Energy transfer pathways in semiconducting carbon nanotubes revealed using two-dimensional white-light spectroscopy

Thin film networks of highly purified semiconducting carbon nanotubes (CNTs) are being explored for energy harvesting and optoelectronic devices because of their exceptional transport and optical properties. The nanotubes in these films are in close contact, which permits energy to flow through the films, although the pathways and mechanisms for energy transfer are largely unknown. Here we use a broadband continuum to collect femtosecond two-dimensional white-light spectra. The continuum spans 500 to 1,300 nm, resolving energy transfer between all combinations of bandgap (S-1) and higher (S-2) transitions. We observe ultrafast energy redistribution on the S-2 states, non-Forster energy transfer on the S-1 states and anti-correlated energy levels. The two-dimensional spectra reveal competing pathways for energy transfer, with S-2 excitons taking routes depending on the bandgap separation, whereas S-1 excitons relax independent of the bandgap. These observations provide a basis for understanding and ultimately controlling the photophysics of energy flow in CNT-based devices.