CsPbIBr2钙钛矿太阳能电池湿度稳定机制研究

doi:10.6023/A24030093

摘要/Abstract

制备环境中的湿度与钙钛矿太阳能电池的稳定性和器件的可重复性息息相关. 明确环境湿度对钙钛矿薄膜的影响机制对于效率优化至关重要. 本工作系统性地研究了环境湿度对CsPbIBr₂薄膜的制备以及电池性能的影响. 薄膜制备过程中, 发现环境湿度提高了薄膜的结晶速率并有利于α-CsPbIBr₂的低温制备(40 ℃). 但相对湿度超过40%时, 钙钛矿薄膜覆盖率逐渐降低, 形成晶体网络甚至是晶体小岛, CsPbIBr₂组分与O₂的反应加剧, 生成了PbO、Pb⁰以及易挥发的卤素单质. CsPbIBr₂钙钛矿太阳能电池的光电转换效率从相对湿度0%的10.79%降低至相对湿度60%的0.10%. PbO具有稳定α相的作用, 相对湿度40%条件制备的CsPbIBr₂钙钛矿太阳能电池在无封装条件下1656 h后仍保持初始效率的96%, 展现了良好的稳定性.

关键词: CsPbIBr₂, 钙钛矿太阳能电池, 湿度影响, 相转变, 结晶促进

The stability and reproducibility of perovskite solar cells (PSCs) are sensitive to fabrication environment, particularly moisture. Understanding the impact of moisture during perovskite film formation is essential for developing effective strategies to enhance performance. Herein, we have systematically investigated the influence of moisture on perovskite film formation as well as photovoltaic properties under varying humidity conditions. It is found that air humidity rapidly alters the physical and thermodynamic properties of the precursor solution during film formation, influencing both the crystallization process and compositional reactions. In the absence of humidity, films primarily forms CsI-PbBr₂•DMSO complexes through the reaction of CsI and PbBr₂•2DMSO clusters, which transform into desired α-phase after annealing at 280 ℃. Under humid conditions, H₂O competes with DMSO to coordinate with PbBr₂, forming PbBr₂•DMSO--H₂O clusters. Additionally, H₂O enhances the mobility of CsI within the wet film, leading to a phase transition to α-phase even at 40 ℃. Increased environmental humidity beyond RH 40% further accelerates the precipitation of PbBr₂•DMSO--H₂O complexes, leading to the formation of 2PbBr₂•2DMSO--H₂O. The interaction between CsI and these complexes creates larger intermediate crystals that are difficult to transform into 3D perovskites. And the complexes grow away from the substrate because of an additional solid-solid interfacial energy barrier between the crystals and the substrate. Thus, perovskite thin film becomes discontinuous, existing as crystal networks and islands, resulting in decreased coverage of the perovskite films. As a result, short-circuit current density and open-circuit voltage decrease, leading a decline in power conversion efficiency (PCE) from 10.79% at RH 0% down to 0.10% at RH 60%. In the presence of adsorbed water, O₂ forms O²⁻ at the surface of perovskite films, reacting with Pb⁰ defects and its components within the film to produce lead oxide (PbO). This product enhances the stability of the crystal phase, allowing PSCs prepared under RH 40% to maintain 96% of its initial efficiency even after 1656 h in ambient air (RH≤20%). During film aging, moisture in the environment causes α-CsPbIBr₂ to initially transform from (100) and (200) facets to (110) facets, and then further to the δ-phase. Therefore, isolating water and oxygen effectively prevents phase transition. The insights gained from this study on the effects of humidity provide valuable guidance for controlling humidity during perovskite film preparation and storage, ultimately contributing to enhanced stability and performance.

Key words: CsPbIBr₂, perovskite solar cells, moisture effect, phase transition, crystallization promotion

引用此文

张林, 张慧, 朱从潭, 郭学益, 杨英. CsPbIBr₂钙钛矿太阳能电池湿度稳定机制研究[J]. 化学学报, 2024, 82(9): 971-978.

Lin Zhang, Hui Zhang, Congtan Zhu, Xueyi Guo, Ying Yang. Investigation of Humidity Stabilization Mechanism in CsPbIBr₂ Perovskite Solar Cells[J]. Acta Chimica Sinica, 2024, 82(9): 971-978.

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图/表 5

图1. 不同湿度中制备的CsPbIBr2钙钛矿薄膜形貌和物相性质表征. 薄膜随退火时间变化的(a) UV-Vis和(b) XRD图; (c)薄膜的SEM图

Figure 1. (a) UV-Vis and (b) XRD patterns and (c) SEM images of CsPbIBr2 perovskite films prepared at different humidity (RH 0~60%) varing with the annealing time

图2. 不同湿度中制备的CsPbIBr2钙钛矿薄膜的(a) Pb 4f和(b) O 1s XPS图, OL表示晶格位置上的O2?. (c)湿度作用示意图

Figure 2. XPS images of (a) Pb 4f and (b) O 1s of CsPbIBr2 perovskite films prepared at different humidity. (c) Schematic diagram of the effect of humidity

图3. CsPbIBr2 PSCs (a)不同湿度条件的J-V曲线和(b)器件光电性能储存稳定性(储存条件: 未封装, RH≤20%); (c) EQE和积分电流密度图; (d)暗态条件下的Nyquist图(偏压0.9 V); (e) VOC随光强的变化曲线; (f)只有电子传输层的CsPbIBr2 SCLC曲线

Figure 3. Photovoltaic performance characterization of CsPbIBr2 PSCs. (a) J-V curves. (b) long-term stability stored under ambient conditon with no more than 20% without encapsution. (c) EQE spectra and integrated current densities. (d) dark fitted Nyquist curves. (e) VOC on light intensity curves. (f) dark SCLC curves of the electron-only devices

图4. 不同湿度中制备的CsPbIBr2钙钛矿薄膜的稳定性表征. (a)外观稳定性; 钙钛矿薄膜的老化UV-Vis曲线: (b) RH 0%制备, N2下保存; (c) RH 0%制备, 低湿度空气保存(RH≤20%); (d) RH 25%制备, 低湿度空气保存(RH≤20%); (e) RH 40%制备, 低湿度空气保存(RH≤20%); (f) RH 0%、(g) 25%和(h) 40%湿度薄膜0 d和90 d的XRD图

Figure 4. Stability characterization of CsPbIBr2 perovskite films prepared under different humidity conditions. (a) Appearance stability. UV-Vis over time: (b) Films prepared at 0% humidity condition but kept in glove box N2; Films prepared at RH (c) 0%, (d) 25% and (e) 40% humidity condition but stored in low humidity air with relative humidity≤20%; XRD plots of films which prepared at RH (f) 0%, (g) 25%, and (h) 40% humidity condition on day 0 and 90

图5. 100 d后CsPbIBr2薄膜(a) Pb 4f和(b) O 1s的XPS图

Figure 5. (a) Pb 4f and (b) O 1s XPS plots of CsPbIBr2 films after 100 d

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CsPbIBr₂钙钛矿太阳能电池湿度稳定机制研究

Investigation of Humidity Stabilization Mechanism in CsPbIBr₂ Perovskite Solar Cells

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