Ligand-Enhanced Energy Transport in Nanocrystal Solids Viewed with Two-Dimensional Electronic Spectroscopy.

We examine CdSe NCs functionalized with the exciton-delocalizing ligand phenyldithiocarbamate (PDTC) using two-dimensional electronic spectroscopy (2DES). PDTC forms hybrid molecular orbitals with CdSe's valence band that relax hole spatial confinement and create potential for enhanced exciton migration in NC solids. We find PDTC broadens the intrinsic line width of individual NCs in solution by ∼30 meV, which we ascribe to modulation of NC band edge states by ligand motion. In PDTC-exchanged solids, photoexcited excitons are mobile and rapidly move to low-energy NC sites over ∼30 ps. We also find placing excitons into high-energy states can accelerate their rate of migration by over an order of magnitude, which we attribute to enhanced spatial delocalization of these states that improves inter-NC wave function overlap. Our work demonstrates that NC surface ligands can actively facilitate inter-NC energy transfer and highlights principles to consider when designing ligands for this application.