Defect and stress co-management via bifunctional molecular engineering for high-efficiency and stable CsPbI<sub>3</sub> perovskite solar cells

Huifang Han; Jia Xu; Jianxi Yao

doi:10.1088/1674-4926/25120041

J. Semicond. > Just Accepted

ARTICLES

Defect and stress co-management via bifunctional molecular engineering for high-efficiency and stable CsPbI₃ perovskite solar cells

Huifang Han^{1, 2}, Jia Xu^{1, 2} and Jianxi Yao^{1, 2,}

+ Author Affiliations

Corresponding author: Jianxi Yao, jianxiyao@ncepu.edu.cn

DOI: 10.1088/1674-4926/25120041CSTR: 32376.14.1674-4926.25120041

Abstract: Inorganic cesium lead iodide (CsPbI₃) perovskites are promising photovoltaic materials owing to their excellent thermal stability and optoelectronic properties. However, CsPbI₃ film fabricated via solution processing typically suffers from high defect densities and detrimental residual tensile stress due to uncontrolled crystallization and thermal expansion mismatch with the substrate, which impedes its practical application. Herein, we introduce ammonium benzenesulfonate (ABS) as a bifunctional additive to modulate crystallization, thereby passivating defects and regulating residual stress. The sulfonate group of ABS coordinates with undercoordinated Pb²⁺ ions, while its ammonium group forms hydrogen bonds with iodide ions. The molecular structure of ABS bridges adjacent [PbI₆]⁴⁻ octahedra at grain boundaries. This dual interaction effectively enhanced crystallinity, suppressed non-radiative recombination, and improved structural stability. As a result, ABS-modified CsPbI₃-based perovskite solar cells achieve an impressive power conversion efficiency (PCE) of 21.21% under standard illumination. Remarkably, they deliver a PCE of 40.85% under indoor lighting conditions. Moreover, unencapsulated devices retains 91% of their initial PCE after 800 hours of storage in ambient air at a relative humidity of 5%.

Key words: perovskite, additive, CsPbI₃, passivation, stability

References

[1]	Liu C, Yang Y, Chen H, et al. Two-dimensional perovskitoids enhance stability in perovskite solar cells. Nature, 2024, 633(8029): 359 doi: 10.1038/s41586-024-07764-8
[2]	Jeong J, Kim M, Seo J, et al. Pseudo-halide anion engineering for α-FAPbI₃ perovskite solar cells. Nature, 2021, 592(7854): 381 doi: 10.1038/s41586-021-03406-5
[3]	Wang Q R, Zhu J W, Zhao Y Y, et al. Cross-layer all-interface defect passivation with pre-buried additive toward efficient all-inorganic perovskite solar cells. Carbon Energy, 2024, 6(9): e566
[4]	Kojima A, Teshima K, Shirai Y, et al. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J Am Chem Soc, 2009, 131(17): 6050 doi: 10.1021/ja809598r
[5]	Best Research-Cell Efficiency Chart. https://www.nrel.gov/pv/cell-efficiency.html (accessed January 2025).
[6]	Rong Y, Hu Y, Mei A, et al. Challenges for commercializing perovskite solar cells. Science, 2018, 361(6408): eaat8235 doi: 10.1126/science.aat8235
[7]	Xiang W C, Liu S F, Tress W. A review on the stability of inorganic metal halide perovskites: Challenges and opportunities for stable solar cells. Energy Environ Sci, 2021, 14(4): 2090 doi: 10.1039/D1EE00157D
[8]	Zhou Y Y, Zhao Y X. Chemical stability and instability of inorganic halide perovskites. Energy Environ Sci, 2019, 12(5): 1495 doi: 10.1039/C8EE03559H
[9]	Zhao Y Y, Gao L, Wang Q R, et al. Reinforced SnO₂ tensile-strength and “buffer-spring” interfaces for efficient inorganic perovskite solar cells. Carbon Energy, 2024, 6(6): e468
[10]	Chu X B, Ye Q F, Wang Z H, et al. Surface in situ reconstruction of inorganic perovskite films enabling long carrier lifetimes and solar cells with 21% efficiency. Nat Energy, 2023, 8(4): 372 doi: 10.1038/s41560-023-01220-z
[11]	Tan C Y, Cui Y Q, Zhang R, et al. In situ reconstructing the buried interface for efficient CsPbI₃ perovskite solar cells. ACS Energy Lett, 2025, 10(2): 703 doi: 10.1021/acsenergylett.4c03282
[12]	Tan X, Wang S B, Zhang Q X, et al. Stabilizing CsPbI₃ perovskite for photovoltaic applications. Matter, 2023, 6(3): 691 doi: 10.1016/j.matt.2022.12.012
[13]	Li R, Chen Q Y, Zhang H, et al. Simultaneous charge extraction enhancement and defect passivation via a planar conjugated molecular interface enable 22. 49%-efficient inorganic perovskite solar cells. Angew Chem Int Ed, 2025, 64(39): e202510925 doi: 10.1002/ange.202510925
[14]	Wang K L, Lu H Z, Li M, et al. Ion–dipole interaction enabling highly efficient CsPbI₃ perovskite indoor photovoltaics. Adv Mater, 2023, 35(31): 2210106 doi: 10.1002/adma.202210106
[15]	Zhang F, Zhu K. Additive engineering for efficient and stable perovskite solar cells. Adv Energy Mater, 2020, 10(13): 190257 doi: 10.1021/acsami.5c09196.s001
[16]	Zhang H, Tian Q W, Xiang W C, et al. Tailored cysteine-derived molecular structures toward efficient and stable inorganic perovskite solar cells. Adv Mater, 2023, 35(31): 2301140 doi: 10.1002/adma.202301140
[17]	Zhao J J, Deng Y H, Wei H T, et al. Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells. Sci Adv, 2017, 3(11): eaao5616 doi: 10.1126/sciadv.aao5616
[18]	Steele J A, Jin H D, Dovgaliuk I, et al. Thermal unequilibrium of strained black CsPbI₃ thin films. Science, 2019, 365(6454): 679 doi: 10.1126/science.aax3878
[19]	Yang S M, Duan Y W, Liu Z K, et al. Recent advances in CsPbX₃ perovskite solar cells: Focus on crystallization characteristics and controlling strategies. Adv Energy Mater, 2023, 13(33): 2201733 doi: 10.1002/aenm.202201733
[20]	Li R, Zhang S A, Zhang H, et al. Customizing aniline-derived molecular structures to attain beyond 22 % efficient inorganic perovskite solar cells. Angew Chem Int Ed, 2024, 63(42): e202410600 doi: 10.1002/anie.202410600
[21]	Wang S L, Sun H R, Wang P Y, et al. Small molecule regulatory strategy for inorganic perovskite solar cells with 368 mV of V_OC deficit and its application in tandem devices. Adv Energy Mater, 2024, 14(26): 2400151 doi: 10.1002/aenm.202400151

Fig. 1. (Color online) Schematic diagram of the fabrication process for γ-CsPbI₃ films.

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Fig. 2. (Color online) (a) (b) Top-view SEM images of CsPbI₃ and CsPbI₃-ABS films, respectively. (c) (d) Grain size statistics of CsPbI₃ and CsPbI₃-ABS films, respectively. (e) XRD patterns of both films. (f) Full width at half maxima (FWHM) values of (110) and (220) peaks. (g) (h) GIXRD patterns collected at diﬀerent tilt angles for CsPbI₃ and CsPbI₃-ABS films, respectively. (i) Linear fit of 2θ versus sin²ψ for CsPbI₃ and CsPbI₃-ABS films.

DownLoad: Full-Size Img PowerPoint

Fig. 3. (Color online) XPS spectra of (a) Cs 3d and (b) Pb 4f for CsPbI₃ and CsPbI₃-ABS films. XPS spectra of (c) O 1s and (d) N 1s for CsPbI₃-ABS and ABS films. (e) Schematic diagram of the proposed interaction mechanism between ABS and CsPbI₃.

DownLoad: Full-Size Img PowerPoint

Fig. 4. (Color online) (a) Steady-state PL of CsPbI₃ and CsPbI₃-ABS films. PL mapping images of (b) CsPbI₃, (c) CsPbI₃-ABS films. (d) TRPL decay curves of CsPbI₃ and CsPbI₃-ABS films. (e) TPV and (f) EIS measurements of the CsPbI₃- and CsPbI₃-ABS-based PSCs.

DownLoad: Full-Size Img PowerPoint

Fig. 5. (Color online) (a) Device structure of the CsPbI₃-based PSCs. (b) J−V curves of CsPbI₃ and CsPbI₃-ABS-based PSCs under forward and reverse scans. (c) EQE spectra with integrated current density of CsPbI₃ and CsPbI₃-ABS-based PSCs. (d) Statistical distributions of photovoltaic parameters of CsPbI₃ and CsPbI₃-ABS-based PSCs. (e) Long-term stability measurements of unencapsulated devices exposed to an ambient environment with 5% RH at 25 °C. (f) J−V curves of the CsPbI₃-ABS-based PSCs under indoor LED lighting (2956 K, 1062 lux).

DownLoad: Full-Size Img PowerPoint

Table 1. Photovoltaic performance parameters of CsPbI₃- and CsPbI₃-ABS-based PSCs.

Sample	Scan direction	V_OC (V)	J_SC (mA∙cm⁻²)	FF (%)	η (%)
CsPbI₃	Reverse	1.18	20.55	79.44	19.26
CsPbI₃	Forward	1.16	20.59	78.31	18.81
CsPbI₃-ABS	Reverse	1.24	20.97	81.41	21.21
CsPbI₃-ABS	Forward	1.23	20.98	81.02	20.98

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[1]	Liu C, Yang Y, Chen H, et al. Two-dimensional perovskitoids enhance stability in perovskite solar cells. Nature, 2024, 633(8029): 359 doi: 10.1038/s41586-024-07764-8
[2]	Jeong J, Kim M, Seo J, et al. Pseudo-halide anion engineering for α-FAPbI₃ perovskite solar cells. Nature, 2021, 592(7854): 381 doi: 10.1038/s41586-021-03406-5
[3]	Wang Q R, Zhu J W, Zhao Y Y, et al. Cross-layer all-interface defect passivation with pre-buried additive toward efficient all-inorganic perovskite solar cells. Carbon Energy, 2024, 6(9): e566
[4]	Kojima A, Teshima K, Shirai Y, et al. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J Am Chem Soc, 2009, 131(17): 6050 doi: 10.1021/ja809598r
[5]	Best Research-Cell Efficiency Chart. https://www.nrel.gov/pv/cell-efficiency.html (accessed January 2025).
[6]	Rong Y, Hu Y, Mei A, et al. Challenges for commercializing perovskite solar cells. Science, 2018, 361(6408): eaat8235 doi: 10.1126/science.aat8235
[7]	Xiang W C, Liu S F, Tress W. A review on the stability of inorganic metal halide perovskites: Challenges and opportunities for stable solar cells. Energy Environ Sci, 2021, 14(4): 2090 doi: 10.1039/D1EE00157D
[8]	Zhou Y Y, Zhao Y X. Chemical stability and instability of inorganic halide perovskites. Energy Environ Sci, 2019, 12(5): 1495 doi: 10.1039/C8EE03559H
[9]	Zhao Y Y, Gao L, Wang Q R, et al. Reinforced SnO₂ tensile-strength and “buffer-spring” interfaces for efficient inorganic perovskite solar cells. Carbon Energy, 2024, 6(6): e468
[10]	Chu X B, Ye Q F, Wang Z H, et al. Surface in situ reconstruction of inorganic perovskite films enabling long carrier lifetimes and solar cells with 21% efficiency. Nat Energy, 2023, 8(4): 372 doi: 10.1038/s41560-023-01220-z
[11]	Tan C Y, Cui Y Q, Zhang R, et al. In situ reconstructing the buried interface for efficient CsPbI₃ perovskite solar cells. ACS Energy Lett, 2025, 10(2): 703 doi: 10.1021/acsenergylett.4c03282
[12]	Tan X, Wang S B, Zhang Q X, et al. Stabilizing CsPbI₃ perovskite for photovoltaic applications. Matter, 2023, 6(3): 691 doi: 10.1016/j.matt.2022.12.012
[13]	Li R, Chen Q Y, Zhang H, et al. Simultaneous charge extraction enhancement and defect passivation via a planar conjugated molecular interface enable 22. 49%-efficient inorganic perovskite solar cells. Angew Chem Int Ed, 2025, 64(39): e202510925 doi: 10.1002/ange.202510925
[14]	Wang K L, Lu H Z, Li M, et al. Ion–dipole interaction enabling highly efficient CsPbI₃ perovskite indoor photovoltaics. Adv Mater, 2023, 35(31): 2210106 doi: 10.1002/adma.202210106
[15]	Zhang F, Zhu K. Additive engineering for efficient and stable perovskite solar cells. Adv Energy Mater, 2020, 10(13): 190257 doi: 10.1021/acsami.5c09196.s001
[16]	Zhang H, Tian Q W, Xiang W C, et al. Tailored cysteine-derived molecular structures toward efficient and stable inorganic perovskite solar cells. Adv Mater, 2023, 35(31): 2301140 doi: 10.1002/adma.202301140
[17]	Zhao J J, Deng Y H, Wei H T, et al. Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells. Sci Adv, 2017, 3(11): eaao5616 doi: 10.1126/sciadv.aao5616
[18]	Steele J A, Jin H D, Dovgaliuk I, et al. Thermal unequilibrium of strained black CsPbI₃ thin films. Science, 2019, 365(6454): 679 doi: 10.1126/science.aax3878
[19]	Yang S M, Duan Y W, Liu Z K, et al. Recent advances in CsPbX₃ perovskite solar cells: Focus on crystallization characteristics and controlling strategies. Adv Energy Mater, 2023, 13(33): 2201733 doi: 10.1002/aenm.202201733
[20]	Li R, Zhang S A, Zhang H, et al. Customizing aniline-derived molecular structures to attain beyond 22 % efficient inorganic perovskite solar cells. Angew Chem Int Ed, 2024, 63(42): e202410600 doi: 10.1002/anie.202410600
[21]	Wang S L, Sun H R, Wang P Y, et al. Small molecule regulatory strategy for inorganic perovskite solar cells with 368 mV of V_OC deficit and its application in tandem devices. Adv Energy Mater, 2024, 14(26): 2400151 doi: 10.1002/aenm.202400151

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Received: 24 December 2025 Revised: Online: Accepted Manuscript: 23 January 2026

Article Navigation > Journal of Semiconductors > 2026 > Accepted Manuscript

Huifang Han, Jia Xu, Jianxi Yao. Defect and stress co-management via bifunctional molecular engineering for high-efficiency and stable CsPbI3 perovskite solar cells[J]. Journal of Semiconductors, 2026, In Press. doi: 10.1088/1674-4926/25120041 ****H F Han, J Xu, and J X Yao, Defect and stress co-management via bifunctional molecular engineering for high-efficiency and stable CsPbI3 perovskite solar cells[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/25120041

Citation:

Huifang Han, Jia Xu, Jianxi Yao. Defect and stress co-management via bifunctional molecular engineering for high-efficiency and stable CsPbI₃ perovskite solar cells[J]. Journal of Semiconductors, 2026, In Press. doi: 10.1088/1674-4926/25120041 ****

H F Han, J Xu, and J X Yao, Defect and stress co-management via bifunctional molecular engineering for high-efficiency and stable CsPbI₃ perovskite solar cells[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/25120041

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Defect and stress co-management via bifunctional molecular engineering for high-efficiency and stable CsPbI₃ perovskite solar cells

DOI: 10.1088/1674-4926/25120041

CSTR: 32376.14.1674-4926.25120041

Huifang Han^{1, 2},
Jia Xu^{1, 2},
Jianxi Yao^{1, 2,}

1.
New Energy Generation National Engineering Research Center, North China Electric Power University, Beijing 102206, China
2.
Beijing Key Laboratory of Energy Safety and Clean Utilization, North China Electric Power University, Beijing 102206, China

More Information

Huifang Han got his master’s degree from Wenzhou University in 2018. Now he is a Ph.D. student at North China Electric Power University under the supervision of Prof. Jianxi Yao. His research focuses on all-inorganic perovskite solar cells
Jianxi Yao got his Ph.D. degree from Zhejiang University in 2003. He conducted postdoctoral research at Kyoto University in Japan from 2003 to 2005. From 2005 to 2008, he worked at the Institute of Process Engineering, Chinese Academy of Sciences. Since 2008, he has been working at North China Electric Power University. His present interests include perovskite solar cell materials and devices, and nano photoelectric materials and devices
Corresponding author: jianxiyao@ncepu.edu.cn
Received Date: 2025-12-24
Available Online: 2026-01-23

Abstract

Abstract

Inorganic cesium lead iodide (CsPbI₃) perovskites are promising photovoltaic materials owing to their excellent thermal stability and optoelectronic properties. However, CsPbI₃ film fabricated via solution processing typically suffers from high defect densities and detrimental residual tensile stress due to uncontrolled crystallization and thermal expansion mismatch with the substrate, which impedes its practical application. Herein, we introduce ammonium benzenesulfonate (ABS) as a bifunctional additive to modulate crystallization, thereby passivating defects and regulating residual stress. The sulfonate group of ABS coordinates with undercoordinated Pb²⁺ ions, while its ammonium group forms hydrogen bonds with iodide ions. The molecular structure of ABS bridges adjacent [PbI₆]⁴⁻ octahedra at grain boundaries. This dual interaction effectively enhanced crystallinity, suppressed non-radiative recombination, and improved structural stability. As a result, ABS-modified CsPbI₃-based perovskite solar cells achieve an impressive power conversion efficiency (PCE) of 21.21% under standard illumination. Remarkably, they deliver a PCE of 40.85% under indoor lighting conditions. Moreover, unencapsulated devices retains 91% of their initial PCE after 800 hours of storage in ambient air at a relative humidity of 5%.
- perovskite,
- additive,
- CsPbI₃,
- passivation,
- stability

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References(21)