【摘要】：近年來,一種被稱為鈣鈦礦型太陽能電池的新興光伏技術受到了相關科研和產(chǎn)業(yè)界的廣泛關注。在2009年至今的近八年時間內,鈣鈦礦型太陽能電池的最高能量轉換效率一躍從3.8%提高到了22.1%。該效率不僅超過了發(fā)展較早的染料敏化太陽能電池等新型太陽能電池,更是已經(jīng)逼平甚至超過了諸如多晶硅太陽能電池等發(fā)展多年的產(chǎn)業(yè)化太陽能電池技術。在鈣鈦礦型太陽能電池效率快速發(fā)展的過程中,鈣鈦礦薄膜材料制備工藝的改進及其相關界面的修飾工作對整體器件效率的提高起到了至關重要的作用。本文研究了兩步旋涂法制備鈣鈦礦薄膜的工藝過程和鈣鈦礦薄膜表面修飾對器件性能的影響,并取得了如下成果:(1)將一種寬帶隙小分子材料N,N,N’,N’-四苯基-對氨基聯(lián)苯(TPB)用于旋涂法修飾無空穴傳輸材料的鈣鈦礦型太陽能電池的鈣鈦礦/Au界面,使無空穴傳輸材料器件的平均效率從5.26%提高至6.26%,最高效率達到6.71%。同時通過阻抗譜擬合分析發(fā)現(xiàn)該修飾起電子阻擋層的作用,可以顯著增加的鈣鈦礦/Au界面的復合電阻,從而抑制背表面的電子復合,進而提高了電池效率。(2)發(fā)展了一種兩步旋涂制備CH_3NH_3PbI3-xClx鈣鈦礦薄膜的方法。研究發(fā)現(xiàn)在CH_3NH_3I溶液中摻入CH_3NH_3Cl可以促使鈣鈦礦薄膜形成延[110]方向的擇優(yōu)生長,并對多晶薄膜的結晶性和表面覆蓋度有顯著提高。上述薄膜性能的改善抑制了器件的反向飽和電流密度,從而提高了器件的開路電壓,使器件效率由CH_3NH_3PbI3體系的12.08%提升至CH_3NH_3PbI3-xClx的13.12%。同時通過設計實驗研究了Cl的作用,證明Cl的存在會通過生成一種含氯中間體來改變PbI2向鈣鈦礦的轉化的歷程,從而造成了上述薄膜形貌的變化。(3)在兩步旋涂法基礎上研究了鈣鈦礦制備過程中水氣氛的影響。研究發(fā)現(xiàn)水蒸氣可以加速PbI2與CH_3NH_3X(X=I、Cl)的反應,無需加熱過程即可以實現(xiàn)鈣鈦礦的完全轉化。通過XRD測試分析發(fā)現(xiàn)水的催化反應過程中會有水合中間體生成,該水合中間體的存在會顯著降低鈣鈦礦薄膜的電荷傳輸性能,從而使器件效率顯著下降。但通過溫和的加熱過程即可除去該水合中間體,從而消除該水合中間體引起的復合,使器件效率恢復。在40%濕度下制備的CH_3NH_3PbI3體系器件電池效率達到13.63%,穩(wěn)態(tài)效率達到12%以上;CH_3NH_3PbI3-xClx體系器件的電池效率達到15.50%,穩(wěn)態(tài)效率達到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.
【學位授予單位】：中國科學院大學(中國科學院物理研究所)
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TM914.4

【相似文獻】

相關期刊論文 前10條

1 陳志雄,付剛,唐大海;影響鈣鈦礦結構陶瓷n型半導化的結構因素[J];壓電與聲光;1999年06期

2 王曉莉,姚熹;復雜組成鈣鈦礦材料中的納米分相[J];西安交通大學學報;1995年09期

3 莊志強;王蘊輝;施紅陽;;鈮鎂酸鉛類鈣鈦礦結構鐵電多晶體的制備技術[J];華南理工大學學報(自然科學版);1992年03期

4 趙旭,栗萍,唐貴德,張變芳,禹日程;Nb摻雜對雙鈣鈦礦化合物居里溫度的影響[J];河北師范大學學報;2004年04期

5 李福q，

本文編號：2279928