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基于PTB7,Bis-PC70BM,PC70BM的高效率有机三元太阳能电池

金士琪 徐征 赵谡玲 赵蛟 李杨 邓丽娟

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基于PTB7,Bis-PC70BM,PC70BM的高效率有机三元太阳能电池

金士琪, 徐征, 赵谡玲, 赵蛟, 李杨, 邓丽娟

Efficient organic ternary solar cells based on PTB7 and PC70BM with Bis-PC70BM

Jin Shi-Qi, Xu Zheng, Zhao Su-Ling, Zhao Jiao, Li Yang, Deng Li-Juan
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  • 我们将Bis-PC70BM作为第二种电子受体混入基于PTB7:PC70BM的聚合物太阳能电池中, 制备了三元混合聚合物太阳能电池. 相比于PC70BM, Bis-PC70BM的最低未占分子轨道(lowest unoccupied molecular orbital, LUMO)能级更高, 所以掺入Bis-PC70BM后器件的开路电压(VOC)得到了提升. Bis-PC70BM在PTB7和PC70BM之间起到桥梁的作用, 因此在给体/受体界面创造了更多的电荷传递通道. 而且从原子力显微镜中得到的结果来看, 当混入质量比为3% 的Bis-PC70BM后薄膜的表面形貌更为平整, 平均粗糙度从原来的1.87 nm降到了1.80 nm. 能量转换效率(power conversion efficiency, PCE)达到7.00%, 其中器件的VOC为0.77 V, 短路电流(JSC) 为13.92 mAcm-2, 比PTB7:PC70BM 的器件效率6.07%提高了15%.
    In recent years, solar cells, especially the bulk heterojunction (BHJ) polymer solar cells (PSCs), have attracted considerable attention. BHJ PSCs have several advantages such as easy fabrication, light weight, low cost and flexibility. The research on ternary BHJ PSCs will become a hot topic since incorporating near infrared region (NIR) low bandgap polymer materials into the donor/acceptor system can easily extend the absorption spectral range and improve the photon harvesting. In this paper, we investigate the ternary PSCs based on poly{4, 8-bis[(2-ethylhexyl)-oxy]benzo[1, 2-b:4, 5-b']dithiophene-2, 6-diyl-alt-3-fluoro-2-[(2-ethylhexyl) carbonyl]thieno[3, 4-b]thiophene-4, 6-diyl} (PTB7); Bis adduct of phenyl-C71-butyric acid methyl ester (Bis-PC70BM); [6, 6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). The performance of PSCs based on PTB7 and PC70BM may be improved by doping with Bis-PC70BM which is used as an electron-cascade acceptor material. Ternary blend PSCs with 3% Bis-PC70BM exhibit a power conversion efficiency (PCE) of 7.00%, higher than that (6.07%) of the PTB7 :PC70BM binary blend. The open-circuit voltage (VOC) is 0.77 V, the short-circuit current (JSC) is 13.92 mA cm-2 and the fill factor (FF) is 65%. However, in our research, the absorption spectra for the films with different amount of Bis-PC70BM are hardly changed, implying that doping with Bis-PC70BM would not improve the photon harvesting. The LUMO (HOMO) energy levels of PTB7, Bis-PC70BM and PC70BM are -3.49 eV (-5.31 eV), -3.80 eV (-6.10 eV) and -3.91 eV (-6.20 eV), respectively. Due to the higher LUMO energy levels of Bis-PC70BM relative to PC70BM, the VOC increases when Bis-PC70BM is used. The cascade-like energy levels of ternary blend PSCs can facilitate the charge transfer at the donor/acceptor interface owing to the bridging effect. There are three routes for charge transfer (PTB7-Bis-PC70BM, Bis-PC70BM-PC70BM and PTB7-PC70BM) in ternary PSCs, more than that one in the binary PTB7:PC70BM counterpart. Moreover, PC70BM can provide a driving force to transfer the electrons on the LUMO of Bis-PC70BM to a lower energy orbital (the LUMO of PC70BM), which can facilitate charge transfer from PTB7 to Bis-PC70BM. Atomic force microscopy (AFM) images show that when 3% Bis-PC70BM is used, the film of the ternary blend active layer becomes smoother and the root-mean-square (RMS) roughness decreases from 1.87 nm to 1.80 nm. The decreased roughness is likely good for the contact between the PEDOT:PSS and the active layer, improving the transport rate. We have fabricated hole-only devices using a high-work-function material (Au) as the cathode to block the back injection of electrons in order to investigate charge carrier transport and collection in the PSCs. Result shows that doping with Bis-PC70BM may not change the hole mobility in the device. Besides, the Jph-Veff characteristics shows that doping with 3% Bis-PC70BM can facilitate exciton dissociation and charge collection at a low voltage. Our results indicate that using Bis-PC70BM as an electron-cascade acceptor material in PTB7 :PC70BM blend to fabricate ternary blend PSCs is a promising way to improve the PCE.
      通信作者: 徐征, zhengxu@bjtu.edu.cn
    • 基金项目: 国家自然科学基金(批准号: 61575019, 11474018)、教育部博士点基金(批准号: 20130009130001)和中央高校基本科研业务费专项资金(批准号: 2012JBZ001)资助的课题.
      Corresponding author: Xu Zheng, zhengxu@bjtu.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 61575019, 11474018), the Research Fund for the Doctoral Program of Higher Education (Grant No. 20130009130001), and the Fundamental Research Funds for the Central Universities (Grant No. 2012JBZ001).
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    Cheng Y J, Yang S H, Hsu C S 2009 Chem. Rev. 109 5868

    [2]

    Gnes S, Neugebauer H, Sariciftci N S 2007 Chem. Rev. 107 1324

    [3]

    Dang M T, Hirsch L, Wantz G, Wuest J D 2013 Chem. Rev. 113 3734

    [4]

    Duan C, Zhang K, Zhong C, Huang F, Cao Y 2013 Chem. Soc. Rev. 42 9071

    [5]

    Li G, Zhu R, Yang Y 2012 Nat. Photonics 6 153

    [6]

    Krebs F C, Espinosa N, Hsel M, Sondergaard R R, Jorgensen M 2014 Adv. Mater. 26 29

    [7]

    Yip H L, Jen A K Y 2012 Energy Environ. Sci. 5 5994

    [8]

    Lin Y, Li Y, Zhan X 2012 Chem. Soc. Rev. 41 4245

    [9]

    Zhao X, Zhan X 2011 Chem. Soc. Rev. 40 3728

    [10]

    Li Y F 2012 Acc. Chem. Res. 45 723

    [11]

    Bahrami A, Mohammadnejad S, Abkenar N J 2014 Chin. Phys. B 23 028803

    [12]

    Samadpour M, Zad A I, Molaei M 2014 Chin. Phys. B 23 047302

    [13]

    Ahmadi M, Dafeh S R 2015 Chin. Phys. B 24 0117203

    [14]

    Liu Y, Zhao J, Li Z, Mu C, Ma W, Hu H, Jiang K, Lin H, Ade H, Yan H 2014 Nat. Commun. 5 5293

    [15]

    Zhang S Q, Ye L, Zhao W C, Yang B, Wang Q, Hou J H 2015 Sci. China Chem. 58 248

    [16]

    Chen J D, Cui C H, Li Y Q, Zhou L, Ou Q D, Li C, Li Y F, Tang J X 2015 Adv. Mater. 27 1035

    [17]

    Li H, Zhang Z G, Li Y F, Wang J 2012 Appl. Phys. Lett. 101 163302

    [18]

    Bonaccorso F, Balis N, Stylianakis M M, Savarese M, Adamo C, Gemmi M, Pellegrini V, Stratakis E, Kymakis E 2015 Adv. Funct. Mater. 25 3870

    [19]

    Balis N, Konios D, Stratakis E, Kymakis E 2015 Chem. Nano. Mat. 1 346

    [20]

    Goh T, Huang J S, Bartolome B, Sfeir M Y, Vaisman M, Lee M L, Taylor A D 2015 J. Mater. Chem. A 3 18611

    [21]

    Gupta V, Bharti V, Kumar M, Chand S, Heeger A J 2015 Adv. Mater. 27 4398

    [22]

    Lu L Y, Chen W, Xu T, Yu L P 2015 Nat. Commun. 6 7327

    [23]

    Janssen R A J, Nelson J 2013 Adv. Mater. 25 1847

    [24]

    Cheng P, Li Y, Zhan X 2014 Energy Environ. Sci. 7 2005

    [25]

    Ye L, Zhang S, Qian D, Wang Q, Hou J 2013 J. Phys. Chem. C 117 25360

    [26]

    He Y, Zhao G, Peng B, Li Y 2010 Adv. Funct. Mater. 20 3383

    [27]

    Peet J, Kim J, Coates N E, Ma W L, Moses D, Heeger A J, Bazan G C 2007 Nat. Mater. 6 497

    [28]

    Shuttle C G, Hamilton R, O'Regan B C, Nelson J, Durrant J R 2010 Proc. Natl. Acad. Sci. 107 16448

    [29]

    Lu L Y, Xu T, Chen W, Lee J M, Luo Z Q, Jung I H, Park H I, Kim S O, Yu L P 2013 Nano Lett. 13 2365

    [30]

    Mihailetchi V D, Koster L J A, Hummelen J C, Blom P W M 2004 Phys. Rev. Lett. 93 216601

    [31]

    Shrotriya V, Yao Y, Li G, Yang Y 2006 Appl. Phys. Lett. 89 63505

    [32]

    Malliaras G, Salem J, Brock P, Scott C 1998 Phys. Rev. B 58 R13411

    [33]

    Wang Z, Zhang F, Li L, An Q, Wang J, Zhang J 2014 Appl. Surface Sci. 305 221

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  • 收稿日期:  2015-07-08
  • 修回日期:  2015-10-28
  • 刊出日期:  2016-01-20

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