Slow Singlet Fission Observed in a Polycrystalline Perylenediimide Thin Film
- 18 November 2016
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry Letters
- Vol. 7 (23), 4922-4928
- https://doi.org/10.1021/acs.jpclett.6b02320
Abstract
Singlet exciton fission (SF) is a process wherein an exciton in an organic semiconductor divides its energy to form two excitations. This process can offset thermalization losses in light harvesting technologies, but requires photostable materials with high SF efficiency. We report ultrafast kinetics of polycrystalline films of N-N'-dioctyl-3,4,9,10-perylenedicarboximide (C8-PDI), a chromophore predicted to undergo SF on picosecond time scales. While transient absorption measurements display picosecond dynamics, such kinetics are absent from low-fluence time-resolved emission experiments, indicating they result from singlet-singlet exciton annihilation. A model that accounts for annihilation can reproduce both measurements and highlights that care must be taken when extracting SF rates from time-resolved data. Our model also reveals SF proceeds in C8-PDI over 3.8 ns. Despite this slow rate, SF occurs in high yield (51%) due to a lack of competing singlet deactivation pathways. Our results show perylenediimides are a promising class of SF materials that merit further study.Keywords
Funding Information
- Welch Foundation (F-1885)
- Division of Electrical, Communications and Cyber Systems (ECCS-1542202)
- American Chemical Society Petroleum Research Fund (55184-DNI6)
- University of Texas at Austin
- Dorothy B. Banks Summer Fellowship
- J. M. White Endowed Presidential Fellowship in Chemistry
This publication has 80 references indexed in Scilit:
- External Quantum Efficiency Above 100% in a Singlet-Exciton-Fission–Based Organic Photovoltaic CellScience, 2013
- Magnetic Field Effects on Singlet Fission and Fluorescence Decay Dynamics in Amorphous RubreneThe Journal of Physical Chemistry C, 2012
- Hybrid pentacene/a-silicon solar cells utilizing multiple carrier generation via singlet exciton fissionApplied Physics Letters, 2012
- Efficient Singlet Fission Discovered in a Disordered Acene FilmJournal of the American Chemical Society, 2012
- Geometry and Electronic Coupling in Perylenediimide Stacks: Mapping Structure−Charge Transport RelationshipsJournal of the American Chemical Society, 2010
- Accessing the Triplet Excited State in PerylenediimidesJournal of the American Chemical Society, 2008
- Photophysical properties of tetracene derivatives in solutionSpectrochimica Acta Part A: Molecular Spectroscopy, 1988
- Photochemistry of 3,4,9,10-perylenetetracarboxylic dianhydride dyes. 3. Singlet and triplet excited-state properties of the bis(2,5-di-tert-butylphenyl)imide derivativeThe Journal of Physical Chemistry, 1987
- Structures of eleven perylene-3,4:9,10-bis(dicarboximide) pigmentsActa Crystallographica Section C Crystal Structure Communications, 1986
- Coexistence of Exciton Fission and Fusion in Tetracene CrystalsPhysical Review B, 1970