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J Phys Chem B. 2017 Feb 16;121(6):1405-1412. doi: 10.1021/acs.jpcb.6b11813. Epub 2017 Feb 1.

Influence of Energetic Disorder on Exciton Lifetime and Photoluminescence Efficiency in Conjugated Polymers.

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Max Planck Institute for Polymer Research , Ackermannweg 10, 55128 Mainz, Germany.
Dutch Polymer Institute , P.O. Box 902, 5600 AX Eindhoven, The Netherlands.
Lam Research Corporation , 4300 Cushing Pkwy, Fremont, California 94538, United States.


Using time-resolved photoluminescence (TRPL) spectroscopy the exciton lifetime in a range of conjugated polymers is investigated. For poly(p-phenylenevinylene) (PPV)-based derivatives and a polyspirobifluorene copolymer (PSBF) we find that the exciton lifetime is correlated with the energetic disorder. Better ordered polymers exhibit a single exponential PL decay with exciton lifetimes of a few hundred picoseconds, whereas polymers with a larger degree of disorder show multiexponential PL decays with exciton lifetimes in the nanosecond regime. These observations are consistent with diffusion-limited exciton quenching at nonradiative recombination centers. The measured PL decay time reflects the time that excitons need to diffuse toward these quenching sites. Conjugated polymers with large energetic disorder and thus longer exciton lifetime also exhibit a higher photoluminescence quantum yield due to the slower exciton diffusion toward nonradiative quenching sites.


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