Dimensionality dependence of optical properties and quantum confinement effects of hydrogenated silicon nanostructures

The excited state properties of linear, planar, and spherical hydrogenated silicon nanostructures are studied systematically with use of a time-dependent Hartree - Fock (TDHF) approach with a semiempirical Hamiltonian. The calculated optical gaps decrease significantly from linear, planar, to spherical silicon structures, showing that the optical gap is dimensionality dependent and hence it can be varied by solely managing the shape of the nanostructures. Remarkably, the calculated exciton sizes of the lowest dipole-allowed excited states for both silicon chains and planes are ∼26 Å, revealing that the quantum confinement effect should be significantly enhanced when the sizes of silicon nanostructures are smaller than this value but not dependent on the dimensionality. A similar trend is also observed for hydrogenated silicon spherical clusters. © 2006 American Chemical Society.