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Issue 2, 2016

Polymorphism influences singlet fission rates in tetracene thin films

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Abstract

We report the effect of crystal structure and crystallite grain size on singlet fission (SF) in polycrystalline tetracene, one of the most widely studied SF and organic semiconductor materials. SF has been comprehensively studied in one polymoprh (Tc I), but not in the other, less stable polymorph (Tc II). Using carefully controlled thermal evaporation deposition conditions and high sensitivity ultrafast transient absorption spectroscopy, we found that for large crystallite size samples, SF in nearly pure Tc II films is significantly faster than SF in Tc I films. We also discovered that crystallite size has a minimal impact on the SF rate in Tc II films, but a significant influence in Tc I films. Large crystallites exhibit SF times of 125 ps and 22 ps in Tc I and Tc II, respectively, whereas small crystallites have SF times of 31 ps and 33 ps. Our results demonstrate first, that attention must be paid to polymorphism in obtaining a self-consistent rate picture for SF in tetracene and second, that control of polymorphism can play a significant role towards achieving a mechanistic understanding of SF in polycrystalline systems. In this latter context we show that conventional theory based on non-covalent tetracene couplings is insufficient, thus highlighting the need for models that capture the delocalized and highly mobile nature of excited states in elucidating the full photophysical picture.

Graphical abstract: Polymorphism influences singlet fission rates in tetracene thin films

Supplementary files

Article information


Submitted
18 Sep 2015
Accepted
05 Nov 2015
First published
06 Nov 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 1185-1191
Article type
Edge Article
Author version available

Polymorphism influences singlet fission rates in tetracene thin films

D. H. Arias, J. L. Ryerson, J. D. Cook, N. H. Damrauer and J. C. Johnson, Chem. Sci., 2016, 7, 1185 DOI: 10.1039/C5SC03535J

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