含靛红并苊醌二甲酰亚胺端基的A-D-A型小分子受体材料的合成及其光电性质研究

doi:10.6023/cjoc202011038

摘要/Abstract

以靛红/氮杂靛红并苊醌二甲酰亚胺为受体端基, 以引达省并噻吩衍生物为电子给体, 设计并合成了两个结构新颖的A-D-A型小分子电子传输材料(A1和A2), 结合密度泛函理论计算对比研究了吡啶氮原子的引入对A1和A2的分子结构、吸收光谱以及能级结构的影响. 理论计算和吸收光谱研究发现: 相比A1, 吡啶氮的引入不仅可以提高A2的骨架平面性, 而且还可以使其分子内电荷转移吸收峰发生27 nm的红移. 电化学和理论计算研究表明, 吡啶氮原子的引入增强了A2的电子亲和力, 因而有效地降低了A2的最高已占分子轨道(HOMO)和最低空分子轨道(LUMO)能级. 以A1和A2为电子受体材料, 以商业购买的PBDB-T为电子给体材料, 构造了含PBDB-T:A1或PBDB-T:A2(质量比1:1)共混薄膜的非富勒烯太阳能电池器件, 其最高能量转换效率分别获为5.19%和6.19%.

关键词: 苊醌二甲酰亚胺, A-D-A型小分子受体, 非富勒烯太阳能电池, 能量转换效率

Two novel A-D-A type small molecule acceptors (A1 andA2) are designed and synthesized by adopting isatin- fused acenaphthenequinone imide or nitrogen-doped isatin-fused acenaphthoquinone imide as the terminal groups and indacenodithiophene derivative as the donor core. The effect of pyridal nitrogen on the molecular structure, optical absorption, and energy level of A1 and A2 is comparatively studied by combining density functional theory (DFT) calculation. In comparison with A1, the incorporation of pyridal nitrogen into A2 not only improves backbone coplanarity, but also achieves 27 nm red-shift in the charge transfer peak of solution absorption. Moreover, the investigation of electrochemical analysis and DFT calculation indicates that the pyridal nitrogen-containing A2 exhibits enhanced electron affinity, thereby leading to deeper- lying energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) as compared to its counterpart (A1). Finally, non-fullerene solar cells containing PBDB-T:A1 or PBDB-T:A2 (mass ratio 1:1) blend films are fabricated by usingA1 or A2 as the electron acceptor material and commercial available PBDB-T as the donor material. The highest energy conversion efficiencies of 5.19% and 6.19% are demonstrated for A1 and A2, respectively.

Key words: acenaphthenequinone imide, A-D-A small molecule acceptor, non-fullerene solar cells, energy conversion efficiency

引用此文

吴赛, 陶吴晞, 王果, 赵斌, 陈华杰. 含靛红并苊醌二甲酰亚胺端基的A-D-A型小分子受体材料的合成及其光电性质研究[J]. 有机化学, 2021, 41(5): 2019-2028.

Sai Wu, Wuxi Tao, Guo Wang, Bin Zhao, Huajie Chen. Synthesis and Optoelectronic Properties of A-D-A Type Small Molecule Acceptors Containing Isatin-Fused Acenaphthenequinone Imide Terminal Groups[J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 2019-2028.

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图/表 10

图1. 小分子受体材料(A1和A2)与经典聚合物给体材料(PBDB-T)的化学结构及其非富勒烯太阳能电池的器件结构

Figure 1. Chemical structure of small molecule acceptor material (A1and A2) and well-known polymer donor material (PBDB-T) and their corresponding device structure of non-fullerene solar cells

图2. 化合物A1和A2的合成路线.

Figure 2. Synthetic route of compounds A1 and A2

Compd.	λ_max/nm		λ_max^onset/nm	E_g^a/eV	E_LUMO^b/eV	E_HOMO^c/eV	E_g^d/eV	E_LUMO^e/eV	E_HOMO^e/eV
Compd.	Solution	Film	λ_max^onset/nm	E_g^a/eV	E_LUMO^b/eV	E_HOMO^c/eV	E_g^d/eV	E_LUMO^e/eV	E_HOMO^e/eV
A1	428, 665	433, 700	825	1.50	–3.94	–5.32	1.42	–3.21	–5.08
A2	430, 692	436, 733	858	1.45	–3.97	–5.34	1.37	–3.29	–5.09

表1. A1和A2的吸收光谱、电化学和DFT理论计算数据

Table 1. Optical, electrochemical and DFT-calculated data of A1 and A2

图3. (a) A1和A2在三氯甲烷溶液中的摩尔消光系数以及(b) A1和A2在三氯甲烷溶液中和固态薄膜上的吸收光谱

Figure 3. (a) Molar extinction coefficients of A1 and A2 in chloroform solution, and (b) absorption spectra of A1 and A2 in chloroform solution and as solid-state film

图4. DFT优化得到的分子构型、前线分子轨道分布和HOMO/LUMO能级

Figure 4. Optimized molecular structures, frontier molecular orbitals, and HOMO/LUMO energy levels

图5. A-D-A型小分子受体A1和A2的(a) CV曲线和(b)能级对比示意图

Figure 5. (a) Cyclic voltammogram curves and (b) energy level diagram of A-D-A small molecule acceptors A1 and A2

共混膜	V_OC/V	J_SC/(mA?cm^–2)	FF/%	PCE/%	μ_h/(cm²?V^–1?s^–1)	μ_e/(cm²?V^–1?s^–1)	μ_h/μ_e
PBDB-T:A1	0.96	8.94	59.22	5.19	2.20×10^-4	5.92×10^-5	3.72
PBDB-T:A2	0.89	11.09	62.73	6.19	2.52×10^-4	2.29×10^-4	1.10

表2. 基于不同受体构建的非富勒烯太阳能电池器件的最佳光伏参数

Table 2. Optimal photovoltaic parameters of non-fullerene solar cell devices based on different acceptors

图6. 基于PBDB-T/A1或PBDB-T/A2共混薄膜的非富勒烯太阳能电池器件的(a) J-V曲线和(b) EQE光谱

Figure 6. (a) J-V curves and (b) EQE spectra of non-fullerene solar cell devices based on PBDB-T/A1 or PBDB-T/A2 blend films

图7. PBDB-T/A1或PBDB-T/A2共混薄膜的空穴迁移率(a)和电子迁移率(b)曲线图

Figure 7. (a) Hole mobility and (b) electron mobility curves based on PBDB-T/A1 or PBDB-T/A2 blend films

图8. (a) PBDB-T/A1和 (b) PBDB-T/A2共混薄膜的表面形貌

Figure 8. Surface morphology of blend films (a) PBDB-T/A1 and (b) PBDB-T/A2

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