Du Fuqiang, Wang Hongtao, Zhang Zhuohan, Yang Linqiang, Cao Jinru, Yu Jiangsheng, Tang Weihua
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China.
Mater Horiz. 2021 Mar 1;8(3):1008-1016. doi: 10.1039/d0mh01585g. Epub 2021 Jan 4.
Side-chain engineering on nonfullerene acceptors (NFAs) is crucial for modulating their solubility and crystallinity as well as packing behaviours in active layers to pursue high-performance organic solar cells (OSCs). High weight ratios of side chains are generally used by NFAs for the desired device efficiencies. Side-chain economy has seldom been discussed despite increased cost and difficulties in synthesis when optimizing the molecular design. Herein, we introduce 7H-dibenzo[c,g]carbazole (DCB) as an electron-donating core to design unfused-ring acceptors (UFAs) with a dramatically low weight ratio of side chains. DCB-4F has thus been designed and compared with the carbazole cored analogue (CB-4F). The unique conformation of the DCB core endows DCB-4F with higher solubility (8.2 mg mL in chloroform) compared to CB-4F (2.2 mg mL) when using the same side chains. Featuring a lowest unoccupied molecular orbital (LUMO) level of -3.86 eV and an optical bandgap of 1.55 eV, the DCB-4F film exhibits an absorption profile (maximum 667 nm) complementary to polymer donor PM6. The PM6:DCB-4F as-cast OSCs deliver a power conversion efficiency (PCE) of 9.56% with a high open-circuit voltage (V) of 1.00 V. By adding 10 wt% PCBM into the casting solutions, a greatly improved PCE of 11.17% is readily achieved, which is one of the highest PCEs for as-cast single-junction UFA-based devices. The PM6:DCB-4F based blends show homogeneous nano-fiberous morphology and higher hydrophobicity. The design of conformation-tuned NFAs using sterically hindered DCB-like cores is promising to achieve highly efficient as-cast OSCs.
在非富勒烯受体(NFA)上进行侧链工程对于调节其溶解度、结晶度以及活性层中的堆积行为至关重要,以此来追求高性能有机太阳能电池(OSC)。NFA通常使用高重量比的侧链来实现所需的器件效率。尽管在优化分子设计时合成成本增加且难度加大,但侧链经济性很少被讨论。在此,我们引入7H - 二苯并[c,g]咔唑(DCB)作为给电子核心来设计侧链重量比极低的非稠环受体(UFA)。因此设计了DCB - 4F并与咔唑核心类似物(CB - 4F)进行比较。当使用相同侧链时,DCB核心的独特构象使DCB - 4F相比CB - 4F具有更高的溶解度(在氯仿中为8.2 mg/mL)。DCB - 4F薄膜的最低未占据分子轨道(LUMO)能级为 - 3.86 eV,光学带隙为1.55 eV,其吸收光谱(最大值667 nm)与聚合物给体PM6互补。铸膜态的PM6:DCB - 4F有机太阳能电池具有9.56%的功率转换效率(PCE)以及1.00 V的高开路电压(V)。通过在铸膜溶液中添加10 wt%的PCBM,很容易实现大幅提高的11.17%的PCE,这是铸膜态单结基于UFA的器件中最高的PCE之一。基于PM6:DCB - 4F的共混物呈现出均匀的纳米纤维形态和更高的疏水性。使用空间位阻类似DCB的核心设计构象调节的NFA有望实现高效的铸膜态有机太阳能电池。