Silicon exhibits a large variety of different bulk phases, allotropes, and composite structures, such as, e.g., clathrates or nanostructures, at both higher and lower densities compared with diamond-like Si-I. New Si structures continue to be discovered. These novel forms of Si offer exciting prospects to create Si based materials, which are non-toxic and earth-abundant, with properties tailored precisely towards specific applications. We illustrate how such novel Si based materials either in the bulk or as nanostructures may be used to significantly improve the efficiency of solar energy conversion devices.