水解氧化-溶胶-凝胶法提高钙钛矿太阳能电池中SnO<sub>2</sub>电子传输层性能

赵航; 程泽通; 吕宽心; 陈立泽; 杨育运; 黄兴; 李珍珍

doi:10.13801/j.cnki.fhclxb.20240022.001

水解氧化-溶胶-凝胶法提高钙钛矿太阳能电池中SnO₂电子传输层性能

doi: 10.13801/j.cnki.fhclxb.20240022.001

1.
华北理工大学　冶金与能源学院，唐山 063210
2.
市政工程设计研究院研究监测处，长春 130000
3.
市政设施维护管理中心，长春 130000

基金项目: 国家自然科学基金(52102247)；河北省自然科学基金(F2022209010)；唐山市科技计划项目(21130207C)

详细信息

通讯作者:
李珍珍，博士，副教授，硕士生导师，研究方向为钙钛矿材料与器件　E-mail: zhenlzz@163.com

中图分类号: TM914.4+2；TB332
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出版历程
- 收稿日期: 2023-11-22
- 修回日期: 2023-12-26
- 录用日期: 2024-01-05
- 网络出版日期: 2024-01-23
- 刊出日期: 2024-10-15

Improved extraction performance of SnO₂ ETL for perovskite solar cells by a combined hydrolysis oxidation and sol-gel method

1.
College of Metallurgy and Energy, North China University of Science and Technology, Tangshan 063210, China
2.
Research and Monitoring Division, Municipal Engineering Design and Research Institute, Changchun 130000, China
3.
Municipal Facilities Maintenance and Management Center, Changchun 130000, China

Funds: National Natural Science Foundation of China (52102247); Natural Science Foundation of Hebei Province (F2022209010); Tangshan Science and Technology Planning Project (21130207C)

摘要

摘要: SnO₂由于其高电子迁移率、优良的传导性和低温制备特性，在钙钛矿太阳能电池(PSCs)中得到广泛的应用。目前，制备SnO₂最常用的两种方法是SnCl₂水解氧化法和SnO₂溶胶-凝胶法。然而，SnCl₂水解氧化虽然可以产生结晶良好的SnO₂，但其可控性较差，使得器件性能的重复性较低。另一方面，溶胶-凝胶法制备的基于SnO₂电子输运层的器件具有良好的重复性，但结晶度较差，导致电子输运性能下降。在本文中，采用水解氧化和溶胶-凝胶相结合的方法制备了SnO₂电子传输层。研究结果表明：采用SnCl₂水解氧化法制备高质量的SnO₂结晶层可以作为预生长模板，提高溶胶-凝胶法制备SnO₂的结晶质量。此外，用溶胶-凝胶法制备的SnO₂结晶层覆盖水解氧化SnO₂层可以提高器件制备的重复性。由此方法制备的电子传递层可以有效地提高薄膜晶体的生长质量和电荷的提取能力，最终有助于提高器件的效率及稳定性并减少迟滞。
- SnO₂ /
- 复合电子传输层 /
- 水解氧化 /
- 溶胶-凝胶法 /
- 杂化钙钛矿太阳能电池
Abstract: SnO₂ is widely used in perovskite solar cells (PSCs) due to its high electron mobility, suitable conduction band and low-temperature preparation characteristics. Currently, the two most commonly used methods for preparing SnO₂ are SnCl₂ hydrolysis oxidation or SnO₂ sol-gel preparation. However, although SnCl₂ hydrolysis oxidation can produce well-crystallized SnO₂, its controllability is poor, resulting in low device performance repeatability. On the other hand, the devices based on SnO₂ electronic transport layer prepared by the sol-gel method have good repeatability, but usually have poor crystallinity, leading to a decrease in electron transport performance. In this study, a combination of hydrolysis oxidation and sol-gel methods was used to prepare SnO₂ electronic transport layers. The results of the study demonstrate that using SnCl₂ hydrolysis oxidation to prepare high-quality SnO₂ crystalline layers can serve as a pre-growth template to improve the crystalline quality of sol-gel generated SnO₂. Additionally, covering the hydrolysis oxidation-based SnO₂ layer with sol-gel prepared SnO₂ crystalline layer can improves the repeatability of device preparation. The electron transport layers prepared by this method can effectively enhance the quality of thin film crystal growth and charge extraction capability, ultimately contributing to improving the efficiency, stability, and reducing hysteresis of the devices.
- SnO₂ /
- composite electron transport layer /
- hydrolysis oxidation /
- sol-gel method /
- hybrid PSCs

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图 1 不同制备方法制备的SnO₂电子传输层(ETL)的XRD图谱

Figure 1. XRD patterns of SnO₂ electron transport layers (ETL) prepared by different methods

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图 2 不同方法得到的SnO₂ ETL在ITO上的透射曲线

Figure 2. Transmission curves of SnO₂ ETL obtained by different methods on ITO

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图 3 在 ITO/SnCl₂/SnO₂ (a)、ITO/SnCl₂ (b)、ITO/SnO₂ (c)衬底上制备的(FAPbI₃)_0.83(MAPbBr₃)_0.17钙钛矿薄膜的SEM图像

Figure 3. SEM images of (FAPbI₃)_0.83(MAPbBr₃)_0.17 perovskite films prepared on ITO/SnCl₂/SnO₂ (a), ITO/SnCl₂ (b), ITO/SnO₂ (c) substrate

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图 4 在玻璃、ITO/SnCl₂/SnO₂、ITO/SnCl₂和ITO/SnO₂基底上制备的(FAPbI₃)_0.83(MAPbBr₃)_0.17薄膜的稳态荧光光谱(a)和瞬态荧光光谱(b)

Figure 4. Steady-state fluorescence spectra (a) and transient fluorescence spectra (b) of (FAPbI₃)_0.83(MAPbBr₃)_0.17 films prepared on Glass, ITO/SnCl₂/SnO₂, ITO/SnCl₂ and ITO/SnO₂ substrates

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图 5 器件的暗电流-电压(J-V)曲线：(a) ITO/SnCl₂/SnO₂；(b) ITO/SnCl₂；(c) ITO/SnO₂

Figure 5. Dark current-voltage (J-V) curves of devices: (a) ITO/SnCl₂/SnO₂; (b) ITO/SnCl₂; (c) ITO/SnO₂

V_TFL—Trap-filled limit voltage; N_defect—Density of defects

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图 6 (FAPbI₃)_0.83(MAPbBr₃)_0.17在ITO/SnCl₂/SnO₂、ITO/SnCl₂和ITO/SnO₂ 3种衬底上制备的器件：(a) 归一化开电压衰减曲线；(b)基于开电压衰减计算的电子寿命

Figure 6. (FAPbI₃)_0.83(MAPbBr₃)_0.17 devices prepared on three ITO/SnCl₂/SnO₂, ITO/SnCl₂, and ITO/SnO₂ substrates: (a) Normalized open voltage decay curves; (b) Electron lifetime calculated by open voltage decay

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图 7 (a) 3种方法制备的ETL构建的(FAPbI₃)_0.83(MAPbBr₃)_0.17太阳能电池的J-V曲线；(b)基于3种方法制备的ETL的20个器件(FAPbI₃)_0.83(MAPbBr₃)_0.17器件的效率箱形图

Figure 7. (a) J-V curves of (FAPbI₃)_0.83(MAPbBr₃)_0.17 solar cells fabricated with ETLs prepared by using the three methods; (b) Box plot of efficiencies of 20 devices for (FAPbI₃)_0.83(MAPbBr₃)_0.17 devices based on different ETLs

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图 8 在ITO/SnCl₂/SnO₂、ITO/SnCl₂和ITO/SnO₂衬底上制备的器件在惰性环境中储存14天的效率变化

Figure 8. Efficiency changes of devices prepared on ITO/SnCl₂/SnO₂, ITO/SnCl₂ and ITO/SnO₂ substrates stored in inert environment for 14 days

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表 1 不同衬底(FAPbI₃)_0.83(MAPbBr₃)_0.17薄膜的瞬态荧光光谱(TRPL)拟合参数

Table 1. Transient photoluminescence spectroscopy (TRPL) fitting parameters of (FAPbI₃)_0.83(MAPbBr₃)_0.17 films prepared on different substrates

Sample	τ_1,Value/ns	τ_1,Rel./%	τ_2,Value/ns	τ_2,Rel./%	τ_ave,Value/ns
Glass	5.52	68.48	38.16	31.52	30.36
SnCl₂/SnO₂	2.09	35.87	20.63	64.13	19.64
SnCl₂	4.32	55.79	25.56	44.21	21.83
SnO₂	4.04	58.24	29.91	41.76	25.81
Notes: τ_1,Value and τ_2,Value—Fast decay life and slow decay life; τ_1,Rel. and τ_2,Rel.—Proportion of fast decay lifespan and the proportion of slow decay lifespan; τ_ave,Value—Fluorescence lifetime of perovskite charge carriers.

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表 2 不同制备方法制备的(FAPbI₃)_0.83(MAPbBr₃)_0.17器件作为电子传输层的光电参数

Table 2. Optoelectronic parameters of (FAPbI₃)_0.83(MAPbBr₃)_0.17 devices prepared using different preparation methods as electron transport layers

ETLs	V_oc/V	J_sc/(mA·cm⁻²)	FF/%	PCE/%
SnCl₂-revese	0.99	21.31	62.90	13.30
SnCl₂-forward	0.90	21.25	45.95	8.78
SnO₂-reverse	0.89	21.92	63.43	12.38
SnO₂-forward	0.87	21.44	59.74	11.16
SnCl₂/SnO₂-reverse	1.08	20.81	72.56	16.32
SnCl₂/SnO₂-forward	1.07	20.75	70.51	15.64
Notes: V_oc—Open circuit voltage; J_sc—Short-circuit current; FF—Fill factor; PCE—Photoelectric conversion efficiency of perovskite solar cells.

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