Exciton and biexciton transient absorption spectra of CdSe quantum dots with varying diameters.

Transient absorption (TA) spectroscopy of semiconductor nanocrystals (NCs) is often used for excited state population analysis, but recent results suggest that TA bleach signals associated with multiexcitons in NCs do not scale linearly with exciton multiplicity. In this manuscript, we probe the factors that determine the intensities and spectral positions of exciton and biexciton components in the TA spectra of CdSe quantum dots (QDs) of five diameters. We find that, in all cases, the peak intensity of the biexciton TA spectrum is less than 1.5 times that of the single exciton TA spectrum, in stark contrast to a commonly made assumption that this ratio is 2. The relative intensities of the biexciton and exciton TA signals at each wavelength are determined by at least two factors: the TA spectral intensity and the spectral offset between the two signals. We do not observe correlations between either of these factors and the particle diameter, but we find that both are strongly impacted by replacing the native organic surface-capping ligands with a hole-trapping ligand. These results suggest that surface trapping plays an important role in determining the absolute intensities of TA features for CdSe QDs and not just their decay kinetics. Our work highlights the role of spectral offsets and the importance of surface trapping in governing absolute TA intensities. It also conclusively demonstrates that the biexciton TA spectra of CdSe QDs at the band gap energy are less than twice as intense as those of the exciton.

Electronic Structure and Excited State Dynamics of Cadmium Chalcogenide Nanorods.

The cylindrical quasi-one-dimensional shape of colloidal semiconductor nanorods (NRs) gives them unique electronic structure and optical properties. In addition to the band gap tunability common to nanocrystals, NRs have polarized light absorption and emission and high molar absorptivities. NR-shaped heterostructures feature control of electron and hole locations as well as light emission energy and efficiency. We comprehensively review the electronic structure and optical properties of Cd-chalcogenide NRs and NR heterostructures (e.g., CdSe/CdS dot-in-rods, CdSe/ZnS rod-in-rods), which have been widely investigated over the last two decades due in part to promising optoelectronic applications. We start by describing methods for synthesizing these colloidal NRs. We then detail the electronic structure of single-component and heterostructure NRs and follow with a discussion of light absorption and emission in these materials. Next, we describe the excited state dynamics of these NRs, including carrier cooling, carrier and exciton migration, radiative and nonradiative recombination, multiexciton generation and dynamics, and processes that involve trapped carriers. Finally, we describe charge transfer from photoexcited NRs and connect the dynamics of these processes with light-driven chemistry. We end with an outlook that highlights some of the outstanding questions about the excited state properties of Cd-chalcogenide NRs.