Charge Carrier Resolved Relaxation of the First Excitonic State in CdSe Quantum Dots Probed with Near-Infrared Transient Absorption Spectroscopy

This manuscript describes a global regression analysis of near-infrared (NIR, 900−1300 nm) transient absorptions (TA) of colloidal CdSe quantum dots (QDs) photoexcited to their first (1S_e1S_3/2) excitonic state. Near-IR TA spectroscopy facilitates charge carrier-resolved analysis of excitonic decay of QDs because signals in the NIR are due exclusively to absorptions of photoexcited electrons and holes, as probe energies in this region are not high enough to induce absorptions across the optical bandgap that crowd the visible TA spectra. The response of each observed component of the excitonic decay to the presence of a hole-trapping ligand (1-octanethiol) and an electron-accepting ligand (1,4-benzoquinone), and comparison of time constants to those for recovery of the ground state bleaching feature in the visible TA spectrum, allow for the assignment of the components to (i) a 1.6 ps hole trapping process, (ii) 19 ps and 274 ps surface-mediated electron trapping processes, and (iii) a ∼5 ns recombination of untrapped electrons.