【作者】 孙庆；

【导师】 康博南；

【作者基本信息】 吉林大学 ， 物理电子学， 2025， 博士

【摘要】 可持续发展是通过保护环境、推广清洁能源和合理利用清洁资源,实现经济、社会和生态的长期平衡发展。在这些清洁能源中,太阳能作为储量巨大的清洁能源,具有强大的市场竞争力。太阳能的转换利用,尤其是通过太阳能电池将其转化为电能,正成为实现这一潜力的重要途径。在各类太阳能电池技术中,钙钛矿太阳能电池（PSCs）凭借其结构简单、溶液加工性能优异、制造成本低廉以及出色的光电转换效率,已成为当前研究领域的前沿热点。凭借有机-无机杂化钙钛矿材料的出色光电性能,目前单结PSCs的认证功率转换效率已突破26%。然而,PSCs的性能提升之路并非坦途。其中,电荷传输层与钙钛矿层界面处的非辐射复合会导致显著的光生载流子损失,从而影响器件的效率和稳定性。为解决这一问题,本研究致力于优化电荷传输层与钙钛矿层的界面接触特性,通过界面修饰和缺陷钝化策略抑制界面处光生载流子的非辐射复合,减少缺陷数量,从而提升载流子的传输效率,最终提升PSCs的效率和稳定性。主要研究内容包括:（1）采用宽带隙卤化物材料对PSCs的界面进行优化处理。选用正己基三甲基溴化铵（HTAB）作为界面修饰材料,对空穴传输层聚[双（4-苯基）-（2,4,6-三甲基苯基）胺]（PTAA）进行表面修饰。通过引入HTAB层,PTAA和钙钛矿层（MAPbI₃）之间的界面接触显著改善,提高了MAPbI₃的结晶质量,降低了PSCs中的缺陷态密度,有效抑制了界面载流子非辐射复合,器件性能得到显著提升。实验结果表明,使用HTAB修饰的最佳器件实现了21.01%的高功率转换效率（PCE）,且滞后效应非常小,相较于对照器件（17.71%）显著提升。此外,在相对湿度为25±5%的空气中,未封装器件经过1000小时老化保持了约87%的初始PCE,显示出优异的长期稳定性。（2）采用卤化胆碱(C₅H₁₄ON⁺X^-)钝化钙钛矿的埋底界面及表面缺陷。C₅H₁₄ON⁺X^-和卤素离子可有效钝化带电离子缺陷,而N⁺（CH₃）_3-基团能显著提高钙钛矿的环境稳定性。其中,使用氯化胆碱（CHCl）可有效改善钙钛矿薄膜的结晶特性,提高载流子的迁移速率,并显著降低钙钛矿薄膜的缺陷态密度,这些协同效应共同提升了PSCs的整体性能。实验结果表明,使用CHCl修饰的最佳器件实现了22.61%的优异PCE,且滞后效应非常小。此外,该改性策略显著增强了器件的环境稳定性,在相对湿度为40±5%的空气中,未封装器件经过800小时老化后仍能保持初始PCE的89%。（3）采用两步顺序沉积法,通过引入季铵卤化物（QAH）添加剂调控碘化铅（PbI₂）薄膜形貌,成功制备了具有蓬松多孔结构的PbI₂层。由于有机胺盐在多孔PbI₂层中表现出优异的扩散性能,从而促进了有机胺盐与PbI₂之间的充分反应,最终制备出具有大晶粒尺寸、低缺陷密度和高结晶质量的致密钙钛矿薄膜。实验结果表明,加入2-（乙酰氧基）-n,n,n-三甲基氯化乙烷（AtaCl）的最佳刚性和柔性器件分别实现了23.40%和21.10%的PCE。在相对湿度为40±5%的空气中,优化器件在未封装的情况下老化1000小时后,仍保留了90%以上的初始PCE。同时,优化后的柔性器件展现出卓越的机械耐久性。在曲率半径5mm的弯曲测试条件下,经过10,000次循环弯曲后,仍能保持约85%的初始PCE。（4）在SnO₂电子传输层与钙钛矿吸光层之间引入2,5-呋喃二甲酸（FDCA）作为多功能界面修饰层,成功制备了高性能刚性和柔性PSCs。FDCA中间层具有多重功能优势:首先,它能有效减少界面缺陷数量,提升SnO₂层的电子迁移率;其次,通过调控SnO₂表面能级,使其导带位置上移,从而提升界面电荷提取效率;此外,FDCA还能钝化钙钛矿埋底界面缺陷,促进钙钛矿晶体的生长,并在SnO₂与钙钛矿界面间构建有效的电荷传输通道。实验结果表明,FDCA修饰的最佳刚性器件获得了1.204 V的高开路电压(V_OC),其PCE高达24.53%。在柔性器件方面,FDCA修饰器件获得了22.10%的PCE,在相对湿度为40±5%的空气中,未封装器件经过500小时老化后仍保持90%的初始PCE。同时,优化后的柔性器件展现出良好的机械耐久性,经过10,000次弯曲循环后,仍能保持81%的初始PCE。（5）采用绿色抗溶剂碳酸二甲酯（DMC）替代传统剧毒氯苯（CB）抗溶剂,在提升器件性能的同时实现了环境友好型制备。系统比较了传统剧毒抗溶剂CB与环保型抗溶剂乙酸乙酯（EA）、DMC对钙钛矿薄膜形貌及器件性能的影响。采用DMC作为抗溶剂可显著改善钙钛矿薄膜的结晶特性,获得晶粒尺寸更大、结晶质量更高的钙钛矿薄膜。这种结构优势带来了多重效益:首先,实现了与电子传输层更理想的能级匹配;其次,有效抑制了薄膜缺陷导致的非辐射复合损失;此外,还减少了退火过程中有机组分的挥发,并有效阻碍了PbI₂杂相的形成。实验结果表明,基于DMC抗溶剂制备的最佳器件获得了25.18%的优异PCE,这一数值在该类器件结构中处于领先水平。更重要的是,该器件展现出卓越的环境稳定性,在未封装条件下老化1000小时后,仍能保持92%的初始PCE。上述研究通过系统的界面修饰工程和缺陷钝化策略,显著提升了PSCs的PCE和环境稳定性,为推进PSCs的产业化应用提供了重要的理论依据和技术支撑。更多还原

【Abstract】 Sustainable development is the long-term balanced development of the economy,society,and ecology achieved through environmental protection,promotion of clean energy,and rational utilization of clean resources.Among these clean energy sources,solar energy,as a vast reserve of clean energy,has strong market competitiveness.The conversion and utilization of solar energy,especially through the use of solar cells to convert it into electrical energy,is becoming an important way to realize this potential.Among various solar cell technologies,perovskite solar cells（PSCs）have become a cutting-edge hotspot in the current research field due to their simple structure,excellent solution processing performance,low manufacturing cost,and outstanding photoelectric conversion efficiency.Thanks to the excellent optoelectronic properties of organic-inorganic hybrid perovskite materials,the certified power conversion efficiency of single junction PSCs has exceeded 26%.However,the path to improving the performance of PSCs is not smooth.Among them,non-radiative recombination at the interface between the charge transport layer and the perovskite layer can lead to significant loss of photo generated carriers,thereby affecting the efficiency and stability of the device.To address this issue,this study aims to optimize the interface contact characteristics between the charge transport layer and the perovskite layer.Through interface modification and defect passivation strategies,non-radiative recombination of photo generated charge carriers at the interface is suppressed,reducing the number of defects and improving the transport efficiency of charge carriers,ultimately improving the efficiency and stability of PSCs.The main research contents include:（1）Optimizing the interface of PSCs using wide bandgap halide materials.Using n-hexyltrimethylammonium bromide（HTAB）as the interface modification material,surface modification was carried out on the hole transport layer poly[bis（4-phenyl）-（2,4,6-trimethylphenyl）amine]（PTAA）.By introducing HTAB layer,the interface contact between PTAA and perovskite layer（MAPbI₃）is significantly improved,the crystallization quality of MAPbI₃ is enhanced,the defect state density in PSCs is reduced,and the non-radiative recombination of interface charge carriers is effectively suppressed,resulting in a significant improvement in device performance.The experimental results showed that the champion device modified with HTAB achieved a high power conversion efficiency（PCE）of 21.01%,and the hysteresis effect was very small,significantly improved compared to the control device（17.71%）.In addition,in air with a relative humidity of 25±5%,the device without encapsulation maintained approximately 87%of its initial PCE after 1000 hours of aging,demonstrating excellent long-term stability.（2）Using choline halide(C₅H₁₄ON⁺X^-)to passivate the buried interface and surface defects of perovskite.C₅H₁₄ON⁺X^-and halide ions can effectively passivate charged ion defects,while N⁺（CH₃）_3-groups can significantly improve the environmental stability of perovskite.Among them,the use of choline chloride（CHCl）can effectively improve the crystallization characteristics of perovskite films,increase the migration rate of charge carriers,and significantly reduce the defect state density of perovskite films.These synergistic effects collectively enhance the overall performance of PSCs.The experimental results showed that the champion device modified with CHCl achieved an excellent PCE of 22.61%with very little hysteresis effect.In addition,this modification strategy significantly enhances the environmental stability of the device.In air with a relative humidity of 40±5%,the device without encapsulation can still maintain 89%of its initial PCE after 800 hours of aging.（3）By using a two-step sequential deposition method and introducing quaternary ammonium halide（QAH）additives to regulate the morphology of lead iodide（PbI₂）films,a PbI₂ layer with a fluffy porous structure was successfully prepared.Due to the excellent diffusion performance of organic amine salts in the porous PbI₂ layer,sufficient reaction between organic amine salts and PbI₂ is promoted,resulting in the preparation of dense perovskite films with large grain size,low defect density,and high crystalline quality.The experimental results showed that the champion rigid and flexible devices with the addition of 2-（acetoxy）-n,n,n-trimethylethane chloride（AtaCl）achieved high PCE of 23.40%and 21.10%,respectively.In air with a relative humidity of 40±5%,the optimized device without encapsulation retained over 90%of its initial PCE even after aging for 1000 hours.Meanwhile,the optimized flexible device exhibits excellent mechanical durability.Under the bending test conditions with a curvature radius of 5mm,after 10,000 cycles of bending,the initial PCE can still be maintained at about 85%.（4）High performance rigid and flexible PSCs were successfully prepared by introducing 2,5-furandicarboxylic acid（FDCA）as a multifunctional interface modification layer between the SnO₂ electron transport layer and the perovskite absorber layer.The intermediate layer of FDCA has multiple functional advantages:firstly,it can effectively reduce the number of interface defects and improve the electron mobility of SnO₂ layer;Secondly,by adjusting the surface energy levels of SnO₂ to shift the conduction band position upwards,the efficiency of interface charge extraction can be improved;In addition,FDCA can passivate defects at the buried interface of perovskite,promote the growth of perovskite crystals,and construct effective charge transfer channels between SnO₂ and perovskite interfaces.The experimental results showed that the FDCA modified champion rigid device achieved a high open circuit voltage(V_OC)of 1.204 V,with a high PCE of 24.53%.In terms of flexible devices,FDCA modified devices achieved a PCE of 22.10%,while flexible device without encapsulation maintained its initial PCE of 90%after 500 hours of aging in air with a relative humidity of 40±5%.At the same time,the optimized flexible device exhibits good mechanical durability,maintaining 81%of the initial PCE after 10,000 bending cycles.（5）The use of green antisolvent dimethyl carbonate（DMC）instead of traditional highly toxic chlorobenzene（CB）antisolvent has achieved environmentally friendly preparation while improving device performance.The system compared the effects of traditional highly toxic antisolvent CB with environmentally friendly antisolvents ethyl acetate（EA）and DMC on the morphology and device performance of perovskite films.The use of DMC as an antisolvent can significantly improve the crystallization characteristics of perovskite films,obtaining films with larger grain size and better crystal quality.This structural advantage brings multiple benefits:firstly,it achieves a more ideal energy level matching with the electron transport layer;Secondly,it effectively suppresses non radiative recombination losses caused by film defects;In addition,it also reduces the volatilization of organic components during annealing and effectively hinders the formation of PbI₂ impurities.The experimental results showed that the champion device prepared based on DMC antisolvent achieved an excellent PCE of 25.18%,which is at a leading level in this type of device structure.More importantly,the device without encapsulation exhibits excellent environmental stability,maintaining 92%of its initial PCE even after aging for 1000 hours.The above research has significantly improved the PCE and environmental stability of PSCs through systematic interface modification engineering and defect passivation strategies,providing important theoretical basis and technical support for promoting the industrial application of PSCs.更多还原