A DFT + U Study of Absorption Spectra and Localized Surface Plasmon Resonances of few electrons in Doped ZnO Quantum Dots

Abstract

Quantum plasmonics of few electrons that was reported a few years ago in photodoping experiments has received little or no attention in doped nanomaterials both theoretically and experimentally. There are no studies of quantum plasmonics of large quantum dots of the size of Bohr excitonic radius or less that take electronic and geometric structure of the quantum dots. In this work, we studied extensively the absorption spectra of a protype quantum dot of sizeable ZnO of approximately 3.0 nm in diameter doped with Ga, and Al in diluted limit with density functional theory (DFT) plus Hubbard corrections (U). The localized surface plasmon resonances (LSPRs) were then determined from the real part of the dielectric function by correlating the negative portion of it to resonant spectral lines. Our results show the sensitivity of the spectral lines to distribution of the dopants, the electronic structure of the dopants, the polarization of the electric field, and size of the quantum dots. Even though our findings are based on stoichiometrically simple ZnO, it shows that the DFT + U method with numerical atomic basis can be used at reasonable computational cost to study quantum plasmonics of few electrons taking into account electronic and geometric structures, which is missing currently. The method can be extended to study magneto-optics of diluted magnetic semiconductor QDs.