采用PEABr添加剂获得高效且稳定的碳基CsPbBr<sub>3</sub>太阳能电池

仲婷婷; 张晨; 哈木; 徐望舒; 唐坤鹏; 徐翔; 孙文天; 郝会颖; 董敬敬; 刘昊; 邢杰

doi:10.7498/aps.71.20211344

摘要

全无机CsPbBr₃钙钛矿材料因其本征稳定性好、成本低廉从而在光伏领域展现出巨大的应用潜力, 但目前CsPbBr₃太阳能电池的光电转换效率仍远低于其他体系的钙钛矿太阳能电池. 本文以无空穴传输层结构的碳基CsPbBr₃全无机钙钛矿电池作为研究对象, 以多步旋涂法为基础, 通过在PbBr₂(DMF)溶液中添加2-苯乙胺溴盐(PEABr)来调控CsPbBr₃薄膜的结晶质量, 降低薄膜缺陷态密度, 钝化晶粒间界, 并对其中的关键工艺参数包括CsBr的用量(旋涂次数)、旋涂PbBr₂薄膜时的衬底预热温度以及退火温度进行了优化. 最终在大气环境下获得了兼具稳定和高效的无空穴传输层结构的碳基CsPbBr₃太阳能电池, 器件的光电转换效率达到8.25%, 并在无封装条件下保存1500 h仍可保持90%以上的效率, 对于进一步拓展CsPbBr₃钙钛矿电池的优化设计思路具有重要意义.

关键词:

Abstract

In recent years, organic-inorganic hybrid perovskite solar cells have become a research hotspot in the photovoltaic field because of their excellent power conversion efficiency. However, this hybrid perovskite material's intrinsic instability and the harsh preparation environment limit its further commercial application. All-inorganic CsPbBr₃ perovskite materials have attracted much attention because of their good stability, low cost and can be prepared in an atmospheric environment, showing great application potential. The controllable preparation and growth kinetics of CsPbBr₃ materials need to be further studied, and the conversion efficiency of photovoltaic devices is still low. Considering the instability caused by traditional organic hole transport materials and their high preparation cost, this work focuses on the systematical studies of CsPbBr₃ all-inorganic perovskite cells without a hole transport layer. Growth kinetics material of CsPbBr₃ is controlled by adding 2-phenylethylamine bromide to precursor solution_. The main research contents and results are described as follows.Based on multi-step spin-coating preparation of CsPbBr₃ perovskite films, the perovskite cell preparation method is studied, and the critical process parameters including the spin-coating PbBr₂, amount and number of spin-coating of CsBr, substrate preheating temperature, and the annealing temperature, are optimized. The optimization tests show that the optimal spin-coating of CsBr is obtained by being optimized five times and the spin-coating PbBr₂ is conducted in the atmospheric environment. The optimal preheating temperature of the substrate is 80 ℃, and the optimal annealing temperature is 100 ℃. The perovskite films prepared under this condition are compact, each with a continuous high phase purity and good crystallization performance.The PbBr₂ in DMF is first adopted and the 2-phenylethylamine bromide (PEABr) solution is added to regulate the CsPbBr₃ crystalline quality of the film. The effects of PEABr on the perovskite crystallization process and device performance are systematically investigated. The results show that the introduction of PEABr can effectively optimize the CsPbBr₃. The crystalline properties of the two-dimensional perovskite materials can improve the grain boundaries and improve their transport properties. The prepared perovskite solar cell with PEABr shows the highest power conversion efficiency of 8.25%, and it can maintain the efficiency of more than 90% when being stored for 1500 h under the condition of no encapsulation. Finally, stable, efficient and low-cost all-inorganic CsPbBr₃ solar cells without a hole layer are obtained.

Keywords:

作者及机构信息

中国地质大学(北京)数理学院, 北京　100083

通信作者: 郝会颖, huiyinghaoL@cugb.edu.cn ; 董敬敬, jjdong@cugb.edu.cn ;

基金项目: 中国科学院半导体研究所半导体材料科学重点实验室开放基金(批准号: KLSMS-1901)和国家自然科学基金(批准号: 21875223)资助的课题

Authors and contacts

School of Science, China University of Geosciences (Beijing), Beijing 100083, China

Corresponding author: Hao Hui-Ying, huiyinghaoL@cugb.edu.cn ; Dong Jing-Jing, jjdong@cugb.edu.cn ;

Funds: Project supported by the Open Fund Project of Key Laboratory of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy of Sciences (Grant No. KLSMS-1901) and the National Natural Science Foundation of China (Grant No. 21875223)

文章全文 : translate this paragraph

参考文献

[1]	Liao C S, Yu Z L, He P B, Liu B, Zeng R, Wan Q, Cai M Q 2021 J. Colloid Interface Sci. 597 233 Google Scholar
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施引文献

图 1 多步旋涂法制备FTO/TiO₂/CsPbBr₃/carbon结构电池流程图

Fig. 1. Schematic illustration of FTO/TiO₂/CsPbBr₃/carbon structure cells prepared by multi-step spin-coating method.

下载: 全尺寸图片幻灯片

图 2 旋涂不同CsBr次数所制备的CsPbBr₃薄膜的XRD图谱

Fig. 2. XRD patterns of CsPbBr₃ films prepared by spin-coating different times of CsBr.

下载: 全尺寸图片幻灯片

图 3 旋涂不同CsBr次数所制备的CsPbBr₃薄膜的SEM图　(a) 4层; (b) 5层; (c) 6层; (d) 7层

Fig. 3. SEM images of CsPbBr₃ films prepared by spin-coating different times of CsBr: (a) 4 layers; (b) 5 layers; (c) 6 layers; (d) 7 layers.

下载: 全尺寸图片幻灯片

图 4 旋涂不同CsBr次数所制备太阳能电池的J-V曲线

Fig. 4. J-V curves of solar cells prepared by spin-coating different times of CsBr.

下载: 全尺寸图片幻灯片

图 5 在衬底不同预热温度下制备的钙钛矿薄膜SEM图　(a) 不预热; (b) 70 ℃; (c) 80 ℃; (d) 90 ℃

Fig. 5. SEM images of perovskite films prepared at different preheating temperatures of the substrate: (a) Without preheating; (b) 70 °C; (c) 80 °C; (d) 90 °C.

下载: 全尺寸图片幻灯片

图 6 在衬底不同预热温度下制备的钙钛矿电池的J-V曲线

Fig. 6. J-V curves of solar cells prepared at different preheating temperatures of the substrate.

下载: 全尺寸图片幻灯片

图 7 PbBr₂层不同退火温度所制备的CsPbBr₃薄膜的XRD图谱

Fig. 7. XRD patterns of CsPbBr₃ films prepared by PbBr₂ layer at different annealing temperatures.

下载: 全尺寸图片幻灯片

图 8 PbBr₂层不同退火温度所制备的CsPbBr₃薄膜的AFM图　(a) 90 ℃; (b) 100 ℃; (c) 110 ℃

Fig. 8. AFM diagram of CsPbBr₃ films prepared by PbBr₂ layer at different annealing temperatures: (a) 90 ℃; (b) 100 ℃; (c) 110 ℃

下载: 全尺寸图片幻灯片

图 9 PbBr₂层不同退火温度所制备的CsPbBr₃太阳能电池的J-V曲线

Fig. 9. J-V curves of solar cells prepared by PbBr₂ layer at different annealing temperatures.

下载: 全尺寸图片幻灯片

图 10 PEABr不同添加量所制备的CsPbBr₃薄膜的XRD图谱

Fig. 10. XRD patterns of CsPbBr₃ films prepared with different amounts of PEABr.

下载: 全尺寸图片幻灯片

图 11 不同PEABr添加量在不同倍率下的SEM图　(a)—(c) 不添加; (d)—(f) 50 µL; (g)—(i) 100 µL; (j)—(l) 150 µL

Fig. 11. SEM images of different amounts of PEABr at different magnifications: (a)–(c) Without addition; (d)–(f) 50 µL; (g)–(i) 100 µL; (j)–(l) 150 µL.

下载: 全尺寸图片幻灯片

图 12 PEABr不同添加量所制备的CsPbBr₃的PL谱

Fig. 12. Photoluminescence spectrum of CsPbBr₃ prepared with different amounts of PEABr.

下载: 全尺寸图片幻灯片

图 13 PEABr不同添加量所制备电池的　(a) J-V曲线; (b) 空气中稳定性

Fig. 13. Images of solar cells prepared with different amounts of PEABr: (a) J-V curves; (b) stability in air.

下载: 全尺寸图片幻灯片

表 1 旋涂不同CsBr次数所制备太阳能电池的具体参数

Table 1. Parameters of solar cells prepared by spin-coating different times of CsBr.

旋涂次数 V_OC
/V J_SC
/(mA·cm^–2) PCE
/% FF
/%

4 0.85 5.0 2.37 55
5 1.06 5.8 3.58 58
6 1.10 5.6 3.41 55
7 0.99 5.4 3.16 59

下载: 导出CSV

表 2 在衬底不同预热温度下制备的钙钛矿电池的具体参数

Table 2. Parameters of solar cells prepared at different preheating temperatures of the substrate.

衬底温度 V_OC
/V J_SC
/(mA·cm^–2) PCE
/% FF
/%

不预热 1.13 5.6 3.6 56
70 ℃ 1.15 5.9 4.1 60
80 ℃ 1.15 6.2 4.7 65
90 ℃ 1.13 5.8 4.0 61

下载: 导出CSV

表 3 PbBr₂层不同退火温度所制备的太阳能电池的具体参数

Table 3. Parameters of solar cells prepared by PbBr₂ layer at different annealing temperatures.

退火温度/℃ V_OC
/V J_SC
/(mA·cm^–2) PCE
/% FF
/%

90 1.17 6.9 4.74 58
100 1.20 7.3 5.25 60
110 1.19 6.5 4.82 62

下载: 导出CSV

表 4 PEABr不同添加量所制备的CsPbBr₃电池的具体参数

Table 4. Parameters of solar cells prepared with different amounts of PEABr.

引入量
/(mg·mL^–1) V_OC
/V J_SC
/(mA·cm^–2) PCE
/% FF
/%

w/o 1.20 7.30 5.25 60
5 1.28 8.40 7.16 66
10 1.31 8.51 8.25 73
15 1.30 8.16 7.37 69

下载: 导出CSV

map

[1]	Liao C S, Yu Z L, He P B, Liu B, Zeng R, Wan Q, Cai M Q 2021 J. Colloid Interface Sci. 597 233 Google Scholar
[2]	Li Q H, Ding Y F, He P B, Zeng R, Wan Q, Cai M Q 2021 J. Phys. Chem. Lett. 12 3809 Google Scholar
[3]	Liao C S, Yu Z L, He P B, Zhao Y Q, Liu B, Cai M Q 2020 J. Power Sources 478 229078 Google Scholar
[4]	Yu Z L, Zhao Y Q, Wan Q, Liu B, Yang J L, Cai M Q 2020 J. Phys. Chem. C 124 23052 Google Scholar
[5]	Yu Z L, Zhao Y Q, He P B, Liu B, Yang J L, Cai M Q 2020 J. Phys. Condens. Matter 32 065002 Google Scholar
[6]	Lee M M, Teuscher J, Miyasaka T, Murakami T N, Snaith H J 2012 Science 338 643 Google Scholar
[7]	Jeong J, Kim M, Seo J, et al. 2021 Nature 592 381 Google Scholar
[8]	Shi L, Hao H, Dong J, Zhong T, Zhang C, Hao J, Xing J, Liu H 2019 Nanomaterials (Basel) 9 915 Google Scholar
[9]	Zhong T, Shi L, Hao H, Dong J, Tang K, Xu X, Hamukwaya S L, Liu H, Xing J 2021 ACS Sustainable Chem. Eng. 9 13010 Google Scholar
[10]	Park B W, Seok S I 2019 Adv. Mater. 31 e1805337 Google Scholar
[11]	Zhao Z, Gu F, Rao H, Ye S, Liu Z, Bian Z, Huang C 2019 Adv. Energy Mater. 9 1802671 Google Scholar
[12]	Wang P, Zhang X, Zhou Y, Jiang Q, Ye Q, Chu Z, Li X, Yang X, Yin Z, You J 2018 Nat. Commun. 9 2225 Google Scholar
[13]	Ding X, Cai M, Liu X, Ding Y, Liu X, Wu Y, Hayat T, Alsaedi A, Dai S 2019 ACS Appl. Mater. Interfaces 11 37720 Google Scholar
[14]	Qiu Z, Li N, Huang Z, Chen Q, Zhou H 2020 Small Methods 4 1900877 Google Scholar
[15]	Duan J, Wang Y, Yang X, Tang Q 2020 Angew. Chem. Int. Ed. 59 4391 Google Scholar
[16]	Yuan H, Zhao Y, Duan J, Wang Y, Yang X, Tang Q 2018 J. Mater. Chem. A 6 24324 Google Scholar
[17]	Wang H, Liu H, Li W, Zhu L, Chen H 2020 Nano Energy 77 105160 Google Scholar
[18]	Guo Z N, Chen S, Wang Z Z, Yang Z Y, Liu F, Xu Y H, Wang J H, Yi Y, Zhang H, Liao L, Chu P K, Yu X F 2017 Adv. Mater. 29 1703811 Google Scholar
[19]	Ku Z, Rong Y, Xu M, Liu T, Han H 2013 Sci. Rep. 3 3132 Google Scholar
[20]	Zhao F, Guo Y, Wang X, Tao J, Li Z, Zheng D, Jiang J, Hu Z, Chu J 2020 J. Alloys Compd. 842 155984 Google Scholar
[21]	Cao X, Zhang G, Cai Y, Jiang L, Chen Y, He X, Zeng Q, Jia Y, Xing G, Wei J 2020 Appl. Surf. Sci. 529 147119 Google Scholar
[22]	Gao B, Meng J 2020 Solar Energy 211 1223 Google Scholar
[23]	Xu C, Zhang Z, Hu Y, Sheng Y, Jiang P, Han H, Zhang J 2018 J. Energy Chem. 27 764 Google Scholar
[24]	Cao X, Zhang G, Jiang L, Cai Y, Wang Y, He X, Zeng Q, Chen J, Jia Y, Wei J 2021 Green Chem. 23 2104 Google Scholar
[25]	Duan J, Zhao Y, He B, Tang Q 2018 Angew. Chem. Int. Ed. 57 3787 Google Scholar
[26]	Ding J, Duan J, Guo C, Tang Q 2018 J. Mater. Chem. A 6 21999 Google Scholar
[27]	Li M H, Yeh H H, Chiang Y H, et al. 2018 Adv. Mater. 30 e1801401 Google Scholar
[28]	Chen B, Rudd P N, Yang S, Yuan Y, Huang J 2019 Chem. Soc. Rev. 48 3842 Google Scholar

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采用PEABr添加剂获得高效且稳定的碳基CsPbBr₃太阳能电池