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Reduced recombination via tunable surface fields in perovskite thin films

Nature Energy volume 9, pages 457–466 (2024)Cite this article

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A Publisher Correction to this article was published on 05 April 2024

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Abstract

The ability to reduce energy loss at semiconductor surfaces through passivation or surface field engineering is an essential step in the manufacturing of efficient photovoltaic (PV) and optoelectronic devices. Similarly, surface modification of emerging halide perovskites with quasi-two-dimensional (2D) heterostructures is now ubiquitous to achieve PV power conversion efficiencies (PCEs) >25%, yet a fundamental understanding to how these treatments function is still generally lacking. Here we use a unique combination of depth-sensitive nanoscale characterization techniques to uncover a tunable passivation strategy and mechanism found in perovskite PV devices that were the first to reach the >25% PCE milestone. Namely, treatment with hexylammonium bromide leads to the simultaneous formation of an iodide-rich 2D layer along with a Br halide gradient that extends from defective surfaces and grain boundaries into the bulk three-dimensional (3D) layer. This interface can be optimized to extend the charge carrier lifetime to record values >30 μs and to reduce interfacial recombination velocities to values as low as <7 cm s−1.

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Fig. 1: Improvement in carrier lifetime with HABr treatment.
Fig. 2: Elemental mapping through device depth.
Fig. 3: Carrier dynamics and energetics near perovskite surface.
Fig. 4: Reduced carrier recombination at interfaces.

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All data generated or analysed during this study are included in the published article and its Supplementary Information and Source Data files. Source data are provided with this paper.

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The MATLAB and Python code used in this work are available from the corresponding authors upon reasonable request.

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Acknowledgements

D.W.D., R.B., M.L., M.G.B. and V.B. acknowledge support for this project through the MIT-Tata GridEdge Solar Research Program, which is funded by the Tata Trusts. J.J.Y. was funded by the Institute for Soldier Nanotechnology (ISN) grant W911NF-13-D-0001. This work has also been supported in part by the Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE) award number DE-EE0009512. M.L. and R.B. acknowledge support from the National Science Foundation Graduate Research Fellowship under grant number 1122374. R.B. acknowledges support from MathWorks through the MathWorks Engineering Fellowship. F.U.K. thanks the Jardine Foundation and Cambridge Trust for a doctoral scholarship. S.S.S. was supported by a grant from the Korea Research Institute of Chemical Technology (KRICT), South Korea (KS2022-10); the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade Industry and Energy (MOTIE) of the Republic of Korea (number 20183010014470). S.S.S. was also supported by the Ministry of Education and National Research Foundation of Korea. Following are results of a study on the ‘Leaders in INdustry-university Cooperation 3.0’ Project, supported by the Ministry of Education and National Research Foundation of Korea. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (RS-2023-00220748). Part of this work was conducted at the Molecular Analysis Facility, a National Nanotechnology Coordinated Infrastructure (NNCI) site at the University of Washington, which is supported in part by funds from the National Science Foundation (awards NNCI-2025489, NNCI-1542101), the Molecular Engineering and Sciences Institute and the Clean Energy Institute. We would also like to acknowledge KARA (KAIST Analysis centre for Research Advancement) for help in conducting UPS measurements. D.W.D. thanks D. Fenning (UCSD), R. MacKenzie (Univ. of Nottingham), A. Kanevce (NREL), H. Smith (Princeton), S. Stranks (Univ. of Cambridge), T. Kirchartz (Forschungszentrum Jülich) and L. Krückemeier for valuable discussions and sharing literature survey data of perovskite carrier lifetimes.

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Authors and Affiliations

  1. Research Laboratory of Electronics, Massachusetts Institute of Technology, Cambridge, MA, USA

    Dane W. deQuilettes, Roberto Brenes, Madeleine Laitz, Benjia Dak Dou & Vladimir Bulović

  2. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Jason J. Yoo & Moungi G. Bawendi

  3. Division of Advanced Materials, Korea Research Institute of Chemical Technology, Daejeon, Republic of Korea

    Jason J. Yoo & Seong Sik Shin

  4. Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, MA, USA

    Roberto Brenes, Madeleine Laitz & Vladimir Bulović

  5. Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK

    Felix Utama Kosasih & Caterina Ducati

  6. Department of Bioengineering, University of Washington, Seattle, WA, USA

    Daniel J. Graham

  7. Department of Chemistry, University of Washington, Seattle, WA, USA

    Kevin Ho & Yangwei Shi

  8. Molecular Engineering and Sciences Institute, University of Washington, Seattle, WA, USA

    Yangwei Shi

  9. Department of Nano Engineering and Department of Nano Science and Technology, SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon, Republic of Korea

    Seong Sik Shin

  10. SKKU Institute of Energy Science and Technology (SIEST), Sungkyunkwan University, Suwon, Republic of Korea

    Seong Sik Shin

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  1. Dane W. deQuilettes
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Contributions

D.W.D., J.J.Y., M.G.B., and V.B. conceived and designed the experiments. D.W.D., J.J.Y., M.L., R.B. and B.D.D. performed the optical characterization of the perovskite films. F.U.K. performed the (S)TEM/EDX measurements, and D.W.D. and F.U.K. performed the analysis of the data with supervision from C.D. D.W.D., R.B. and M.L. wrote the MATLAB and Python code for fitting PL data and performing drift-diffusion simulations. J.J.Y. prepared the perovskite films and devices with supervision from S.S.S. K.H. and Y.S. performed the device stability measurements. D.J.G. conducted the ToF-SIMS measurements, and D.W.D. and D.J.G. performed analysis of the data. D.W.D. wrote the first draft of the paper with early drafts edited by J.J.Y. and all authors contributing feedback and comments. M.G.B. and V.B. directed and supervised the research.

Corresponding authors

Correspondence to Seong Sik Shin, Moungi G. Bawendi or Vladimir Bulović.

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Competing interests

V.B. is an adviser to Swift Solar, a US company developing perovskite photovoltaics, and is the co-founder of Ubiquitous Energy, a US company developing visibly transparent photovoltaics. D.W.D. is a co-founder of Optigon Inc., a US company developing metrology tools for the photovoltaics industry. The other authors declare no competing interests.

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The contributions of all researchers involved in the design, execution and reporting of this study were carefully evaluated for authorship criteria. Contributors who did not meet all criteria for authorship are listed in the Acknowledgements section. The roles and responsibilities among all collaborators were agreed upon ahead of the execution of the research.

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Supplementary information

Supplementary Information

Supplementary Methods, Discussion 1, Figs. 1–29, Tables 1–6 and references.

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Supplementary Data 1

ToF-SIMS source data for light and heat stress tests in Supplementary Fig. 14.

Source data

Source Data Fig. 2

ToF-SIMS source data for control, 10 mM HABr and 50 mM HABr Treated in Figure 2g.

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deQuilettes, D.W., Yoo, J.J., Brenes, R. et al. Reduced recombination via tunable surface fields in perovskite thin films. Nat Energy 9, 457–466 (2024). https://doi.org/10.1038/s41560-024-01470-5

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