基于埋底界面修饰策略制备正式钙钛矿太阳电池

商文丽; 王立坤; 张晓春; 岳鑫; 李一锋; 万政慧; 杨华翼; 李婷; 王辉

doi:10.7498/aps.74.20241549

摘要

二氧化锡是正式钙钛矿太阳电池理想的电子传输层材料. 二氧化锡与钙钛矿之间的界面缺陷是制约钙钛矿太阳电池转换效率提高的关键因素. 因此, 本文提出了一种基于埋底界面修饰策略制备正式钙钛矿太阳电池的方法. 通过在二氧化锡中掺杂甲基溴化胺, 形成埋底界面, 减少了二氧化锡与钙钛矿之间的界面缺陷, 提升了二氧化锡的电子迁移率, 并促进高质量钙钛矿材料的生长, 制备的正式钙钛矿太阳电池转换效率达23.12%, 为制备高效正式钙钛矿太阳能电池提供了一种有效策略.

关键词:

Abstract

Normal (n-i-p) perovskite solar cells (PSCs) have received increasing attention due to their advantages such as high conversion efficiency and good stability. Tin dioxide is an ideal electron transport layer material for normal perovskite solar cells. Among various available electron transport layers, tin dioxide stands out because of its excellent stability, low density of defect states, and appropriate energy levels. The interface defects between tin dioxide and perovskite are the key factors restricting the improvement of the conversion efficiency in perovskite solar cells. Therefore, a method of fabricating normal perovskite solar cells based on the buried interface modification strategy is proposed in this work. By doping methylammonium bromide into tin dioxide to form a buried interface, the interface defects between tin dioxide and perovskite are reduced, the electron mobility of tin dioxide is enhanced, and the growth of high-quality perovskite materials is promoted. The conversion efficiency of the normal perovskite solar cells reaches 23.12%, providing an effective strategy for fabricating high-efficiency normal perovskite solar cells.

Keywords:

作者及机构信息

1.
辽宁师范大学物理与电子技术学院, 大连　116029

2.
西安电子科技大学微电子学院, 西安　710071

3.
中国科学院大连化学物理研究所, 大连　116023

4.
大连科技学院实验实训中心, 大连　116025

通信作者: 李婷, tingli430@lnnu.edu.cn ; 王辉, hwang1606@dicp.ac.cn

基金项目: 辽宁省科技厅博士启动基金(批准号: 2021-BS-200)资助的课题.

Authors and contacts

1.
School of Physics and Electronic Techonlogy, Liaoning Normal Unversity, Dalian 116029, China

2.
School of Microelectronics, Xidian University, Xi’an 710071, China

3.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

4.
Experimental Training Center, Dalian University of Science and Technology, Dalian 116025, China

Corresponding author: LI Ting, tingli430@lnnu.edu.cn ; WANG Hui, hwang1606@dicp.ac.cn

Funds: Project supported by the Doctor Foundation of Science and Technology Department of Liaoning Province, China (Grant No. 2021-BS-200).

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参考文献

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施引文献

图 1 SnO₂的XPS光谱　(a)未修饰样品(红线)和埋底界面修饰样品(蓝线)的Sn 3d; (b)未修饰样品(红线)和埋底界面修饰样品(蓝线)的O 1s; (c)未修饰样品Sn 3d的拟合光谱; (d)未修饰样品O 1s的拟合光谱; (e) 埋底界面修饰样品Sn 3d的拟合光谱; (f) 埋底界面修饰样品O 1s的拟合光谱

Fig. 1. XPS spectra of SnO₂: (a) Sn 3d for unmodified samples (red line) and buried interface modified samples (blue line); (b) O 1s for unmodified samples (red line) and buried interface modified samples (blue line); (c) fitting spectra of Sn 3d for unmodified samples; (d) fitting spectra of O 1s for unmodified samples; (e) fitting spectra of Sn 3d for buried interface modified samples; (f) fitting spectra of O 1s for buried interface modified samples.

下载: 全尺寸图片幻灯片

图 2 (a) SnO₂薄膜的电子迁移率; (b) 未修饰样品(红线)和埋底界面修饰样品(蓝线) SnO₂的透过率光谱

Fig. 2. (a) Electron mobility of SnO₂ films; (b) transmission spectra of SnO₂ for unmodified samples (red line) and buried interface modified samples (blue line).

下载: 全尺寸图片幻灯片

图 3 SnO₂薄膜的SEM图　(a)未修饰样品, (b)埋底界面修饰样品; SnO₂薄膜的AFM图　(c)未修饰样品, (d)埋底界面修饰样品; SnO₂薄膜的水接触角图　(e)未修饰样品, (f)埋底界面修饰样品

Fig. 3. SEM images of SnO₂ films for (a) unmodified samples, (b) buried interface modified samples; AFM images of SnO₂ films for (c) unmodified samples, (d) buried interface modified samples; water contact angle images of SnO₂ films for (e) unmodified samples, (f) buried interface modified samples.

下载: 全尺寸图片幻灯片

图 4 钙钛矿薄膜的SEM图　(a)未修饰样品; (b)埋底界面修饰样品; (c)钙钛矿薄膜晶粒尺寸数量分布柱状图

Fig. 4. SEM images of perovskite films: (a) Unmodified samples; (b) buried interface modified samples; (c) histogram of grain size distribution in perovskite thin films.

下载: 全尺寸图片幻灯片

图 5 钙钛矿薄膜的AFM图, 其中(a)未修饰样品, (b)埋底界面修饰样品; 钙钛矿薄膜的水接触角图, 其中(c)未修饰样品, (d)埋底界面修饰样品

Fig. 5. AFM images of perovskite films for (a) unmodified samples, (b) buried interface modified samples; water contact angle images of perovskite thin films for (c) unmodified samples, (d) buried interface modified samples.

下载: 全尺寸图片幻灯片

图 6 未修饰样品(红线)和埋底界面修饰样品(蓝线)的XRD图和(001)晶相的放大图

Fig. 6. XRD patterns of unmodified samples (red line), buried interface modified samples (blue line), and enlarged images of the (001) crystal phase.

下载: 全尺寸图片幻灯片

图 7 钙钛矿薄膜的(a) PL图谱和(b) TRPL图谱, 其中红线为未修饰样品, 蓝线为埋底界面修饰样品

Fig. 7. (a) PL spectra and (b) TRPL spectra of unmodified samples (red line) and buried interface modified samples (blue line).

下载: 全尺寸图片幻灯片

图 8 未修饰样品(红线)和埋底界面修饰样品(蓝线)的SCLC曲线

Fig. 8. SCLC curves of unmodified samples (red line) and buried interface modified samples (blue line).

下载: 全尺寸图片幻灯片

图 9 钙钛矿电池　(a) 正向和反向扫描的J-V曲线; (b) PCE箱线图; (c) V_OC箱线图; (d) J_SC箱线图; (e) FF箱线图; (f) V_OC随光强变化曲线图; (g) EQE曲线图; (h) 莫特-肖特基曲线

Fig. 9. Perovskite solar cells: (a) J-V curves for forward and reverse scans; (b) box plot of PCE; (c) box plot of V_OC; (d) box plot of J_SC; (e) box plot of FF; (f) curves of V_OC varying with light intensity; (g) EQE curves; (h) Mott-Schottky curves.

下载: 全尺寸图片幻灯片

表 1 未修饰样品钙钛矿薄膜; 埋底界面修饰样品的钙钛矿薄膜的TRPL光谱拟合参数

Table 1. TRPL spectral fitting parameters for unmodified perovskite film samples and buried interface modified perovskite film samples.

	$ \tau $₁/ns	A₁	$ \tau $₂/ns	A₂	T_average/ns
Glass/FTO/SnO₂/PVK	20.83	430.0	229.93	1.31	27.63
Glass/FTO/SnO₂+MABr/PVK	16.62	3165.42	243.48	1.24	17.91

下载: 导出CSV

表 2 钙钛矿太阳能电池参数

Table 2. Parameters of Perovskite Solar Cells.

Devices		V_OC/V	J_sc/(mA·cm^–2)	FF/%	PCE/%
glass/FTO/SnO₂/PVK/Spiro-OMeTAD/Au	Forward	1.09	25.67	63.88	17.70
glass/FTO/SnO₂/PVK/Spiro-OMeTAD/Au	Reverse	1.11	25.96	75.08	21.57
glass/FTO/SnO₂+MABr/PVK/Spiro-OMeTAD/Au	Forward	1.12	25.84	77.78	22.56
glass/FTO/SnO₂+MABr/PVK/Spiro-OMeTAD/Au	Reverse	1.12	25.80	79.90	23.12

下载: 导出CSV

[1]	Zhang Y Q, Liu X T, Li P W, Duan Y Y, Hu X T, Li F Y, Song Y L 2019 Nano Energy 56 733 Google Scholar
[2]	Liang C, Li P W, Zhang Y Q, Gu H, Cai Q B, Liu X T, Wang J F, Wen H, Shao G S 2017 J. Power Sources 372 235 Google Scholar
[3]	Yang S M, Wen J L, Liu Z K, Che Y H, Xu J, Wang J G, Xu D F, Yuan N Y, Ding J N, Duan Y W, Liu S Z 2021 Adv. Energy Mater. 12 2103019 Google Scholar
[4]	Bu T L, Li J, Zheng F, Chen W J, Wen X M, Ku Z L, Peng Y, Zhong J, Cheng Y B, Huang F Z 2018 Nat. Commun. 9 4609 Google Scholar
[5]	You S, Zeng H P, Ku Z L, Wang X Z, Wang Z, Rong Y G, Zhao Y, Zheng X, Luo L, Li L, Zhang S J, Li M, Gao X Y, Li X 2020 Adv. Mater. 32 2003990 Google Scholar
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[7]	Yang Y G, Lu H Z, Feng S L, Yang L F, Dong H, Wang J O, Tian C, Li L N, Lu H L, Jeong J, Zakeeruddin S M, Liu Y H, Grätzel M, Hagfeldt A 2021 Energy Environ. Sci. 14 3447 Google Scholar
[8]	Jiang Q, Zhao Y, Zhang X W, Yang X L, Chen Y, Chu Z M, Ye Q F, Li X X, Yin Z X, You J B 2019 Nat. Photonics 13 460 Google Scholar
[9]	Lou Q, Han Y F, Liu C, Zheng K H, Zhang J S, Chen X, Du Q, Chen C, Ge Z Y 2021 Adv. Energy Mater. 11 2101416 Google Scholar
[10]	Zhang Z A, Jiang J K, Liu X, Wang X, Wang L Y, Qiu Y K, Zhang Z F, Zheng Y T, Wu X Y, Liang J H, Tian C C, Chen C C, 2021 Small 18 2105184 Google Scholar
[11]	Liu Z Z, Deng K M, Hu J, Li L 2019 Angew. Chem. Int. Ed. 58 11497 Google Scholar
[12]	Jung E H, Chen B, Bertens K, Vafaie M, Teale S, Proppe A, Hou Y, Zhu T, Zheng C, Sargent E H 2020 ACS Energy Lett. 5 2796 Google Scholar
[13]	Parida B, Jin I S, Jung J W 2021 Chem. Mater. 33 5850 Google Scholar
[14]	Park S Y, Zhu K 2022 Adv. Mater. 34 2110438 Google Scholar
[15]	Yu Z H, Yang Z B, Ni Z Y, Shao Y C, Chen B, Lin Y Z, Wei H T, Yu Z J, Holman Z, Huang J S 2020 Nat. Energy 5 657 Google Scholar
[16]	Yang L, Feng J S, Liu Z K, Duan Y W, Zhan S, Yang S M, He K, Li Y, Zhou Y W, Yuan N Y, Ding J N, Liu S Z 2022 Adv. Mater. 34 2201681 Google Scholar
[17]	Osman M B S, Dessouky A Z M T, Kenawy M A, El-Sharkawy A A 1996 J. Therm. Anal. 46 1697 Google Scholar
[18]	Yu H, Yeom H I, Lee J W, Lee K, Hwang D, Yun J, Ryu J, Lee J, Bae S, Kim S K, Jang J 2018 Adv. Mater. 30 1704825 Google Scholar
[19]	Yang D, Zhou X, Yang R X, Yang Z, Yu W, Wang X L, Li C, Liu S Z, Chang R P H 2016 Energy Environ. Sci. 9 3071 Google Scholar
[20]	Kim M, Jeong J, Lu H Z, Lee T K, Eickemeyer F T, Liu Y H, Choi I W, Choi S J, Jo Y, Kim H B, Mo S I, Kim Y K, Lee H, An N G, Cho S, Tress W R, Zakeeruddin S M, Hagfeldt A, Kim J Y, Grätzel M, Kim D S 2022 Science 375 302 Google Scholar
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[22]	Chen Z L, Dong Q F, Liu Y, Bao C X, Fang Y J, Lin Y, Tang S, Wang Q, Xiao X, Bai Y, Deng Y H, Huang J S 2017 Nat. Commun. 8 1890 Google Scholar
[23]	Wang H Y, Xu H J, Wu S H, Wang Y, Wang Y, Wang X H, Liu X D, Huang P 2023 Chem. Eng. J. 476 146587 Google Scholar
[24]	Li Y, Zheng J L, Chen X L, Sun C, Jiang H, Li G R, Zhang X Y 2021 J. Alloys Compd. 886 161300 Google Scholar
[25]	Yang S M, Liu W D, Han Y, Liu Z K, Zhao W J, Duan C Y, Che Y H, Gu H S, Li Y B, Liu S Z 2020 Adv. Energy Mater. 10 2002882 Google Scholar
[26]	Li Z, Sun X L, Zheng X P, Li B, Gao D P, Zhang S F, Wu X W, Li S, Gong J Q, Luther J M , Li Z A, Zhu Z L 2023 Science 382 284 Google Scholar
[27]	Ji X F, Bi L Y, Fu Q, Li B L, Wang J W, Jeong S Y, Feng K, Ma S X, Liao Q G, Lin F R, Woo H Y, Lu L F, Jen A K Y, Guo X G 2023 Adv. Mater. 35 2303665 Google Scholar
[28]	Heo J, Lee S W, Yong J, Park H, Lee Y K, Shin J, Whang D R, Chang D W, Park H J 2023 Chem. Eng. J. 474 145632 Google Scholar

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