聚丙烯酸钠界面工程制备高效稳定的全无机CsPbBr3钙钛矿太阳能电池

doi:10.6023/A24120384

摘要/Abstract

钙钛矿太阳能电池(Perovskite Solar Cells, PSCs)作为第三代太阳能电池, 近年来发展迅速, 特别是全无机CsPbBr₃钙钛矿太阳能电池因其优异的环境稳定性而备受关注. 本工作在全无机钙钛矿太阳能电池的上界面引入聚丙烯酸钠(Polyacrylic Acid Sodium, PAAS)使其形成具有界面钝化作用的高分子层, 对钙钛矿层提供保护的同时钝化其界面缺陷、提高能级匹配度. 研究表明, PAAS溶液浓度为1.5 mg•mL⁻¹时对钙钛矿界面钝化效果最好, 制备出的CsPbBr₃钙钛矿薄膜具有晶粒粒径更大、纯度更高等优良特性, 且在与碳电极界面处的表面形貌更加平整, 有利于光生载流子的生成与传输. 最终基于此制备出了最高开路电压(Open Circuit Voltage, V_OC) 1.58 V, 短路电流密度(Short Circuit Current, J_SC)为8.09 mA•cm⁻², 填充因子(Fill Factor, FF)为77.21%, 光电转换效率(Photoelectric Conversion Efficiency, PCE)达9.90%的最优器件.

关键词: 全无机钙钛矿太阳能电池, CsPbBr₃, 聚丙烯酸钠, 缺陷钝化, 两步旋涂

As the third generation of solar cells, the perovskite solar cells (PSCs) have developed rapidly in recent years, especially the all-inorganic PSCs, which have caught lots of attention from researchers for their excellent stability in thermal and humidity and high voltage. However, in the field of CsPbBr₃ PSCs, the perovskite films made from a multi-step spin-coating method have inferior quality, which hinders their development. In this report, we propose a method of replacing methanol with green solvent water to dissolve CsBr to achieve the goal of using a two-step spin-coating method to fabricate the perovskite films without any environmental damage. Meanwhile, polyacrylic acid sodium (PAAS) was introduced into the upper interface between the CsPbBr₃ films and carbon electrode to form a polymer layer with interface passivation. It was confirmed by infrared spectroscopy (IR) that the PAAS was successfully introduced. Through the analysis with X-ray diffraction (XRD), atomic force microscope (AFM) and scanning electron microscope (SEM), the perovskite films were found to be more uniform and smoother, which will exhibit the non-radioactive recombination at the interface after the PAAS modification. We assume that the PAAS polymer layer works as a defect passivator for the perovskite films and provides a water-proof protection for the perovskite films while improving the energy level matching for faster carriers' mobility. Meanwhile, the results of ultraviolet-visible spectroscopy (UV-vis) and other electrochemical characterizations suggested that the perovskite films with PAAS modification had a stronger ability to generate carriers and more effective suppression for the recombination of photo-generated carriers. Adjusting the concentration of the PAAS solution, we found that when the concentration comes to 1.5 mg•mL⁻¹, the optimized device gains superb photovoltaic performance than the pristine devices with highest open circuit voltage (V_OC) of 1.58 V, short circuit current density (J_SC) of 8.09 mA•cm⁻², fill factor (FF) of 77.21% and photoelectric conversion efficiency (PCE) of 9.90%, marking a giant leap in the field of all-inorganic PSCs.

Key words: all-inorganic perovskite solar cells, CsPbBr₃, polyacrylic acid sodium, defect passivation, two-step spin-coating

引用此文

朱文昊, 汪玉杰, 李浩, 汪杨, 郑松志, 王则远, 陈劭添, 孙伟海, 赵小敏. 聚丙烯酸钠界面工程制备高效稳定的全无机CsPbBr₃钙钛矿太阳能电池[J]. 化学学报, 2025, 83(6): 616-623.

Wenhao Zhu, Yujie Wang, Hao Li, Yang Wang, Songzhi Zheng, Zeyuan Wang, Shaotian Chen, Weihai Sun, Xiaomin Zhao. Interface Engineering Using Polyacrylic Acid Sodium for the Fabrication of Highly Efficient and Stable All-Inorganic CsPbBr₃ Perovskite Solar Cells[J]. Acta Chimica Sinica, 2025, 83(6): 616-623.

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图/表 9

图1. 空白组及旋涂不同浓度的PAAS溶液的PVK薄膜的XRD图(a)和局部放大图(b); 空白组和PAAS修饰的PVK薄膜的2D AFM (c, d)和3D AFM (e, f)图像

Figure 1. (a) XRD patterns and (b) local magnified XRD patterns of PVK films spin-coated with different concentrations of PAAS; 2D (c, d) and 3D (e, f) AFM images of PVK films with and without PAAS modification

图2. 旋涂不同浓度PAAS溶液的PVK薄膜的SEM图(a~e)及对应的粒径分布图(f~j)

Figure 2. SEM images (a~e) and corresponding particle size distribution histograms (f~j) of PVK films spin-coated with different concentrations of PAAS solutions

图3. (a) PAAS的标准红外衍射光谱; 空白组和PAAS修饰的PVK薄膜的(b)红外衍射光谱, (c) UV-vis光谱, (d) PL光谱和(e) TRPL光谱; (f)不同浓度PAAS溶液处理后的器件J-V曲线

Figure 3. (a) Standard IR spectra of PAAS; (b) IR spectra, (c) UV-vis spectra, (d) PL spectra and (e) TRPL spectra of PVK films with and without PAAS modification; (f) J-V curves of devices treated with different concentrations of PAAS solutions

Sample	τ₁/ns	A₁/%	τ₂/ns	A₂/%	τ_ave/ns
Pristine	0.7428	75.778	7.89456	28.87	6.478
With PAAS	0.87323	77.266	10.08985	26.927	8.256

表1. 引入PAAS前后PVK薄膜的TRPL参数

Table 1. TRPL parameters of PVK film with and without PAAS introduction

Concentration	V_OC/V	J_SC/(mA•cm⁻²)	FF/%	PCE/%
Pristine	1.51	7.23	75.19	8.22
0.5 mg•mL⁻¹	1.54	7.43	75.95	8.71
1.0 mg•mL⁻¹	1.56	7.88	76.05	9.26
1.5 mg•mL⁻¹	1.58	8.09	77.21	9.90
2.0 mg•mL⁻¹	1.52	7.48	75.83	8.63

表2. 不同浓度PAAS溶液处理的器件的具体光伏参数

Table 2. Specific photovoltaic parameters of devices treated with different concentrations of PAAS solutions

图4. 空白组与经PAAS修饰后的PSCs的(a)暗态J-V特性曲线、(b) C-V曲线图、(c) M-S曲线图、(d) EIS谱图(插图: 等效电路图)、(e) TPC和(f) TPV衰减曲线

Figure 4. (a) The dark-state J-V characteristic curves, (b) C-V curves, (c) M-S curves, (d) EIS spectra (insert: equivalent circuit), (e) TPC and (f) TPV attenuation curves of the PSCs with and without PAAS modification

图5. 空白组与经PAAS修饰后的钙钛矿薄膜的水接触角

Figure 5. The water contact angle of the PVK films with and without PAAS modification

图6. (a~d)空白组和经PAAS修饰后的20个独立器件的VOC、JSC、FF和PCE参数箱线图和(e, f) 30-d VOC、JSC、FF和PCE稳定性数据图

Figure 6. (a~d) Box-plot of distribution of VOC, JSC, FF and PCE parameters for 20 independent PSCs and (e, f) 30-d VOC, JSC, FF and PCE stability data for PSCs with and without PAAS modification

修饰层材料	器件结构	V_OC/V	J_SC/(mA•cm⁻²)	FF/%	PCE/%
I₂^[24]	FTO/TiO₂/CsPbBr₃/carbon	1.55	5.26	85.54	9.88
PMMA^[25]	ITO/SnO₂/CsPbBr₃/carbon	1.58	7.93	76.51	9.60
PVAC^[46]	FTO/TiO₂/CsPbBr₃/carbon	1.54	7.28	76.91	8.62
Carotene^[47]	FTO/TiO₂/CsPbBr₃ carbon	1.32	8.81	66.11	7.81
PQDs^[48]	FTO/TiO₂/CsPbBr₃/carbon	1.31	6.55	75.60	7.93
NiO NCs^[33]	ITO/SnO₂/CsPbBr₃/carbon	1.57	7.57	82.22	9.19
HBr^[49]	FTO/TiO₂/CsPbBr₃/carbon	1.36	7.47	68.00	6.91
PAAS	FTO/TiO₂/CsPbBr₃/carbon	1.58	8.09	77.21	9.90

表3. CsPbBr3基器件界面修饰及其对光伏参数影响的文献综述

Table 3. Review of interface modification of CsPbBr3-based devices and their effects on photovoltaic parameters

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聚丙烯酸钠界面工程制备高效稳定的全无机CsPbBr₃钙钛矿太阳能电池

Interface Engineering Using Polyacrylic Acid Sodium for the Fabrication of Highly Efficient and Stable All-Inorganic CsPbBr₃ Perovskite Solar Cells

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