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Free keywords:
CDSE QUANTUM DOTS; SURFACE-PLASMON RESONANCES; ANISOTROPIC SEMICONDUCTOR
NANOCRYSTALS; PHOTOINDUCED CHARGE SEPARATION; DISCRETE-DIPOLE
APPROXIMATION; OCTAPOD SHAPED NANOCRYSTALS; CORE/SHELL NANOCRYSTALS;
OPTICAL-PROPERTIES; SELECTIVE GROWTH; EPITAXIAL-GROWTHMaterials Science; Physics;
Abstract:
Rod-shaped CdTe-Cu2-xTe nano-heterostructures with tunable dimensions of both sub-units and a type II band alignment were prepared by Cd2+/Cu+ cation exchange. The light absorption properties of the heterostructures are dominated by the excitonic and plasmonic contributions arising, respectively, from the CdTe and the Cu2-xTe sub-units. These results were confirmed over a wide range of sub-unit length fractions through optical modelling based on the discrete dipole approximation (DDA). Although assuming electronically independent sub-units, our modelling results indicate a negligible ground state interaction between the CdTe exciton and the Cu2-xTe plasmon. This lack of interaction may be due to the low spectral overlap between exciton and plasmon, but also to localization effects in the vacancy-doped sub-unit. The electronic interaction between both sub-units was evaluated with pump-probe spectroscopy by assessing the relaxation dynamics of the excitonic transition. In particular, the CdTe exciton decays faster in the presence of the Cu2-xTe sub-unit, and the decay gets faster with increasing its length. This points towards an increased probability of Auger mediated recombination due to the high carrier density in the Cu2-xTe sub-unit. This indication is supported through length-fraction dependent band structure calculations, which indicate a significant leakage of the CdTe electron wavefunction into the Cu2-xTe sub-unit that increases along with the shortening of the CdTe sub-unit, thus enhancing the probability of Auger recombination. Therefore, for the application of type II chalcogenide-chalcogenide heterostructures based on Cu and Cd for photoenergy conversion, a shorter Cu-based sub-unit may be advantageous, and the suppression of high carrier density within this sub-unit is of high importance.
