低剂量异辛酸亚锡调控两步法制备Sn-Pb混合钙钛矿太阳能电池

doi:10.15541/jim20240191

无机材料学报 ›› 2024, Vol. 39 ›› Issue (12): 1339-1347.DOI: 10.15541/jim20240191 CSTR: 32189.14.10.15541/jim20240191

所属专题：【能源环境】钙钛矿(202412)；【能源环境】太阳能电池(202412)

低剂量异辛酸亚锡调控两步法制备Sn-Pb混合钙钛矿太阳能电池

王煜¹^,²(), 熊浩², 黄孝坤³, 江琳沁²(), 吴波¹(), 黎健生³, 杨爱军³

1.福州大学先进制造学院, 晋江 362200
2.福建江夏学院钙钛矿绿色应用福建省高校重点实验室, 福州 350108
3.福建省计量科学研究院国家光伏产业计量测试中心, 福州 350003

收稿日期:2024-04-15 修回日期:2024-07-10 出版日期:2024-07-26 网络出版日期:2024-07-26
通讯作者: 江琳沁, 教授. E-mail: linqinjiang@fjjxu.edu.cn;
吴波, 教授. E-mail: wubo@fzu.edu.cn
作者简介:王煜(1999-), 男, 硕士研究生. E-mail: 719351445@qq.com
基金资助:
国家自然科学基金(52102158);福建省高校产学研联合创新科技计划(2023H6037);钙钛矿绿色应用福建省高校重点实验室开放基金(JXKFB202204)

Regulation of Low-dose Stannous Iso-octanoate for Two-step Prepared Sn-Pb Alloyed Perovskite Solar Cells

WANG Yu¹^,²(), XIONG Hao², HUANG Xiaokun³, JIANG Linqin²(), WU Bo¹(), LI Jiansheng³, YANG Aijun³

1. School of Advance Manufacturing, Fuzhou University, Jinjiang 362200, China
2. Key Laboratory of Green Perovskites Application of Fujian Province Universities, Fujian Jiangxia University, Fuzhou 350108, China
3. PV Metrology Institute, Fujian Metrology Institute, Fuzhou 350003, China

Received:2024-04-15 Revised:2024-07-10 Published:2024-07-26 Online:2024-07-26
Contact: JIANG Linqin, professor. E-mail: linqinjiang@fjjxu.edu.cn;
WU Bo, professor, E-mail: wubo@fzu.edu.cn
About author:WANG Yu (1999-), male, Master candidate. E-mail: 719351445@qq.com
Supported by:
National Natural Science Foundation of China(52102158);University-Industry-Research Joint Innovation Project(2023H6037);Key Laboratory of Green Perovskites Application of Fujian Provincial Universities, Fujian Jiangxia University(JXKFB202204)

摘要/Abstract

摘要：

锡铅(Sn-Pb)混合钙钛矿在制备过程中常使用大量的氟化亚锡(SnF₂)添加剂来抑制Sn²⁺离子的氧化, 然而SnF₂过量会影响薄膜质量、器件的光电转化效率(PCE)和稳定性。因此, 开发低剂量的新型抗氧化剂对于实现高性能Sn-Pb混合钙钛矿电池至关重要。本研究采用两步法制备Sn-Pb混合钙钛矿薄膜, 在第一步中引入较低剂量的异辛酸亚锡(SnOct₂)替代SnF₂来抑制Sn²⁺的氧化。研究表明该添加剂可提高薄膜的结晶质量, 使得薄膜平均晶粒尺寸达到850 nm, 并且晶界数量减少。添加SnOct₂的薄膜在手套箱存放7 d后仍含有93.5%的Sn²⁺, 且由于SnOct₂具有优异的抗氧化性, 使得添加SnOct₂后器件的陷阱态密度更低, 从7.20×10¹⁵ cm^-3降低到4.74×10¹⁵ cm^-3, 抑制了非辐射复合。除此之外, SnOct₂还改善了钙钛矿薄膜的表面能级。最终, 添加0.030 mmol SnOct₂的Sn-Pb混合钙钛矿电池的PCE达到17.25%, 较添加0.10 mmol SnF₂的器件(11.63%)有显著提高; 且在氮气中保存50 d后, PCE仍保存其初始值的70%以上。

关键词: 锡铅混合钙钛矿, 太阳能电池, 添加剂工程, 两步法, 稳定性

Abstract:

In the preparation of Sn-Pb alloyed perovskite, a large amount of stannous fluoride (SnF₂) additive is often employed to inhibit the oxidation of Sn²⁺ ions. However, excessive SnF₂ deteriorates quality of the film, photoelectric conversion efficiency (PCE) and stability of the device. Therefore, the development of new antioxidants at low doses is essential to achieve high-performance Sn-Pb alloyed perovskite solar cells. In this study, a two-step process was used to prepare Sn-Pb alloyed perovskite film. In the first step, low-dose stannous iso-octanoate (SnOct₂) was introduced to replace SnF₂to inhibit the oxidation of Sn²⁺. This study showed that the additive could improve the crystallization quality of the film, and the average grain size of the film with SnOct₂ could reach 850 nm while the amount of grain boundaries was reduced. The film with the addition of SnOct₂ still contained 93.5% Sn²⁺ after storage for 7 d in the glove box. And due to the excellent oxidation resistance of SnOct₂, the device with the additional SnOct₂ had a lower defect state density, which was reduced from 7.20×10¹⁵ to 4.74×10¹⁵cm^-3, inhibiting the non-radiative recombination. In addition, SnOct₂ improved the surface energy levels of perovskite films. Finally, PCE of Sn-Pb alloyed perovskite cell supplemented with 0.030 mmol SnOct₂ reached 17.25%, superior to that of device supplemented with 0.10 mmol SnF₂ (11.63%). After storage in nitrogen for 50 d, more than 70% of initial PCE was still preserved.

Key words: Sn-Pb alloyed perovskite, solar cell, additive engineering, two-step method, stability

中图分类号:

TQ174

王煜, 熊浩, 黄孝坤, 江琳沁, 吴波, 黎健生, 杨爱军. 低剂量异辛酸亚锡调控两步法制备Sn-Pb混合钙钛矿太阳能电池[J]. 无机材料学报, 2024, 39(12): 1339-1347.

WANG Yu, XIONG Hao, HUANG Xiaokun, JIANG Linqin, WU Bo, LI Jiansheng, YANG Aijun. Regulation of Low-dose Stannous Iso-octanoate for Two-step Prepared Sn-Pb Alloyed Perovskite Solar Cells[J]. Journal of Inorganic Materials, 2024, 39(12): 1339-1347.

图/表 11

图1 不同Sn-Pb混合钙钛矿薄膜的XRD图谱

Fig. 1 XRD patterns of different Sn-Pb alloyed perovskite films

图2 不同Sn-Pb混合钙钛矿薄膜的SEM照片

Fig. 2 SEM images of different Sn-Pb alloyed perovskite films (a-d) Surfaces; (e-h) Cross sections

图3 PVK-0.10SF薄膜与PVK-0.030SO薄膜的XPS谱图

Fig. 3 XPS spectra of PVK-0.10SF and PVK-0.030SO films (a) Sn3d; (b) I3d; Sn4+/Sn2+ ratios of (c) PVK-0.10SF and (d) PVK-0.030SO perovskite films

图4 不同Sn-Pb混合钙钛矿薄膜的光学性能与能级

Fig. 4 Optical properties and energy levels of different Sn-Pb alloyed perovskite films (a) UV-VIS-NIR spectra; (b) UPS spectra; (c) Tauc plots; (d) Energy levels of VBM, CBM, and Fermi derived from the UPS spectra

图5 PSC-0.10SF与PSC-0.030SO器件的光伏性能与稳定性

Fig. 5 Photovoltaic performance and stability of PSC-0.10SF and PSC-0.030SO devices (a) Structure diagram of Sn-Pb alloyed perovskite solar cell; (b) J-V curves of the best-performance PSCs fabricated with SnF2 and SnOct2; (c) Stability of unencapsulated PSCs stored in the N2 glove box for 50 d; (d) Stability of unencapsulated PSCs stored in air for 20 d

表S1 不同添加剂制备的10个Sn-Pb混合PSC器件的参数统计

Table S1 Average parameters of 10 Sn-Pb alloyed PSC devices with different additive

Sample	V_OC/V	J_SC/(mA·cm^-2)	FF/%	PCE/%
PSC-0.10SF	0.628±0.021	23.17±2.24	73.76±4.77	10.73±0.89
PSC-0.015SO	0.698±0.004	26.45±0.66	75.03±3.05	13.86±0.48
PSC-0.030SO	0.728±0.009	28.64±0.58	80.83±0.57	16.86±0.38
PSC-0.045SO	0.701±0.011	27.67±0.79	77.34±2.59	15.01±0.73

图S1 不同Sn-Pb混合钙钛矿薄膜的半峰宽(FWHM)

Fig. S1 FWHM of different Sn-Pb alloyed perovskite films

图S2 不同Sn-Pb混合钙钛矿薄膜的晶粒尺寸分布图

Fig. S2 Grain size distributions of different Sn-Pb alloyed perovskite films

图S3 不同Sn-Pb混合钙钛矿薄膜的接触角测试

Fig. S3 Contact angle tests of different Sn-Pb alloyed perovskite films

图S4 不同Sn-Pb混合PSCs光伏参数分布图(10个电池)

Fig. S4 Photovoltaic parameter distributions of different Sn-Pb alloyed PSCs (10 devices)

图S5 不同Sn-Pb混合钙钛矿薄膜的内部缺陷

Fig. S5 Internal defects of different Sn-Pb alloyed perovskite films (a, b) I-V curves of FTO/SnO2/FAxMA1-xPb0.7Sn0.3InBr1-n/PCBM/Ag; (c) EIS plots; (d) Leakage current diagram

参考文献 45

[1]	CHUNG I, LEE B, HE J, et al. All-solid-state dye-sensitized solar cells with high efficiency. Nature, 2012, 485(7399):486.
[2]	KOJIMA A, TESHIMA K, SHIRAI Y, et al. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. Journal of the American Chemical Society, 2009, 131(170):6050. DOI PMID
[3]	SNAITH H J. Perovskites: the emergence of a new era for low-cost, high-efficiency solar cells. The Journal of Physical Chemistry Letters, 2013, 4(21):3623.
[4]	GRÄTZEL M. The light and shade of perovskite solar cells. Nature Materials, 2014, 13(9):838. DOI PMID
[5]	LIANG Z, ZHANG Y, XU H, et al. Homogenizing out-of-plane cation composition in perovskite solar cells. Nature, 2023, 624(7992):557.
[6]	LIAO W, ZHAO D, YU Y, et al. Fabrication of efficient low bandgap perovskite solar cells by combining formamidinium tin iodide with methylammonium lead iodide. Journal of the American Chemical Society, 2016, 138(38):12360.
[7]	HU S, OTSUKA K, MURDEY R, et al. Optimized carrier extraction at interfaces for 23.6% efficient tin-lead perovskite solar cells. Energy and Environmental Science, 2022, 15: 2096.
[8]	LIN R, XU J, WEI M, et al. All-perovskite tandem solar cells with improved grain surface passivation. Nature, 2022, 603(7899):73.
[9]	LIU C, FAN J, LI H, et al. Highly efficient perovskite solar cells with substantial reduction of lead content. Scientific Reports, 2016, 6(1):35705. DOI PMID
[10]	ZHU L, YUH B, SCHOEN S, et al. Solvent-molecule-mediated manipulation of crystalline grains for efficient planar binary lead and tin triiodide perovskite solar cells. Nanoscale, 2016, 8(14):7621.
[11]	LIAN X, CHEN J, ZHANG Y, et al. Highly efficient Sn/Pb binary perovskite solar cell via precursor engineering: a two-step fabrication process. Advanced Functional Materials, 2019, 29(5):1807024.
[12]	ZHU T, YANG Y, GONG X. Recent advancements and challenges for low-toxicity perovskite materials. ACS Applied Materials & Interfaces, 2020, 12(24):26776.
[13]	YANG Z, RAJAGOPAL A, CHUEH C C, et al. Stable low-bandgap Pb-Sn binary perovskites for tandem solar cells. Advanced Materials, 2016, 28(40):8990.
[14]	SONG T B, YOKOYAMA T, STOUMPOS C C, et al. Importance of reducing vapor atmosphere in the fabrication of tin-based perovskite solar cells. Journal of the American Chemical Society, 2017, 139(2):836.
[15]	KE W, KANATZIDIS M G. Prospects for low-toxicity lead-free perovskite solar cells. Nature Communications, 2019, 10(1):965. DOI PMID
[16]	LEE S J, SHIN S S, KIM Y C, et al. Fabrication of efficient formamidinium tin iodide perovskite solar cells through SnF₂-pyrazine complex. Journal of the American Chemical Society, 2016, 138(12):3974.
[17]	YU B B, XU L, LIAO M, et al. Synergy effect of both 2, 2, 2-trifluoroethylamine hydrochloride and SnF₂ for highly stable FASnI_3-_xCl_x perovskite solar cells. Solar RRL, 2019, 3(3):1800290.
[18]	XIAO M, GU S, ZHU P, et al. Tin-based perovskite with improved coverage and crystallinity through tin-fluoride-assisted heterogeneous nucleation. Advanced Optical Materials, 2018, 6(1):1700615.
[19]	WANG F, JIANG X, CHEN H, et al. 2D-Quasi-2D-3D hierarchy structure for tin perovskite solar cells with enhanced efficiency and stability. Joule, 2018, 2(12):2732.
[20]	CAO D H, STOUMPOS C C, YOKOYAMA T, et al. Thin films and solar cells based on semiconducting two-dimensional Ruddlesden-Popper (CH₃(CH₂)₃NH₃)₂(CH₃NH₃)_n_-1Sn_nI₃_n₊₁perovskites. ACS Energy Letters, 2017, 2(5):982.
[21]	ZHAO Z, GU F, WANG C, et al. Orientation regulation of photoactive layer in tin-based perovskite solar cells with allylammonium cations. Solar RRL, 2020, 4(10):2000315.
[22]	DAI X, ZHANG L, QIAN Y, et al. Controlling vertical composition gradients in Sn-Pb mixed perovskite solar cells via solvent engineering. Journal of Inorganic Materials, 2023, 38(9):1089.
[23]	TAI Q, GUO X, TANG G, et al. Antioxidant grain passivation for air-stable tin-based perovskite solar cells. Angewandte Chemie International Edition, 2019, 58(3):806.
[24]	LIN Z, LIU C, LIU G, et al. Preparation of efficient inverted tin-based perovskite solar cells via the bidentate coordination effect of 8-hydroxyquinoline. Chemical Communications, 2020, 56(28):4007.
[25]	MENG X, WU T, LIU X, et al. Highly reproducible and efficient FASnI₃ perovskite solar cells fabricated with volatilizable reducing solvent. The Journal of Physical Chemistry Letters, 2020, 11(8):2965.
[26]	MENG X, WANG Y, LIN J, et al. Surface-controlled oriented growth of FASnI₃ crystals for efficient lead-free perovskite solar cells. Joule, 2020, 4(4):902.
[27]	MENG X, LIN J, LIU X, et al. Highly stable and efficient FASnI₃-based perovskite solar cells by introducing hydrogen bonding. Advanced Materials, 2019, 31(42):1903721.
[28]	XU X, CHUEH C C, YANG Z, et al. Ascorbic acid as an effective antioxidant additive to enhance the efficiency and stability of Pb/Sn-based binary perovskite solar cells. Nano Energy, 2017, 34: 392.
[29]	TONG J H, SONG Z N, KIM H D, et al. Carrier lifetimes of >1 μs in Sn-Pb perovskites enable efficient all-perovskite tandem solar cells. Science, 2019, 364(6439):475.
[30]	WANG J T, UDDIN M A, CHEN B, et al. Enhancing photostability of Sn-Pb perovskite solar cells by an alkylammonium pseudo-halogen additive. Advanced Energy Materials, 2023, 13(15):2204115.
[31]	BING J, KIM J, ZHANG M, et al. The impact of a dynamic two- step solution process on film formation of Cs_0.15(MA_0.7FA_0.3)_0.85PbI₃ perovskite and solar cell performance. Small, 2019, 15(9):1804858
[32]	WANG J, DATTA K, LI J, et al. Understanding the film formation kinetics of sequential deposited narrow-bandgap Pb-Sn hybrid perovskite films. Advanced Energy Materials, 2020, 10(22):2000566.
[33]	LI S, ZHANG X, XUE X, et al. Importance of tin (II) acetate additives in sequential deposited fabrication of Sn-Pb-based perovskite solar cells. Journal of Alloys and Compounds, 2022, 904: 164050.
[34]	OKU T. Crystal structures of CH₃NH₃PbI₃ and related perovskite compounds used for solar cells. Solar Cells-New Approaches and Reviews, 2015, 1: 77.
[35]	BAHRAM A N, MOSSAIN M, JAKOBY M, et al. Vacuum- assisted growth of low-bandgap thin films (FA_0.8MA_0.2Sn_0.5Pb_0.5I₃) for all-perovskite tandem solar cells. Advanced Energy Materials, 2020, 10(5):1902583.
[36]	MA Y, ZHENG F, LI S, et al. Regulating the crystallization growth of Sn-Pb mixed perovskites using the 2D perovskite (4-AMP) PbI₄ substrate for high-efficiency and stable solar cells. ACS Applied Materials & Interfaces, 2023, 15(29):34862.
[37]	FEI C, LI B, ZHANG R, et al. Highly efficient and stable perovskite solar cells based on monolithically grained CH₃NH₃PbI₃ film. Advanced Energy Materials, 2017, 7(9):1602017.
[38]	LI C, ZHANG N, GAO P. Lessons learned: how to report XPS data incorrectly about lead-halide perovskites. Materials Chemistry Frontiers, 2023, 7(18):3797.
[39]	ZHANG Z, LIANG J, WANG J, et al. Resolving mixed intermediate phases in methylammonium-free Sn-Pb alloyed perovskites for high-performance solar cells. Nano-Micro Letters, 2022, 14(1):165. DOI PMID
[40]	SUN Y, YANG S, PANG Z, et al. Preferred film orientation to achieve stable and efficient Sn-Pb binary perovskite solar cells. ACS Applied Materials & Interfaces, 2021, 13(9):10822.
[41]	ZHANG W, HUANG L, ZHENG W, et al. Revealing key factors of efficient narrow-bandgap mixed lead-tin perovskite solar cells via numerical simulations and experiments. Nano Energy, 2022, 96: 107078.
[42]	RAOUI Y, EZ-ZAHRAOUY H, KAZIM S, et al. Energy level engineering of charge selective contact and halide perovskite by modulating band offset: mechanistic insights. Journal of Energy Chemistry, 2021, 54: 822.
[43]	DUIJINSTEE E, BALL J, CONE V, et al. Toward understanding space-charge limited current measurements on metal halide perovskites. ACS Energy Letters, 2020, 5(2):376.
[44]	BUBE R. Trap density determination by space-charge-limited currents. Journal of Applied Physics, 1962, 33(5):1733.
[45]	CAO J, LIU C K, PIRADI V, et al. Ultrathin self-assembly two-dimensional metal-organic framework films as hole transport layers in ideal-bandgap perovskite solar cells. ACS Energy Letters, 2022, 7(10):3362.

低剂量异辛酸亚锡调控两步法制备Sn-Pb混合钙钛矿太阳能电池

Regulation of Low-dose Stannous Iso-octanoate for Two-step Prepared Sn-Pb Alloyed Perovskite Solar Cells

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