Excitons in InP, GaP, and GaxIn1−xP quantum dots: Insights from time-dependent density functional theory

Colloidal quantum dots (QDs) of group III-V are considered as promising candidates for next-generation environmentally friendly light emitting devices, yet there appears to be only limited understanding of the underlying electronic and excitonic properties. Using large-scale density functional theory with the hybrid B3LYP functional solving the single-particle states and time-dependent density functional theory accounting for the many-body excitonic effects, we have identified the structural, electronic, and excitonic optical properties of InP, GaP, and GaInP QDs containing up to a thousand atoms or more. The calculated optical gap of InP QD appears in excellent agreement with available experiments, and it scales nearly linearly with the inverse diameter. The radiative exciton decay lifetime is found to increase surprisingly linearly with increasing the dot size. For GaP QDs we predict an unusual electronic state crossover at a diameter of around 1.5 nm, whereby the nature of the lowest unoccupied molecular orbital (LUMO) state switches its symmetry from ${\mathrm{\ensuremath{\Gamma}}}₅$-like at a larger diameter to ${\mathrm{\ensuremath{\Gamma}}}₁$-like at a smaller diameter. After the crossover, the absorption intensity of the band-edge exciton states is significantly enhanced. Finally, we find that Vegard's law holds very well for GaInP random alloyed quantum dots down to ultrasmall sizes with less than a hundred atoms. The obtained energy gap bowing parameter of this common-cation compound in QD regime appears positive, size-dependent, and much smaller than its bulk parentage. The volume deformation, dominating over the charge exchange and structure relaxation effects, is mainly responsible for the QD energy gap bowing. The impact of excitonic effects on the optical bowing is found to be marginal. The present work provides a road map for a variety of electronic and optical properties of colloidal QDs in group III-V that can guide spectroscopic studies.