锯齿形给体-受体齐聚物的设计、合成及光伏性能研究

doi:10.6023/cjoc202505006

摘要/Abstract

给体-受体(D-A)型共轭齐聚物因其明确的分子结构及易纯化等特性在光电材料领域展现出独特优势. 当前, 以苯并噻二唑(BTz)和萘并二噻二唑(NTz)为缺电子单元的D-A型齐聚物多局限于线性共轭构型. 本工作基于引达省并二噻吩(IDT)与三亚苯并二噻二唑(TPTz), 设计并合成了两种具有锯齿形拓扑结构的D-A齐聚物VG1与VG2. 研究表明, 由于TPTz基团的V形结构, 随着共轭长度的增加, VG2的带隙略微降低0.04 eV, 但其摩尔吸光显著提升. 进一步将二者应用于有机光伏器件发现, 基于VG2:Y6的器件获得较高的能量转换效率, 达2.56%. 这归因于VG2:Y6器件中更低的带隙以下的辐射复合损失和更低的非辐射能量损失. 本研究为调控共轭齐聚物拓扑结构与光电性能关系提供了新思路.

关键词: 给体-受体(D-A)结构, 齐聚物, 有机太阳能电池, 给体材料, 构效关系

Donor-acceptor (D-A) conjugated oligomers exhibit unique advantages in optoelectronic materials due to their well-defined molecular structures and ease of purification. However, current D-A oligomers incorporating electron-deficient units like benzothiadiazole (BTz) and naphthobisthiadiazole (NTz) are largely restricted to linear configurations. In this study, two novel D-A conjugated oligomers (VG1 and VG2) with zigzag-shaped topological structures were designed and synthesized by integrating the electron-donating indacenodithiophene (IDT) unit with the previously developed strong electron- withdrawing triphenylenobisthiadiazole (TPTz) unit. Due to the unique V-shaped structure of TPTz unit, VG2 demonstrates a slightly reduced bandgap by 0.04 eV as the number of repeating units increases, while its light absorption coefficient is significantly enhanced. When applied to organic photovoltaic devices, the VG2:Y6-based device achieves a power conversion efficiency (PCE) of 2.56%, outperforming the VG1:Y6 system (2.37%). This improvement is attributed to the reduced radiative recombination losses below the bandgap and lower non-radiative energy losses in the VG2:Y6 device. This work offers a new strategy for modulating the topological structure of conjugated oligomers and their optoelectronic properties.

Key words: donor-acceptor (D-A) structure, oligomers, organic solar cells, donor materials, structure-property-performance relationship

引用此文

赵瑜, 张紫越, 许书伟, 胡华伟, 吴宏伟, 张琳萍, 陈丰坤. 锯齿形给体-受体齐聚物的设计、合成及光伏性能研究[J]. 有机化学, 2025, 45(11): 4210-4219.

Yu Zhao, Ziyue Zhang, Shuwei Xu, Huawei Hu, Hongwei Wu, Linping Zhang, Fengkun Chen. Zigzag-Shaped Donor-Acceptor Oligomers: Synthesis, Properties and Photovoltaic Applications[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4210-4219.

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图/表 6

Scheme 1. Synthetic route to the V-shaped oligomers

Figure 1. Optimized geometry and frontier molecular orbitals of (a) VG1 and (b) VG2 calculated at the B3LYP/6-31 G(d, p) level

Compd.	λ_solution^a/ nm	λ_film^a/ nm	λ_em^b/ nm	E_g^opt^c/ eV	E_HOMO^d/ eV	E_LUMO^d/ eV	Φ_FL-solid^f/ %	Φ_FL-solution^g/ %	τ_s^e/ns	k_r^h/ (10⁸ s^－1)	k_nr^h/ (10⁸ s^－1)
VG1	380, 457, 535	387, 469	647	2.05	－5.10	－3.09	0.8	45.3	4.3	1.05	1.27
VG2	383, 469, 515	389, 483, 572	650	2.01	－5.07	－3.09	1.8	41.3	3.4	1.21	1.72

Table 1. Optical and electrochemical data of VG1 and VG2

Figure 2. (a) Absorption spectra in DCM solution; (b) Films and (c) emission spectrum in DCM; (d) CV and DPV curves in DCM

Device	V_oc/V	J_sc/(mA•cm^－2)	FF/%	PCE/%	E_g/eV	ΔE₁/eV	ΔE₂/eV	ΔE₃/eV	E_loss/eV	EQE_EL/%
VG1:Y6	0.68	10.49	32.95	2.37	1.382	0.261	0.105	0.318	0.684	4.36×10^－4
VG2:Y6	0.78	10.44	31.33	2.56	1.371	0.260	0.035	0.298	0.592	9.78×10^－4

Table 2. Photovoltaic parameters of devices based on VG1 and VG2

Figure 3. (a) J-V curves of OSCs based on VG1 and VG2; (b) EQE spectra; (c) EQEEL curves of the corresponding OSC devices; (d) Jsc and (e) Voc against the light intensity of based on VG1 and VG2; (f) Summary of the detailed Eloss

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