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有机-无机杂化钙钛矿太阳能电池器件因其高效率受到广泛关注, 而界面问题是制备高效钙钛矿太阳能电池的关键问题之一. 本文研究了一种高效的乙二胺四乙酸(ethylene diamine tetraacetic acid, EDTA)/SnO2双层复合结构, 将超薄的EDTA层与ITO(锡-铟氧化物)电极接触, SnO2层与钙钛矿界面接触, 作为电子传输层(ETL)用于制备钙钛矿太阳能电池. 有趣的是, 复合ETL的顶部SnO2侧的表面形态可以通过调整下面的EDTA层来进行微调. 通过调整EDTA膜厚, 可以调控钙钛矿层结晶过程中的成核过程, 调节了电子传输层与钙钛矿层之间的载流子提取过程. 本文中制备的钙钛矿太阳能电池的回滞效应可以忽略, 并且经过第三方认证, 已经实现了20.2%的能量转换效率.Organic-inorganic hybrid perovskite solar cell devices have received wide attention because of their high efficiency, and interface problem is one of the key problems in the preparation of perovskite solar cells. An efficient double-layered ethylene diamine tetraacetic acid (EDTA)/SnO2 composite structure, the ultrathin EDTA layer in contact with ITO electrode and an SnO2 layer interfaced with the perovskite, is developed as an electron-transport layer (ETL) in the preparation of perovskite solar cells. It is interesting that the surface morphology of the top SnO2 side of the composite ETL can be finely adjusted by tuning the underneath EDTA layer. These control the nucleation process in crystallization of the perovskite layer and adjust carrier extraction process between the electron transport and perovskite layers. High performance perovskite solar cells having a certified power conversion efficiency of 20.2% with negligible hysteresis are achieved.
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Keywords:
- perovskite solar cells /
- interface modification /
- EDTA /
- crystallization
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Google Scholar
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图 1 使用不同EDTA排布方法制备的PSCs的J-V特性图
Fig. 1. J-V characteristics of PSCs with different arrangement mode of using EDTA.
图 2 在ITO电极上通过旋涂的方法制备EDTA/SnO2双层ETL的示意图
Fig. 2. A schematic diagram of the double-layered EDTA/SnO2 composite layer prepared via spin-coating of EDTA and SnO2 in sequence on top of an ITO electrode.
图 3 在不同EDTA溶液浓度的双层EDTA/SnO2复合ETL上制备的钙钛矿薄膜样品的SEM图像 (a) 无EDTA (b) 0.1 mg/mL (c) 0.15 mg/mL (d) 0.2 mg/mL (e) 0.3 mg/mL. (f)使用Image-Pro软件根据(a)—(e)进行计算得出的粒径分布
Fig. 3. SEM top surface images of perovskite film specimens fabricated on double-layered EDTA/SnO2 composite ETLs with different EDTA precursors: (a) No EDTA; (b) 0.1 mg/mL; (c) 0.15 mg/mL; (d) 0.2 mg/mL; (e) 0.3 mg/mL; (f) particle size distribution calculated according to (a)–(e) using Image-Pro software.
图 4 沉积在双层EDTA (mg/mL)/SnO2复合膜上钙钛矿样品的X射线衍射图, EDTA溶液浓度为0—0.3 mg/mL
Fig. 4. X-ray diffraction diagrams from perovskite specimens deposited on double-layered EDTA (mg/ml)/SnO2 composite films of varying EDTA concentration ranging from 0 to 0.3 mg/mL as indicated.
图 5 SnO2薄膜的AFM图像 (a)在ITO衬底上, 在有不同厚度的EDTA中间层的ITO/EDTA衬底上, 使用的EDTA溶液浓度分别为(b) 0.1, (c) 0.15, (d) 0.2以及(e) 0.3 mg/mL
Fig. 5. AFM images of SnO2 films on an ITO substrate (a) or a substrate having EDTA interlayer with a concentration of (b) 0.1, (c) 0.15, (d) 0.2, and (e) 0.3 mg/mL.
图 6 在使用不同浓度的EDTA前驱体溶液的EDTA/SnO2复合ETL上制备的钙钛矿薄膜的 (a)吸收光谱; (b) Tauc-Plot图分析光学带隙(Eg); (c)稳态PL光谱(479 nm激发); (d) TRPL光谱(800 nm监测)
Fig. 6. (a) Absorbance spectra, (b) Tauc plot to analyze optical band gap (Eg), (c) steady-state PL spectra (excited at 479 nm), and (d) TRPL spectra (excited at 479 nm and monitored at 800 nm) of perovskite films with different concentration of EDTA precursors.
图 7 使用不同厚度的EDTA中间层构成的EDTA/SnO2复合ETL的PSCs的性能 (a) J-V特性曲线; (b) EQE光谱; (c) 暗电流曲线以及(d) Device 0和3稳定在最大功率点处输出功率和光电流测量
Fig. 7. Performance of PSCs: (a) J-V characteristics under a standard solar illumination; (b) EQE spectra; (c) J-V characteristics under darkness measured from Device 0 to Device 4, and (d) Stabilized PCEs and J at the maximum power point measured from Device 0 and Device 3.
图 8 不同EDTA前驱体浓度的EDTA/SnO2复合ETL上制备的总计150个器件的VOC, JSC, FF, PCE的统计图
Fig. 8. Statistical graph of VOC, JSC, FF, and PCE of 150 cells prepared on EDTA/SnO2 composite ETLs with different concentration of EDTA precursor.
表 1 用不同方法使用EDTA制备ETL的器件的光伏参数表
Table 1. Photovoltaic parameters derived from J-V measurements of devices prepared with different ways of using EDTA.
(ITO)/ETL VOC/
VJSC/
(mA·cm–2)FF
/%PCE
/%SnO2 1.047 23.20 75.42 18.32 EDTA(0.2 mg/mL) 1.044 21.97 71.63 16.43 SnO2: EDTAa 1.077 23.07 76.67 19.05 SnO2/EDTA (0.2 mg/mL) 1.059 23.55 78.59 18.05 EDTA (0.2 mg/mL)/SnO2 1.068 23.65 81.37 20.55 a 溶液中SnO2∶EDTA质量比为133.5∶1. 
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表 2 EDTA/SnO2表面钙钛矿薄膜的结晶特性
Table 2. The crystallization of the perovskite films on top of the EDTA/SnO2 surface.
EDTA
concentration/
(mg·ML–1)Perovskite films SEM X-ray diffraction Grain size/
nm2θ at (100)/
(°)Intensity
at (100)∆L at (100)/
nm0 557 14.00 0.543 516 0.1 784 14.00 0.671 765 0.15 834 14.00 0.839 811 0.2 925 14.00 1.000 888 0.3 704 14.00 0.756 664
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表 3 由沉积在纯SnO2表面或EDTA/SnO2复合表面的钙钛矿薄膜的TRPL光谱的双指数拟合得到的衰减时间
Table 3. Decay times obtained by a biexponential fit of TRPL spectra from perovskite films deposited on a pure SnO2 surface or on EDTA/SnO2 composite surfaces.
EDTA
concentration/
(mg·mL–1)τ1/ns A1/% a τ2/ns A2/% a τavg/ns 0 48.7 70.2 745.4 29.8 652.3 0.1 38.3 78.1 710.9 21.9 602.4 0.15 36.8 78.1 484.4 21.9 389.0 0.2 33.8 81.3 465.5 18.7 361.9 0.3 35.3 80.9 659.6 19.1 544.6 aAi is the fraction of τi component.
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表 4 在标准太阳模拟光源下由J-V测量得到的PSCs详细光伏参数表
Table 4. Photovoltaic parameters derived from J-V measurements of devices prepared with different based on reverse and forward scans under standard illumination.
Devices Scan direction VOC/V JSC/
(mA·cm–2)FF/% PCE/% H-index/
%RP/Ω RS/
ΩDevice 0 RS 1.047 23.20 75.35 18.3 8.25 3757 3.64 (control) FS 1.052 23.03 69.32 16.79 Device 1 RS 1.062 23.42 77.53 19.28 6.95 4409 3.26 FS 1.047 23.12 74.12 17.94 Device 2 RS 1.068 23.61 79.60 20.07 3.99 4683 3.02 FS 1.063 23.41 77.42 19.27 Device 3 RS 1.068 23.65 81.37 20.55 2.53 5537 2.88 FS 1.064 23.48 80.18 20.03 Device 4 RS 1.057 23.60 78.49 19.58 6.69 5135 3.19 FS 1.051 23.22 74.88 18.27
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[1] Kojima A, Teshima K, Shirai Y, Miyasaka T 2009 J. Am. Chem. Soc. 131 6050
Google Scholar
[2] https://www.nrel.gov/pv/cell-efficiency.html [2022-2-14]
[3] Snaith H J, Abate A, Ball J M, Eperon G E, Leijtens T, Noel N K, Stranks S D, Wang J T-W, Wojciechowski K, Zhang W 2014 J. Phys. Chem. Lett. 5 1511
Google Scholar
[4] Kim H S, Jang I H, Ahn N, Choi M, Guerrero A, Bisquert J, Park N G 2015 J. Phys. Chem. Lett. 6 4633
Google Scholar
[5] Dong Q, Wang M, Zhang Q, Chen F, Zhang S, Bian J, Ma T, Wang L, Shi Y 2017 Nano Energy 38 358
Google Scholar
[6] Li W, Zhang W, Van Reenen S, Sutton R J, Fan J, Haghighirad A A, Johnston M B, Wang L, Snaith H J 2016 Energy Environ. Sci. 9 490
Google Scholar
[7] Yang J, Siempelkamp B D, Mosconi E, De Angelis F, Kelly T L 2015 Chem. Mater. 27 4229
Google Scholar
[8] Dong Q, Shi Y, Wang K, Li Y, Wang S, Zhang H, Xing Y, Du Y, Bai X, Ma T 2015 J. Phys. Chem. C 119 10212
[9] Jiang Q, Chu Z, Wang P, Yang X, Liu H, Wang Y, Yin Z, Wu J, Zhang X, You J 2017 Adv. Mater. 29 1703852
Google Scholar
[10] Sun M, Liang C, Zhang H, Ji C, Sun F, You F, Jing X, He Z 2018 J. Mater. Chem. A 6 24793
Google Scholar
[11] Jiang Q, Zhao Y, Zhang X, Yang X, Chen Y, Chu Z, Ye Q, Li X, Yin Z, You J 2019 Nat. Photonics 13 460
Google Scholar
[12] Jiang Q, Zhang L, Wang H, Yang X, Meng J, Liu H, Yin Z, Wu J, Zhang X, You J 2016 Nat. Energy 2 16177
[13] Yang G, Tao H, Qin P, Ke W, Fang G 2016 J. Mater. Chem. A 4 3970
Google Scholar
[14] Wang F, Zhang Y, Yang M, Du J, Xue L, Yang L, Fan L, Sui Y, Yang J, Zhang X 2019 Nano Energy 63 103825
Google Scholar
[15] Ke W, Xiao C, Wang C, Saparov B, Duan H S, Zhao D, Xiao Z, Schulz P, Harvey S P, Liao W, Meng W, Yu Y, Cimaroli A J, Jiang C-S, Zhu K, Al-Jassim M, Fang G, Mitzi D B, Yan Y 2016 Adv. Mater. 28 5214
Google Scholar
[16] Yang G, Wang C, Lei H, Zheng X, Qin P, Xiong L, Zhao X, Yan Y, Fang G 2017 J. Mater. Chem. A 5 1658
Google Scholar
[17] Ma J, Yang G, Qin M, Zheng X, Lei H, Chen C, Chen Z, Guo Y, Han H, Zhao X, Fang G 2017 Adv. Sci. 4 1700031
Google Scholar
[18] Li N, Niu X, Pei F, Liu H, Cao Y, Liu Y, Xie H, Gao Y, Chen Q, Mo F, Zhou H 2019 Sol. RRL 4 1900217
[19] Hafer E, Holzgrabe U, Kraus K, Adams K, Hook J M, Diehl B 2020 Magnetic Resonance in Chemistry 58 653
Google Scholar
[20] Li X, Liu X, Zhang W, Wang H-Q, Fang J 2017 Chem. Mater. 29 4176
Google Scholar
[21] Yang D, Yang R, Wang K, Wu C, Zhu X, Feng J, Ren X, Fang G, Priya S, Liu S 2018 Nat. Commun. 9 3239
Google Scholar
[22] Li X, Zhang W, Wang X, Wu Y, Gao F, Fang J 2015 J. Mater. Chem. A 3 504
Google Scholar
[23] Li X, Zhang W, Wang X, Gao F, Fang J 2014 ACS Appl. Mater. Interfaces 6 20569
Google Scholar
[24] Pham H T, Duong T, Rickard W D A, Kremer F, Weber K J, Wong-Leung J 2019 J. Phys. Chem. C 123 26718
Google Scholar
[25] Xie L Q, Chen L, Nan Z A, Lin H X, Wang T, Zhan D P, Yan J W, Mao B W, Tian Z Q 2017 J. Am. Chem. Soc. 139 3320
Google Scholar
[26] Turren-Cruz S-H, Hagfeldt A, Saliba M 2018 Science 362 449
Google Scholar
[27] Warren B E 1990 X-Ray Diffraction (Second Edition) (New York: Dover Publication)
[28] Guo Z, He Z, Sun M, Zhang H, Xu Y, Li X, Liang C, Jing X 2018 Polymer 153 398
Google Scholar
[29] Mitchell G R, Windle A H 1982 Polymer 23 1269
Google Scholar
[30] Zhao L, Li Q, Hou C-H, Li S, Yang X, Wu J, Zhang S, Hu Q, Wang Y, Zhang Y, Jiang Y, Jia S, Shyue J-J, Russell T P, Gong Q, Hu X, Zhu R 2022 J. Am. Chem. Soc. 144 1700
Google Scholar
[31] Tauc J 1968 Mater. Res. Bull. 3 37
Google Scholar
[32] Son D-Y, Lee J-W, Choi Y J, Jang I-H, Lee S, Yoo P J, Shin H, Ahn N, Choi M, Kim D, Park N-G 2016 Nat. Energy 1 16081
Google Scholar
[33] Kim M, Kim G-H, Lee T K, Choi I W, Choi H W, Jo Y, Yoon Y J, Kim J W, Lee J, Huh D, Lee H, Kwak S K, Kim J Y, Kim D S 2019 Joule 3 2179
Google Scholar
[34] Chen S, Wen X, Huang S, Huang F, Cheng Y-B, Green M, Ho-Baillie A 2017 Sol. RRL 1 1600001
Google Scholar
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