Annihilation-limited long-range exciton transport in high-mobility conjugated copolymer films

Shi, Yuping; Roy, Partha P.; Higashitarumizu, Naoki; Lee, Tsung-Yen; Li, Quanwei; Javey, Ali; Landfester, Katharina; McCulloch, Iain; Fleming, Graham R.

doi:10.1073/pnas.2413850122

Annihilation-limited long-range exciton transport in high-mobility conjugated copolymer films

Journal Article · Tue Apr 22 00:00:00 EDT 2025 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2413850122· OSTI ID:2561454

; Roy, Partha P.; Higashitarumizu, Naoki; ; Li, Quanwei; ; Landfester, Katharina; McCulloch, Iain;

A combination of ultrafast, long-range, and low-loss excitation energy transfer from the photoreceptor location to a functionally active site is essential for cost-effective polymeric semiconductors. Delocalized electronic wavefunctions along π-conjugated polymer (CP) backbone can enable efficient intrachain transport, while interchain transport is generally thought slow and lossy due to weak chain–chain interactions. In contrast to the conventional strategy of mitigating structural disorder, amorphous layers of rigid CPs, exemplified by highly planar poly(indacenodithiophene-co-benzothiadiazole) (IDT-BT) donor-accepter copolymer, exhibit trap-free transistor performance and charge-carrier mobilities similar to amorphous silicon. Here, we report long-range exciton transport in HJ -aggregated IDTBT thin-film, in which the competing exciton transport and exciton–exciton annihilation (EEA) dynamics are spectroscopically separated using a phase-cycling-based scheme and shown to depart from the classical diffusion-limited and strong-coupling regime. In the thin film, we find an annihilation-limited mechanism with ≪100% per-encounter annihilation probability, facilitating the minimization of EEA-induced excitation losses. In contrast, excitons on isolated IDTBT chains diffuse over 350 nm with 0.56 cm ² s ⁻¹ diffusivity, before eventually annihilating with unit probability on first contact. We complement the pump–probe studies with temperature-dependent photocurrent and EEA measurements from 295 K to 77 K and find a remarkable correspondence of annihilation rate and photocurrent activation energies in the 140 K to 295 K temperature range.

View Journal Article

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: US Department of Energy; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Materials Sciences & Engineering Division (SC-22.2)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2561454

Alternate ID(s):: OSTI ID: 2569044

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 17 Vol. 122; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

An improved experimental determination of external photoluminescence quantum efficiency de Mello, John C.; Wittmann, H. Felix; Friend, Richard H. Advanced Materials, Vol. 9, Issue 3 https://doi.org/10.1002/adma.19970090308	journal	March 1997
Two-Dimensional Carrier Distribution in Top-Gate Polymer Field-Effect Transistors: Correlation between Width of Density of Localized States and Urbach Energy Kronemeijer, Auke J.; Pecunia, Vincenzo; Venkateshvaran, Deepak Advanced Materials, Vol. 26, Issue 5 https://doi.org/10.1002/adma.201303060	journal	October 2013
A New Conjugated Polymer that Enables the Integration of Photovoltaic and Light‐Emitting Functions in One Device Xu, Ye; Cui, Yong; Yao, Huifeng Advanced Materials, Vol. 33, Issue 22 https://doi.org/10.1002/adma.202101090	journal	April 2021
Ultrafast Spectroscopy of Semiconductors and Semiconductor Nanostructures Shah, Jagdeep Springer Series in Solid-State Sciences https://doi.org/10.1007/978-3-662-03299-2	book	January 1996
Conjugated polymer nano-systems for hyperthermia, imaging and drug delivery Sarkar, Santu; Levi-Polyachenko, Nicole Advanced Drug Delivery Reviews, Vol. 163-164 https://doi.org/10.1016/j.addr.2020.01.002	journal	January 2020
Progress of Conjugated Polymers as Emerging Thermoelectric Materials Wang, Suhao; Zuo, Guangzheng; Kim, Jongho Progress in Polymer Science, Vol. 129 https://doi.org/10.1016/j.progpolymsci.2022.101548	journal	June 2022
Semiconducting Polymers for Neural Applications Dimov, Ivan B.; Moser, Maximilian; Malliaras, George G. Chemical Reviews, Vol. 122, Issue 4 https://doi.org/10.1021/acs.chemrev.1c00685	journal	January 2022
The Impact of Driving Force and Temperature on the Electron Transfer in Donor–Acceptor Blend Systems Unger, Thomas; Wedler, Stefan; Kahle, Frank-Julian The Journal of Physical Chemistry C, Vol. 121, Issue 41 https://doi.org/10.1021/acs.jpcc.7b09213	journal	October 2017
Microstructural Model of Indacenodithiophene-co-benzothiadiazole Polymer: π-Crossing Interactions and Their Potential Impact on Charge Transport Makki, Hesam; Burke, Colm A.; Troisi, Alessandro The Journal of Physical Chemistry Letters, Vol. 14, Issue 39, p. 8867-8873 https://doi.org/10.1021/acs.jpclett.3c02305	journal	September 2023
Chain Stiffness of Donor–Acceptor Conjugated Polymers in Solution Danielsen, Scott P. O.; Bridges, Colin R.; Segalman, Rachel A. Macromolecules, Vol. 55, Issue 2 https://doi.org/10.1021/acs.macromol.1c02229	journal	January 2022
Reconciling the Driving Force and the Barrier to Charge Separation in Donor–Nonfullerene Acceptor Films Allen, Taylor G.; Kafourou, Panagiota; Larson, Bryon W. ACS Energy Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acsenergylett.1c01563	journal	September 2021
Chain Coupling and Luminescence in High-Mobility, Low-Disorder Conjugated Polymers Thomas, Tudor H.; Rivett, Jasmine P. H.; Gu, Qifei ACS Nano, Vol. 13, Issue 12 https://doi.org/10.1021/acsnano.9b07147	journal	November 2019
Charge-Transfer and Energy-Transfer Processes in π-Conjugated Oligomers and Polymers: A Molecular Picture Brédas, Jean-Luc; Beljonne, David; Coropceanu, Veaceslav Chemical Reviews, Vol. 104, Issue 11 https://doi.org/10.1021/cr040084k	journal	November 2004
Conjugated Polymer-Based Organic Solar Cells Günes, Serap; Neugebauer, Helmut; Sariciftci, Niyazi Serdar Chemical Reviews, Vol. 107, Issue 4, p. 1324-1338 https://doi.org/10.1021/cr050149z	journal	April 2007
Indacenodithiophene Semiconducting Polymers for High-Performance, Air-Stable Transistors Zhang, Weimin; Smith, Jeremy; Watkins, Scott E. Journal of the American Chemical Society, Vol. 132, Issue 33 https://doi.org/10.1021/ja1049324	journal	August 2010
The Effect of Ring Expansion in Thienobenzo[ b ]indacenodithiophene Polymers for Organic Field-Effect Transistors Chen, Hu; Wadsworth, Andrew; Ma, Chun Journal of the American Chemical Society, Vol. 141, Issue 47 https://doi.org/10.1021/jacs.9b09367	journal	October 2019
Modification of Indacenodithiophene-Based Polymers and Its Impact on Charge Carrier Mobility in Organic Thin-Film Transistors Wadsworth, Andrew; Chen, Hu; Thorley, Karl J. Journal of the American Chemical Society, Vol. 142, Issue 2 https://doi.org/10.1021/jacs.9b09374	journal	December 2019
Quenching of Excitons by Holes in Poly(3-hexylthiophene) Films Ferguson, Andrew J.; Kopidakis, Nikos; Shaheen, Sean E. The Journal of Physical Chemistry C, Vol. 112, Issue 26 https://doi.org/10.1021/jp7113412	journal	May 2008
Approaching disorder-free transport in high-mobility conjugated polymers Venkateshvaran, Deepak; Nikolka, Mark; Sadhanala, Aditya Nature, Vol. 515, Issue 7527 https://doi.org/10.1038/nature13854	journal	November 2014
Lessons from nature about solar light harvesting Scholes, Gregory D.; Fleming, Graham R.; Olaya-Castro, Alexandra Nature Chemistry, Vol. 3, Issue 10 https://doi.org/10.1038/nchem.1145	journal	September 2011
Simultaneous optimization of charge-carrier mobility and optical gain in semiconducting polymer films Yap, Boon Kar; Xia, Ruidong; Campoy-Quiles, Mariano Nature Materials, Vol. 7, Issue 5 https://doi.org/10.1038/nmat2165	journal	April 2008
Band-like temperature dependence of mobility in a solution-processed organic semiconductor Sakanoue, Tomo; Sirringhaus, Henning Nature Materials, Vol. 9, Issue 9 https://doi.org/10.1038/nmat2825	journal	August 2010
A general relationship between disorder, aggregation and charge transport in conjugated polymers Noriega, Rodrigo; Rivnay, Jonathan; Vandewal, Koen Nature Materials, Vol. 12, Issue 11 https://doi.org/10.1038/nmat3722	journal	August 2013
2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion Kang, Keehoon; Watanabe, Shun; Broch, Katharina Nature Materials, Vol. 15, Issue 8 https://doi.org/10.1038/nmat4634	journal	May 2016
Short contacts between chains enhancing luminescence quantum yields and carrier mobilities in conjugated copolymers Thomas, Tudor H.; Harkin, David J.; Gillett, Alexander J. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10277-y	journal	June 2019
A universal Urbach rule for disordered organic semiconductors Kaiser, Christina; Sandberg, Oskar J.; Zarrabi, Nasim Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24202-9	journal	June 2021
Dynamic self-stabilization in the electronic and nanomechanical properties of an organic polymer semiconductor Dobryden, Illia; Korolkov, Vladimir V.; Lemaur, Vincent Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30801-x	journal	June 2022
Exciton annihilation in molecular aggregates suppressed through quantum interference Kumar, Sarath; Dunn, Ian S.; Deng, Shibin Nature Chemistry, Vol. 15, Issue 8 https://doi.org/10.1038/s41557-023-01233-x	journal	June 2023
Charge transport in high-mobility conjugated polymers and molecular semiconductors Fratini, Simone; Nikolka, Mark; Salleo, Alberto Nature Materials, Vol. 19, Issue 5 https://doi.org/10.1038/s41563-020-0647-2	journal	April 2020
Functional nanoparticles through π-conjugated polymer self-assembly MacFarlane, Liam R.; Shaikh, Huda; Garcia-Hernandez, J. Diego Nature Reviews Materials, Vol. 6, Issue 1 https://doi.org/10.1038/s41578-020-00233-4	journal	October 2020
Polymer photocatalysts for solar-to-chemical energy conversion Banerjee, Tanmay; Podjaski, Filip; Kröger, Julia Nature Reviews Materials, Vol. 6, Issue 2 https://doi.org/10.1038/s41578-020-00254-z	journal	November 2020
Separating single- from multi-particle dynamics in nonlinear spectroscopy Malý, Pavel; Lüttig, Julian; Rose, Peter A. Nature, Vol. 616, Issue 7956 https://doi.org/10.1038/s41586-023-05846-7	journal	March 2023
Rewiring photosynthetic electron transport chains for solar energy conversion Lawrence, Joshua M.; Egan, Rachel M.; Hoefer, Thomas Nature Reviews Bioengineering, Vol. 1, Issue 12 https://doi.org/10.1038/s44222-023-00093-x	journal	August 2023
Conjugated polymers for visible-light-driven photocatalysis Dai, Chunhui; Liu, Bin Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/C9EE01935A	journal	January 2020
Engineering organic polymers as emerging sustainable materials for powerful electrocatalysts Cui, Xun; Wu, Mingjie; Liu, Xueqin Chemical Society Reviews, Vol. 53, Issue 3 https://doi.org/10.1039/D3CS00727H	journal	January 2024
Mobility enhancement in conjugated polymer field-effect transistors through chain alignment in a liquid-crystalline phase Sirringhaus, H.; Wilson, R. J.; Friend, R. H. Applied Physics Letters, Vol. 77, Issue 3 https://doi.org/10.1063/1.126991	journal	July 2000
Interplay between intrachain and interchain interactions in semiconducting polymer assemblies: The HJ-aggregate model Yamagata, H.; Spano, F. C. The Journal of Chemical Physics, Vol. 136, Issue 18 https://doi.org/10.1063/1.4705272	journal	May 2012
Perpendicular crossing chains enable high mobility in a noncrystalline conjugated polymer Coker, Jack F.; Moro, Stefania; Gertsen, Anders S. Proceedings of the National Academy of Sciences, Vol. 121, Issue 37 https://doi.org/10.1073/pnas.2403879121	journal	September 2024
Non-Markovian Quantum-Classical Ratchet for Ultrafast Long-Range Electron-Hole Separation in Condensed Phases Kato, Akihito; Ishizaki, Akihito Physical Review Letters, Vol. 121, Issue 2 https://doi.org/10.1103/PhysRevLett.121.026001	journal	July 2018
Charge transport physics of a unique class of rigid-rod conjugated polymers with fused-ring conjugated units linked by double carbon-carbon bonds Xiao, Mingfei; Carey, Remington L.; Chen, Hu Science Advances, Vol. 7, Issue 18 https://doi.org/10.1126/sciadv.abe5280	journal	April 2021
Efficient energy transport in an organic semiconductor mediated by transient exciton delocalization Sneyd, Alexander J.; Fukui, Tomoya; Paleček, David Science Advances, Vol. 7, Issue 32 https://doi.org/10.1126/sciadv.abh4232	journal	August 2021
High n-type and p-type conductivities and power factors achieved in a single conjugated polymer Yu, Zi-Di; Lu, Yang; Wang, Zi-Yuan Science Advances, Vol. 9, Issue 8 https://doi.org/10.1126/sciadv.adf3495	journal	February 2023
Comparing Photosynthetic and Photovoltaic Efficiencies and Recognizing the Potential for Improvement Blankenship, R. E.; Tiede, D. M.; Barber, J. Science, Vol. 332, Issue 6031, p. 805-809 https://doi.org/10.1126/science.1200165	journal	May 2011
The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors Bakulin, A. A.; Rao, A.; Pavelyev, V. G. Science, Vol. 335, Issue 6074 https://doi.org/10.1126/science.1217745	journal	February 2012
Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes Gelinas, S.; Rao, A.; Kumar, A. Science, Vol. 343, Issue 6170 https://doi.org/10.1126/science.1246249	journal	December 2013
Integrated Optoelectronic Devices Based on Conjugated Polymers Sirringhaus, H. Science, Vol. 280, Issue 5370 https://doi.org/10.1126/science.280.5370.1741	journal	June 1998
All-Polymer Optoelectronic Devices Ho, P. K. Science, Vol. 285, Issue 5425 https://doi.org/10.1126/science.285.5425.233	journal	July 1999
Long-range exciton transport in conjugated polymer nanofibers prepared by seeded growth Jin, Xu-Hui; Price, Michael B.; Finnegan, John R. Science, Vol. 360, Issue 6391 https://doi.org/10.1126/science.aar8104	journal	May 2018
Photosynthetic Excitons van Amerongen, Herbert; van Grondelle, Rienk; Valkunas, Leonas World Scientific https://doi.org/10.1142/3609	book	January 2000
H- and J-Aggregate Behavior in Polymeric Semiconductors Spano, Frank C.; Silva, Carlos Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040513-103639	journal	April 2014

Similar Records

Using Molecular Structure to Tune Intrachain and Interchain Charge Transport in Indacenodithiophene-Based Copolymers

Journal Article · Thu Jul 25 20:00:00 EDT 2024 · Journal of the American Chemical Society · OSTI ID:2476383

Annihilation-limited long-range exciton transport in high-mobility conjugated copolymer films

Citation Formats

References (50)

Similar Records

Related Subjects