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Nature Energy volume 10, pages 1427–1438 (2025)
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Liquid-state 4-tert-butylpyridine is essential for achieving high performance in n–i–p perovskite solar cells. 4-tert– Butylpyridine effectively dissolves the lithium bis(trifluoromethanesulfonyl)imide dopant and stabilizes lithium ions. However, its high volatility and corrosive nature can degrade the perovskite layer and promote the formation of byproducts and pinholes in the hole transport layer under thermal stress, ultimately compromising device stability. Here we introduce a non-volatile, solid-state alternative—4-(N-carbazolyl)pyridine (4CP)—which stabilizes lithium ions and facilitates the formation of lithium bis(trifluoromethanesulfonyl)imide complexes. Perovskite solar cells incorporating 4CP achieve a power conversion efficiency of 26.2% (25.8% certified) and maintain 80% of their initial performance for over 3,000 h at maximum power point tracking. The unencapsulated devices retain 90% of their initial efficiency after 200 thermal shock cycles between −80 °C and 80 °C, and under continuous exposure to 65 °C and 85 °C. The adoption of 4CP could help improve the stability of n–i–p perovskite solar cells.
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The data that support the findings of this study are available within the Article and its Supplementary Information. Source data are provided with this paper.
McMeekin, D. P. et al. A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells. Science 351, 151–155 (2016).
Article Google Scholar
Saliba, M. et al. Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency. Energy Environ. Sci. 9, 1989–1997 (2016).
Article Google Scholar
Jeon, N. J. et al. A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat. Energy 3, 682–689 (2018).
Article MathSciNet Google Scholar
Yoo, J. J. et al. Efficient perovskite solar cells via improved carrier management. Nature 590, 587–593 (2021).
Article Google Scholar
Turren-Cruz, S.-H., Hagfeldt, A. & Saliba, M. Methylammonium-free, high-performance, and stable perovskite solar cells on a planar architecture. Science 362, 449–453 (2018).
Article Google Scholar
Jeong, J. et al. Pseudo-halide anion engineering for α-FAPbI3 perovskite solar cells. Nature 592, 381–385 (2021).
Article Google Scholar
Park, J. et al. Controlled growth of perovskite layers with volatile alkylammonium chlorides. Nature 616, 724–730 (2023).
Article Google Scholar
Kim, J. et al. Susceptible organic cations enable stable and efficient perovskite solar cells. Joule 9, 101879 (2025).
Article Google Scholar
Chen, H. et al. Improved charge extraction in inverted perovskite solar cells with dual-site-binding ligands. Science 384, 189–193 (2024).
Article Google Scholar
Peng, W. et al. Reducing nonradiative recombination in perovskite solar cells with a porous insulator contact. Science 379, 683–690 (2023).
Article Google Scholar
Li, G. et al. Highly efficient p–i–n perovskite solar cells that endure temperature variations. Science 379, 399–403 (2023).
Article Google Scholar
Li, B. et al. Highly efficient and scalable p–i–n perovskite solar cells enabled by poly-metallocene interfaces. J. Am. Chem. Soc. 146, 13391–13398 (2024).
Article Google Scholar
Li, Z. et al. Stabilized hole-selective layer for high-performance inverted p–i–n perovskite solar cells. Science 382, 284–289 (2023).
Article Google Scholar
Yang, W. S. et al. Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells. Science 356, 1376–1379 (2017).
Article Google Scholar
Jung, E. H. et al. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature 567, 511–515 (2019).
Article Google Scholar
Min, H. et al. Perovskite solar cells with atomically coherent interlayers on SnO2 electrodes. Nature 598, 444–450 (2021).
Article Google Scholar
Kim, C. et al. Trimming defective perovskite layer surfaces for high-performance solar cells. Energy Environ. Sci. 17, 8582–8592 (2024).
Article Google Scholar
Min, H. et al. Efficient, stable solar cells by using inherent bandgap of α-phase formamidinium lead iodide. Science 366, 749–753 (2019).
Article Google Scholar
Rombach, F. M., Haque, S. A. & Macdonald, T. J. Lessons learned from spiro-OMeTAD and PTAA in perovskite solar cells. Energy Environ. Sci. 14, 5161–5190 (2021).
Article Google Scholar
Ouedraogo, N. A. N. et al. Oxidation of spiro-OMeTAD in high-efficiency perovskite solar cells. ACS Appl. Mater. Interfaces 14, 34303–34327 (2022).
Article Google Scholar
Hawash, Z., Ono, L. K. & Qi, Y. Moisture and oxygen enhance conductivity of LiTFSI-doped spiro-MeOTAD hole transport layer in perovskite solar cells. Adv. Mater. Interfaces 3, 1600117 (2016).
Article Google Scholar
Juarez-Perez, E. J. et al. Role of the dopants on the morphological and transport properties of spiro-MeOTAD hole transport layer. Chem. Mater. 28, 5702–5709 (2016).
Article Google Scholar
Wang, S. et al. Unveiling the role of tBP–LiTFSI complexes in perovskite solar cells. J. Am. Chem. Soc. 140, 16720–16730 (2018).
Article Google Scholar
Jena, A. K., Ikegami, M. & Miyasaka, T. Severe morphological deformation of spiro-OMeTAD in (CH3NH3)PbI3 solar cells at high temperature. ACS Energy Lett. 2, 1760–1761 (2017).
Article Google Scholar
Shin, Y. S. et al. De-doping engineering for efficient and heat-stable perovskite solar cells. Joule 9, 101779 (2025).
Article Google Scholar
Al-Ashouri, A. et al. Conformal monolayer contacts with lossless interfaces for perovskite single junction and monolithic tandem solar cells. Energy Environ. Sci. 12, 3356–3369 (2019).
Article Google Scholar
Jegorovė, A. et al. Starburst carbazole derivatives as efficient hole transporting materials for perovskite solar cells. Sol. RRL 6, 2100877 (2022).
Article Google Scholar
Radhakrishna, K., Manjunath, S. B., Devadiga, D., Chetri, R. & Nagaraja, A. T. Review on carbazole-based hole transporting materials for perovskite solar cell. ACS Appl. Energy Mater. 6, 3635–3664 (2023).
Article Google Scholar
Puerto Galvis, C. E., González Ruiz, D. A., Martínez-Ferrero, E. & Palomares, E. Challenges in the design and synthesis of self-assembling molecules as selective contacts in perovskite solar cells. Chem. Sci. 15, 1534–1556 (2024).
Article Google Scholar
Wang, S. et al. Role of 4-tert-butylpyridine as a hole transport layer morphological controller in perovskite solar cells. Nano Lett. 16, 5594–5600 (2016).
Article Google Scholar
Habisreutinger, S. N., Noel, N. K., Snaith, H. J. & Nicholas, R. Investigating the role of 4-tert-butylpyridine in perovskite solar cells. Adv. Energy Mater. 7, 1601079 (2017).
Article Google Scholar
Kim, G. et al. Impact of strain relaxation on performance of α-formamidinium lead iodide perovskite solar cells. Science 370, 108–112 (2020).
Article Google Scholar
Kim, M. et al. Methylammonium chloride induces intermediate phase stabilization for efficient perovskite solar cells. Joule 3, 2179–2192 (2019).
Article Google Scholar
Duijnstee, E. A. et al. Understanding the degradation of methylenediammonium and its role in phase-stabilizing formamidinium lead triiodide. J. Am. Chem. Soc. 145, 10275–10284 (2023).
Article Google Scholar
Tian, L. et al. Divalent cation replacement strategy stabilizes wide-bandgap perovskite for Cu(In,Ga)Se2 tandem solar cells. Nat. Photon. 19, 479–485 (2025).
Shibayama, N. et al. Control of molecular orientation of spiro-OMeTAD on substrates. ACS Appl. Mater. Interfaces 12, 50187–50191 (2020).
Article Google Scholar
Coropceanu, V. et al. Charge transport in organic semiconductors. Chem. Rev. 107, 926–952 (2007).
Article Google Scholar
Malinauskas, T. et al. Enhancing thermal stability and lifetime of solid-state dye-sensitized solar cells via molecular engineering of the hole-transporting material spiro-OMeTAD. ACS Appl. Mater. Interfaces 7, 11107–11116 (2015).
Article Google Scholar
Sanehira, E. M. et al. Influence of electrode interfaces on the stability of perovskite solar cells: reduced degradation using MoOx/Al for hole collection. ACS Energy Lett. 1, 38–45 (2016).
Article Google Scholar
Ye, L. et al. Superoxide radical derived metal-free spiro-OMeTAD for highly stable perovskite solar cells. Nat. Commun. 15, 7889 (2024).
Article Google Scholar
Cho, Y. et al. Elucidating mechanisms behind ambient storage-induced efficiency improvements in perovskite solar cells. ACS Energy Lett. 6, 925–933 (2021).
Article Google Scholar
Shen, Y., Deng, K., Chen, Q., Gao, G. & Li, L. Crowning lithium ions in hole-transport layer toward stable perovskite solar cells. Adv. Mater. 34, 2200978 (2022).
Article Google Scholar
Laoire, C. O., Mukerjee, S., Abraham, K. M., Plichta, E. J. & Hendrickson, M. A. Influence of nonaqueous solvents on the electrochemistry of oxygen in the rechargeable lithium−air battery. J. Phys. Chem. C 114, 9178–9186 (2010).
Aetukuri, N. B. et al. Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li–O2 batteries. Nat. Chem. 7, 50–56 (2015).
Article Google Scholar
Lamberti, F. et al. Evidence of spiro-OMeTAD de-doping by tert-butylpyridine additive in hole-transporting layers for perovskite solar cells. Chem 5, 1806–1817 (2019).
Article Google Scholar
Kim, S. et al. Enhancing thermal stability of perovskite solar cells through thermal transition and thin film crystallization engineering of polymeric hole transport layers. ACS Energy Lett. 9, 4501–4508 (2024).
Article Google Scholar
Yang, J. & Kelly, T. L. Decomposition and cell failure mechanisms in lead halide perovskite solar cells. Inorg. Chem. 56, 92–101 (2017).
Article Google Scholar
Divitini, G. et al. In situ observation of heat-induced degradation of perovskite solar cells. Nat. Energy 1, 15012 (2016).
Article Google Scholar
Li, H. et al. Dynamics parameter correction for predicting the long-term stability of organic photovoltaics. Macromolecules 57, 6548–6558 (2024).
Article Google Scholar
Hawash, Z., Ono, L. K., Raga, S. R., Lee, M. V. & Qi, Y. Air-exposure induced dopant redistribution and energy level shifts in spin-coated spiro-MeOTAD films. Chem. Mater. 27, 562–569 (2015).
Article Google Scholar
Pan, H. et al. Advances in design engineering and merits of electron transporting layers in perovskite solar cells. Mater. Horiz. 7, 2276–2291 (2020).
Article Google Scholar
Yao, Y. et al. Organic hole-transport layers for efficient, stable, and scalable inverted perovskite solar cells. Adv. Mater. 34, 2203794 (2022).
Article Google Scholar
Dong, Y. et al. Dopant-induced interactions in spiro-OMeTAD: advancing hole transport for perovskite solar cells. Mater. Sci. Eng. R 162, 100875 (2025).
Article Google Scholar
Euvrard, J. et al. p-Type molecular doping by charge transfer in halide perovskite. Mater. Adv. 2, 2956–2965 (2021).
Article Google Scholar
You, S. et al. Bifunctional hole-shuttle molecule for improved interfacial energy level alignment and defect passivation in perovskite solar cells. Nat. Energy 8, 515–525 (2023).
Article Google Scholar
Li, W. et al. Montmorillonite as bifunctional buffer layer material for hybrid perovskite solar cells with protection from corrosion and retarding recombination. J. Mater. Chem. A 2, 13587–13592 (2014).
Article Google Scholar
Domanski, K. et al. Migration of cations induces reversible performance losses over day/night cycling in perovskite solar cells. Energy Environ. Sci. 10, 604–613 (2017).
Article Google Scholar
Christians, J. A. et al. Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability. Nat. Energy 3, 68–74 (2018).
Article Google Scholar
Khenkin, M. V. et al. Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures. Nat. Energy 5, 35–49 (2020).
Article Google Scholar
Lin, Y.-H. et al. A piperidinium salt stabilizes efficient metal-halide perovskite solar cells. Science 369, 96–102 (2020).
Article Google Scholar
Lang, F. et al. Radiation hardness and self-healing of perovskite solar cells. Adv. Mater. 28, 8726–8731 (2016).
Article Google Scholar
Tu, Y. et al. Perovskite solar cells for space applications: progress and challenges. Adv. Mater. 33, 2006545 (2021).
Article Google Scholar
Miyazawa, Y. et al. Tolerance of perovskite solar cell to high-energy particle irradiations in space environment. iScience 2, 148–155 (2018).
Article Google Scholar
Yang, J., Bao, Q., Shen, L. & Ding, L. Potential applications for perovskite solar cells in space. Nano Energy 76, 105019 (2020).
Article Google Scholar
Dong, B. et al. Self-assembled bilayer for perovskite solar cells with improved tolerance against thermal stresses. Nat. Energy 10, 342–353 (2025).
Article Google Scholar
Bulut, M. Thermal design, analysis, and testing of the first Turkish 3U communication CubeSat in low earth orbit. J. Therm. Anal. Calorim. 143, 4341–4353 (2021).
Article Google Scholar
Lamb, D. A., Irvine, S. J. C., Baker, M. A., Underwood, C. I. & Mardhani, S. Thin film cadmium telluride solar cells on ultra-thin glass in low earth orbit—3 years of performance data on the AlSat-1N CubeSat mission. Prog. Photovolt. Res. Appl. 29, 1000–1007 (2021).
Article Google Scholar
McAndrews, G. R. et al. Why perovskite thermal stress is unaffected by thin contact layers. Adv. Energy Mater. 14, 2400764 (2024).
Article Google Scholar
Valiev, M. et al. NWChem: a comprehensive and scalable open-source solution for large scale molecular simulations. Comput. Phys. Commun. 181, 1477–1489 (2010).
Article Google Scholar
Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 38, 3098–3100 (1988).
Article Google Scholar
Lee, C., Yang, W. & Parr, R. G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988).
Article Google Scholar
Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).
Article Google Scholar
Jorgensen, W. L., Maxwell, D. S. & Tirado-Rives, J. Development and testing of the OPLS All-Atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).
Article Google Scholar
Jensen, K. P. & Jorgensen, W. L. Halide, ammonium, and alkali metal ion parameters for modeling aqueous solutions. J. Chem. Theory Comput. 2, 1499–1509 (2006).
Article Google Scholar
Yeh, I.-C. & Berkowitz, M. L. Ewald summation for systems with slab geometry. J. Chem. Phys. 111, 3155–3162 (1999).
Article Google Scholar
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This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (RS-2024-00338765, 2021R1A2C3004202), the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry and Energy (MOTIE) of the Republic of Korea (RS-2025-02309702) and the Nano and Material Technology Development Program through the NRF funded by the Ministry of Science and ICT (RS-2025-25442266).
These authors contributed equally: Kihoon Kim, Sangjin Yang.
KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul, South Korea
Kihoon Kim, Chanhyeok Kim, Youngmin Kim, Jinsoo Park & Hanul Min
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan, South Korea
Sangjin Yang, Jeewon Park, Seokhwan Jeong, Zhe Sun, Seung-Jae Shin & Changduk Yang
Graduate School of Carbon Neutrality, Ulsan National Institute of Science and Technology, Ulsan, South Korea
Minseok Kang & Changduk Yang
Division of Advanced Materials, Korea Research Institute of Chemical Technology, Daejeon, South Korea
Bong Joo Kang
Space Testing Center, Korea Testing Laboratory, Jinju, South Korea
Juhong Oh
Department of Electrical and Electronic Engineering, Advanced Technology Institute, University of Surrey, Guildford, UK
Jae Sung Yun
Department of Integrative Energy Engineering, Korea University, Seoul, South Korea
Hanul Min
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C.Y., H.M. and S.Y. conceived the idea. K.K. fabricated the PSCs and performed characterization of the perovskite films. S.Y. synthesized the 4CP and performed the related characterizations. C.K. carried out the model PSC fabrication. Jeewon Park carried out PL characterizations. S.J. carried out TGA and DSC characterization. Y.K. and Jinsoo Park performed SEM and conductivity measurement. Z.S. carried out in situ PL measurement. M.K. conducted ATR-FTIR measurements. B.J.K. carried out PLQY measurements. J.O. and J.S.Y. performed the thermal shock test. C.Y. supervised the project. S.-J.S. performed the theoretical simulation. The paper was mainly written by S.-J.S., C.Y. and H.M., and all authors commented on the paper.
Correspondence to Seung-Jae Shin, Changduk Yang or Hanul Min.
The authors declare no competing interests.
Nature Energy thanks Thomas J. Macdonald, Jovana Milic and the other anonymous reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Figs. 1–19 and Tables 1 and 2.
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Statistical source J–V data.
Statistical source J–V data and source J–V curve.
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Kim, K., Yang, S., Kim, C. et al. Non-volatile solid-state 4-(N-carbazolyl)pyridine additive for perovskite solar cells with improved thermal and operational stability. Nat Energy 10, 1427–1438 (2025). https://doi.org/10.1038/s41560-025-01864-z
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