Silicon Carbide Nanostructures from Reactions between Vapors of Organochlorosilanes and Liquid of Sodium‐Factors Affecting Morphology and Composition

Cubic shells and spherical nanoparticles of β‐SiC were produced at 1273 K by processing the ceramic precursors formed from the reactions between vapors of organochlorosilanes, Me 2 SiCl 2 , MeSiCl 3 , MeSiHCl 2 , and PhSiCl 3 , and liquid Na at 523‐723 K. From Me 2 SiCl 2 , a flexible linear polycarbosilane precursor was synthesized and covered the NaCl byproduct surface to form a cubic shape. Hollow cubic β‐SiC shells were produced after the NaCl templates were removed. From MeSiCl 3 , a rigid cross‐linked polycarbosilane was produced and phase segregated from the NaCl byproduct. The precursor was transformed into nanoparticles without special morphology. MeSiHCl 2 produced a cross‐linked polysilane precursor at low temperatures, which can be converted into a mixture of β‐SiC and Si nanoparticles. At high temperatures, the polysilane converted to polycarbosilane and produced hollow cubic β‐SiC shells. The carbon‐rich PhSiCl 3 generated cube‐like particles as the final product, which contained β‐SiC and carbon.