Planar MA-Free Perovskite Solar Cells and Electric Field-Induced Phase Instability Zheng, Erjin; Niu, Zhiyin; Tosado, Gabriella A. The Journal of Physical Chemistry C, Vol. 124, Issue 34 https://doi.org/10.1021/acs.jpcc.0c05357	journal	August 2020
Long-Lived Hot Carriers in Formamidinium Lead Iodide Nanocrystals Papagiorgis, Paris; Protesescu, Loredana; Kovalenko, Maksym V. The Journal of Physical Chemistry C, Vol. 121, Issue 22 https://doi.org/10.1021/acs.jpcc.7b02308	journal	May 2017
Hot Carriers in Halide Perovskites: How Hot Truly? Lim, Jia Wei Melvin; Giovanni, David; Righetto, Marcello The Journal of Physical Chemistry Letters, Vol. 11, Issue 7 https://doi.org/10.1021/acs.jpclett.0c00504	journal	March 2020
Unraveling the Effect of Surface Ligands on the Auger Process in an Inorganic Perovskite Quantum-Dot System Zhang, Jiachen; Zhang, Lei; Zhang, Qun The Journal of Physical Chemistry Letters, Vol. 13, Issue 13 https://doi.org/10.1021/acs.jpclett.2c00357	journal	March 2022
Cubic Perovskite Structure of Black Formamidinium Lead Iodide, α-[HC(NH ₂ ) ₂ ]PbI ₃ , at 298 K Weller, Mark T.; Weber, Oliver J.; Frost, Jarvist M. The Journal of Physical Chemistry Letters, Vol. 6, Issue 16 https://doi.org/10.1021/acs.jpclett.5b01432	journal	July 2015
Comparison of Phonon Damping Behavior in Quantum Dots Capped with Organic and Inorganic Ligands Schnitzenbaumer, Kyle J.; Dukovic, Gordana Nano Letters, Vol. 18, Issue 6 https://doi.org/10.1021/acs.nanolett.8b00800	journal	May 2018
Hot Carrier Dynamics in Perovskite Nanocrystal Solids: Role of the Cold Carriers, Nanoconfinement, and the Surface Hopper, Thomas R.; Gorodetsky, Andrei; Jeong, Ahhyun Nano Letters, Vol. 20, Issue 4 https://doi.org/10.1021/acs.nanolett.9b04491	journal	March 2020
Stabilization of Black Perovskite Phase in FAPbI ₃ and CsPbI ₃ Masi, Sofia; Gualdrón-Reyes, Andrés F.; Mora-Seró, Iván ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00801	journal	May 2020
Improved Phase Stability of Formamidinium Lead Triiodide Perovskite by Strain Relaxation Zheng, Xiaojia; Wu, Congcong; Jha, Shikhar K. ACS Energy Letters, Vol. 1, Issue 5 https://doi.org/10.1021/acsenergylett.6b00457	journal	October 2016
Perovskite Quantum Dot Solar Cells with 15.6% Efficiency and Improved Stability Enabled by an α-CsPbI ₃ /FAPbI ₃ Bilayer Structure Li, Fangchao; Zhou, Sijie; Yuan, Jianyu ACS Energy Letters, Vol. 4, Issue 11 https://doi.org/10.1021/acsenergylett.9b01920	journal	October 2019
Size-Dependent Lattice Structure and Confinement Properties in CsPbI ₃ Perovskite Nanocrystals: Negative Surface Energy for Stabilization Zhao, Qian; Hazarika, Abhijit; Schelhas, Laura T. ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02395	journal	November 2019
Probing the Origin of the Open Circuit Voltage in Perovskite Quantum Dot Photovoltaics Wieliczka, Brian M.; Márquez, José A.; Bothwell, Alexandra M. ACS Nano, Vol. 15, Issue 12 https://doi.org/10.1021/acsnano.1c05642	journal	December 2021
Dismantling the “Red Wall” of Colloidal Perovskites: Highly Luminescent Formamidinium and Formamidinium–Cesium Lead Iodide Nanocrystals Protesescu, Loredana; Yakunin, Sergii; Kumar, Sudhir ACS Nano, Vol. 11, Issue 3 https://doi.org/10.1021/acsnano.7b00116	journal	March 2017
Perovskite Quantum Dot Photovoltaic Materials beyond the Reach of Thin Films: Full-Range Tuning of A-Site Cation Composition Hazarika, Abhijit; Zhao, Qian; Gaulding, E. Ashley ACS Nano, Vol. 12, Issue 10 https://doi.org/10.1021/acsnano.8b05555	journal	September 2018
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
Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics Wheeler, Lance M.; Sanehira, Erin M.; Marshall, Ashley R. Journal of the American Chemical Society, Vol. 140, Issue 33 https://doi.org/10.1021/jacs.8b04984	journal	July 2018
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
Slow cooling and highly efficient extraction of hot carriers in colloidal perovskite nanocrystals Li, Mingjie; Bhaumik, Saikat; Goh, Teck Wee Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14350	journal	February 2017
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
Defects in perovskite-halides and their effects in solar cells Ball, James M.; Petrozza, Annamaria Nature Energy, Vol. 1, Issue 11 https://doi.org/10.1038/nenergy.2016.149	journal	October 2016
Charge transport and localization in atomically coherent quantum dot solids Whitham, Kevin; Yang, Jun; Savitzky, Benjamin H. Nature Materials, Vol. 15, Issue 5 https://doi.org/10.1038/nmat4576	journal	February 2016
Charge transport in strongly coupled quantum dot solids Kagan, Cherie R.; Murray, Christopher B. Nature Nanotechnology, Vol. 10, Issue 12 https://doi.org/10.1038/nnano.2015.247	journal	November 2015
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
Flexible and efficient perovskite quantum dot solar cells via hybrid interfacial architecture Hu, Long; Zhao, Qian; Huang, Shujuan Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-020-20749-1	journal	January 2021
Large guanidinium cation mixed with methylammonium in lead iodide perovskites for 19% efficient solar cells Jodlowski, Alexander D.; Roldán-Carmona, Cristina; Grancini, Giulia Nature Energy, Vol. 2, Issue 12 https://doi.org/10.1038/s41560-017-0054-3	journal	December 2017
Ligand-assisted cation-exchange engineering for high-efficiency colloidal Cs1−xFAxPbI3 quantum dot solar cells with reduced phase segregation Hao, Mengmeng; Bai, Yang; Zeiske, Stefan Nature Energy, Vol. 5, Issue 1 https://doi.org/10.1038/s41560-019-0535-7	journal	January 2020
Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals Akkerman, Quinten A.; Rainò, Gabriele; Kovalenko, Maksym V. Nature Materials, Vol. 17, Issue 5 https://doi.org/10.1038/s41563-018-0018-4	journal	February 2018
Perovskite solar cells with atomically coherent interlayers on SnO2 electrodes Min, Hanul; Lee, Do Yoon; Kim, Junu Nature, Vol. 598, Issue 7881 https://doi.org/10.1038/s41586-021-03964-8	journal	October 2021
Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells? Richardson, Giles; O'Kane, Simon E. J.; Niemann, Ralf G. Energy & Environmental Science, Vol. 9, Issue 4 https://doi.org/10.1039/C5EE02740C	journal	January 2016
Thermal degradation of CH ₃ NH ₃ PbI ₃ perovskite into NH ₃ and CH ₃ I gases observed by coupled thermogravimetry–mass spectrometry analysis Juarez-Perez, Emilio J.; Hawash, Zafer; Raga, Sonia R. Energy & Environmental Science, Vol. 9, Issue 11 https://doi.org/10.1039/C6EE02016J	journal	January 2016
Hot carrier solar cells and the potential of perovskites for breaking the Shockley–Queisser limit Kahmann, Simon; Loi, Maria A. Journal of Materials Chemistry C, Vol. 7, Issue 9 https://doi.org/10.1039/C8TC04641G	journal	January 2019
Emerging perovskite quantum dot solar cells: feasible approaches to boost performance Chen, Jingxuan; Jia, Donglin; Johansson, Erik M. J. Energy & Environmental Science, Vol. 14, Issue 1 https://doi.org/10.1039/D0EE02900A	journal	January 2021
Polymorphism in metal halide perovskites Alaei, Aida; Circelli, Abigail; Yuan, Yihang Materials Advances, Vol. 2, Issue 1 https://doi.org/10.1039/D0MA00643B	journal	January 2021
23.7% Efficient inverted perovskite solar cells by dual interfacial modification Degani, Matteo; An, Qingzhi; Albaladejo-Siguan, Miguel Science Advances, Vol. 7, Issue 49 https://doi.org/10.1126/sciadv.abj7930	journal	December 2021
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
Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics Swarnkar, A.; Marshall, A. R.; Sanehira, E. M. Science, Vol. 354, Issue 6308 https://doi.org/10.1126/science.aag2700	journal	October 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
Rethinking the A cation in halide perovskites Lee, Jin-Wook; Tan, Shaun; Seok, Sang Il Science, Vol. 375, Issue 6583 https://doi.org/10.1126/science.abj1186	journal	February 2022
Damp heat–stable perovskite solar cells with tailored-dimensionality 2D/3D heterojunctions Azmi, Randi; Ugur, Esma; Seitkhan, Akmaral Science, Vol. 376, Issue 6588 https://doi.org/10.1126/science.abm5784	journal	April 2022
Investigations on Average Fluorescence Lifetimes for Visualizing Multi-Exponential Decays Li, Yahui; Natakorn, Sapermsap; Chen, Yu Frontiers in Physics, Vol. 8 https://doi.org/10.3389/fphy.2020.576862	journal	October 2020

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36 MATERIALS SCIENCE
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Title: Ion-Assisted Ligand Exchange for Efficient and Stable Inverted FAPbI3 Quantum Dot Solar Cells

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Title: Ion-Assisted Ligand Exchange for Efficient and Stable Inverted FAPbI₃ Quantum Dot Solar Cells