Size-Tunable Band Structure and Optical Properties of Colloidal Silicon Nanocrystals Synthesized via Thermal Disproportionation of Hydrogen Silsesquioxane Polymers.

Dodecane-capped silicon nanocrystals (NCs) were synthesized by using a low-temperature (800-1100 °C) polymer variant of traditional hydrogen silsesquioxane thermal disproportionation. Highly crystalline Si NCs having tunable diameters (3.0-6.7 nm) and thus photoluminescence (PL) peaks (1.68-1.29 eV) were attained via changes in the maximum annealing temperature. Modifications in the NC band structure with diameter were explored by comparison of emission with absorption spectra obtained from diffuse reflectance spectroscopy. Large apparent energy shifts between onsets and PL were noted, being significant for smaller NCs (≤∼4.0 nm). This, along with comparatively "softer" onsets, is commensurate with density of states elongation around PL peaks associated with increasing confinement predicted for indirect semiconductor nanostructures. Tauc analyses of absorption additionally revealed three distinguishable optical transitions in all NCs: attributed to indirect Γ-Δ in lower energy ranges (likely the emission progenitor), indirect Γ-L overtaken by quasi-direct Γ-X wave function mixing for NC diameters ≤∼4.0 nm within the midenergy regime, and direct Γ-Γ transitions at energies nearing and above ∼3 eV.