易挥发性配体高导电性ZnO墨水的宏量制备及其柔性太阳电池

Al doped ZnO (AZO) with high crystallinity were prepared in large-scale by using low volatility ligands. As the ligands with low volatility would affect the conductivity of AZO, the easy volatility ligands or thermo labile ligands were used to exchange them for improving the conductivity. And in order to further increase the AZO conductivity, the Ag was used to clad on AZO nanocrystals forming the nano-composites ink (AZO@Ag) with core-shell structure. The stable and high conductive ink could be applied in roll-to-roll flexible solar cells. The ligands would be removed in the low-temperature annealing process, the nanocrystals with high quality and low defects could use as electron transport layer or transparent electrode. Meanwhile, the shell layer of Ag would deposit on the flexible substrate forming an ultrathin layer on the low- temperature annealing process, which might form double-layer transparent electrode with the Ag/AZO, and the AZO could protect the Ag layer. The ink performance cause by different ligands and ligands exchange, and the effect of covering amount for the shell layer of Ag were further discussed.

项目提出采用低挥发性的配体宏量制备高结晶度的Al掺杂氧化锌AZO纳米晶，后利用易挥发性或易分解的配体通过交换置换低挥发性配体制备稳定性好的AZO印刷墨水；进一步采用高导电性的金属Ag包覆AZO来提高其电导率，得到核-壳结构的AZO@Ag复合材料，宏量制备高稳定性、高电导率的透明电极印刷墨水，应用于柔性太阳电池。采用卷对卷印刷成膜，利用低温加热除去易挥发性、易分解配体制备缺陷少的AZO膜作阴极缓冲层或透明电极，同时，低温加热熔融Ag并使Ag渗透至柔性基底形成Ag/AZO双电层透明电极，AZO覆盖能有效保护Ag层。深入研究不同的配体及配体交换对AZO及其印刷墨水的性能影响，并探讨Ag包覆形式及包覆量对Ag/AZO双电层透明电极性能及光伏应用的影响。

该项目已在Adv. Sci., Chem. Commun., ACS Appl. Mater. Interfaces, J. Mater. Chem. C, Org. Electron., Sci. China Chem.等刊物上发表SCI 论文7 篇，其中影响因子大于 3 以上7篇。通过原位法在金（Au）纳米粒子修饰的羧基化碳纳米管（CNT）中生长ZnO纳米粒子得到杂化材料ZnO@CNT-Au，通过低温无配体法合成AZO纳米粒，后引入表面活性剂配体制备AZO纳米粒子，以及采用一种可弯曲且厚度不敏感的多巴胺(PDA)修饰AZO，制备得到缺陷少，导电性好，厚度不敏感的膜，而PDA修饰的AZO还展现出耐弯折性和强的粘附力，以上制备的材料用于聚合物太阳能电池的电子传输层，电池器件取得好的光伏性能，特别是在基于Ag网格基底的全柔性器件中实现了11.5%效率的突破，有利于实现大面积柔性可穿戴器件的卷对卷印刷制备(Org. Electron. 2016, Sci. China Chem. 2018, Adv. Sci. 2019 )。以氧化铈和以铷掺杂氧化镍材料分别作为电子传输层和空穴传输层应用于钙钛矿太阳电池中，有效提高了器件的光伏性能和稳定性，并研究通过反溶剂法去调控钙钛矿薄膜层，钝化了钙钛矿薄膜的缺陷，有效提高了钙钛矿太阳电池的性能 (Chem. Commun.2018, Org. Electron. 2019, ACS Appl. Mater. Interfaces 2019, J. Mater. Chem. C 2019 )。

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