多酸促进无机—有机杂化钙钛矿光电转换性能及光伏器件
发布时间：2019-02-25 13:17
【摘要】：近期,以新一代光敏材料——钙钛矿型无机有机杂化铅卤化物为代表的一系列光电转换材料引起科研工作者们的广泛关注。提高钙钛矿材料以及基于钙钛矿材料的光电器件光伏性能是一个重要的研究课题。多金属氧酸盐(多酸),拥有许多优异的理化性质,最重要的是多酸是一类优秀的电子接收材料,令其能够加速光生电子-空穴的分离,提高光电转换效率。本文将多酸引入至钙钛矿材料以及钙钛矿光伏器件体系中,旨在提高它们的光电性能,具体工作如下:1.我们将多酸引入到钙钛矿材料前驱体溶液中,在室温及常规条件下,利用经典的“一步成膜法”制备成平面型光电导和光检测器件。光电导测试结果表明,多酸/钙钛矿复合物的光电流是单纯钙钛矿的三倍。单色光检测结果表明,由于多酸的引入使得钙钛矿对365 nm单色光的灵敏度由0.646A·W-1提高到1.175 A·W-1,对420 nm单色光的灵敏度由0.224 A·W-1提高到0.621 A·W-1。光电导性能和光检测性的提高表明,在钙钛矿内部光生载流子的分离-复合竞争过程中,多酸的引入促进了载流子的分离并加快其迁移,因而充分地削弱了光生电子-空穴的再结合现象。2.基于全印刷无空穴传输层钙钛矿太阳能电池模型,我们将多酸(PW12)引入到(5-AVA)x(MA)1-xPbI3钙钛矿材料中来提高太阳能电池的光伏性能。经过多酸分子掺杂,钙钛矿电池的平均效率从9.17%提升至11.35%,提高程度为24%。在考察钙钛矿成核生长过程中,我们发现了多酸可以诱导奥斯瓦尔德熟化作用的发生——钙钛矿小晶粒相互融合生长成大尺寸的钙钛矿多晶膜,晶粒尺寸由5μm生长至30μm。生长后的大尺寸晶粒薄膜的缺陷态密度大幅度减小,促进了载流子的传输。正因为这种显著的形貌调控机制,使这类全印刷钙钛矿太阳能电池器件的光电性能显著改善。3.我们制备了以多酸/TiO_2为致密层的全印刷无空穴传输层钙钛矿太阳能电池。利用多酸可以捕捉光生电子、抑制载流子复合并促进其迁移的能力有效地提高了电池的光电转换效率,由9.42%提升至10.65%,提高幅度约为13%。另外,通过电化学阻抗分析,我们认为适量的多酸可以有效地促进电子转移,形成电子浅陷阱,而过量的多酸反而会促进电子-空穴的复合,形成电子深陷阱。4.我们利用静电吸附原理巧妙地使呈负电性的多酸和表面呈正电性的氧化亚铜纳米晶复合。光电测试结果表明,与单纯Cu2O相比,PW10Mo2/Cu2O复合物膜电极的光电流响应提高了179%,另外,复合物膜电极的光电转换效率提高了125%。提高的原因是多酸在复合物中起到了电子浅陷阱的作用,抑制光激发的电子-空穴再结合,加速了电子的迁移。
[Abstract]:Recently, a series of photoelectric conversion materials, represented by perovskite-type inorganic organic hybrid lead halide, have attracted wide attention of researchers. It is an important research topic to improve the photovoltaic performance of perovskite materials and photovoltaic devices based on perovskite materials. Polyoxometalates (polyoxometalates) have many excellent physical and chemical properties. The most important is that polyacids are a kind of excellent electron receiving materials, which can accelerate the separation of photogenerated electrons and holes and improve the efficiency of photoelectric conversion. In this paper, polyacids are introduced into perovskite materials and perovskite photovoltaic device systems in order to improve their photoelectric properties. The specific work is as follows: 1. In this paper, we introduce polyacid into perovskite precursor solution. At room temperature and under conventional conditions, a planar photoconductive and optical detector is prepared by the classical "one-step film forming method". The photoconductivity test results show that the photocurrent of polyacid / perovskite composite is three times higher than that of perovskite alone. The results of monochromatic light detection showed that the sensitivity of perovskite to the 1.175 nm monochromatic light was increased from 0.646 A W-1 to 1.175 AW-1 due to the introduction of polyacid. Sensitivity to 420 nm monochromatic light increased from 0.224 A W / 1 to 0.621 A W / 1. The improvement of photoconductivity and photodetection shows that the introduction of polyacids promotes the separation and migration of carriers in perovskite during the process of separation and composite competition of photogenerated carriers. Therefore, the recombination of photogenerated electrons and holes is fully weakened. 2. Based on the all-print hole-free transport layer perovskite solar cell model, we introduce polyacid (PW12) into (5-AVA) x (MA) 1-xPbI3) perovskite material to improve the photovoltaic performance of solar cells. The average efficiency of perovskite battery was increased from 9.17% to 11.35%, and the increase was 24%. During the investigation of perovskite nucleation and growth, we found that polyacid can induce Oswald ripening, in which perovskite grains fuse and grow into large perovskite polycrystalline films, and the grain size increases from 5 渭 m to 30 渭 m. The density of defect states of the grown large-size grain films decreases greatly, which promotes carrier transport. The photoelectric properties of these all-printed perovskite solar cell devices have been greatly improved because of this remarkable morphology regulation mechanism. We prepared fully printed hole-free perovskite solar cells with polyacid / TiO_2 as dense layer. Using polyacid can capture photogenerated electrons, inhibit carrier recombination and promote its migration. The photoelectric conversion efficiency of the battery is improved from 9.42% to 10.65%, and the increase is about 13%. In addition, by electrochemical impedance analysis, we think that proper amount of polyacid can effectively promote electron transfer and form electron shallow trap, while excessive polyacid can promote electron hole recombination and form electron deep trap. 4. We use the principle of electrostatic adsorption to skillfully combine the negatively charged polyacids and the surface positively charged cuprous oxide nanocrystals. The photocurrent response of PW10Mo2/Cu2O composite membrane electrode was increased by 179% compared with that of pure Cu2O, and the photoelectric conversion efficiency of the composite membrane electrode was increased by 125%. The reason for the increase is that polyacids act as electron shallow traps in the complex, inhibit photoinduced electron-hole rebinding, and accelerate electron migration.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB34
本文编号：2430216
[Abstract]:Recently, a series of photoelectric conversion materials, represented by perovskite-type inorganic organic hybrid lead halide, have attracted wide attention of researchers. It is an important research topic to improve the photovoltaic performance of perovskite materials and photovoltaic devices based on perovskite materials. Polyoxometalates (polyoxometalates) have many excellent physical and chemical properties. The most important is that polyacids are a kind of excellent electron receiving materials, which can accelerate the separation of photogenerated electrons and holes and improve the efficiency of photoelectric conversion. In this paper, polyacids are introduced into perovskite materials and perovskite photovoltaic device systems in order to improve their photoelectric properties. The specific work is as follows: 1. In this paper, we introduce polyacid into perovskite precursor solution. At room temperature and under conventional conditions, a planar photoconductive and optical detector is prepared by the classical "one-step film forming method". The photoconductivity test results show that the photocurrent of polyacid / perovskite composite is three times higher than that of perovskite alone. The results of monochromatic light detection showed that the sensitivity of perovskite to the 1.175 nm monochromatic light was increased from 0.646 A W-1 to 1.175 AW-1 due to the introduction of polyacid. Sensitivity to 420 nm monochromatic light increased from 0.224 A W / 1 to 0.621 A W / 1. The improvement of photoconductivity and photodetection shows that the introduction of polyacids promotes the separation and migration of carriers in perovskite during the process of separation and composite competition of photogenerated carriers. Therefore, the recombination of photogenerated electrons and holes is fully weakened. 2. Based on the all-print hole-free transport layer perovskite solar cell model, we introduce polyacid (PW12) into (5-AVA) x (MA) 1-xPbI3) perovskite material to improve the photovoltaic performance of solar cells. The average efficiency of perovskite battery was increased from 9.17% to 11.35%, and the increase was 24%. During the investigation of perovskite nucleation and growth, we found that polyacid can induce Oswald ripening, in which perovskite grains fuse and grow into large perovskite polycrystalline films, and the grain size increases from 5 渭 m to 30 渭 m. The density of defect states of the grown large-size grain films decreases greatly, which promotes carrier transport. The photoelectric properties of these all-printed perovskite solar cell devices have been greatly improved because of this remarkable morphology regulation mechanism. We prepared fully printed hole-free perovskite solar cells with polyacid / TiO_2 as dense layer. Using polyacid can capture photogenerated electrons, inhibit carrier recombination and promote its migration. The photoelectric conversion efficiency of the battery is improved from 9.42% to 10.65%, and the increase is about 13%. In addition, by electrochemical impedance analysis, we think that proper amount of polyacid can effectively promote electron transfer and form electron shallow trap, while excessive polyacid can promote electron hole recombination and form electron deep trap. 4. We use the principle of electrostatic adsorption to skillfully combine the negatively charged polyacids and the surface positively charged cuprous oxide nanocrystals. The photocurrent response of PW10Mo2/Cu2O composite membrane electrode was increased by 179% compared with that of pure Cu2O, and the photoelectric conversion efficiency of the composite membrane electrode was increased by 125%. The reason for the increase is that polyacids act as electron shallow traps in the complex, inhibit photoinduced electron-hole rebinding, and accelerate electron migration.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB34
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