Compositional engineering for lead-free antimony bismuth alloy-based halide perovskite solar cells

Ziyu Cai; Junchi Zhu; Chenyuan Ding; Tao Dong; Boyang Yu; Wenzheng Hu; Jiayi Xie; Feng Ye; Qiufeng Ye; Zebo Fang

doi:10.1088/1674-4926/24120038

J. Semicond. > 2025, Volume 46 > Issue 5 > 052803

ARTICLES

Compositional engineering for lead-free antimony bismuth alloy-based halide perovskite solar cells

Ziyu Cai^{1, §}, Junchi Zhu^{1, §}, Chenyuan Ding¹, Tao Dong¹, Boyang Yu¹, Wenzheng Hu¹, Jiayi Xie¹, Feng Ye^2,, Qiufeng Ye^1, and Zebo Fang^1,

+ Author Affiliations

Corresponding author: Feng Ye, yefeng@usx.edu.cn; Qiufeng Ye, 2021000026@usx.edu.cn; Zebo Fang, csfzb@usx.edu.cn

DOI: 10.1088/1674-4926/24120038CSTR: 32376.14.1674-4926.24120038

Abstract: Owing to their low toxicity and remarkable stability, perovskites based on antimony and bismuth have garnered significant interest in recent years. However, A₃B₂X₉ perovskite materials derived from antimony and bismuth face several challenges, including excessively wide band gaps, elevated defect densities, and suboptimal film quality, all of which hinder advancements in device efficiency. While extensive studies have been undertaken to investigate the effects of modulating the A-site and X-site elements in lead-free A₃B₂X₉ perovskites, there remains a notable scarcity of reports addressing the impact of modifications to the B-site element. In this study, we investigated the alloying of antimony and bismuth within the 2D Cs₃B₂I₆Br₃ perovskite. By systematically varying the ratios of two elements, we found that the incorporation of both antimony and bismuth at the B-site significantly enhances the quality of the perovskite films. Our findings indicate that a 1 : 1 ratio of antimony to bismuth produces the densest films, the highest photoluminescence intensity, and superior photovoltaic performance. Ultimately, the devices fabricated using this optimal ratio achieved an open-circuit voltage (V_OC) of 1.01 V and a power conversion efficiency (PCE) of 0.645%.

Key words: low toxicity, lead free, antimony bismuth alloy, perovskite solar cells

References

[1]	Liang Z, Zhang Y, Xu H F, et al. Homogenizing out-of-plane cation composition in perovskite solar cells. Nature, 2023, 624(7992), 557 doi: 10.1038/s41586-023-06784-0
[2]	Wang Z H, Han Z Y, Chu X B, et al. Regulation of wide bandgap perovskite by rubidium thiocyanate for efficient silicon/perovskite tandem solar cells. Adv Mater, 2024, 36(50), 2407681 doi: 10.1002/adma.202407681
[3]	Chin X Y, Turkay D, Steele J A, et al. Interface passivation for 31.25%-efficient perovskite/silicon tandem solar cells. Science, 2023, 381(6653), 59 doi: 10.1126/science.adg0091
[4]	Park B W, Philippe B, Zhang X L, et al. Bismuth based hybrid perovskites A₃Bi₂I₉ (A: Methylammonium or cesium) for solar cell application. Adv Mater, 2015, 27(43), 6806 doi: 10.1002/adma.201501978
[5]	Lan C F, Liang G X, Zhao S, et al. Lead-free formamidinium bismuth perovskites (FA)₃Bi₂I₉ with low bandgap for potential photovoltaic application. Sol Energy, 2019, 177, 501 doi: 10.1016/j.solener.2018.11.050
[6]	Yu B B, Liao M, Yang J X, et al. Alloy-induced phase transition and enhanced photovoltaic performance: The case of Cs₃Bi₂I_9–xBr_x perovskite solar cells. J Mater Chem A, 2019, 7(15), 8818 doi: 10.1039/C9TA01978B
[7]	Harikesh P C, Mulmudi H K, Ghosh B, et al. Rb as an alternative cation for templating inorganic lead-free perovskites for solution processed photovoltaics. Chem Mater, 2016, 28(20), 7496 doi: 10.1021/acs.chemmater.6b03310
[8]	Jiang F Y, Yang D W, Jiang Y Y, et al. Chlorine-incorporation-induced formation of the layered phase for antimony-based lead-free perovskite solar cells. J Am Chem Soc, 2018, 140(3), 1019 doi: 10.1021/jacs.7b10739
[9]	Zhang Y F, Liu F Z, Su H H, et al. Controlling the intermediate phase to improve the crystallinity and orientation of Cs₃Sb₂Cl_xI_9-x films for efficient solar cells. Adv Funct Materials, 2023, 33(40), 2304063 doi: 10.1002/adfm.202304063
[10]	Bai F, Hu Y H, Hu Y Q, et al. Lead-free, air-stable ultrathin Cs₃Bi₂I₉ perovskite nanosheets for solar cells. Sol Energy Mater Sol Cells, 2018, 184, 15 doi: 10.1016/j.solmat.2018.04.032
[11]	Umar F, Zhang J, Jin Z X, et al. Dimensionality controlling of Cs₃Sb₂I₉ for efficient all-inorganic planar thin film solar cells by HCl-assisted solution method. Adv Opt Mater, 2019, 7(5), 1801368 doi: 10.1002/adom.201801368
[12]	Shi M, Fu P, Tian W M, et al. Tuning the optoelectronic property of all-inorganic lead-free perovskite via finely microstructural modulation for photovoltaics. Small Meth, 2024, 8(2), 2300405 doi: 10.1002/smtd.202300405
[13]	Kang J, Chen S, Hao M M, et al. Alloying Sb into all inorganic lead-free CsBi₃I₁₀ for improving the crystal growth and photovoltaic performance. J Mater Chem A, 2022, 10(37), 19618 doi: 10.1039/D2TA02245A
[14]	Al-Anesi B, Grandhi G K, Pecoraro A, et al. Antimony-bismuth alloying: The key to a major boost in the efficiency of lead-free perovskite-inspired photovoltaics. Small, 2023, 19(46), 2303575 doi: 10.1002/smll.202303575
[15]	Chen G Q, Wang P, Wu Y Q, et al. Lead-free halide perovskite Cs₃Bi_2xSb_2–2xI₉ (x ≈ 0.3) possessing the photocatalytic activity for hydrogen evolution comparable to that of (CH₃NH₃)PbI₃. Adv Mater, 2020, 32(39), 2001344 doi: 10.1002/adma.202001344

Fig. 1. (Color online) (a) Schematic illustration of the spin-coating process. (b) Device architecture. (c) Crystal structure of Cs₃(Sb_xBi_1–x)₂I₆Br₃ perovskite. (d) Optical images of film with different ratios of antimony and bismuth.

DownLoad: Full-Size Img PowerPoint

Fig. 2. (Color online) (a)–(e) Top-view SEM images of different Cs₃(Sb_xBi_1–x)₂I₆Br₃ perovskite. (f)–(j) AFM images of different Cs₃(Sb_xBi_1–x)₂I₆Br₃ perovskite.

DownLoad: Full-Size Img PowerPoint

Fig. 3. (Color online) The XRD patterns of Cs₃(Sb_xBi_1–x)₂I₆Br₃ perovskite.

DownLoad: Full-Size Img PowerPoint

Fig. 4. (Color online) (a) Absorbance spectra. (b) Tauc plots of absorbance. (c) PL spectra and (d) J−V curves of different Cs₃(Sb_xBi_1−x)₂I₆Br₃ perovskite.

DownLoad: Full-Size Img PowerPoint

Table 1. The best device efficiencies with different ratios of antimony and bismuth.

Ratio	V_OC(V)	J_SC(mA/cm²)	FF (%)	Efficiency (%)
100% Sb	0.75	0.31	46.6	0.11
75% Sb−25% Bi	0.82	0.64	37.4	0.198
50% Sb−50% Bi	1.01	1.33	48.0	0.645
25% Sb−75% Bi	0.87	0.90	41.3	0.324
100% Bi	0.69	0.98	38.1	0.258

DownLoad: CSV

[1]	Liang Z, Zhang Y, Xu H F, et al. Homogenizing out-of-plane cation composition in perovskite solar cells. Nature, 2023, 624(7992), 557 doi: 10.1038/s41586-023-06784-0
[2]	Wang Z H, Han Z Y, Chu X B, et al. Regulation of wide bandgap perovskite by rubidium thiocyanate for efficient silicon/perovskite tandem solar cells. Adv Mater, 2024, 36(50), 2407681 doi: 10.1002/adma.202407681
[3]	Chin X Y, Turkay D, Steele J A, et al. Interface passivation for 31.25%-efficient perovskite/silicon tandem solar cells. Science, 2023, 381(6653), 59 doi: 10.1126/science.adg0091
[4]	Park B W, Philippe B, Zhang X L, et al. Bismuth based hybrid perovskites A₃Bi₂I₉ (A: Methylammonium or cesium) for solar cell application. Adv Mater, 2015, 27(43), 6806 doi: 10.1002/adma.201501978
[5]	Lan C F, Liang G X, Zhao S, et al. Lead-free formamidinium bismuth perovskites (FA)₃Bi₂I₉ with low bandgap for potential photovoltaic application. Sol Energy, 2019, 177, 501 doi: 10.1016/j.solener.2018.11.050
[6]	Yu B B, Liao M, Yang J X, et al. Alloy-induced phase transition and enhanced photovoltaic performance: The case of Cs₃Bi₂I_9–xBr_x perovskite solar cells. J Mater Chem A, 2019, 7(15), 8818 doi: 10.1039/C9TA01978B
[7]	Harikesh P C, Mulmudi H K, Ghosh B, et al. Rb as an alternative cation for templating inorganic lead-free perovskites for solution processed photovoltaics. Chem Mater, 2016, 28(20), 7496 doi: 10.1021/acs.chemmater.6b03310
[8]	Jiang F Y, Yang D W, Jiang Y Y, et al. Chlorine-incorporation-induced formation of the layered phase for antimony-based lead-free perovskite solar cells. J Am Chem Soc, 2018, 140(3), 1019 doi: 10.1021/jacs.7b10739
[9]	Zhang Y F, Liu F Z, Su H H, et al. Controlling the intermediate phase to improve the crystallinity and orientation of Cs₃Sb₂Cl_xI_9-x films for efficient solar cells. Adv Funct Materials, 2023, 33(40), 2304063 doi: 10.1002/adfm.202304063
[10]	Bai F, Hu Y H, Hu Y Q, et al. Lead-free, air-stable ultrathin Cs₃Bi₂I₉ perovskite nanosheets for solar cells. Sol Energy Mater Sol Cells, 2018, 184, 15 doi: 10.1016/j.solmat.2018.04.032
[11]	Umar F, Zhang J, Jin Z X, et al. Dimensionality controlling of Cs₃Sb₂I₉ for efficient all-inorganic planar thin film solar cells by HCl-assisted solution method. Adv Opt Mater, 2019, 7(5), 1801368 doi: 10.1002/adom.201801368
[12]	Shi M, Fu P, Tian W M, et al. Tuning the optoelectronic property of all-inorganic lead-free perovskite via finely microstructural modulation for photovoltaics. Small Meth, 2024, 8(2), 2300405 doi: 10.1002/smtd.202300405
[13]	Kang J, Chen S, Hao M M, et al. Alloying Sb into all inorganic lead-free CsBi₃I₁₀ for improving the crystal growth and photovoltaic performance. J Mater Chem A, 2022, 10(37), 19618 doi: 10.1039/D2TA02245A
[14]	Al-Anesi B, Grandhi G K, Pecoraro A, et al. Antimony-bismuth alloying: The key to a major boost in the efficiency of lead-free perovskite-inspired photovoltaics. Small, 2023, 19(46), 2303575 doi: 10.1002/smll.202303575
[15]	Chen G Q, Wang P, Wu Y Q, et al. Lead-free halide perovskite Cs₃Bi_2xSb_2–2xI₉ (x ≈ 0.3) possessing the photocatalytic activity for hydrogen evolution comparable to that of (CH₃NH₃)PbI₃. Adv Mater, 2020, 32(39), 2001344 doi: 10.1002/adma.202001344

Search

GET CITATION

shu

Export: BibTex EndNote

Article Metrics

Article views: 264 Times PDF downloads: 40 Times Cited by: 0 Times

History

Received: 09 December 2024 Revised: 05 February 2025 Online: Accepted Manuscript: 03 March 2025Uncorrected proof: 17 March 2025Published: 15 May 2025

Article Navigation > Journal of Semiconductors > 2025 > 46(5): 052803

Ziyu Cai, Junchi Zhu, Chenyuan Ding, Tao Dong, Boyang Yu, Wenzheng Hu, Jiayi Xie, Feng Ye, Qiufeng Ye, Zebo Fang. Compositional engineering for lead-free antimony bismuth alloy-based halide perovskite solar cells[J]. Journal of Semiconductors, 2025, 46(5): 052803. doi: 10.1088/1674-4926/24120038 ****Z Y Cai, J C Zhu, C Y Ding, T Dong, B Y Yu, W Z Hu, J Y Xie, F Ye, Q F Ye, and Z B Fang, Compositional engineering for lead-free antimony bismuth alloy-based halide perovskite solar cells[J]. J. Semicond., 2025, 46(5), 052803 doi: 10.1088/1674-4926/24120038

Citation:

Z Y Cai, J C Zhu, C Y Ding, T Dong, B Y Yu, W Z Hu, J Y Xie, F Ye, Q F Ye, and Z B Fang, Compositional engineering for lead-free antimony bismuth alloy-based halide perovskite solar cells[J]. J. Semicond., 2025, 46(5), 052803 doi: 10.1088/1674-4926/24120038

Citation:

PDF( 6820 KB)

Compositional engineering for lead-free antimony bismuth alloy-based halide perovskite solar cells

DOI: 10.1088/1674-4926/24120038

CSTR: 32376.14.1674-4926.24120038

1.
Zhejiang Engineering Research Center of MEMS, Shaoxing University, Shaoxing 312000, China
2.
School of Textile Science and Engineering, Shaoxing University, Shaoxing 312000, China

More Information

Ziyu Cai got his bachelor’s degree in 2017 from Applied Technology College of Soochow University. Currently, he is a master student in School of Mathematics Information of Shaoxing University under the supervision of the Associate Professor Qiufeng Ye. His research focuses on lead-free perovskite solar cells
Qiufeng Ye received his PhD degree from University of Chinese Academy of Sciences (2021). He is currently a Associate Professor of Shaoxing University. His research is mainly focused on perovskite materials and their applications in photovoltaic
Zebo Fang received his PhD degree from Lanzhou University. He is currently a Professor of Shaoxing University and the Dean of School of Mathematical Information, Shaoxing University. His research is mainly focused on Semiconductor high k materials and optoelectronic devices
Corresponding author: yefeng@usx.edu.cn; 2021000026@usx.edu.cn; csfzb@usx.edu.cn
Received Date: 2024-12-09
Revised Date: 2025-02-05

Available Online: 2025-03-03

Abstract

Abstract

Owing to their low toxicity and remarkable stability, perovskites based on antimony and bismuth have garnered significant interest in recent years. However, A₃B₂X₉ perovskite materials derived from antimony and bismuth face several challenges, including excessively wide band gaps, elevated defect densities, and suboptimal film quality, all of which hinder advancements in device efficiency. While extensive studies have been undertaken to investigate the effects of modulating the A-site and X-site elements in lead-free A₃B₂X₉ perovskites, there remains a notable scarcity of reports addressing the impact of modifications to the B-site element. In this study, we investigated the alloying of antimony and bismuth within the 2D Cs₃B₂I₆Br₃ perovskite. By systematically varying the ratios of two elements, we found that the incorporation of both antimony and bismuth at the B-site significantly enhances the quality of the perovskite films. Our findings indicate that a 1 : 1 ratio of antimony to bismuth produces the densest films, the highest photoluminescence intensity, and superior photovoltaic performance. Ultimately, the devices fabricated using this optimal ratio achieved an open-circuit voltage (V_OC) of 1.01 V and a power conversion efficiency (PCE) of 0.645%.
- low toxicity,
- lead free,
- antimony bismuth alloy,
- perovskite solar cells

^§Ziyu Cai and Junchi Zhu contributed equally to this work and should be considered as co-first authors.

FullText(HTML)

References(15)