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While the silicon photonic crystals have promised revolutionary developments in the field of optical telecommunications and optical computing, it has only recently been realized that their prowess to trap and slow photons could potentially and significantly improve the efficiency of silicon solar cells. In this work n-doped and p-doped inverse silicon opals are synthesized and processed to optimize their electrical charge transport properties, which are shown to be of semiconductor device quality. Moreover a prototype p-i-n junction solar cell based on the inverse silicon opal is reduced to practice and its optoelectronic behavior is evaluated.