Efficient Energy Transport in an Organic Semiconductor Mediated by Transient Exciton Delocalization

Overview

Journal Sci Adv

Specialties Biology
Science

Date 2021 Aug 5

PMID 34348902

Citations 18

Authors

Alexander J Sneyd

Tomoya Fukui

David Palecek

Suryoday Prodhan

Isabella Wagner

Yifan Zhang

Jooyoung Sung

Sean M Collins

Thomas J A Slater

Zahra Andaji-Garmaroudi

Liam R MacFarlane

J Diego Garcia-Hernandez

Linjun Wang

George R Whittell

Justin M Hodgkiss

Kai Chen

David Beljonne

Ian Manners

Richard H Friend

Akshay Rao

Affiliations

Soon will be listed here.

Abstract

Efficient energy transport is desirable in organic semiconductor (OSC) devices. However, photogenerated excitons in OSC films mostly occupy highly localized states, limiting exciton diffusion coefficients to below ~10 cm/s and diffusion lengths below ~50 nm. We use ultrafast optical microscopy and nonadiabatic molecular dynamics simulations to study well-ordered poly(3-hexylthiophene) nanofiber films prepared using living crystallization-driven self-assembly, and reveal a highly efficient energy transport regime: transient exciton delocalization, where energy exchange with vibrational modes allows excitons to temporarily re-access spatially extended states under equilibrium conditions. We show that this enables exciton diffusion constants up to 1.1 ± 0.1 cm/s and diffusion lengths of 300 ± 50 nm. Our results reveal the dynamic interplay between localized and delocalized exciton configurations at equilibrium conditions, calling for a re-evaluation of exciton dynamics and suggesting design rules to engineer efficient energy transport in OSC device architectures not based on restrictive bulk heterojunctions.

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References

Wang L, Beljonne D . Flexible Surface Hopping Approach to Model the Crossover from Hopping to Band-like Transport in Organic Crystals. J Phys Chem Lett. 2015; 4(11):1888-94. DOI: 10.1021/jz400871j. View

Dumele O, Chen J, Passarelli J, Stupp S . Supramolecular Energy Materials. Adv Mater. 2020; 32(17):e1907247. DOI: 10.1002/adma.201907247. View

Yang X, Loos J, Veenstra S, Verhees W, Wienk M, Kroon J . Nanoscale morphology of high-performance polymer solar cells. Nano Lett. 2005; 5(4):579-83. DOI: 10.1021/nl048120i. View

Bai X, Qiu J, Wang L . An efficient solution to the decoherence enhanced trivial crossing problem in surface hopping. J Chem Phys. 2018; 148(10):104106. DOI: 10.1063/1.5020693. View

Zhu C, Nangia S, Jasper A, Truhlar D . Coherent switching with decay of mixing: an improved treatment of electronic coherence for non-Born-Oppenheimer trajectories. J Chem Phys. 2004; 121(16):7658-70. DOI: 10.1063/1.1793991. View

Paquin F, Latini G, Sakowicz M, Karsenti P, Wang L, Beljonne D . Charge separation in semicrystalline polymeric semiconductors by photoexcitation: is the mechanism intrinsic or extrinsic?. Phys Rev Lett. 2011; 106(19):197401. DOI: 10.1103/PhysRevLett.106.197401. View

Wang L, Prezhdo O . A Simple Solution to the Trivial Crossing Problem in Surface Hopping. J Phys Chem Lett. 2015; 5(4):713-9. DOI: 10.1021/jz500025c. View

Chowdhury M, Sajjad M, Savikhin V, Hergue N, Sutija K, Oosterhout S . Tuning crystalline ordering by annealing and additives to study its effect on exciton diffusion in a polyalkylthiophene copolymer. Phys Chem Chem Phys. 2017; 19(19):12441-12451. DOI: 10.1039/c7cp00877e. View

Chen K, Gallaher J, Barker A, Hodgkiss J . Transient Grating Photoluminescence Spectroscopy: An Ultrafast Method of Gating Broadband Spectra. J Phys Chem Lett. 2015; 5(10):1732-7. DOI: 10.1021/jz5006362. View

10.

Engel G, Calhoun T, Read E, Ahn T, Mancal T, Cheng Y . Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems. Nature. 2007; 446(7137):782-6. DOI: 10.1038/nature05678. View

11.

Cao J, Cogdell R, Coker D, Duan H, Hauer J, Kleinekathofer U . Quantum biology revisited. Sci Adv. 2020; 6(14):eaaz4888. PMC: 7124948. DOI: 10.1126/sciadv.aaz4888. View

12.

Granucci G, Persico M . Critical appraisal of the fewest switches algorithm for surface hopping. J Chem Phys. 2007; 126(13):134114. DOI: 10.1063/1.2715585. View

13.

Qiu J, Bai X, Wang L . Crossing Classified and Corrected Fewest Switches Surface Hopping. J Phys Chem Lett. 2018; 9(15):4319-4325. DOI: 10.1021/acs.jpclett.8b01902. View

14.

Fukui T, Garcia-Hernandez J, MacFarlane L, Lei S, Whittell G, Manners I . Seeded Self-Assembly of Charge-Terminated Poly(3-hexylthiophene) Amphiphiles Based on the Energy Landscape. J Am Chem Soc. 2020; 142(35):15038-15048. DOI: 10.1021/jacs.0c06185. View

15.

Schnedermann C, Sung J, Pandya R, Dev Verma S, Chen R, Gauriot N . Ultrafast Tracking of Exciton and Charge Carrier Transport in Optoelectronic Materials on the Nanometer Scale. J Phys Chem Lett. 2019; 10(21):6727-6733. PMC: 6844127. DOI: 10.1021/acs.jpclett.9b02437. View

16.

Berera R, van Grondelle R, Kennis J . Ultrafast transient absorption spectroscopy: principles and application to photosynthetic systems. Photosynth Res. 2009; 101(2-3):105-18. PMC: 2744833. DOI: 10.1007/s11120-009-9454-y. View

17.

Tao D, Feng C, Cui Y, Yang X, Manners I, Winnik M . Monodisperse Fiber-like Micelles of Controlled Length and Composition with an Oligo(p-phenylenevinylene) Core via "Living" Crystallization-Driven Self-Assembly. J Am Chem Soc. 2017; 139(21):7136-7139. DOI: 10.1021/jacs.7b02208. View

18.

Guo J, Ohkita H, Benten H, Ito S . Near-IR femtosecond transient absorption spectroscopy of ultrafast polaron and triplet exciton formation in polythiophene films with different regioregularities. J Am Chem Soc. 2009; 131(46):16869-80. DOI: 10.1021/ja906621a. View

19.

Tamai Y, Ohkita H, Benten H, Ito S . Exciton Diffusion in Conjugated Polymers: From Fundamental Understanding to Improvement in Photovoltaic Conversion Efficiency. J Phys Chem Lett. 2015; 6(17):3417-28. DOI: 10.1021/acs.jpclett.5b01147. View

20.

Qiu J, Bai X, Wang L . Subspace Surface Hopping with Size-Independent Dynamics. J Phys Chem Lett. 2019; 10(3):637-644. DOI: 10.1021/acs.jpclett.8b03763. View