Hot Exciton Dissociation in Graphene Nanoribbons

Exciton dissociation in semiconducting nanostructures is crucial for optoelectronic applications, especially when free-carrier generation is required. Despite considerable research, the question of whether and how such generation occurs in strongly excitonic systems remains elusive. Here, we use one-dimensional precision graphene nanoribbons (GNRs) as a model system to investigate exciton dissociation. We systematically explore the interplay between ribbon length (l), excitation energy, and band dispersion in various precision GNRs. Ultrafast Terahertz conductivity measurements reveal that hot exciton dissociation dominates carrier generation, with ribbon length significantly influencing free carrier lifetimes. We identify a critical Bjerrum length (RB) of approximately 20nm that determines whether photoexcited hot carriers in GNRs can dissociate before forming tightly bound excitons. For shorter ribbons (l<2RB), rapid ~ps exciton formation prevails. Furthermore, the charge-carrier band dispersion in GNRs plays a critical role in determining dissociation efficiency. Long GNRs with strongly dispersed bands, and consequently low effective carrier masses, exhibit higher mobilities that promote efficient hot-exciton dissociation. These results advance fundamental understanding of dimensionality, energetics, and electronic structure in excitonic materials, providing design principles for optoelectronic devices based on excitonic materials.