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Recently, the power conversion efficiency (PCE) of organic-inorganic hybrid perovskite solar cells has been enhanced rapidly from 3.8% to 25.8%, which is a top research topic in the field of photovoltaic power generation. However, the preparation of the hybrid perovskite solar cells has high environmental requirements, and the absorber layer is easily caused by the environmental influence and decomposition, resulting in the degradation of device performance. The all-inorganic CsPbBr3 perovskite material has good stability, can be prepared directly in air, and is more economical, showing great potential applications. However, the PCE of all-inorganic CsPbBr3 perovskite solar cells is not high, and at this stage, there is still much room for exploring high-quality controllable preparation of CsPbBr3 films. In this paper, we aim to prepare efficient and stable CsPbBr3 perovskite solar cells with additive engineering. Polymer is one of the most effective additives in perovskite solar cells. The use of polymer additive in perovskite layer can improve the shape-form, structure, and band gap of the film, thus improving the quality of perovskite film. Polyvinylidene fluoride (PVDF) is a cheap polymer with hydrophobic F ions and long flexible polymer chains, and can be used to prepare efficient and stable perovskite solar cells. In this paper, CsPbBr3 perovskite films are prepared by multi-part spin-coating method. PVDF with enriched hydrophobic F is added into the PbBr2 precursor solution as an additive to adjust the crystalline quality of the perovskite film, and the effects of PVDF on the growth process and device performance of the perovskite film are systematically studied. The results show that the PVDF can be used as a template to promote the growth of perovskite crystals, improve the crystal structure and film shape, thus reducing the defect density and charge recombination, and increasing the PCE of the device to 8.17%. The original efficiency of more than 90% can be maintained after 1400 h of storage under unencapsulated condition. Finally, high-efficiency, stable and low-cost CsPbBr3 perovskite solar cells are obtained, which is important in further expanding the optimized design ideas of CsPbBr3 perovskite solar cells. The PVDF can form hydrogen bonds with perovskite or interact with lead ions to improve the structural stability of perovskite, and the F ions in PVDF can improve the moisture stability of perovskite layers. -
Keywords:
- CsPbBr3 /
- polyvinylidene fluoride /
- addictive /
- perovskite solar cells
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图 1 CsPbBr3薄膜的制备工艺图
Figure 1. Fabrication process of CsPbBr3 film.
图 2 不同浓度PVDF处理的PbBr2薄膜的SEM图像 (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL
Figure 2. SEM images of PbBr2 films treated with different PVDF concentration: (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL.
图 3 不同浓度PVDF处理的CsPbBr3薄膜的SEM图像 (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL
Figure 3. SEM images of CsPbBr3 films treated with different PVDF concentration: (a) 0 mg/mL; (b) 0.3 mg/mL; (c) 0.5 mg/mL; (d) 1.0 mg/mL.
图 4 PVDF处理前后CsPbBr3薄膜的AFM图像 (a) 控制组; (b) 0.5 mg/mL PVDF
Figure 4. AFM images of CsPbBr3 films before and after PVDF treatment: (a) Control; (b) 0.5 mg/mL PVDF.
图 5 PVDF不同添加量所制备的CsPbBr3薄膜的XRD图谱
Figure 5. XRD patterns of CsPbBr3 films prepared with different amounts of PVDF.
图 6 PVDF不同添加量所制备的CsPbBr3薄膜 (a) XPS全谱图; (b)—(d)分别对应Cs 3d, Pb 4f及Br 3d的高分辨率XPS图谱
Figure 6. XPS spectra of CsPbBr3 films prepared with different amounts of PVDF: (a) XPS full spectrum; (b)–(d) correspond to the high-resolution XPS spectra of Cs 3d, Pb 4f and Br 3d, respectively.
图 7 控制组和0.5 mg PVDF处理的CsPbBr3薄膜的FTIR光谱
Figure 7. FTIR spectra of control and 0.5 mg PVDF-treated perovskite films.
图 8 PVDF处理前后CsPbBr3薄膜的水接触角θca (a) 控制组, θca = 57.30°; (b) 0.5 mg PVDF, θca = 66.31°
Figure 8. Water contact angle θca of CsPbBr3 films before and after PVDF treatment: (a) Control, θca = 57.30°; (b) 0.5 mg PVDF, θca = 66.31°.
图 9 PVDF制备CsPbBr3钙钛矿晶体 (a) 生长过程; (b) 作用机理; (c) 器件结构示意图
Figure 9. CsPbBr3 perovskite crystal prepared by PVDF: (a) Schematic growth process; (b) mechanism of action; (c) structural schematic of the device.
图 10 PVDF不同添加量所制备的CsPbBr3薄膜 (a) UV-vis光谱图; (b) 稳态PL光谱图
Figure 10. CsPbBr3 films prepared with different amounts of PVDF: (a) UV-vis spectra; (b) steady-state PL spectra.
图 11 PVDF不同添加量所制备的CsPbBr3 PSCs的J-V曲线图
Figure 11. J-V curves of CsPbBr3 PSCs prepared with different amounts of PVDF.
图 12 PVDF不同添加量所制备的CsPbBr3-PSCs的各特性的箱试图(每组准备了26个电池装置) (a) FF; (b) VOC; (c) Jsc; (d) PCE
Figure 12. Box attempts of different characteristics for CsPbBr3 PSCs prepared with different amounts of PVDF (26 cell devices were prepared for each group): (a) FF; (b) VOC; (c) Jsc; (d) PCE.
图 13 PVDF不同添加量所制备的CsPbBr3 PSCs的瞬态VOC测量光谱
Figure 13. Transient VOC spectrogram of CsPbBr3 PSCs prepared with different amounts of PVDF.
图 14 PVDF不同添加量所制备的CsPbBr3-PSCs在空气中的稳定性
Figure 14. Stability of CsPbBr3-PSCs prepared with different amounts of PVDF in air.
表 1 PVDF不同添加量所制备的CsPbBr3 PSCs的光伏参数
Table 1. Photovoltaic parameters of CsPbBr3 PSCs prepared with different amounts of PVDF.
器件薄膜类型 开路电压
VOC/V短路电流
Jsc/(mA·cm–2)光电转换效
率PCE/%填充因子
FF/%Control 1.34 6.77 6.81 75 0.3 mg PVDF 1.36 7.03 7.12 74 0.5 mg PVDF 1.31 8.26 8.17 76 1.0 mg PVDF 1.33 7.39 7.40 75 
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[1] Wang D, Li W J, Du Z B, Li G D, Sun W H, Wu J H, Lan Z 2020 ACS Appl. Mater. Interfaces 12 10579
Google Scholar
[2] Liu G C, Liu Z H, Wang L, Xie X Y 2021 Chem. Phys. 542 111061
Google Scholar
[3] Jin I S, Park S H, Kim K S, Jung J W 2020 J. Alloys Compd. 847 156512
Google Scholar
[4] Wan X J, Yu Z, Tian W M, Huang F Z, Jin S Y, Yang X C, Cheng Y B, Hagfeldt A, Sun L C 2020 J. Energy Chem. 46 8
Google Scholar
[5] Fu Y J, Sun Y P, Tang H, Wang L Y, Yu H Z, Cao D R 2021 Dye. Pigment. 191 109339
Google Scholar
[6] Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050
Google Scholar
[7] Huo X N, Wang K X, Yin R, Sun W W, Sun Y S, Gao Y K, You T T, Yin P G 2022 Sol. Energy Mater. Sol. Cells 247 111963
Google Scholar
[8] Zhu J W, He B L, Gong Z K, Ding Y, Zhang W Y, Li X K, Zong Z H, Chen H Y, Tang Q W 2020 ChemSusChem 13 1834
Google Scholar
[9] Ma J J, Li Y H, Li J, Qin M C, Wu X, Lv Z Y, Hsu Y J, Lu X H, Wu Y C, Fang G J 2020 Nano Energy 75 104933
Google Scholar
[10] Yu J X, Liu G X, Chen C M, Li Y, Xu M R, Wang T L, Zhao G, Zhang L 2020 J. Mater. Chem. C 8 6326
Google Scholar
[11] Liu X Y, Liu Z Y, Tan X H, Ye H B, Sun B, Xi S, Shi T L, Tang Z R, Liao G L 2019 J. Power Sources 439 227092
Google Scholar
[12] Su G D, He B L, Gong Z K, Ding Y, Duan J L, Zhao Y Y, Chen H Y, Tang Q W 2019 Electrochim. Acta 328 135102
Google Scholar
[13] Duan J L, Zhao Y Y, He B L, Tang Q W 2018 Angew. Chemie Int. Ed. 130 3787
Google Scholar
[14] Duan J L, Zhao Y Y, Yang X Y, Wang Y D, He B L, Tang Q W 2018 Adv. Energy Mater. 8 1802346
[15] Wang K, Jin Z W, Liang L, Bian H, Bai D L, Wang H R, Zhang J R, Wang Q, Liu S Z 2018 Nat. Commun. 9 4395
Google Scholar
[16] Lin Y H, Sakai N, Da P, Wu J, Sansom H C, Ramadan A J, Mahesh S, Liu J, Oliver R D J, Lim J, Aspitarte L, Sharma K, Madhu P K, Morales-Vilches A B, Nayak P K, Bai S, Gao F, Grovenor C R M, Johnston M B, Labram J G, Durrant J R, Ball J M, Wenger B, Stannowski B, Snaith H J 2020 Sciences 369 96
Google Scholar
[17] Zhu H W, Liu Y H, Eickemeyer F T, Pan L F, Ren D, Ruiz-Preciado M A, Carlsen B, Yang B W, Dong X F, Wang Z W, Liu H L, Wang S R, Zakeeruddin S M, Hagfeldt A, Dar M I, Li X G, Grätzel M 2020 Adv. Mater. 32 1907757
Google Scholar
[18] Zhao Y P, Zhu P C, Wang M H, Huang S, Zhao Z P, Tan S, Han T H, Lee J W, Huang T Y, Wang R, Xue J J, Meng D, Huang Y, Marian J, Zhu J, Yang Y 2020 Adv. Mater. 32 1907769
Google Scholar
[19] Zheng H Y, Xu X X, Xu S D, Liu G Z, Chen S H, Zhang X X, Chen T W, Pan X 2019 J. Mater. Chem. C 7 4441
Google Scholar
[20] Xiang W C, Chen Q, Wang Y Y, Liu M J, Huang F Z, Bu T L, Wang T S, Cheng Y B, Gong X, Zhong J, Liu P, Yao X, Zhao X J 2017 J. Mater. Chem. A 5 5486
Google Scholar
[21] Chen C, Wang X, Li Z P, Du X F, Shao Z P, Sun X H, Liu D C, Gao C Y, Hao L Z, Zhao Q Q, Zhang B Q, Cui G L, Pang S P 2022 Angew. Chemie Int. Ed. 61 e202113932
Google Scholar
[22] Chang C Y, Chu C Y, Huang Y C, Huang C W, Chang S Y, Chen C A, Chao C Y, Su W F 2015 ACS Appl. Mater. Interfaces 7 4955
Google Scholar
[23] Qi Y, Qu J, Moore J, Gollinger K, Shrestha N, Zhao Y, Pradhan N, Tang J, Dai Q 2022 Org. Electron. 104 106487
Google Scholar
[24] Bi D Q, Yi C Y, Luo J S, Décoppet J D, Zhang F, Zakeeruddin S M, Li X, Hagfeldt A, Grätzel M 2016 Nat. Energy 1 317
Google Scholar
[25] Santhosh N, Daniel R I, Acchutharaman K R, Pandian M S, Ramasamy P 2022 Mater. Today Commun. 31 103446
Google Scholar
[26] Zheng H Y, Liu G Z, Wu W W, Xu H F, Pan X 2021 J. Energy Chem. 57 593
Google Scholar
[27] Cao X B, Zhang G S, Jiang L, Cai Y F, Wang Y, He X, Zeng Q G, Chen J Z, Jia Y, Wei J Q 2021 Green Chem. 23 2104
Google Scholar
[28] Gao B, Meng J 2020 Sol. Energy 211 1223
Google Scholar
[29] Paek S, Schouwink P, Athanasopoulou E N, Cho K T, Grancini G, Lee Y, Zhang Y, Stellacci F, Nazeeruddin M K, Gao P 2017 Chem. Mater. 29 3490
Google Scholar
[30] Zhang Y, Zhuang X H, Zhou K, Cai C, Hu Z Y, Zhang J, Zhu Y J 2017 J. Mater. Chem. C 5 9037
Google Scholar
[31] Chu Z D, Yang M J, Schulz P, Wu D, Ma X, Seifert E, Sun L Y, Li X Q, Zhu K, Lai K J 2017 Nat. Commun. 8 2230
Google Scholar
[32] Lau C F J, Deng X F, Zheng J H, Kim J C, Zhang Z L, Zhang M, Bing J M, Wilkinson B, Hu L, Patterson R, Huang S J, Ho-Baillie A 2018 J. Mater. Chem. A 6 5580
Google Scholar
[33] Luo J S, Jia C Y, Wan Z Q, Han F, Zhao B W, Wang R L 2017 J. Power Sources 342 886
Google Scholar
[34] Liu Z, Shi T, Tang Z, Sun B, Liao G 2016 Nanoscale 8 7017
Google Scholar
[35] Chen H, Liu T, Zhou P, Li S, Ren J, He H C, Wang J S, Wang N, Guo S J 2020 Adv. Mater. 32 1905661
Google Scholar
[36] Zhang P, Cao F R, Tian W, Li L 2022 Sci. China Mater. 65 321
Google Scholar
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