CC BY-NC-ND 4.0 · Organic Materials 2021; 03(02): 191-197
DOI: 10.1055/a-1472-7302
Focus Issue: Peter Bäuerle 65th Birthday
Short Communication

Mapping the Side-Chain Length of Small-Molecule Acceptors towards the Optimal Hierarchical Morphology in Ternary Organic Solar Cells

Zichun Zhou
a   Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
Shengjie Xu
a   Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
a   Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
b   School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
› Author Affiliations
Funding Information This work was financially supported by the National Key R&D Program of China (2017YFA0204700), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB12010200), the National Natural Science Foundation of China (21572234, 21661132006, 91833304, 21805289) and the Youth Innovation Promotion Association CAS (No. 2020031).


Using multiple light-absorbing materials to realize a broader and better absorption spectrum in multi-component organic photovoltaics has achieved significant success to obtain high power conversion efficiency. Meanwhile, the good materials combinations with matched electronic structure and proper blend morphology for charge generation and transport are of primary importance for implementation of the multi-component strategy. Hierarchical morphology has been clearly demonstrated to improve all performance parameters in ternary organic photovoltaics but shows strong dependence on the molecular structures. Here we develop four small-molecule electron acceptors with different alkyl chain lengths to find the optimal solution of alkyl chain towards the defined hierarchical morphology and carry out a clear and comprehensive investigation of the alkyl chain length effects on the structure–morphology–device performance relationships in ternary blends. There is a positive correlation between the power conversion efficiencies of the four ternary systems and their short-circuit current density parameters, manifesting the significance of distinguishing optimal alkyl side chain length of small-molecule electron acceptors for defined hierarchical morphology to afford efficient carrier generation. The non-optimal side chains would retard the BTR crystallization and make the PC71BM domain sizes incontrollable, leading to a morphology without a defined hierarchy. Such a detailed mapping of the alkyl side chain length of small-molecule electron acceptors provides new insight into the materials combinations for the next-step high-performance multi-component organic photovoltaics.

Supporting Information

Supporting Information for this article is available online at

Dedicated to Professor Peter Bäuerle on the occasion of his 65th birthday.

Supporting Information

Publication History

Received: 17 January 2021

Accepted: 18 March 2021

Accepted Manuscript online:
01 April 2021

Article published online:
27 May 2021

© 2021. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes, or adapted, remixed, transformed or built upon. (

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

  • References and Notes

  • Fabrication of organic solar cells: The devices were developed with a conventional structure of ITO/PEDOT:PSS/active layer/PNDIT-F3N/Al. The ITO-coated glass substrates were cleaned with sequential ultrasonication in a soap–deionized water mixture, deionized water, acetone and isopropanol. The washed substrates were further treated with oxygen plasma for 10 min to eliminate any remaining organic components. A thin layer (approximately 30 nm) of PEDOT:PSS (Clevios P VP 4083) was first spin-coated on the ITO substrates at 3,000 r.p.m. and baked at 150 °C for 5 min under ambient conditions. The substrates were then transferred into a nitrogen-filled glove box. Subsequently, the active layer was spin-coated on the PEDOT:PSS layer via spin-coating from a chloroform solution of BTR, NITI and PC71 BM at various spin rates. The best PCE was achieved via spin coating 25 mg BTR, 10 mg NITI and 25 mg PC71BM (1:0.4:1) in 1 ml chloroform at 1,500 r.p.m. The resultant film thickness was approximately 300 nm and obtained via a surface profilometer (Dektak XT, Bruker). Here, SVA with THF was used to optimize the blend morphology and promote device performance. SVA was conducted in a 60-mm glass Petri dish containing 200 µL THF at various durations in a glove box. The optimal duration in this study was 60 s. Then, PNDIT-F3N (as the electron transport layer) was spin-coated on the active layer at 3,000 r.p.m. from the alcohol solution. In the final stage, aluminium (100 nm) was thermally evaporated onto the active layer as the top electrode. Shadow masks were used to define the device area (0.03262 cm2) of the devices.
  • Device characterization: The current density–voltage (JV) characteristics of unencapsulated photovoltaic devices were measured under N2 using a Keithley 2400 source meter. A 300 W xenon arc solar simulator (Oriel) calibrated by a standard Si diode was used to simulate the AM 1.5 G solar irradiation. The EQE was performed using certified IPCE equipment.
  • 1 Gasparini N, Salleo A, McCulloch I, Baran D. Nat. Rev. Mater. 2019; 4: 229
  • 2 Lu L, Kelly MA, You W, Yu L. Nat. Photonics 2015; 9: 491
  • 3 Xu X, Li Y, Peng Q. Nano Select 2020; 1: 30
  • 4 Naveed HB, Ma W. Joule 2018; 2: 621
  • 5 Huang W, Cheng P, Yang YM, Li G, Yang Y. Adv. Mater. 2018; 20: 1705706
  • 6 Baran D, Ashraf RS, Hanifi DA, Abdelsamie M, Gasparini N, Röhr JA, Holliday S, Wadsworth A, Lockett S, Neophytou M, Emmott CJ, Nelson J, Brabec CJ, Amassian A, Salleo A, Kirchartz T, Durrant JR, McCulloch I. Nat. Mater. 2017; 16: 363
  • 7 Gasparini N, Jiao X, Heumueller T, Baran D, Matt GJ, Fladischer S, Spiecker E, Ade H, Brabec CJ, Ameri T. Nat. Energy 2016; 1: 16118
  • 8 Zhang J, Zhao Y, Fang J, Yuan L, Xia B, Wang G, Wang Z, Zhang Y, Ma W, Yan W, Su W, Wei Z. Small 2017; 2: 1700229
  • 9 Zhou Z, Xu S, Song J, Jin Y, Yue Q, Qian Y, Liu F, Zhang F, Zhu X. Nat. Energy 2018; 3: 952
  • 10 Nian L, Kan Y, Gao K, Zhang M, Li N, Zhou G, Jo SB, Shi X, Lin F, Rong Q, Liu F, Zhou G, Jen AK.-Y. Joule 2020; 4: 2223
  • 11 Song J, Li C, Zhu L, Guo J, Xu J, Zhang X, Weng K, Zhang K, Min J, Hao X, Zhang Y, Liu F, Sun Y. Adv. Mater. 2019; 31: 1905645
  • 12 Zhan L, Li S, Lau T.-K, Cui Y, Lu X, Shi M, Li C.-Z, Li H, Hou J, Chen H. Energy Environ. Sci. 2020; 13: 635
  • 13 Jiang K, Wei Q, Lai JY. L, Peng Z, Kim HK, Yuan J, Ye L, Ade H, Zou Y, Yan H. Joule 2019; 3: 3020
  • 14 Arunagiri L, Peng Z, Zou X, Yu H, Zhang G, Wang Z, Lai JY. L, Zhang J, Zheng Y, Cui C, Huang F, Zou Y, Wong KS, Chow PC. Y, Ade H, Yan H. Joule 2020; 4: 1790
  • 15 Xiao Z, Jia X, Ding L. Sci. Bull. 2017; 62: 1562
  • 16 Qin J, Zhang L, Xiao Z, Chen S, Sun K, Zang Z, Yi C, Yuan Y, Jin Z, Hao F, Chen Y, Bao Q, Ding L. Sci. Bull. 2020; 65: 1979
  • 17 Liu L, Liu Q, Xiao Z, Yang S, Yuan Y, Ding L. Sci. Bull. 2019; 64: 1083
  • 18 Zhang M, Zhu L, Zhou G, Hao T, Qiu C, Zhao Z, Hu Q, Larson BW, Zhu H, Ma Z, Tang Z, Feng W, Zhang Y, Russell TP, Liu F. Nat. Commun. 2021; 12: 309
  • 19 Zhou Z, Liu W, Zhou G, Zhang M, Qian D, Zhang J, Chen S, Xu S, Yang C, Gao F, Zhu H, Liu F, Zhu X. Adv. Mater. 2019; 32: 1906324
  • 20 Pang S, Zhang R, Duan C, Zhang S, Gu X, Liu X, Huang F, Cao Y. Adv. Energy Mater. 2019; 9: 1901740
  • 21 Cui Y, Yao H, Zhang J, Xian K, Zhang T, Hong L, Wang Y, Xu Y, Ma K, An C, He C, Wei Z, Gao F, Hou J. Adv. Mater. 2020; 32: 1908205
  • 22 Gao K, Miao J, Xiao L, Deng W, Kan Y, Liang T, Wang C, Huang F, Peng J, Cao Y, Liu F, Russell TP, Wu H, Peng X. Adv. Mater. 2016; 28: 4727
  • 23 Hong L, Yao H, Wu Z, Cui Y, Zhang T, Xu Y, Yu R, Liao Q, Gao B, Xian K, Woo HY, Ge Z, Hou J. Adv. Mater. 2019; 31: 1903441
  • 24 Liu T, Pan X, Meng X, Liu Y, Wei D, Ma W, Huo L, Sun X, Lee TH, Huang M, Choi H, Kim JY, Choy WC, Sun Y. Adv. Mater. 2017; 29: 1604251
  • 25 Song J, Zhang M, Yuan M, Qian Y, Sun Y, Liu F. Small Methods 2018; 2: 1700229
  • 26 Jiang Z. J. Appl. Crystallogr. 2015; 48: 917
  • 27 Min J, Luponosov YN, Gasparini N, Richter M, Bakirov AV, Shcherbina MA, Chvalun SN, Grodd L, Grigorian S, Ameri T, Ponomarenko SA, Brabec CJ. Adv. Energy Mater. 2015; 5: 1500386
  • 28 Bange S, Schubert M, Neher D. Phys. Rev. B: Condens. Matter 2010; 81: 035209
  • 29 Juska G, Arlauskas K, Viliunas M, Kocka J. Phys. Rev. Lett. 2000; 84: 4946
  • 30 Kyaw AK. K, Wang DH, Luo C, Cao Y, Nguyen T.-Q, Bazan GC, Heeger AJ. Adv. Energy Mater. 2014; 4: 1301469
  • 31 Zhang G, Xia R, Chen Z, Xiao J, Zhao X, Liu S, Yip H.-L, Cao Y. Adv. Energy Mater. 2018; 8: 1801609
  • 32 Lenes M, Morana M, Brabec CJ, Blom PW. M. Adv. Funct. Mater. 2009; 19: 1106
  • 33 Proctor CM, Kuik M, Nguyen T.-Q. Prog. Polym. Sci. 2013; 38: 1941
  • 34 Cowan SR, Roy A, Heeger AJ. Phys. Rev. B: Condens. Matter 2010; 82: 245207
  • 35 Ran NA, Love JA, Heiber MC, Jiao X, Hughes MP, Karki A, Wang M, Brus VV, Wang H, Neher D, Ade H, Bazan GC, Nguyen T.-Q. Adv. Energy Mater. 2017; 8: 1701073
  • 36 Müller-Buschbaum P. Adv. Mater. 2014; 26: 7692
  • 37 Rivnay J, Mannsfeld SC, Miller CE, Salleo A, Toney MF. Chem. Rev. 2012; 112: 5488
  • 38 Zhang M, Zhu L, Qiu C, Zhang Y, Liu F. Acta. Polym. Sin. 2019; 50: 352
  • 39 Ma W, Tumbleston JR, Wang M, Gann E, Huang F, Ade H. Adv. Energy Mater. 2013; 3: 864