SnCl2敏化的TiO2表面对PbI2粒子的诱导吸附

doi:10.6023/A24040124

摘要/Abstract

近年来, 钙钛矿电池因其性能高、造价低且柔性好的优点而获得了极大的关注和发展, 但其薄膜制备工艺还不够成熟. 本工作主要关注两步法沉积钙钛矿时PbI₂晶种层的沉积. 受银镜反应中SnCl₂敏化思想的启发, 本工作提出采用SnCl₂敏化层来增加PbI₂粒子在TiO₂基底上的吸附能力. 为验证其可行性, 首先通过分子动力学模拟SnCl₂敏化的TiO₂表面对PbI₂粒子的诱导吸附, 分析了SnCl₂、PbI₂、TiO₂三者的相互结合能. 模拟结果表明, SnCl₂与TiO₂及PbI₂粒子都有较大的结合能, 因此可以很好地提高PbI₂粒子在TiO₂基底上的吸附能力. 最后, 通过PbI₂的溶液沉积实验和表征也验证了SnCl₂敏化层对PbI₂薄膜沉积质量具有较好的改善作用.

关键词: 钙钛矿电池, 薄膜, 桥梁粒子, 诱导吸附

In recent years, perovskite solar cells have emerged as a bright star in the realm of renewable energy, capturing the attention of researchers and industry experts with their high conversion efficiencies, low costs, and exceptional flexibility. Despite these advantages, the Achilles' heel of perovskite solar cells lies in the delicate art of film preparation. The challenges inherent in this process, if not overcome, could potentially hinder the technology's march towards commercialization. This paper delves into a critical aspect of perovskite film formation—the deposition of the PbI₂ seed layer in the two-step synthesis of perovskite materials. The seed layer, serving as the cornerstone for the growth of the perovskite lattice, plays a decisive role in the ultimate performance of the solar cell. Inspired by the role of SnCl₂ in the silver mirror reaction, this paper proposes the use of an SnCl₂ sensitization layer to enhance the adsorption capacity of PbI₂ particles on TiO₂ substrates. To validate this hypothesis, we conducted a series of molecular dynamics simulations. These simulations provided a microscopic perspective on the deposition process, contrasting the adsorption and deposition behaviors of PbI₂ particles on pristine TiO₂ surfaces with those on TiO₂ surfaces pre-treated with SnCl₂. The findings indicated that the substrate sensitized with SnCl₂ could significantly reduce the energy of PbI₂ particles during the deposition process, facilitating their adsorption and deposition on the substrate. To further analyze the binding energies among SnCl₂, PbI₂, and TiO₂, additional simulations focused on their interactions. These simulations confirmed that SnCl₂ could act as an effective bridge, promoting a tighter bond between PbI₂ and TiO₂. Complementing the simulations, experimental validation was carried out through PbI₂ solution deposition. The resulting films, analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD), confirmed the positive impact of the SnCl₂ sensitization layer on the quality of PbI₂ film deposition.

Key words: perovskite solar cells, film, "bridge" particles, induced adsorption

引用此文

王馨雨, 许雄文. SnCl₂敏化的TiO₂表面对PbI₂粒子的诱导吸附[J]. 化学学报, 2024, 82(8): 865-870.

Xinyu Wang, Xiongwen Xu. The Induced Adsorption of PbI₂ Particles on the SnCl₂-Sensitized TiO₂ Surface[J]. Acta Chimica Sinica, 2024, 82(8): 865-870.

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图/表 10

图1. SnCl2与PbI2在TiO2基底上的吸附量对比

Figure 1. Comparison of the adsorption amounts of SnCl2 and PbI2 on the TiO2 substrate

图2. 随着沉积分子数量的增加, PbI2在两种基底上的模拟结果快照

Figure 2. As the number of deposited molecules increases, snapshots of the simulation results of PbI2 on both substrates

图3. PbI2粒子分布数量统计

Figure 3. Statistical distribution of PbI2 particle counts

图4. 沉积过程中PbI2能量变化趋势

Figure 4. Trends in the energy of PbI2 during deposition

粒子对 (固定粒子-移动粒子)	总能量(×10^-20/J)	标准差
TiO₂-PbI₂	－8.106	±0.61
TiO₂-SnCl₂	－11.800	±0.39
SnCl₂-PbI₂	－22.229	±0.14
PbI₂-PbI₂	－22.979	±0.44

表1. 单个粒子模拟结果

Table 1. Individual particle simulation results

图5. SnCl2对沉积PbI2薄膜影响的SEM图像对比: (a)未经处理的TiO2基底表面, (b)经过SnCl2敏化后的TiO2基底表面, (c)正常沉积的PbI2薄膜, (d) SnCl2敏化的基底沉积的PbI2薄膜, (e) EDS检测结果, 测量误差为0.01%

Figure 5. Comparison of SEM images showing the influence of SnCl2 on deposited PbI2 films: (a) Untreated TiO2 substrate surface, (b) TiO2 substrate surface after sensitization with SnCl2, (c) PbI2 film deposited on normal substrate, (d) PbI2 film deposited on SnCl2-sensitized substrate, (e) EDS detection results. The testing error is 0.01%

图6. SnCl2对沉积PbI2薄膜影响的XRD峰谱对比

Figure 6. Comparison of XRD spectra showing the influence of SnCl2 on deposited PbI2 films

图7. 基底模型: (a)未敏化的TiO2基底模型; (b) SnCl2敏化的TiO2基底模型

Figure 7. The substrate model: (a) The TiO2 substrate without SnCl2 sensitized; (b) the TiO2 substrate with SnCl2 sensitized

原子类型	ε/(kcal•mol⁻¹)	σ/Å
O	0.06	3.93^[27]
Ti	0.017	2.8929^[27]
Pb	0.66	4.297^[27]
Sn	0.56	4.392^[28]
Cl	0.23	3.947^[28]
I	0.51	4.15^[29]

表2. 各个原子的势函数参数

Table 2. The potential function parameters for each atom

图8. 实验步骤示意图: (a)两步法沉积钙钛矿薄膜, (b)三步法沉积钙钛矿薄膜

Figure 8. Schematic of experimental steps: (a) Two-step coating for depositing perovskite films, (b) three-step coating for depositing perovskite films

参考文献 29

[1]	Wei, J.; Zhao, Q.; Li, H.; Shi, C.-L.; Tian, J.-J.; Cao, G.-Z.; Yu, D.-P. Sci. China Technol. Sci. 2014, 44, 801 (in Chinese).
	(魏静, 赵清, 李恒, 施成龙, 田建军, 曹国忠, 俞大鹏, 中国科学: 技术科学, 2014, 44, 801.)
[2]	Green, M. A. Prog. Photovolt: Res. Appl. 2009, 17, 183.
[3]	Jackson, P.; Hariskos, D.; Lotter, E.; Paetel, S.; Wuerz, R.; Menner, R.; Wischmann, W.; Powalla, M. Photovolt: Res. Appl. 2011, 19, 894.
[4]	O'Regan, B.; Gratzel, M. Nature 1991, 353, 737.
[5]	Hardin, B. E.; Snaith, H. J.; McGehee, M. D. Nat. Photonics 2013, 6, 162.
[6]	Seo, J. H.; Gutacker, A.; Sun, Y. M.; Wu, H. B.; Huang, F.; Cao, Y.; Scherf, U.; Heeger, A. J.; Bazan, G. C. J. Am. Chem. Soc. 2011, 133, 8416.
[7]	Deb, S. K. Sol. Energy Mater. Sol. Cells. 2005, 88, 1.
[8]	Anaraki, E. H.; Kermanpur, A.; Steier, L.; Domanski, K.; Matsui, T.; Tress, W.; Saliba, M.; Abate, A.; Grätzel, M.; Hagfeldt, A.; Correa- Baena, J. P. Energy Environ. Sci. 2016, 9, 3128.
[9]	Qiu, L. B.; Deng, J.; Lu, X.; Yang, Z. B.; Peng, H. S. Angew. Chem. Int. Ed. 2014, 53, 10425.
[10]	Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. J. Am. Chem. Soc. 2009, 131, 6050.
[11]	Pan, T.; Zhou, W.; Wei, Q.; Peng, Z. J.; Wang, H.; Jiang, X. Y.; Zang, Z. H.; Li, H. S.; Yu, D. N.; Zhou, Q. L.; Pan, M. L.; Zhou, W. J.; Ning, Z. J. Adv. Mater. 2023, 35, 2208522.
[12]	Lee, J. W.; Lee, D. K.; Jeong, D. N.; Park, N. G. Adv. Funct. Mater. 2019, 29, 1807047.
[13]	Chen, H. N.; Wei, Z. H.; He, H. X.; Zheng, X. L.; Wong, K. S.; Yang, S. H. Adv. Energy. Mater. 2016, 6, 1502087.
[14]	Tidhar, Y.; Edri, E.; Weissman, H.; Zohar, D.; Hodes, G.; Cahen, D.; Rybtchinski, B.; Kirmayer, S. J. Am. Chem. Soc. 2014, 136, 13249. doi: 10.1021/ja505556s pmid: 25171634
[15]	Huang, Z. Q.; Duan, X. P.; Zhang, Y.; Hu, X. T.; Tan, L. C.; Chen, Y. W. Nat. Energy. 2016, 155, 166.
[16]	Thanh, N. T. K.; Maclean, N.; Mahiddine, S. Chem. Rev. 2014, 114, 7610.
[17]	Deng, Y. H.; Zheng, X. P.; Bai, Y.; Wang, Q.; Zhao, J. J.; Huang, J. S. Nat. Energy 2018, 3, 560.
[18]	Ryu, S.; Noh, J. H.; Jeon, N. J.; Kim, Y. C.; Yang, S.; Seo, J. W.; Seok, S. I. Energy. Environ. Sci. 2014, 7, 2614.
[19]	Stranks, S. D.; Eperon, G. E.; Grancini, G.; Menelaou, C.; Alcocer, M. J. P.; Leijtens, T.; Herz, L. M.; Petrozza, A.; Snaith, H. J. Science 2013, 342, 341. doi: 10.1126/science.1243982 pmid: 24136964
[20]	Zhou, Y. Y.; Yang, M. J.; Wu, W. W.; Vasiliev, A. L.; Zhu, K.; Padture, N. P. J. Mater. Chem. A 2015, 3, 8178.
[21]	Carvajal, J. J.; Pujol, M. C.; Díaz, F. In Springer handbook of crystal growth, Vol. 39, Eds.: Dhanaraj, G.; Byrappa, K.; Prasad, V.; Dudley, M., Springer, Berlin, 2010, Chapter C.21.
[22]	Zhumekenov, A. A.; Burlakov, V. M.; Saidaminov, M. I.; Alofi, A.; Hague, M. A.; Turedi, B.; Davaasuren, B.; Dursun, I.; Cho, N.; El-Zohry, A. M.; De Bastiani, M.; Giugni, A.; Torre, B.; Di Fabrizio, E.; Mohammed, O. F.; Rothenberger, A.; Wu, T.; Goriely, A.; Bakr, O. M. ACS Energy. Lett. 2017, 2, 1782.
[23]	Nayak, P. K.; Moore, D. T.; Wenger, B.; Nayak, S.; Haghighirad, A. A.; Fineberg, A.; Noel, N. K.; Reid, O. G.; Rumbles, G.; Kukura, P.; Vincent, K. A.; Snaith, H. J. Nat. Commun. 2016, 7, 13303.
[24]	Xu, Q.; Wang, J.; Shao, W.; Ouyang, X.; Wang, X.; Zhang, X.; Guo, Y. Nanoscale 2020, 17, 9727.
[25]	Yu, Y. H.; Xu, X. W.; Liu, J. P.; Liu, Y. H.; Cai, W. H.; Chen, J. X. Surf. Sci. 2021, 714, 121916.
[26]	Liang, S.-S. In China Glass Industry Annual Conference and Technical Symposium, Eds.: China Architectural and Industrial Glass Association, 2006, pp. 289-294 (in Chinese).
	(梁水生, 中国建筑玻璃与工业玻璃协会, 中国玻璃行业年会暨技术研讨会, 2006, pp. 289-294.)
[27]	Park, J. H.; Aluru, N. R. Mol. Simulat. 2009, 35, 31.
[28]	Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A., III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024.
[29]	Mayo, S. L.; Olafson, B. D.; Goddard, W. A., III. J. Phys. Chem. 1990, 94, 8897.

SnCl₂敏化的TiO₂表面对PbI₂粒子的诱导吸附

The Induced Adsorption of PbI₂ Particles on the SnCl₂-Sensitized TiO₂ Surface

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