Quantum plasmons and intraband excitons in doped nanoparticles: Failure of the Tamm-Dancoff approximation and importance of electron-hole attraction

Abstract

We use excited-state quantum chemistry techniques to investigate the intraband absorption of doped semiconductor nanoparticles as a function of doping density, nanoparticle radius, and material properties. The excess electrons are modeled as interacting particles confined in a sphere. We compare the predictions of various single-excitation theories, including time-dependent Hartree-Fock, the random-phase approximation, and configuration interaction with single excitations. We find that time-dependent Hartree-Fock most accurately describes the character of the excitation, as compared to equation-of-motion coupled-cluster theory with single and double excitations. The excitation evolves from confinement-dominated, to excitonic, to plasmonic with increasing number of electrons at fixed density, and the threshold number of electrons to produce a plasmon increases with density due to quantum confinement. Exchange integrals (attractive electron-hole interactions) are essential to properly describe excitons, and de-excitations (i.e. avoidance of the Tamm-Dancoff approximation) are essential to properly describe plasmons. We propose a schematic model whose analytic solutions closely reproduce our numerical calculations. Our results are in good agreement with experimental spectra of doped ZnO nanoparticles at a doping density of 1.4 × 10 20 cm −3 .

Dopant levels in large nanocrystals using stochastic optimally tuned range-separated hybrid density functional theory

“…Understanding the properties of dopants in semiconductor nanostructures is a crucial issue for technological applications since it is often the dopants that functionalize a device and control its desired properties. [1][2][3][4][5]7,8 In particular, doped silicon quantum dots have shown promise in photovoltaic and photonic applications due to their size tunability and processability. 6,9,10 A key dopant property is its activation energy, which often behaves differently in the nanoscale.…”