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

doi:10.6023/A24120384

Abstract

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

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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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Fig. & Tab. 9

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

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

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

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

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

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

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

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

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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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