有机铅钙钛矿光伏器件制备工艺及其界面修饰方法研究
发布时间：2018-10-18 17:59
【摘要】：近年来,一种被称为钙钛矿型太阳能电池的新兴光伏技术受到了相关科研和产业界的广泛关注。在2009年至今的近八年时间内,钙钛矿型太阳能电池的最高能量转换效率一跃从3.8%提高到了22.1%。该效率不仅超过了发展较早的染料敏化太阳能电池等新型太阳能电池,更是已经逼平甚至超过了诸如多晶硅太阳能电池等发展多年的产业化太阳能电池技术。在钙钛矿型太阳能电池效率快速发展的过程中,钙钛矿薄膜材料制备工艺的改进及其相关界面的修饰工作对整体器件效率的提高起到了至关重要的作用。本文研究了两步旋涂法制备钙钛矿薄膜的工艺过程和钙钛矿薄膜表面修饰对器件性能的影响,并取得了如下成果:(1)将一种宽带隙小分子材料N,N,N’,N’-四苯基-对氨基联苯(TPB)用于旋涂法修饰无空穴传输材料的钙钛矿型太阳能电池的钙钛矿/Au界面,使无空穴传输材料器件的平均效率从5.26%提高至6.26%,最高效率达到6.71%。同时通过阻抗谱拟合分析发现该修饰起电子阻挡层的作用,可以显著增加的钙钛矿/Au界面的复合电阻,从而抑制背表面的电子复合,进而提高了电池效率。(2)发展了一种两步旋涂制备CH_3NH_3PbI3-xClx钙钛矿薄膜的方法。研究发现在CH_3NH_3I溶液中掺入CH_3NH_3Cl可以促使钙钛矿薄膜形成延[110]方向的择优生长,并对多晶薄膜的结晶性和表面覆盖度有显著提高。上述薄膜性能的改善抑制了器件的反向饱和电流密度,从而提高了器件的开路电压,使器件效率由CH_3NH_3PbI3体系的12.08%提升至CH_3NH_3PbI3-xClx的13.12%。同时通过设计实验研究了Cl的作用,证明Cl的存在会通过生成一种含氯中间体来改变PbI2向钙钛矿的转化的历程,从而造成了上述薄膜形貌的变化。(3)在两步旋涂法基础上研究了钙钛矿制备过程中水气氛的影响。研究发现水蒸气可以加速PbI2与CH_3NH_3X(X=I、Cl)的反应,无需加热过程即可以实现钙钛矿的完全转化。通过XRD测试分析发现水的催化反应过程中会有水合中间体生成,该水合中间体的存在会显著降低钙钛矿薄膜的电荷传输性能,从而使器件效率显著下降。但通过温和的加热过程即可除去该水合中间体,从而消除该水合中间体引起的复合,使器件效率恢复。在40%湿度下制备的CH_3NH_3PbI3体系器件电池效率达到13.63%,稳态效率达到12%以上;CH_3NH_3PbI3-xClx体系器件的电池效率达到15.50%,稳态效率达到14%以上。
[Abstract]:In recent years, a new photovoltaic technology called perovskite solar cell has been paid more and more attention. In the last eight years since 2009, the maximum energy conversion efficiency of perovskite solar cells has increased from 3.8% to 22.1%. This efficiency not only exceeds the new solar cells such as dyestuff sensitized solar cells, but also exceeds the industrial solar cell technology, such as polysilicon solar cells, which has been developed for many years. During the rapid development of the efficiency of perovskite-type solar cells, the improvement of the preparation process of perovskite thin film materials and the modification of the interface play an important role in improving the efficiency of the whole device. In this paper, the process of preparing perovskite film by two-step spin coating and the effect of surface modification of perovskite film on the performance of perovskite film are studied. The main results are as follows: (1) A wide band gap small molecular material, NZN (N) N (N) (N) -tetraphenyl-p-aminobenzene (TPB), was used to modify the perovskite / Au interface of perovskite solar cells without hole transport materials by spin-coating method, and the main results were as follows: (1) the perovskite / Au interface was modified by spin coating. The average efficiency of hole-free material devices is increased from 5.26% to 6.26%, and the highest efficiency is 6.71%. At the same time, the impedance spectrum fitting analysis shows that the modified electron barrier layer can significantly increase the composite resistance of the perovskite / Au interface, thus inhibiting the electronic recombination on the back surface. Thus, the efficiency of the battery was improved. (2) A two-step spin coating method for preparing CH_3NH_3PbI3-xClx perovskite films was developed. It is found that the addition of CH_3NH_3Cl in CH_3NH_3I solution can promote the preferential growth of perovskite thin films along [110] direction, and improve the crystallinity and surface coverage of polycrystalline films. The improvement of the film performance inhibits the reverse saturation current density and increases the open circuit voltage of the device. The device efficiency increases from 12.08% of the CH_3NH_3PbI3 system to 13.12% of the CH_3NH_3PbI3-xClx system. At the same time, the function of Cl is studied by designing experiments. It is proved that the existence of Cl can change the process of the conversion of PbI2 to perovskite by the formation of an intermediate containing chlorine. As a result, the morphology of the films was changed. (3) the effect of water atmosphere on the preparation of perovskite was studied on the basis of two-step spin coating method. It has been found that water vapor can accelerate the reaction of PbI2 with CH_3NH_3X (CH_3NH_3X) and realize the complete transformation of perovskite without heating process. It was found by XRD analysis that hydrated intermediates would be formed during the catalytic reaction of water. The existence of the hydrated intermediates would significantly reduce the charge transport performance of perovskite films and thus the device efficiency would be significantly reduced. However, the hydrated intermediate can be removed by a mild heating process, thus eliminating the recombination caused by the hydrated intermediate and restoring the device efficiency. At 40% humidity, the battery efficiency of CH_3NH_3PbI3 system is 13.63%, the steady-state efficiency of CH_3NH_3PbI3-xClx system is over 12%, and that of CH_3NH_3PbI3-xClx system is 15.50% and 14% respectively.
【学位授予单位】：中国科学院大学(中国科学院物理研究所)
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TM914.4
[Abstract]:In recent years, a new photovoltaic technology called perovskite solar cell has been paid more and more attention. In the last eight years since 2009, the maximum energy conversion efficiency of perovskite solar cells has increased from 3.8% to 22.1%. This efficiency not only exceeds the new solar cells such as dyestuff sensitized solar cells, but also exceeds the industrial solar cell technology, such as polysilicon solar cells, which has been developed for many years. During the rapid development of the efficiency of perovskite-type solar cells, the improvement of the preparation process of perovskite thin film materials and the modification of the interface play an important role in improving the efficiency of the whole device. In this paper, the process of preparing perovskite film by two-step spin coating and the effect of surface modification of perovskite film on the performance of perovskite film are studied. The main results are as follows: (1) A wide band gap small molecular material, NZN (N) N (N) (N) -tetraphenyl-p-aminobenzene (TPB), was used to modify the perovskite / Au interface of perovskite solar cells without hole transport materials by spin-coating method, and the main results were as follows: (1) the perovskite / Au interface was modified by spin coating. The average efficiency of hole-free material devices is increased from 5.26% to 6.26%, and the highest efficiency is 6.71%. At the same time, the impedance spectrum fitting analysis shows that the modified electron barrier layer can significantly increase the composite resistance of the perovskite / Au interface, thus inhibiting the electronic recombination on the back surface. Thus, the efficiency of the battery was improved. (2) A two-step spin coating method for preparing CH_3NH_3PbI3-xClx perovskite films was developed. It is found that the addition of CH_3NH_3Cl in CH_3NH_3I solution can promote the preferential growth of perovskite thin films along [110] direction, and improve the crystallinity and surface coverage of polycrystalline films. The improvement of the film performance inhibits the reverse saturation current density and increases the open circuit voltage of the device. The device efficiency increases from 12.08% of the CH_3NH_3PbI3 system to 13.12% of the CH_3NH_3PbI3-xClx system. At the same time, the function of Cl is studied by designing experiments. It is proved that the existence of Cl can change the process of the conversion of PbI2 to perovskite by the formation of an intermediate containing chlorine. As a result, the morphology of the films was changed. (3) the effect of water atmosphere on the preparation of perovskite was studied on the basis of two-step spin coating method. It has been found that water vapor can accelerate the reaction of PbI2 with CH_3NH_3X (CH_3NH_3X) and realize the complete transformation of perovskite without heating process. It was found by XRD analysis that hydrated intermediates would be formed during the catalytic reaction of water. The existence of the hydrated intermediates would significantly reduce the charge transport performance of perovskite films and thus the device efficiency would be significantly reduced. However, the hydrated intermediate can be removed by a mild heating process, thus eliminating the recombination caused by the hydrated intermediate and restoring the device efficiency. At 40% humidity, the battery efficiency of CH_3NH_3PbI3 system is 13.63%, the steady-state efficiency of CH_3NH_3PbI3-xClx system is over 12%, and that of CH_3NH_3PbI3-xClx system is 15.50% and 14% respectively.
【学位授予单位】：中国科学院大学(中国科学院物理研究所)
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TM914.4
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