苯基取代苯并二噻吩二酮构建新型聚合物及其光伏性能研究

doi:10.6023/A23100439

摘要/Abstract

随着材料和器件的不断发展, 有机光伏(OPV)的器件效率不断提升, 但制备仍存在较多额外加工工艺, 不利于其大规模生产. 如何合理调控活性层材料的溶解性、结晶性和两相形貌来简化器件制备工艺, 实现高性能的as-cast器件将十分具有科学意义. 本工作通过设计合成苯基取代的苯并二噻吩二酮单元(二维BDD)作为共聚单元, 制备了三种新型聚合物材料. 当二维BDD单元摩尔分数为10%时, FBDT-m10能实现良好的聚集性能和加工性能, 与Y6-BO共混制备的as-cast器件就可以得到良好的活性层形貌, 最终实现了71.14%的填充因子及16.06%的器件效率.

关键词: 芳香取代, 苯并二噻吩二酮, 聚合物给体, 有机太阳电池

Owing to the continuous development of materials and devices, the power conversion efficiency (PCE) of organic photovoltaics (OPV) has been improved continuously. However, there are some extra treatments used, which are not conducive to the large-scale production of OPV. Reasonably adjusting the solubility, crystallinity, and phase morphology of active layer could be of great importance to simplify processibility and directly obtain high-performance as-cast devices. In this work, a new phenyl substituted benzodithiophenedione unit (m-PhEh-BDD) was designed and synthesized through a facile selective acylation due to the aromatic difference between benzene and thiophene rings. When m-PhEh-BDD used as the third unit to modify the PM6, two new random polymers, namely FBDT-m10 and FBDT-m20 were obtained successfully. For direct comparison, the m-PhEh-BDD-based alternating polymer FBDT-m100 was also synthesized. With the mole content of m-PhEh-BDD moiety increasing, the highest occupied molecular orbital (HOMO) levels of the polymers gradually downshift but their bandgap values almost are identical. Moreover, FBDT-m100 shows less aggregation ability than PM6, suggesting that m-PhEh-BDD unit can modulate the aggregation behavior. Owing to the suitable aggregation and processibility, FBDT-m10 with moderate content of m-PhEh-BDD exhibits the best compatibility with non-fullerene acceptor Y6-BO, resulting in the superior blend morphology. Therefore, the as-cast devices based on FBDT-m10 can obtain the champion PCE of 16.06%, with a good fill factor of 71.14%. Additionally, the FBDT-m10-based device shows better storage stability than that based on PM6. After 7 d of storage, FBDT-m10-based device can maintain 87% of its initial PCE whereas the PM6-based device only kept 58% of its initial PCE. When the m-PhEh-BDD content increasing, the as-cast devices of the same storage time encounter a decrease in PCE, indicating suitable m-PhEh-BDD content is beneficial for long-term stability. This work demonstrates that the further exploitation on phenyl-substituted benzodithiophenedione unit could be a potential venue to achieve promising polymers for high-performing and stable organic solar cells.

Key words: aromatic substitution, benzodithiophenedione, polymer donor, organic photovoltaics

引用此文

邓燧楠, 刘海珍, 张连杰, 罗文君, 罗妹, 张泽升, 梁嘉豪, 王新康, 陈军武. 苯基取代苯并二噻吩二酮构建新型聚合物及其光伏性能研究[J]. 化学学报, 2024, 82(3): 257-264.

Suinan Deng, Haizhen Liu, Lianjie Zhang, Wenjun Luo, Mei Luo, Zesheng Zhang, Jiahao Liang, Xinkang Wang, Junwu Chen. Construction of Novel Polymers with Phenyl Substituted Benzodithiophenedione for Photovoltaic Performance Study[J]. Acta Chimica Sinica, 2024, 82(3): 257-264.

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图/表 10

图1. 目标聚合物的分子结构

Figure 1. Chemical structures of target polymers

图2. 聚合物的(a)溶液吸收、(b)薄膜吸收及(c)能级示意图

Figure 2. (a) Normalized solution, (b) pristine film absorption and (c) energy diagram of relevant polymers

Donor	λ_{max_solu.}/nm	λ_{max_film}/nm	ε_max/(L•mol⁻¹•cm⁻¹)	λ_onset/eV	E_g^opt/eV
FBDT-m10	619	618	7.26×10⁴	692	1.79
FBDT-m20	612	619	7.10×10⁴	698	1.78
FBDT-m100	578	578	6.0×10⁴	700	1.77

表1. 聚合物材料的光学性能及电化学性能参数

Table 1. The optical and electrochemical performance parameters

图3. (a) J-V测试曲线; (b) EQE测试曲线和(c)存放稳定性

Figure 3. (a) J-V curves, (b) EQE curves and (c) storage stability

Donor	ETL	V_oc/ (V)	J_sc/ (mA•cm⁻²)	FF/ %	PCE_best/ %
FBDT-m10	PFN-Br	0.87	24.55	74.20	15.87
FBDT-m20		0.88	23.57	69.17	14.36
FBDT-m100		0.87	22.75	55.32	10.97
FBDT-m10	PDINO	0.87	25.92	71.14	16.06
FBDT-m20		0.86	25.79	68.69	15.25
FBDT-m100		0.86	24.48	48.68	10.26

表2. 基于Y6-BO器件的光伏性能参数

Table 2. Performance parameters of Y6-BO-based devices

图4. (a)激子解离特性曲线和(b) Jsc的光强依赖特性曲线

Figure 4. (a) Jph versus Veff and (b) Jsc versus light intensity curves

图5. (a)聚合物纯膜空穴以及共混薄膜的(b)空穴和(c)电子的SCLC J1/2-V特性曲线

Figure 5. SCLC J1/2-V characteristics of (a) pristine polymer films and blend films for (b) hole and (c) electron mobilities

Material	α	µ_h/ (cm²•V⁻¹•s⁻¹)	µ_e/ (cm²•V⁻¹•s⁻¹)	µ_h/μ_e
FBDT-m10	—	7.61×10⁻⁵	—	—
FBDT-m20	—	7.89×10⁻⁵	—	—
FBDT-m100	—	5.16×10⁻⁵	—	—
FBDT-m10:Y6-BO	0.95	3.71×10⁻⁴	2.87×10⁻⁴	1.29
FBDT-m20:Y6-BO	0.94	3.88×10⁻⁴	2.61×10⁻⁴	1.49
FBDT-m100:Y6-BO	0.93	2.29×10⁻⁴	1.02×10⁻⁴	2.25

表3. 相关器件的光伏性能参数表

Table 3. Performance parameters of relevant OPV devices

图6. 单体的合成路线

Figure 6. Synthetic route of monomer

图7. 聚合物的合成路线

Figure 7. Synthetic route of polymer

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