Ultrafast interface charge transfer dynamics on P3HT/MWCNT nanocomposites probed by resonant Auger spectroscopy

The interfacial electronic structure and charge transfer dynamics of poly-3-hexylthiophene (P3HT) and multi-walled carbon nanotube (Fe-MWCNT) nanocomposites were investigated by near-edge X-ray absorption fine structure (NEXAFS) and resonant Auger (RAS) spectroscopies around the sulfur K-edge. Nanocomposites with 5 wt% (P3HT/Fe-MWCNT-5%) and 10 wt% (P3HT/Fe-MWCNT-10%) of Fe-MWCNT species were prepared and compared with pristine P3HT film. The quantitative NEXAFS analysis shows a strong π–π interchain interaction of the pristine P3HT polymer film, which is reduced by the presence of the Fe-MWCNT. S–KL2,3L2,3 RAS spectra were measured at photon energies corresponding to the main electronic transitions appearing in the S–K edge NEXAFS spectrum. Ultrafast charge transfer times were estimated from the RAS spectra using the core-hole clock approach with the S 1s core-hole lifetime as an internal clock. The π–π interchain charge transfer time increases from 4.7 fs on pristine P3HT polymer to 6.5 fs on the P3HT/Fe-MWCNT-5% nanocomposite. The electronic coupling between P3HT and Fe-MWCNT species occurs mainly through the P3HT π* molecular orbital. The increase of Fe-MWCNT concentration from 5 to 10 wt% reduces the charge transfer rate at the resonance maximum due probably to Fe-MWCNT aggregation, reducing the P3HT and Fe-MWCNT electronic coupling.