Photovoltaic devices, such as solar cells, and methods for their manufacture are disclosed. A device may be characterized by an architecture where two more materials having different electron affinities are regularly arrayed such that their presence alternates within distances of between about 1 nm and about 100 nm. The materials are present in a matrix based on a porous template with an array of template pores. The porous template is formed by anodizing a layer of metal. A photovoltaic device may include such a porous template disposed between a base electrode and a transparent conducting electrode. A first charge-transfer material fills the template pores, A second (complementary) charge-transfer material fills additional space not occupied by the first charge-transfer material.