技术领域Technical field
本发明涉及一种宽带隙钙钛矿太阳能电池的制备方法及其应用，尤其是一种可制备出表面致密平滑、结晶度高、缺陷态密度低且晶体取向好的宽带隙钙钛矿薄膜及其钙钛矿太阳能电池器件的简单方法，属于光电材料与器件技术领域。The invention relates to a method for preparing a wide band gap perovskite solar cell and its application, particularly a method for preparing a wide band gap perovskite film with a dense and smooth surface, high crystallinity, low defect state density and good crystal orientation. Its simple method of perovskite solar cell devices belongs to the field of optoelectronic materials and device technology.
背景技术Background technique
能源一直是人类文明发展的重要推动力，化石能源的使用加速了科技的发展，提高了社会生产力。但是在社会现代化步伐加快的同时，“能源危机”以及化石能源燃烧所带来的环境污染问题也随之产生，这也越来越受到人们的重视。拓展可再生、环境友好的新能源势在必行。于是，水能、风能、太阳能、生物质能、地热能、潮汐能等可再生能源的研究与开发应运而生。其中，“取之不尽，用之不竭”的太阳能是最清洁的能源，且获得便利，这对于社会的可持续发展至关重要。因此，太阳能作为未来人类重要的能源供给被寄予很大希望，而开发低成本、高效率的新型太阳能电池也成为近年来的研究热点。Energy has always been an important driving force for the development of human civilization. The use of fossil energy has accelerated the development of science and technology and improved social productivity. However, as the pace of social modernization accelerates, the "energy crisis" and environmental pollution problems caused by the burning of fossil energy have also arisen, which have attracted more and more people's attention. It is imperative to expand renewable and environmentally friendly new energy sources. As a result, the research and development of renewable energy sources such as water energy, wind energy, solar energy, biomass energy, geothermal energy, and tidal energy came into being. Among them, "inexhaustible" solar energy is the cleanest energy, and it is convenient to obtain, which is crucial to the sustainable development of society. Therefore, solar energy has great hopes as an important energy supply for mankind in the future, and the development of new low-cost, high-efficiency solar cells has also become a research hotspot in recent years.
目前市场上占主导地位的硅基太阳能电池技术成熟，光电转换效率相对较高，但生产成本高，工艺复杂。第二代多元化合物薄膜太阳能电池光电转换效率较高，器件性能稳定，但这类电池使用的材料部分元素具有毒性或者储量稀少，限制了大面积的推广使用。因此，研究者们一直致力于寻找光电转换效率高、成本低、工艺简单、绿色环保的替代材料。有机-无机杂化钙钛矿太阳能电池以其优异的光电性质以及低成本、可低温处理、可大面积工艺制造等独特的优势在光伏研究领域取得了前所未有的进步，被认为是最有潜力的“第三代光伏材料”的代表之一。短短十年时间，其光电转换效率从3.8％迅猛提升到25.5％，接近占市场主导地位的晶硅太阳能电池的效率记录。其效率提升速度远超过传统晶硅、碲化镉和铜铟镓硒等第一、第二代光伏材料，因此，钙钛矿光伏器件有望成为下一代光伏器件的领跑者。Currently, silicon-based solar cells, which dominate the market, have mature technology and relatively high photoelectric conversion efficiency, but their production costs are high and their processes are complex. The second-generation multi-compound thin-film solar cells have high photoelectric conversion efficiency and stable device performance. However, some elements of the materials used in this type of cells are toxic or have scarce reserves, which limits their large-area promotion and use. Therefore, researchers have been committed to finding alternative materials with high photoelectric conversion efficiency, low cost, simple process, and green environmental protection. Organic-inorganic hybrid perovskite solar cells have made unprecedented progress in the field of photovoltaic research due to their excellent photoelectric properties and unique advantages such as low cost, low-temperature processing, and large-area manufacturing, and are considered to have the most potential. One of the representatives of "third generation photovoltaic materials". In just ten years, its photoelectric conversion efficiency has rapidly increased from 3.8% to 25.5%, which is close to the efficiency record of crystalline silicon solar cells that dominate the market. Its efficiency improvement rate is much faster than the first and second generation photovoltaic materials such as traditional crystalline silicon, cadmium telluride and copper indium gallium selenide. Therefore, perovskite photovoltaic devices are expected to become the leader of the next generation of photovoltaic devices.
然而，其效率还远低于单节太阳能电池的理论肖克利-奎伊瑟效率限制。将宽带隙顶部子电池和窄带隙底部子电池互连制造的串联光伏结构已被证明是一种可以提高器件光伏性能，使其超出单节太阳能电池效率限制并降低光伏发电平均成本的有效策略。相对于高速发展的窄带隙太阳能电池，宽带隙太阳能电池受到合适材料和研究方法的选择的高度限制。甲铵铅混合卤素钙钛矿的带隙连续可调性满足串联结构中顶部和底部电池之间电流和吸收范围匹配的带隙要求，成为宽带隙钙钛矿太阳能电池吸光材料的理想候选者。尽管宽带隙钙钛矿太阳能电池的研究已取得了显着进展，但在操作条件下，当钙钛矿的组分中溴含量超过20％时，通常在混合卤素钙钛矿合金中观察到可逆相偏析,即形成富含溴化物和富含碘化物的区域。这种所谓的“胡克效应”会导致宽带隙钙钛矿太阳能电池中较大的开路电压损失以及差的长期运行稳定性。此外，钙钛矿太阳能电池在1.7-1.9eV的最佳光学带隙范围内获得最大效率仍低于20％，这限制了低成本，溶液加工的钙钛矿基串联光伏组件的开发与应用。However, its efficiency is still well below the theoretical Shockley-Quisser efficiency limit of a single solar cell. Tandem photovoltaic structures fabricated by interconnecting wide-bandgap top sub-cells and narrow-bandgap bottom sub-cells have proven to be an effective strategy to improve device photovoltaic performance beyond single-cell solar cell efficiency limits and reduce the average cost of photovoltaic power generation. In contrast to the rapidly developing narrow-bandgap solar cells, wide-bandgap solar cells are highly restricted by the selection of suitable materials and research methods. The continuous tunability of the band gap of methylammonium lead mixed halide perovskites meets the band gap requirements for current and absorption range matching between the top and bottom cells in a tandem structure, making it an ideal candidate for light-absorbing materials in wide-bandgap perovskite solar cells. Although significant progress has been made in the research of wide bandgap perovskite solar cells, under operating conditions, reversibility is usually observed in mixed halogen perovskite alloys when the bromine content in the composition of the perovskite exceeds 20%. Phase segregation, that is, the formation of bromide-rich and iodide-rich regions. This so-called "Hooke effect" can lead to large open-circuit voltage losses and poor long-term operating stability in wide-bandgap perovskite solar cells. In addition, the maximum efficiency achieved by perovskite solar cells in the optimal optical band gap range of 1.7-1.9 eV is still less than 20%, which limits the development and application of low-cost, solution-processed perovskite-based tandem photovoltaic modules.
现在研究人员将重点放在组成调节，界面控制和器件结构优化上，很少有人关注钙钛矿前驱体溶液所用的溶剂。对于溶液处理的薄膜，溶剂效应可能会对薄膜质量产生重大影响，例如陷阱密度，晶体尺寸，稳定性。离子液体醋酸甲铵作为钙钛矿前驱体溶液的溶剂已成功在空气环境中制备出高器件效率和具有出色稳定性的钙钛矿太阳能电池。但是，对于宽带隙钙钛矿中这种离子液体溶剂的使用如何转化为钙钛矿薄膜的整体质量以及器件性能知之甚少。本发明研究首次在宽带隙钙钛矿中将醋酸甲铵作为钙钛矿前驱体溶液的溶剂，并对钙钛矿薄膜和器件性能的变化及相关机制原理进行深入探究。相较于传统混合溶剂DMF/DMSO，离子液体醋酸甲铵作为宽带隙钙钛矿前驱体溶剂，并采用一步加热旋涂技术制备的宽带隙钙钛矿薄膜及其钙钛矿太阳能电池的性能和稳定性都得到了很大提升。Now researchers focus on composition adjustment, interface control and device structure optimization, and few people pay attention to the solvent used in the perovskite precursor solution. For solution-processed films, solvent effects can have a significant impact on film quality, such as trap density, crystal size, stability. The ionic liquid methylammonium acetate has been used as a solvent in the perovskite precursor solution to successfully prepare perovskite solar cells with high device efficiency and excellent stability in an air environment. However, little is known about how the use of such ionic liquid solvents in wide-bandgap perovskites translates into the overall quality of the perovskite film and thus device performance. The research of this invention is the first to use methylammonium acetate as the solvent of the perovskite precursor solution in a wide bandgap perovskite, and conducts in-depth exploration of the changes in perovskite film and device performance and related mechanism principles. Compared with the traditional mixed solvent DMF/DMSO, the ionic liquid methylammonium acetate is used as the wide band gap perovskite precursor solvent, and the performance and performance of the wide band gap perovskite film and its perovskite solar cell are prepared using one-step heating spin coating technology. Stability has been greatly improved.
发明内容Contents of the invention
本发明解决的技术问题是针对宽带隙钙钛矿薄膜及其钙钛矿太阳能电池易在光照条件下发生光致相分离，降低薄膜的质量和器件性能，提出一种宽带隙钙钛矿薄膜及其钙钛矿太阳能电池的制备方法。The technical problem solved by the present invention is to propose a wide band gap perovskite film and its perovskite solar cell that are prone to photoinduced phase separation under illumination conditions, thereby reducing the quality of the film and device performance. Preparation method of its perovskite solar cell.
为了解决上述技术问题，本发明提出的技术方案是：一种宽带隙钙钛矿太阳能电池的制备方法，包括以下步骤：In order to solve the above technical problems, the technical solution proposed by the present invention is: a preparation method of a wide bandgap perovskite solar cell, which includes the following steps:
(1)将碘化铅，溴化铅，甲基碘化铵和甲基溴化铵按照摩尔比3:1:3:1溶解于离子液体醋酸甲铵中配制宽带隙钙钛矿前驱体溶液，在50-70℃下搅拌6-12小时；(1) Dissolve lead iodide, lead bromide, methylammonium iodide and methylammonium bromide in the ionic liquid methylammonium acetate according to the molar ratio of 3:1:3:1 to prepare a wide bandgap perovskite precursor solution , stir at 50-70°C for 6-12 hours;
(2)在清洗并且处理好的ITO透明导电玻璃上旋涂电子传输材料；(2) Spin-coat the electron transmission material on the cleaned and processed ITO transparent conductive glass;
(3)在旋涂好电子传输材料的ITO透明导电玻璃上旋涂界面材料；(3) Spin-coat the interface material on the ITO transparent conductive glass spin-coated with the electron transmission material;
(4)在沉积有电子传输材料和界面材料的ITO基底上，采用一步加热旋涂技术制备宽带隙钙钛矿薄膜，经过退火处理后得到致密光滑，结晶度高，缺陷态密度低且晶体取向好的宽带隙钙钛矿薄膜(4) On the ITO substrate deposited with electron transport materials and interface materials, a one-step heated spin coating technology is used to prepare a wide bandgap perovskite film. After annealing treatment, the film is dense and smooth, with high crystallinity, low defect state density and crystal orientation. Good wide bandgap perovskite films
(5)在此宽带隙钙钛矿薄膜上旋涂空穴传输材料；(5) Spin-coat hole transport materials on this wide bandgap perovskite film;
(6)在空穴传输材料上真空蒸镀界面修饰材料和金属电极。(6) Vacuum evaporate the interface modification material and metal electrode on the hole transport material.
优选的，所述的步骤(1)中宽带隙钙钛矿前驱体溶液的浓度为300-600mg/mL。Preferably, the concentration of the wide-bandgap perovskite precursor solution in step (1) is 300-600 mg/mL.
优选的，所述的步骤(2)中透明导电ITO电极上沉积的电子传输层为CPTA,其中CPTA以2-6mg/mL的浓度溶于DMF溶液中，具体步骤为：旋涂CPTA后，在140℃下退火10-30min。Preferably, the electron transport layer deposited on the transparent conductive ITO electrode in step (2) is CPTA, wherein CPTA is dissolved in a DMF solution at a concentration of 2-6 mg/mL. The specific steps are: after spin-coating CPTA, Anneal at 140℃ for 10-30min.
优选的，所述的步骤(3)中在旋涂好电子传输材料的ITO透明导电玻璃上旋涂的界面材料为BACl,其中BACl以10-30mg/mL的浓度溶于DMSO溶液中。Preferably, the interface material spin-coated on the ITO transparent conductive glass spin-coated with the electron transport material in step (3) is BACl, where BACl is dissolved in the DMSO solution at a concentration of 10-30 mg/mL.
优选的，所述的步骤(4)中制备宽带隙钙钛矿薄膜的加热旋涂技术的基底温度为70-120℃，退火温度为80-120℃，退火时间30s-30min。Preferably, the substrate temperature of the heated spin coating technology used to prepare the wide bandgap perovskite film in step (4) is 70-120°C, the annealing temperature is 80-120°C, and the annealing time is 30s-30min.
优选的，所述的步骤(5)中在宽带隙钙钛矿薄膜上旋涂的的空穴传输材料为Spiro-OMeTAD，具体操作如下：Preferably, the hole transport material spin-coated on the wide bandgap perovskite film in step (5) is Spiro-OMeTAD. The specific operation is as follows:
(1)将73.2mg的Spiro-OMeTAD溶解在1mL的氯苯中；(1) Dissolve 73.2 mg of Spiro-OMeTAD in 1 mL of chlorobenzene;
(2)将520mg的锂盐溶解在1mL的乙腈溶液中；(2) Dissolve 520 mg of lithium salt in 1 mL of acetonitrile solution;
(3)将17.6μL锂盐溶液添加到Spiro-OMeTAD溶液中；(3) Add 17.6 μL lithium salt solution to the Spiro-OMeTAD solution;
(4)将28.8μLTBP溶液添加到Spiro-OMeTAD溶液中；(4) Add 28.8μL TBP solution to Spiro-OMeTAD solution;
(5)将混合溶液常温搅拌2小时。(5) Stir the mixed solution at room temperature for 2 hours.
优选的，所述的步骤(6)中在宽带隙钙钛矿薄膜上真空蒸镀的界面修饰材料为MoO3，金属电极为Ag，具体步骤为：Preferably, the interface modification material vacuum evaporated on the wide bandgap perovskite film in step (6) is MoO3 and the metal electrode is Ag. The specific steps are:
(1)修饰层MoO3的厚度为5nm；(1) The thickness of the modification layer MoO3 is 5nm;
(2)金属Ag电极的厚度为100nm。(2) The thickness of the metal Ag electrode is 100nm.
优选的，包括以下步骤：Preferably, it includes the following steps:
步骤(1)将刻蚀好的ITO导电玻璃依次在乙醇、超纯水加清洗剂、超纯水、丙酮、乙醇中各超声20min，氮气吹干后放入120℃的烘箱中烘烤30min，得到洁净的ITO基底。Step (1) Ultrasonicate the etched ITO conductive glass in ethanol, ultrapure water plus cleaning agent, ultrapure water, acetone, and ethanol for 20 minutes each, blow dry with nitrogen, and bake in an oven at 120°C for 30 minutes. Obtain a clean ITO substrate.
步骤(2)将236.93mg的碘化铅，81.18mg的甲基碘化铵，62.87mg的溴化铅，19.01mg的甲基溴化铵溶于离子液体醋酸甲铵中，在60℃下搅拌12小时；Step (2) Dissolve 236.93 mg of lead iodide, 81.18 mg of methyl ammonium iodide, 62.87 mg of lead bromide, and 19.01 mg of methyl ammonium bromide in the ionic liquid methyl ammonium acetate, and stir at 60°C 12 hours;
步骤(3)将73.2mg的Spiro-OMeTAD溶解在1mL的氯苯中；将520mg的锂盐溶解在1mL的乙腈溶液中；添加17.6μL锂盐溶液到Spiro-OMeTAD溶液中；添加28.8μLTBP溶液到Spiro-OMeTAD溶液中；混合溶液整体搅拌2小时；Step (3) Dissolve 73.2 mg of Spiro-OMeTAD in 1 mL of chlorobenzene; dissolve 520 mg of lithium salt in 1 mL of acetonitrile solution; add 17.6 μL of lithium salt solution to the Spiro-OMeTAD solution; add 28.8 μL of TBP solution to Spiro-OMeTAD solution; stir the entire mixed solution for 2 hours;
步骤(4)将步骤(1)中清洗干净的ITO基片紫外臭氧处理15分钟；Step (4) Treat the ITO substrate cleaned in step (1) with UV ozone for 15 minutes;
步骤(5)取电子传输材料CPTA 40μL滴到步骤(4)处理好的ITO基板上，在4000转每分钟的转速下旋涂30秒，再将旋涂有CPTA的ITO在140℃下退火15分钟；Step (5) Drop 40 μL of the electron transport material CPTA onto the ITO substrate processed in step (4), spin-coat it at 4000 rpm for 30 seconds, and then anneal the ITO spin-coated with CPTA at 140°C for 15 seconds. minute;
步骤(6)在步骤(5)退火完成的旋涂有电子传输层的ITO导电基底上旋涂BACl界面材料，旋涂条件为每分钟4000转，旋涂时间为30秒；Step (6) Spin-coat the BACl interface material on the ITO conductive substrate spin-coated with the electron transport layer that has been annealed in step (5). The spin-coating conditions are 4000 revolutions per minute and the spin-coating time is 30 seconds;
步骤(7)将步骤(6)中旋涂完界面材料的ITO导电基底放置在加热旋涂仪基底上，预热5min；Step (7) Place the ITO conductive substrate spin-coated with the interface material in step (6) on the base of the heated spin coater and preheat for 5 minutes;
步骤(8)取步骤(2)中配制好的钙钛矿前驱体溶液90μL滴到步骤7)中预热的ITO基片上，旋涂成膜，然后进行退火，得到钙钛矿薄膜。旋涂钙钛矿前驱体溶液的转速为每分钟4000转，旋涂时间为20秒，在空气中100℃下退火5min；Step (8) Drop 90 μL of the perovskite precursor solution prepared in step (2) onto the ITO substrate preheated in step 7), spin-coat to form a film, and then anneal to obtain a perovskite film. The rotation speed of spin-coating the perovskite precursor solution is 4000 revolutions per minute, the spin-coating time is 20 seconds, and annealed in air at 100°C for 5 minutes;
步骤(9)将步骤(3)中配制的空穴传输材料旋涂到步骤(8)退火好的钙钛矿薄膜上，旋涂Spiro-OMeTAD采用每分钟3000转，旋涂时间为30秒，形成空穴传输层；Step (9) Spin-coat the hole transport material prepared in step (3) onto the perovskite film annealed in step (8). Spin-coat Spiro-OMeTAD at 3000 revolutions per minute, and the spin-coating time is 30 seconds. Form a hole transport layer;
步骤(10)采用真空蒸镀技术，在步骤(9)的空穴传输层上蒸镀5nm MoO3，然后再蒸镀100nm金属电极Ag，制得钙钛矿太阳能电池。Step (10) uses vacuum evaporation technology to evaporate 5 nm MoO3 on the hole transport layer in step (9), and then evaporate 100 nm metal electrode Ag to prepare a perovskite solar cell.
为了解决上述问题，本发明提出的另一技术方案是：所述的宽带隙钙钛矿太阳能电池的制备方法制备的钙钛矿太阳能电池。In order to solve the above problems, another technical solution proposed by the present invention is a perovskite solar cell prepared by the method for preparing a wide bandgap perovskite solar cell.
为了解决上述问题，本发明提出的另一技术方案是：所述的宽带隙钙钛矿太阳能电池在光电领域中的应用。In order to solve the above problems, another technical solution proposed by the present invention is the application of the wide bandgap perovskite solar cell in the field of optoelectronics.
本发明的有益效果：Beneficial effects of the present invention:
(1)将碘化铅，溴化铅，甲基碘化铵和甲基溴化铵按照摩尔比3:1:3:1溶解于离子液体醋酸甲铵作为宽带隙钙钛矿前驱体溶液的溶剂，并采用一步加热旋涂技术制备宽带隙钙钛矿薄膜，加快了晶体的成核过程，前驱体溶液中更强的N-H···Br氢键的存在又延缓了钙钛矿晶体的生长过程，解耦了晶体成核和晶体生长过程，得到了表面致密平滑，结晶度高，缺陷态密度低且晶体取向好的宽带隙钙钛矿薄膜；(1) Dissolve lead iodide, lead bromide, methyl ammonium iodide and methyl ammonium bromide in the ionic liquid methylammonium acetate according to the molar ratio of 3:1:3:1 as a wide bandgap perovskite precursor solution. Solvent, and a one-step heated spin coating technology is used to prepare a wide bandgap perovskite film, which accelerates the nucleation process of the crystal. The presence of stronger N-H···Br hydrogen bonds in the precursor solution delays the growth of the perovskite crystal. The process decouples the crystal nucleation and crystal growth processes, resulting in a wide-bandgap perovskite film with a dense and smooth surface, high crystallinity, low defect state density and good crystal orientation;
(2)在空气中采用一步加热旋涂技术相较于反溶剂法不仅操作简单，无毒可在具有高湿度的空气中制备，大大减少了薄膜的制备成本,在产业化方面更有优势；(2) Compared with the anti-solvent method, the one-step heating spin coating technology in the air is not only simple to operate, non-toxic and can be prepared in air with high humidity, which greatly reduces the preparation cost of the film, and has more advantages in industrialization;
(3)使用本发明的方法制备的宽带隙钙钛矿太阳能电池的光电转换效率大于20％，这是大于1.7eV的宽带隙钙钛矿太阳能电池效率首次报道超过20％，与此相成鲜明对比的是，在氮气氛围下传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿太阳能电池的光电转换效率为15.53％。(3) The photoelectric conversion efficiency of the wide-bandgap perovskite solar cell prepared using the method of the present invention is greater than 20%. This is the first time that the efficiency of a wide-bandgap perovskite solar cell greater than 1.7eV has been reported to exceed 20%, which is in sharp contrast to this. In contrast, the photoelectric conversion efficiency of a wide-bandgap perovskite solar cell prepared by the traditional mixed solvent DMF/DMSO under a nitrogen atmosphere was 15.53%.
(4)使用本发明的方法制备的宽带隙钙钛矿太阳能电池的器件性能和稳定性都有了明显的提升。(4) The device performance and stability of the wide-bandgap perovskite solar cells prepared using the method of the present invention are significantly improved.
附图说明Description of the drawings
下面结合附图对本发明的作进一步说明。The present invention will be further described below in conjunction with the accompanying drawings.
图1是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的紫外-可见吸收光谱图；Figure 1 is the ultraviolet-visible absorption spectrum of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention;
图2是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的SEM对比图；Figure 2 is a SEM comparison diagram of a wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention;
图3是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的XRD对比图；Figure 3 is an XRD comparison chart of a wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention;
图4是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的GIWAXS对比图；Figure 4 is a GIWAXS comparison chart of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention;
图5是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿前驱体溶液的质子核磁共振对比图；Figure 5 is a proton nuclear magnetic resonance comparison diagram of a wide-bandgap perovskite precursor solution prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention;
图6是本发明的基于离子液体醋酸甲铵制备的不同前驱体溶液的质子核磁共振谱图；Figure 6 is a proton nuclear magnetic resonance spectrum of different precursor solutions prepared based on the ionic liquid methylammonium acetate of the present invention;
图7是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿太阳能电池的光电转换效率J-V曲线对比图；Figure 7 is a comparison chart of the photoelectric conversion efficiency J-V curve of the wide-bandgap perovskite solar cell prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention;
图8是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿太阳能电池在氮气保护下的光电转换效率随时间变化的曲线对比图；Figure 8 is a graph comparing the photoelectric conversion efficiency with time under nitrogen protection of the wide-bandgap perovskite solar cell prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention;
图9是本发明的基于离子液体醋酸甲铵制备的宽带隙钙钛矿太阳能电池的光电转换效率J-V曲线图；Figure 9 is a J-V curve of the photoelectric conversion efficiency of the wide-bandgap perovskite solar cell prepared based on the ionic liquid methylammonium acetate of the present invention;
图10是本发明的基于离子液体醋酸甲铵制备的宽带隙钙钛矿太阳能电池示意图。Figure 10 is a schematic diagram of a wide-gap perovskite solar cell prepared based on ionic liquid methylammonium acetate of the present invention.
具体实施方式Detailed ways
实施例1Example 1
本实施例为发明的宽带隙钙钛矿太阳能电池制备方法及其钙钛矿太阳能电池，本实施例宽带隙钙钛矿太阳能电池表面致密平滑，结晶度高，缺陷态密度低且晶体取向好，主要包括以下步骤：This embodiment is the invented method for preparing a wide band gap perovskite solar cell and its perovskite solar cell. The wide band gap perovskite solar cell in this embodiment has a dense and smooth surface, high crystallinity, low defect state density and good crystal orientation. It mainly includes the following steps:
步骤1)将刻蚀好的ITO导电玻璃依次在乙醇、超纯水加清洗剂、超纯水、丙酮、乙醇中各超声20min。氮气吹干后放入120℃的烘箱中烘烤30min，得到洁净的ITO基底。Step 1) Ultrasonicate the etched ITO conductive glass in ethanol, ultrapure water plus cleaning agent, ultrapure water, acetone, and ethanol for 20 minutes each. Blow dry with nitrogen and bake in an oven at 120°C for 30 minutes to obtain a clean ITO substrate.
步骤2)将236.93mg的碘化铅，81.18mg的甲基碘化铵，62.87mg的溴化铅，19.01mg的甲基溴化铵溶于离子液体醋酸甲铵中，在60℃下搅拌12小时。Step 2) Dissolve 236.93 mg of lead iodide, 81.18 mg of methyl ammonium iodide, 62.87 mg of lead bromide, and 19.01 mg of methyl ammonium bromide in the ionic liquid methyl ammonium acetate, and stir at 60°C for 12 Hour.
步骤3)将73.2mg的Spiro-OMeTAD溶解在1mL的氯苯中；将520mg的锂盐溶解在1mL的乙腈溶液中；添加17.6μL锂盐溶液到Spiro-OMeTAD溶液中；添加28.8μLTBP溶液到Spiro-OMeTAD溶液中；混合溶液整体搅拌2小时。Step 3) Dissolve 73.2 mg of Spiro-OMeTAD in 1 mL of chlorobenzene; dissolve 520 mg of lithium salt in 1 mL of acetonitrile solution; add 17.6 μL of lithium salt solution to Spiro-OMeTAD solution; add 28.8 μL of TBP solution to Spiro -OMeTAD solution; stir the entire mixed solution for 2 hours.
步骤4)将步骤1)中清洗干净的ITO基片紫外臭氧处理15分钟。Step 4) Treat the ITO substrate cleaned in step 1) with UV ozone for 15 minutes.
步骤5)取电子传输材料CPTA 40μL滴到步骤4)处理好的ITO基板上，在4000转每分钟的转速下旋涂30秒，再将旋涂有CPTA的ITO在140℃下退火15分钟。Step 5) Drop 40 μL of the electron transport material CPTA onto the ITO substrate processed in step 4), spin-coat it at 4000 rpm for 30 seconds, and then anneal the ITO spin-coated with CPTA at 140°C for 15 minutes.
步骤6)在步骤5)退火完成的旋涂有电子传输层的ITO导电基底上旋涂BACl界面材料，旋涂条件为每分钟4000转，旋涂时间为30秒。Step 6) Spin-coat the BACl interface material on the ITO conductive substrate spin-coated with the electron transport layer that has been annealed in step 5). The spin-coating conditions are 4000 revolutions per minute and the spin-coating time is 30 seconds.
步骤7)将步骤6)中旋涂完界面材料的ITO导电基底放置在加热旋涂仪基底上，预热5min。Step 7) Place the ITO conductive substrate spin-coated with the interface material in step 6) on the base of the heated spin coater and preheat for 5 minutes.
步骤8)取步骤2)中配制好的钙钛矿前驱体溶液90μL滴到步骤7)中预热的ITO基片上，旋涂成膜，然后进行退火，得到钙钛矿薄膜。旋涂钙钛矿前驱体溶液的转速为每分钟4000转，旋涂时间为20秒，在空气中100℃下退火5min。Step 8) Drop 90 μL of the perovskite precursor solution prepared in step 2) onto the ITO substrate preheated in step 7), spin-coat to form a film, and then anneal to obtain a perovskite film. The rotation speed of spin-coating the perovskite precursor solution is 4000 revolutions per minute, the spin-coating time is 20 seconds, and the solution is annealed in air at 100°C for 5 minutes.
步骤9)将步骤3)中配制的空穴传输材料旋涂到步骤8)退火好的钙钛矿薄膜上，旋涂Spiro-OMeTAD采用每分钟3000转，旋涂时间为30秒，形成空穴传输层。Step 9) Spin-coat the hole transport material prepared in step 3) onto the annealed perovskite film in step 8). Spin-coat Spiro-OMeTAD at 3000 revolutions per minute and spin-coating time for 30 seconds to form holes. transport layer.
步骤10)采用真空蒸镀技术，在步骤9)的空穴传输层上蒸镀5nm MoO3，然后再蒸镀100nm金属电极Ag，制得钙钛矿太阳能电池。Step 10) Use vacuum evaporation technology to evaporate 5 nm MoO3 on the hole transport layer in step 9), and then evaporate 100 nm metal electrode Ag to prepare a perovskite solar cell.
步骤11)在标准测试条件下(AM 1.5G光照)，本实例所制备基于醋酸甲铵制备的钙钛矿电池器件性能参数分别是，能量转换效率20.59％，开路电压为1.22V，短路电流为20.85mA/cm2，填充因子为81.11％；Step 11) Under standard test conditions (AM 1.5G illumination), the performance parameters of the perovskite cell device prepared in this example based on methylammonium acetate are: energy conversion efficiency 20.59%, open circuit voltage 1.22V, short circuit current: 20.85mA/cm2 , filling factor is 81.11%;
图1是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的紫外-可见吸收光谱图，不同溶剂制备的宽带隙钙钛矿薄膜的光学带隙均为1.71eV；Figure 1 is the ultraviolet-visible absorption spectrum of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention. The optical band gaps of the wide-bandgap perovskite film prepared with different solvents are uniform. is 1.71eV;
图2是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的SEM对比图，基于传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的晶粒尺寸在250nm左右，而基于离子液体醋酸甲铵制备的宽带隙钙钛矿薄膜的晶粒尺寸达到微米级且薄膜表面光滑；Figure 2 is a SEM comparison diagram of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention. The crystal grains of the wide-bandgap perovskite film prepared based on the traditional mixed solvent DMF/DMSO The size is about 250nm, and the grain size of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate reaches the micron level and the film surface is smooth;
图3是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的XRD对比图，基于离子液体醋酸甲铵制备的宽带隙钙钛矿薄膜的峰衍射强度更高，衍射峰半高宽更小，表明薄膜的结晶度更好；Figure 3 is an XRD comparison chart of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention. The peak diffraction intensity of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate. Higher, the half-height width of the diffraction peak is smaller, indicating that the crystallinity of the film is better;
图4是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿薄膜的GIWAXS对比图，基于离子液体醋酸甲铵制备的宽带隙钙钛矿薄膜的结晶取向度更好，晶体沿垂直于基底生长程度更高，有利于电荷的传输；Figure 4 is a GIWAXS comparison chart of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention. The crystal orientation degree of the wide-bandgap perovskite film prepared based on the ionic liquid methylammonium acetate. Better, the crystal grows vertically to the substrate to a higher degree, which is beneficial to charge transport;
图5是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿前驱体溶液的质子核磁共振对比图，基于离子液体醋酸甲铵制备的宽带隙钙钛矿前驱体溶液中检测到醋酸甲铵和前驱体之间存在一定的相互作用，而在传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿前驱体溶液中并没有观测到；Figure 5 is a proton nuclear magnetic resonance comparison diagram of the wide-bandgap perovskite precursor solution prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention. The wide-bandgap perovskite precursor prepared based on the ionic liquid methylammonium acetate. A certain interaction between methylammonium acetate and the precursor was detected in the bulk solution, but was not observed in the wide-bandgap perovskite precursor solution prepared by the traditional mixed solvent DMF/DMSO;
图6是本发明的基于离子液体醋酸甲铵制备的不同前驱体溶液的质子核磁共振谱图，离子液体醋酸甲铵和碘以及溴元素都会形成氢键，其中N-H···Br氢键比N-H···I氢键更强，对于富溴元素的宽带隙钙钛矿，离子液体醋酸甲铵和溴元素之间的相互作用有利于宽带隙钙钛矿薄膜的制备；Figure 6 is a proton nuclear magnetic resonance spectrum of different precursor solutions prepared based on the ionic liquid methylammonium acetate of the present invention. The ionic liquid methylammonium acetate can form hydrogen bonds with iodine and bromine elements, in which the N-H···Br hydrogen bond ratio is N-H ···I hydrogen bonds are stronger. For bromine-rich wide bandgap perovskites, the interaction between ionic liquid methylammonium acetate and bromine elements is beneficial to the preparation of wide bandgap perovskite films;
图7是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿太阳能电池的光电转换效率J-V曲线对比图，基于离子液体醋酸甲铵制备的宽带隙钙钛矿太阳能电池的效率达到20.59％，这是基于大于1.7eV的宽带隙钙钛矿器件效率首次被报道超过20％；Figure 7 is a comparison chart of the photoelectric conversion efficiency J-V curve of the wide-bandgap perovskite solar cell prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention. The wide-bandgap perovskite prepared based on the ionic liquid methylammonium acetate The efficiency of the solar cell reached 20.59%, which is the first time that the efficiency of a wide-bandgap perovskite device based on greater than 1.7eV has been reported to exceed 20%;
图8是本发明的基于离子液体醋酸甲铵和传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿太阳能电池在氮气保护下的光电转换效率随时间变化的曲线对比图。在氮气氛围下，基于离子液体醋酸甲铵制备的宽带隙钙钛矿太阳能电池在放置超过1200小时后仍然保持初始效率的95％以上，而基于传统混合溶剂DMF/DMSO制备的宽带隙钙钛矿太阳能电池的效率在同等条件的储藏下衰减至初始效率的83％；Figure 8 is a graph comparing the photoelectric conversion efficiency with time under nitrogen protection of the wide-bandgap perovskite solar cell prepared based on the ionic liquid methylammonium acetate and the traditional mixed solvent DMF/DMSO of the present invention. In a nitrogen atmosphere, wide-bandgap perovskite solar cells based on the ionic liquid methylammonium acetate still maintain more than 95% of the initial efficiency after being left for more than 1,200 hours, while wide-bandgap perovskites based on the traditional mixed solvent DMF/DMSO The efficiency of solar cells decays to 83% of the initial efficiency under the same storage conditions;
对比例1Comparative example 1
本实施例为发明的宽带隙钙钛矿太阳能电池，主要包括以下步骤：This embodiment is the invented wide bandgap perovskite solar cell, which mainly includes the following steps:
步骤1)将刻蚀好的ITO导电玻璃依次在乙醇、超纯水加清洗剂、超纯水、丙酮、乙醇中各超声20min。氮气吹干后放入120℃的烘箱中烘烤30min，得到洁净的ITO基底。Step 1) Ultrasonicate the etched ITO conductive glass in ethanol, ultrapure water plus cleaning agent, ultrapure water, acetone, and ethanol for 20 minutes each. Blow dry with nitrogen and bake in an oven at 120°C for 30 minutes to obtain a clean ITO substrate.
步骤2)将315.37mg的碘化铅，27.19mg的甲基碘化铵，57.45mg的甲基溴化铵溶于离子液体醋酸甲铵中，在60℃下搅拌12小时。Step 2) Dissolve 315.37 mg of lead iodide, 27.19 mg of methyl ammonium iodide, and 57.45 mg of methyl ammonium bromide in the ionic liquid methyl ammonium acetate, and stir at 60°C for 12 hours.
步骤3)将73.2mg的Spiro-OMeTAD溶解在1mL的氯苯中；将520mg的锂盐溶解在1mL的乙腈溶液中；添加17.6μL锂盐溶液到Spiro-OMeTAD溶液中；添加28.8μLTBP溶液到Spiro-OMeTAD溶液中；混合溶液整体搅拌2小时。Step 3) Dissolve 73.2 mg of Spiro-OMeTAD in 1 mL of chlorobenzene; dissolve 520 mg of lithium salt in 1 mL of acetonitrile solution; add 17.6 μL of lithium salt solution to Spiro-OMeTAD solution; add 28.8 μL of TBP solution to Spiro -OMeTAD solution; stir the entire mixed solution for 2 hours.
步骤4)将步骤1)中清洗干净的ITO基片紫外臭氧处理15分钟。Step 4) Treat the ITO substrate cleaned in step 1) with UV ozone for 15 minutes.
步骤5)取电子传输材料CPTA 40μL滴到步骤4)处理好的ITO基板上，在4000转每分钟的转速下旋涂30秒，再将旋涂有CPTA的ITO在140℃下退火15分钟。Step 5) Drop 40 μL of the electron transport material CPTA onto the ITO substrate processed in step 4), spin-coat it at 4000 rpm for 30 seconds, and then anneal the ITO spin-coated with CPTA at 140°C for 15 minutes.
步骤6)在步骤5)退火完成的旋涂有电子传输层的ITO导电基底上旋涂BACl界面材料，旋涂条件为每分钟4000转，旋涂时间为30秒。Step 6) Spin-coat the BACl interface material on the ITO conductive substrate spin-coated with the electron transport layer that has been annealed in step 5). The spin-coating conditions are 4000 revolutions per minute and the spin-coating time is 30 seconds.
步骤7)将步骤6)中旋涂完界面材料的ITO导电基底放置在加热旋涂仪基底上，预热5min。Step 7) Place the ITO conductive substrate spin-coated with the interface material in step 6) on the base of the heated spin coater and preheat for 5 minutes.
步骤8)取步骤2)中配制好的钙钛矿前驱体溶液90μL滴到步骤7)中预热的ITO基片上，旋涂成膜，然后进行退火，得到钙钛矿薄膜。旋涂钙钛矿前驱体溶液的转速为每分钟4000转，旋涂时间为20秒，在空气中100℃下退火5min。Step 8) Drop 90 μL of the perovskite precursor solution prepared in step 2) onto the ITO substrate preheated in step 7), spin-coat to form a film, and then anneal to obtain a perovskite film. The rotation speed of spin-coating the perovskite precursor solution is 4000 revolutions per minute, the spin-coating time is 20 seconds, and the solution is annealed in air at 100°C for 5 minutes.
步骤9)将步骤3)中配制的空穴传输材料旋涂到步骤8)退火好的钙钛矿薄膜上，旋涂Spiro-OMeTAD采用每分钟3000转，旋涂时间为30秒，形成空穴传输层。Step 9) Spin-coat the hole transport material prepared in step 3) onto the annealed perovskite film in step 8). Spin-coat Spiro-OMeTAD at 3000 revolutions per minute and spin-coating time for 30 seconds to form holes. transport layer.
步骤10)采用真空蒸镀技术，在步骤9)的空穴传输层上蒸镀5nm MoO3，然后再蒸镀100nm金属电极Ag，制得钙钛矿太阳能电池。Step 10) Use vacuum evaporation technology to evaporate 5 nm MoO3 on the hole transport layer in step 9), and then evaporate 100 nm metal electrode Ag to prepare a perovskite solar cell.
步骤11)在标准测试条件下(AM 1.5G光照)，本对比例使用离子液体醋酸甲铵作为宽带隙钙钛矿前体溶液的溶剂，所用的宽带隙钙钛矿前体材料为碘化铅，甲基碘化铵，甲基溴化铵，制备的钙钛矿电池器件性能参数分别是，能量转换效率18.81％，开路电压为1.17V，短路电流为19.94mA/cm2，填充因子为80.41％。Step 11) Under standard test conditions (AM 1.5G illumination), this comparative example uses ionic liquid methylammonium acetate as the solvent of the wide-bandgap perovskite precursor solution, and the wide-bandgap perovskite precursor material used is lead iodide. , methyl ammonium iodide, methyl ammonium bromide, the performance parameters of the perovskite battery device prepared are respectively, the energy conversion efficiency is 18.81%, the open circuit voltage is 1.17V, the short circuit current is 19.94mA/cm2 , and the fill factor is 80.41 %.
图9是本发明的基于离子液体醋酸甲铵制备的宽带隙钙钛矿太阳能电池的光电转换效率J-V曲线图，所用的宽带隙钙钛矿前体材料为碘化铅，甲基碘化铵，甲基溴化铵。所制备的器件效率为18.81％,逊色于以碘化铅，溴化铅，甲基碘化铵，甲基溴化铵为宽带隙钙钛矿前体材料制备的宽带隙钙钛矿前体溶液。实施例1中离子液体醋酸甲铵和碘以及溴元素都会形成氢键，其中N-H···Br氢键比N-H···I氢键更强，对于富溴元素的宽带隙钙钛矿，离子液体醋酸甲铵和溴元素之间的相互作用有利于宽带隙钙钛矿薄膜的制备。Figure 9 is a J-V curve of the photoelectric conversion efficiency of the wide-bandgap perovskite solar cell prepared based on the ionic liquid methylammonium acetate of the present invention. The wide-bandgap perovskite precursor materials used are lead iodide and methylammonium iodide. Methyl ammonium bromide. The efficiency of the device prepared is 18.81%, which is inferior to the wide-bandgap perovskite precursor solution prepared using lead iodide, lead bromide, methylammonium iodide, and methylammonium bromide as wide-bandgap perovskite precursor materials. . In Example 1, the ionic liquid methylammonium acetate forms hydrogen bonds with iodine and bromine elements, in which the N-H···Br hydrogen bond is stronger than the N-H···I hydrogen bond. For bromine-rich wide bandgap perovskite, ions The interaction between liquid methylammonium acetate and bromine element is beneficial to the preparation of wide-gap perovskite films.
本发明的不局限于上述实施例所述的具体技术方案，凡采用等同替换形成的技术方案均为本发明要求的保护范围。The present invention is not limited to the specific technical solutions described in the above embodiments. All technical solutions formed by using equivalent substitutions fall within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011423449.0ACN112542549B (en) | 2020-12-08 | 2020-12-08 | Wide-bandgap perovskite solar cell and preparation and application thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011423449.0ACN112542549B (en) | 2020-12-08 | 2020-12-08 | Wide-bandgap perovskite solar cell and preparation and application thereof |
| Publication Number | Publication Date |
|---|---|
| CN112542549A CN112542549A (en) | 2021-03-23 |
| CN112542549Btrue CN112542549B (en) | 2023-10-20 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011423449.0AActiveCN112542549B (en) | 2020-12-08 | 2020-12-08 | Wide-bandgap perovskite solar cell and preparation and application thereof |
| Country | Link |
|---|---|
| CN (1) | CN112542549B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115915873A (en)* | 2021-09-28 | 2023-04-04 | 天合光能股份有限公司 | A large-area perovskite layer and its preparation method |
| CN114292195A (en)* | 2021-12-29 | 2022-04-08 | 青岛科技大学 | Method for designing white-light perovskite through strain regulation |
| CN114551742B (en)* | 2022-02-23 | 2023-11-17 | 电子科技大学 | Silicon-based high-speed perovskite light source and preparation method thereof |
| CN114843406B (en)* | 2022-04-02 | 2024-05-24 | 湖北文理学院 | Preparation method of organic-inorganic hybrid perovskite thin film and preparation method of semitransparent solar cell |
| CN115312667B (en)* | 2022-04-26 | 2025-07-11 | 苏州大学 | A confined annealing method and a method for preparing a perovskite film or a solar cell |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108321299A (en)* | 2018-02-22 | 2018-07-24 | 南京工业大学 | Low-dimensional lead-free perovskite thin film and preparation method of lead-free perovskite solar cell |
| CN108336249A (en)* | 2018-02-22 | 2018-07-27 | 南京工业大学 | Low-dimensional perovskite solar cell based on linear organic diamine and preparation method and application thereof |
| CN108365102A (en)* | 2018-02-22 | 2018-08-03 | 南京工业大学 | Stable and efficient two-dimensional layered perovskite solar cell and preparation method thereof |
| CN108666424A (en)* | 2018-01-05 | 2018-10-16 | 南京工业大学 | Perovskite solar cell prepared by taking methylamine acetate room-temperature molten salt as green solvent, and method and application thereof |
| CN111710780A (en)* | 2020-06-18 | 2020-09-25 | 西北工业大学 | Preparation method of cathode in-situ modified perovskite solar cells without electron transport layer |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI485154B (en)* | 2013-05-09 | 2015-05-21 | Univ Nat Cheng Kung | Organic hybrid solar cell with perovskite structure light absorbing material and manufacturing method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666424A (en)* | 2018-01-05 | 2018-10-16 | 南京工业大学 | Perovskite solar cell prepared by taking methylamine acetate room-temperature molten salt as green solvent, and method and application thereof |
| CN108321299A (en)* | 2018-02-22 | 2018-07-24 | 南京工业大学 | Low-dimensional lead-free perovskite thin film and preparation method of lead-free perovskite solar cell |
| CN108336249A (en)* | 2018-02-22 | 2018-07-27 | 南京工业大学 | Low-dimensional perovskite solar cell based on linear organic diamine and preparation method and application thereof |
| CN108365102A (en)* | 2018-02-22 | 2018-08-03 | 南京工业大学 | Stable and efficient two-dimensional layered perovskite solar cell and preparation method thereof |
| CN111710780A (en)* | 2020-06-18 | 2020-09-25 | 西北工业大学 | Preparation method of cathode in-situ modified perovskite solar cells without electron transport layer |
| Title |
|---|
| Distribution of bromine in mixed iodide-bromide organolead perovskites and its impact on photovoltaic performance;Zhou, Yang等;《Journal of Materials Chemistry A》;第4卷;第16191-16197页* |
| Room-Temperature Molten Salt for Facile Fabrication of Efficient and Stable Perovskite Solar Cells in Ambient Air;Lingfeng Chao等;《Chem》;第5卷;第995-1006页，及支持文件* |
| Publication number | Publication date |
|---|---|
| CN112542549A (en) | 2021-03-23 |
| Publication | Publication Date | Title |
|---|---|---|
| CN112542549B (en) | Wide-bandgap perovskite solar cell and preparation and application thereof | |
| CN113437222B (en) | A kind of lead-free tin-based perovskite film, lead-free tin-based perovskite solar cell and preparation method thereof | |
| CN107240643B (en) | Bromo element adulterates methylamine lead iodine perovskite solar battery and preparation method thereof | |
| CN114678472B (en) | A FAPbI3 perovskite film and a method for preparing an efficient perovskite solar cell | |
| CN114284439B (en) | A method for preparing CsPbI3 perovskite film and high-efficiency solar cell under high humidity environment and its application | |
| CN113410400B (en) | A tin-based perovskite thin film and its quality improvement method and tin-based perovskite solar cell | |
| CN109585661B (en) | Preparation method of interface-enhanced highlight-thermal stable perovskite film | |
| CN111584718B (en) | A kind of high-efficiency organic solar cell and preparation method thereof | |
| CN111092160A (en) | Method for passivating lower interface of perovskite solar cell with inverse structure | |
| CN115020596A (en) | A double-layer electron transport layer and its perovskite solar cell and its preparation method and application | |
| CN110098335A (en) | A kind of perovskite solar battery and preparation method thereof based on ionic liquid modification hole transmission layer | |
| CN114583061A (en) | Lead-free tin-based perovskite thin film with three-dimensional structure and preparation method of solar cell thereof | |
| CN114914362A (en) | Preparation method of efficient and stable titanium ore solar cell | |
| CN110676385A (en) | A carbon-based perovskite solar cell based on a multifunctional interface modification layer | |
| CN107180914B (en) | A kind of preparation method of perovskite thin film battery | |
| CN107994123B (en) | Perovskite type solar cell and preparation method thereof | |
| CN106098948A (en) | The perovskite thin film of single step flash method growing large-size crystal grain and the preparation method of plane solaode | |
| CN111063806B (en) | Perovskite solar cell and preparation method thereof | |
| CN108198939A (en) | A kind of organic solar batteries of zinc oxide composite film based on multi-layer doping magnalium as electron transfer layer | |
| CN111403606A (en) | A kind of perovskite solar cell doped with lycopene and preparation method thereof | |
| CN110165020A (en) | One kind being based on CdS/SnO2Mix the efficient Sb of N-type layer2Se3Hull cell and preparation method thereof | |
| CN115566106A (en) | CsPbI 2 Light-assisted preparation method of Br film and photovoltaic device based on same | |
| CN112259623B (en) | A method for improving the crystallinity of the light absorption layer of copper indium gallium selenide (CIGS) thin film solar cells | |
| CN111092156B (en) | A kind of perovskite solar cell and preparation method thereof | |
| CN111653669A (en) | A kind of small molecule organic solar cell and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |