Ultrafast Spectroscopic Signature of Charge Transfer between Single-Walled Carbon Nanotubes and C₆₀

The time scales for interfacial charge separation and recombination play crucial roles in determining efficiencies of excitonic photovoltaics. Near-infrared photons are harvested efficiently by semiconducting single-walled carbon nanotubes (SWCNTs) paired with appropriate electron acceptors, such as fullerenes (<i>e</i>.<i>g</i>., C₆₀). However, little is known about crucial photochemical events that occur on femtosecond to nanosecond time scales at such heterojunctions. Here, we present transient absorbance measurements that utilize a distinct spectroscopic signature of charges within SWCNTs, the absorbance of a trion quasiparticle, to measure both the ultrafast photoinduced electron transfer time (τ_pet) and yield (ϕ_pet) in photoexcited SWCNT–C₆₀ bilayer films. The rise time of the trion-induced absorbance enables the determination of the photoinduced electron transfer (PET) time of τ_pet ≤ 120 fs, while an experimentally determined trion absorbance cross section reveals the yield of charge transfer (ϕ_pet ≈ 38 ± 3%). The extremely fast electron transfer times observed here are on par with some of the best donor:acceptor pairs in excitonic photovoltaics and underscore the potential for efficient energy harvesting in SWCNT-based devices