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

A detailed understanding of ultrafast exciton dynamics is crucial for improving the efficiency of organic light-harvesting-devices. Here, the authors track exciton localization on a sub-50 fs timescale in an organic semiconductor using time resolved soft x-ray absorption spectroscopy. 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 pi ->pi* 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.

Automated summary

This study tracks the dynamics of excitons in organic semiconductors using time-resolved X-ray absorption spectroscopy. The localization dynamics of excitons were found to influence the efficiency of charge transfer and separation, and a rapid evolution process of excitonic states was observed.