One- and Two-Photon Absorption in CdS Nanodots and Wires: The Role of Dimensionality in the One- and Two-Photon Luminescence Excitation Spectrum

Abstract

We investigate the spectral dependence of the linear and two-photon absorption of wurtzite CdS nanoparticles (dots and rods) by means of quantitative one- and two-photon photoluminescence excitation spectroscopy and effective mass theory modeling. Absolute two-photon absorption cross sections free from spectrally varying beam related uncertainties are obtained by means of a new reference dye-based method. The two-photon spectrum features of rods strongly differ from those of dots, due to the distinct energy structure of quasi-one-dimensional systems. The transversal confinement is found to dominate the energy of the absorption maxima while the longitudinal one dominates their absorption intensity. This suggests two-photon transition energy and intensity can be controlled independently in nanorods. For both geometries we observe a sizable spectral shift between the first one- and two-photon absorption maxima, which we conclude is inherent to the small rates of near-bandgap two-photon transitions rather than to the particular geometry of the absorber. The provided understanding of the spectral dependence of the two-photon absorption of CdS dots and rods is of strong interest for the design of nanocrystals with optimized two-photon absorption properties for bioimaging and phototherapy applications.