Two-Dimensional Electronic Spectroscopy Unravels sub-100 fs Electron and Hole Relaxation Dynamics in Cd-Chalcogenide Nanostructures

[Image: see text] We use two-dimensional electronic spectroscopy (2DES) to disentangle the separate electron and hole relaxation pathways and dynamics of CdTe nanorods on a sub-100 fs time scale. By simultaneously exciting and probing the first three excitonic transitions (S1, S2, and S3) and exploiting the unique combination of high temporal and spectral resolution of 2DES, we derive a complete picture for the state-selective carrier relaxation. We find that hot holes relax from the 1Σ(3/2) to the 1Σ(1/2) state (S2 → S1) with 30 ± 10 fs time constant, and the hot electrons relax from the Σ′ to the Σ state (S3 → S1) with 50 ± 10 fs time constant. This observation would not have been possible with conventional transient absorption spectroscopy due to the spectral congestion of the transitions and the very fast relaxation time scales.