Organic photosensitive optoelectronic devices are disclosed. The devises are thin-film crystalline organic optoelectronic devices capable of generating a voltage when exposed to light, and prepared by a method including the steps of: depositing a first organic layer over a first electrode; depositing a second organic layer over the first organic layer; depositing a confining layer over the second organic layer to form a stack; annealing the stack; and finally depositing a second electrode over the second organic layer.