Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

Smith, Kendall A.; Lin, Yen -Hao; Mok, Jorge W.; Yager, Kevin G.; Strzalka, Joseph; Nie, Wanyi; Mohite, Aditya D.; Verduzco, Rafael

doi:10.1021/acs.macromol.5b01383

Title: Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

Journal Article · Tue Nov 03 00:00:00 EST 2015 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.5b01383· OSTI ID:1245027

Smith, Kendall A. ^[1]; Lin, Yen -Hao ^[1]; Mok, Jorge W. ^[1]; Yager, Kevin G. ^[2]; Strzalka, Joseph ^[3]; Nie, Wanyi ^[4]; Mohite, Aditya D. ^[4]; Verduzco, Rafael ^[1]

Rice Univ., Houston, TX (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

All-conjugated block copolymers may be an effective route to self-assembled photovoltaic devices, but we lack basic information on the relationship between molecular characteristics and photovoltaic performance. Here, we synthesize a library of poly(3-hexylthiophene) (P3HT) block poly((9,9-dialkylfluorene)-2,7-diyl-alt-[4,7-bis(alkylthiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (PFTBT) donor-block-acceptor all-conjugated block copolymers and carry out a comprehensive study of processing conditions, crystallinity, domain sizes, and side-chain structure on photovoltaic device performance. We find that all block copolymers studied exhibit an out-of-plane crystal orientation after deposition, and on thermal annealing at high temperatures the crystal orientation flips to an in-plane orientation. By varying processing conditions on polymer photovoltaic devices, we show that the crystal orientation has only a modest effect (15-20%) on photovoltaic performance. The addition of side-chains to the PFTBT block is found to decrease photovoltaic power conversion efficiencies by at least an order of magnitude. Through grazing-incidence X-ray measurements we find that the addition of side-chains to the PFTBT acceptor block results in weak segregation and small (< 10 nm) block copolymer self-assembled donor and acceptor domains. This work is the most comprehensive to date on all-conjugated block copolymer systems and suggests that photovoltaic performance of block copolymers depends strongly on the miscibility of donor and acceptor blocks, which impacts donor and acceptor domain sizes and purity. Lastly, strategies for improving the device performance of block copolymer photovoltaics should seek to increase segregation between donor and acceptor polymer domains.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC00112704

OSTI ID:: 1245027

Alternate ID(s):: OSTI ID: 1246785

Report Number(s):: BNL-111803-2016-JA; 125949

Journal Information:: Macromolecules, Vol. 48, Issue 22; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 38 works

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References (38)

The future of organic photovoltaics Mazzio, Katherine A.; Luscombe, Christine K. Chemical Society Reviews, Vol. 44, Issue 1 https://doi.org/10.1039/C4CS00227J	journal	January 2015
Technological status of organic photovoltaics (OPV) Carlé, Jon E.; Krebs, Frederik C. Solar Energy Materials and Solar Cells, Vol. 119 https://doi.org/10.1016/j.solmat.2013.08.044	journal	December 2013
Assumptions and the levelized cost of energy for photovoltaics Darling, Seth B.; You, Fengqi; Veselka, Thomas Energy & Environmental Science, Vol. 4, Issue 9 https://doi.org/10.1039/c0ee00698j	journal	January 2011
Organic photovoltaics: Challenges and opportunities Gaudiana, Russell Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 15 https://doi.org/10.1002/polb.23083	journal	April 2012
Bulk Heterojunction Solar Cells: Morphology and Performance Relationships Huang, Ye; Kramer, Edward J.; Heeger, Alan J. Chemical Reviews, Vol. 114, Issue 14 https://doi.org/10.1021/cr400353v	journal	May 2014
Rod–coil and all-conjugated block copolymers for photovoltaic applications Yassar, Abderrahim; Miozzo, Luciano; Gironda, Ramona Progress in Polymer Science, Vol. 38, Issue 5 https://doi.org/10.1016/j.progpolymsci.2012.10.001	journal	May 2013
25th Anniversary Article: No Assembly Required: Recent Advances in Fully Conjugated Block Copolymers Robb, Maxwell J.; Ku, Sung-Yu; Hawker, Craig J. Advanced Materials, Vol. 25, Issue 40 https://doi.org/10.1002/adma.201302677	journal	September 2013
Block copolymer strategies for solar cell technology Topham, Paul D.; Parnell, Andrew J.; Hiorns, Roger C. Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 16 https://doi.org/10.1002/polb.22302	journal	June 2011
Optoelectronics using block copolymers Botiz, Ioan; Darling, Seth B. Materials Today, Vol. 13, Issue 5 https://doi.org/10.1016/S1369-7021(10)70083-3	journal	May 2010
Block copolymers for photovoltaics Darling, Seth B. Energy & Environmental Science, Vol. 2, Issue 12 https://doi.org/10.1039/b912086f	journal	January 2009
Synthesis and morphology of all-conjugated donor-acceptor block copolymers based on poly(3-hexylthiophene) and poly(naphthalene diimide) Wang, Jin; Ueda, Mitsuru; Higashihara, Tomoya Journal of Polymer Science Part A: Polymer Chemistry, Vol. 52, Issue 8 https://doi.org/10.1002/pola.27097	journal	January 2014
One-Pot Synthesis and Characterization of All-Conjugated Poly(3-alkylthiophene)- block -poly(dialkylthieno[3,4- b ]pyrazine) Willot, Pieter; Moerman, David; Leclère, Philippe Macromolecules, Vol. 47, Issue 19 https://doi.org/10.1021/ma501757e	journal	October 2014
Photophysics and morphology of a polyfluorene donor-acceptor triblock copolymer for solar cells Yan, Chao; Cadby, Ashley J.; Parnell, Andrew J. Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 23 https://doi.org/10.1002/polb.23386	journal	September 2013
All-Polymer Solar Cells Based on Fully Conjugated Block Copolymers Composed of Poly(3-hexylthiophene) and Poly(naphthalene bisimide) Segments Nakabayashi, Kazuhiro; Mori, Hideharu Macromolecules, Vol. 45, Issue 24 https://doi.org/10.1021/ma302170e	journal	December 2012
Conjugated Block Copolymer Photovoltaics with near 3% Efficiency through Microphase Separation Guo, Changhe; Lin, Yen-Hao; Witman, Matthew D. Nano Letters, Vol. 13, Issue 6 https://doi.org/10.1021/nl401420s	journal	May 2013
Efficient Polythiophene/Polyfluorene Copolymer Bulk Heterojunction Photovoltaic Devices: Device Physics and Annealing Effects McNeill, Christopher R.; Halls, Jonathan J. M.; Wilson, Richard Advanced Functional Materials, Vol. 18, Issue 16 https://doi.org/10.1002/adfm.200800182	journal	August 2008
Dual electron donor/electron acceptor character of a conjugated polymer in efficient photovoltaic diodes McNeill, Christopher R.; Abrusci, Agnese; Zaumseil, Jana Applied Physics Letters, Vol. 90, Issue 19 https://doi.org/10.1063/1.2738197	journal	May 2007
Determining the Role of Polymer Molecular Weight for High-Performance All-Polymer Solar Cells: Its Effect on Polymer Aggregation and Phase Separation Kang, Hyunbum; Uddin, Mohammad Afsar; Lee, Changyeon Journal of the American Chemical Society, Vol. 137, Issue 6 https://doi.org/10.1021/ja5123182	journal	February 2015
High Performance All-Polymer Solar Cell via Polymer Side-Chain Engineering Zhou, Yan; Kurosawa, Tadanori; Ma, Wei Advanced Materials, Vol. 26, Issue 22 https://doi.org/10.1002/adma.201306242	journal	March 2014
All-Polymer Solar Cell with High Near-Infrared Response Based on a Naphthodithiophene Diimide (NDTI) Copolymer Zhou, Erjun; Nakano, Masahiro; Izawa, Seiichiro ACS Macro Letters, Vol. 3, Issue 9 https://doi.org/10.1021/mz5004272	journal	August 2014
High-Efficiency All-Polymer Solar Cells Based on a Pair of Crystalline Low-Bandgap Polymers Mu, Cheng; Liu, Peng; Ma, Wei Advanced Materials, Vol. 26, Issue 42 https://doi.org/10.1002/adma.201402473	journal	September 2014
Low-Bandgap Donor/Acceptor Polymer Blend Solar Cells with Efficiency Exceeding 4% Mori, Daisuke; Benten, Hiroaki; Okada, Izumi Advanced Energy Materials, Vol. 4, Issue 3 https://doi.org/10.1002/aenm.201301006	journal	October 2013
All-Polymer Bulk Heterojuction Solar Cells with 4.8% Efficiency Achieved by Solution Processing from a Co-Solvent Earmme, Taeshik; Hwang, Ye-Jin; Subramaniyan, Selvam Advanced Materials, Vol. 26, Issue 35, p. 6080-6085 https://doi.org/10.1002/adma.201401490	journal	July 2014
Polymer/Polymer Blend Solar Cells Improved by Using High-Molecular-Weight Fluorene-Based Copolymer as Electron Acceptor Mori, Daisuke; Benten, Hiroaki; Ohkita, Hideo ACS Applied Materials & Interfaces, Vol. 4, Issue 7, p. 3325-3329 https://doi.org/10.1021/am300623f	journal	June 2012
Influence of Aggregation on the Performance of All-Polymer Solar Cells Containing Low-Bandgap Naphthalenediimide Copolymers Schubert, Marcel; Dolfen, Daniel; Frisch, Johannes Advanced Energy Materials, Vol. 2, Issue 3 https://doi.org/10.1002/aenm.201100601	journal	January 2012
Ternary Photovoltaic Blends Incorporating an All-Conjugated Donor–Acceptor Diblock Copolymer Mulherin, Rhiannon C.; Jung, Stefan; Huettner, Sven Nano Letters, Vol. 11, Issue 11 https://doi.org/10.1021/nl202691n	journal	November 2011
High-Performance All-Polymer Solar Cells Based on Face-On Stacked Polymer Blends with Low Interfacial Tension Kang, Hyunbum; Kim, Ki-Hyun; Choi, Joonhyeong ACS Macro Letters, Vol. 3, Issue 10 https://doi.org/10.1021/mz500415a	journal	September 2014
n-Type Semiconducting Naphthalene Diimide-Perylene Diimide Copolymers: Controlling Crystallinity, Blend Morphology, and Compatibility Toward High-Performance All-Polymer Solar Cells Hwang, Ye-Jin; Earmme, Taeshik; Courtright, Brett A. E. Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/ja513260w	journal	March 2015
Synthesis, Purification, and Characterization of Well-Defined All-Conjugated Diblock Copolymers PF8TBT- b -P3HT Sommer, Michael; Komber, Hartmut; Huettner, Sven Macromolecules, Vol. 45, Issue 10 https://doi.org/10.1021/ma300533k	journal	May 2012
Synthesis and crystallinity of all-conjugated poly(3-hexylthiophene) block copolymers Lin, Yen-Hao; Smith, Kendall A.; Kempf, Chloe N. Polym. Chem., Vol. 4, Issue 2 https://doi.org/10.1039/C2PY20830J	journal	January 2013
Polythiophene- block -polyfluorene and Polythiophene- block -poly(fluorene- co -benzothiadiazole): Insights into the Self-Assembly of All-Conjugated Block Copolymers Verduzco, Rafael; Botiz, Ioan; Pickel, Deanna L. Macromolecules, Vol. 44, Issue 3 https://doi.org/10.1021/ma102728z	journal	February 2011
Two-dimensional charge transport in self-organized, high-mobility conjugated polymers Sirringhaus, H.; Brown, P. J.; Friend, R. H. Nature, Vol. 401, Issue 6754, p. 685-688 https://doi.org/10.1038/44359	journal	October 1999
Advances in Molecular Design and Synthesis of Regioregular Polythiophenes Osaka, Itaru; McCullough, Richard D. Accounts of Chemical Research, Vol. 41, Issue 9 https://doi.org/10.1021/ar800130s	journal	September 2008
Nanoimprint-Induced Molecular Orientation in Semiconducting Polymer Nanostructures Hlaing, Htay; Lu, Xinhui; Hofmann, Tommy ACS Nano, Vol. 5, Issue 9 https://doi.org/10.1021/nn202515z	journal	August 2011
Nanostructured Surfaces Frustrate Polymer Semiconductor Molecular Orientation Johnston, Danvers E.; Yager, Kevin G.; Hlaing, Htay ACS Nano, Vol. 8, Issue 1 https://doi.org/10.1021/nn4060539	journal	December 2013
Structure formation in P3HT/F8TBT blends Sepe, Alessandro; Rong, Zhuxia; Sommer, Michael Energy Environ. Sci., Vol. 7, Issue 5 https://doi.org/10.1039/c3ee44125c	journal	January 2014
Lamellar and liquid crystal ordering in solvent-annealed all-conjugated block copolymers Lin, Yen-Hao; Yager, Kevin G.; Stewart, Bridget Soft Matter, Vol. 10, Issue 21 https://doi.org/10.1039/C3SM53090F	journal	January 2014
Exciton diffusion and dissociation in conjugated polymer/fullerene blends and heterostructures Haugeneder, A.; Neges, M.; Kallinger, C. Physical Review B, Vol. 59, Issue 23 https://doi.org/10.1103/PhysRevB.59.15346	journal	June 1999

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Improved efficiency of single-component active layer photovoltaics by optimizing conjugated diblock copolymers Shi, Dengke; Wang, Huabin; Sun, Hua New Journal of Chemistry, Vol. 44, Issue 7 https://doi.org/10.1039/c9nj05869a	journal	January 2020
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Preparation of donor–acceptor polyfluorenes with pendant carboxyl or amine functionalities and their photoluminescence properties Ando, Daiki; Ijichi, Jumpei; Uno, Takahiro Polymer Bulletin, Vol. 76, Issue 12 https://doi.org/10.1007/s00289-019-02701-6	journal	February 2019
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Title: Molecular origin of photovoltaic performance in donor-block-acceptor all-conjugated block copolymers

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