Harvesting Singlet Fission for Solar Energy Conversion: One- versus Two-Electron Transfer from the Quantum Mechanical Superposition

Singlet fission, the creation of two triplet excitons from one singlet exciton, is being explored to increase the efficiency of solar cells and photo detectors based on organic semiconductors, such as pentacene and tetracene. A key question is how to extract multiple electron-hole pairs from multiple excitons. Recent experiments in our laboratory on the pentacene/C(60) system (Chan, W.-L.; et al. Science 2011, 334, 1543-1547) provided preliminary evidence for the extraction of two electrons from the multiexciton (ME) state resulting from singlet fission. The efficiency of multielectron transfer is expected to depend critically on other dynamic processes available to the singlet (S(1)) and the ME, but little is known about these competing channels. Here we apply time-resolved photoemission spectroscopy to the tetracene/C(60) interface to probe one- and two-electron transfer from S(1) and ME states, respectively. Unlike ultrafast (~100 fs) singlet fission in pentacene where two-electron transfer from the multiexciton state resulting from singlet fission dominates, the relatively slow (~7 ps) singlet fission in tetracene allows both one- and two-electron transfer from the S(1) and the ME states that are in a quantum mechanical superposition. We show evidence for the formation of two distinct charge transfer states due to electron transfer from photoexcited tetracene to the lowest unoccupied molecular orbital (LUMO) and the LUMO+1 levels in C(60), respectively. Kinetic analysis shows that ~60% of the S(1) ⇔ ME quantum superposition transfers one electron through the S(1) state to C(60) while ~40% undergoes two-electron transfer through the ME state. We discuss design principles at donor/acceptor interfaces for optimal multiple carrier extraction from singlet fission for solar energy conversion.