Linking optical spectra to free charges in donor/acceptor heterojunctions: cross-correlation of transient microwave and optical spectroscopy

Abstract

The primary photoexcited species in excitonic semiconductors is a bound electron–hole pair, or exciton. An important strategy for producing separated electrons and holes in photoexcited excitonic semiconductors is the use of donor/acceptor heterojunctions, but the degree to which the carriers can escape their mutual Coulomb attraction is still debated for many systems. Here, we employ a combined pump–probe ultrafast transient absorption (TA) spectroscopy and time-resolved microwave conductivity (TRMC) study on a suite of model excitonic heterojunctions consisting of mono-chiral semiconducting single-walled carbon nanotube (s-SWCNT) electron donors and small-molecule electron acceptors. Comparison of the charge-separated state dynamics between TA and TRMC photoconductance reveals a quantitative match over the 0.5 microsecond time scale. Charge separation yields derived from TA allow extraction of s-SWCNT hole mobilities of ca. 1.5 cm² V⁻¹ s⁻¹ (at 9 GHz) by TRMC. The correlation between the techniques conclusively demonstrates that photoinduced charge carriers separated across these heterojunctions do not form bound charge transfer states, but instead form free/mobile charge carriers.