Embodiments of the invention relate to methods for depositing silicon-containing materials on a substrate. In one example, a method for selectively and epitaxially depositing a silicon-containing material is provided which includes positioning and heating a substrate containing a crystalline surface and a non-crystalline surface within a process chamber, exposing the substrate to a process gas containing neopentasilane, and depositing an epitaxial layer on the crystalline surface. In another example, a method for blanket depositing a silicon-containing material is provide which includes positioning and heating a substrate containing a crystalline surface and feature surfaces within a process chamber and exposing the substrate to a process gas containing neopentasilane and a carbon source to deposit a silicon carbide blanket layer across the crystalline surface and the feature surfaces. Generally, the silicon carbide blanket layer contains a silicon carbide epitaxial layer selectively deposited on the crystalline surface.