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llye88

铁虫 (小有名气)

应助: 0 (幼儿园)
金币: 244
红花: 6
帖子: 60
在线: 25.3小时
虫号: 738181
注册: 2009-04-02
性别: GG
专业: 高分子物理与高分子物理化

[交流] 2014年两维共轭光伏聚合物的侧链设计规律已有1人参与

聚合物光伏材料的分子结构与其光伏性能具有十分密切的关系。2011年中科院化学所的研究人员首次将两维共轭结构引入到苯并二噻吩(BDT)单元中，设计了噻吩取代BDT两维共轭结构单元，并将这一单元与各种共轭结构单元共聚，获得了一系列的具有两维共轭结构的共轭聚合物。这类两维共轭聚合物与烷氧基取代的对应聚合物相比，光伏能量转换效率（PCE）都得到了有效的提升。其中基于二维共轭聚合物PBDTTT-C-T的常规器件的效率达到7.6%（Angew. Chem. Int. Ed., 2011, 50, 9697）。2012年，他们与香港大学/华南理工大学合作，通过使用新型器件结构，使PBDTTT-C-T的光伏效率进一步提高到9% ( Adv. Mater. 2012，24，3046; Adv. Mater. 2014, 26, 4043)。
最近他们在两维共轭苯并二噻吩(2D-BDT)单元的进一步开发和优化方面取得了一系列进展。他们将线性烷硫基引入到PBDTTT-EFT上，设计合成了PBDT-TS1, 基于PBDT-TS1/PC71BM的单结正向器件效率高达9.5%，是目前世界上最高的结果（ Chem. Mater. 2014, 26, 3603）。同时，他们将三种共轭侧链：噻吩烷基、呋喃烷基、硒吩烷基引入到PBDTTT-EFT上，设计的新型聚合物PBDTTT-EFS也达到8.8%（Macromolecules, 2014，DOI: 10.1021/ma500829r）。以PBDTTT-C-T、PBDT-TS1为突出代表的两维共轭聚合物被国内外同行认为是目前最为优异的一类聚合物光伏材料，2014年他们应邀在Accounts of Chemical Reserch 上撰写综述，总结了两维共轭聚合物的侧链设计规律( Acc. Chem. Res. 2014, 47, 1595)。

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Recently, the benzodithiophene- (BDT-) based polymers with conjugated side groups attracted considerable attention due to their superior properties in polymer solar cells (PSCs), so the investigation of the side chain effects on the photovoltaic properties of this type of polymers is an interesting and important topic for molecular design. Herein, three conjugated polymers based on BDT and thieno[3,4-b]thiophene units with furan, thiophene and selenophene as side groups, named as PBDTTT-EFF, PBDTTT-EFT, and PBDTTT-EFS, were synthesized and applied in polymer solar cells. The polymers were characterized in parallel by absorption spectroscopy, thermogravimetric analysis (TGA), density functional theory (DFT), ultraviolet photoemission spectroscopy (UPS), X-ray diffraction (XRD), and photovoltaic measurements. The results show that the dihedral angles between the BDT and conjugated side groups play important roles in affecting the absorption bands, HOMO levels, crystallinities, and aggregation sizes of the polymers. The photovoltaic results indicate that PBDTTT-EFT and PBDTTT-EFS show similar photovoltaic characteristics in device, and PCEs of 9.0% and 8.78% were obtained, respectively. The device of PBDTTT-EFF shows a Voc of 0.69 V and a Jsc of 11.77 mA/cm2, which are lower than those in the devices based on the other two polymers. Overall, this work suggests that the photovoltaic properties of the BDT-based polymers can be effectively tuned by introducing conjugated side groups with varied steric hindrance.

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