Direct observation of ultrafast exciton localization in an organic semiconductor with soft X-ray transient absorption spectroscopy.

Garratt, D; Misiekis, L; Wood, D; Larsen, E W; Matthews, M; Alexander, O; Ye, P; Jarosch, S et al. · Nat Commun · 2022

basic_science · Level V

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Abstract

The localization dynamics of excitons in organic semiconductors influence the efficiency of charge transfer and separation in these materials. Here we apply time-resolved X-ray absorption spectroscopy to track photoinduced dynamics of a paradigmatic crystalline conjugated polymer: poly(3-hexylthiophene) (P3HT) commonly used in solar cell devices. The π→π<sup>*</sup> transition, the first step of solar energy conversion, is pumped with a 15 fs optical pulse and the dynamics are probed by an attosecond soft X-ray pulse at the carbon K-edge. We observe X-ray spectroscopic signatures of the initially hot excitonic state, indicating that it is delocalized over multiple polymer chains. This undergoes a rapid evolution on a sub 50 fs timescale which can be directly associated with cooling and localization to form either a localized exciton or polaron pair.