Formation mechanism and optical characterization of polymorphic silicon nanostructures by DC arc-discharge

Abstract

Silicon nanoparticles (Si NPs), silicon nanosheets (Si NSs), and silicon nanoribbons (Si NRs) were fabricated by means of DC arc-discharge under diverse atmospheres (hydrogen, mixtures of hydrogen and inert gas). It is shown that these as-prepared Si NPs are approximately 5–50 nm in diameter, Si NSs are about 10–30 nm in width and about 2.8 nm in thickness, and Si NRs consist of fine sheets with a length as long as 200 nm, width of 13 nm, and thickness of 3.1 nm. BET measurements reveal that the specific surfaces are 110.9, 108.8, and 164.2 m² g⁻¹ for Si NPs, Si NSs, Si NRs, respectively. Formation mechanisms for polymorphic Si nanostructures are elucidated, revealing that the anisotropic or isotropic growth of Si nanostructures is greatly induced by high energetic inert gas and hydrogen atoms, and finally results in the formation of polymorphic Si nanostructures. A visible down-shift of Raman frequency for these Si nanostructures is mainly attributed to the size effect. The band gaps are experimentally measured as 2.89 eV (Si NPs), 2.92 eV (Si NSs), and 3.02 eV (Si NRs) for direct transition, and 1.99 eV (Si NPs), 1.26 eV (Si NSs), and 1.36 eV (Si NRs) for indirect transition. These are noticeably enlarged with respect to bulk Si (1.1 eV).