Abstract: A semiconductive heterojunction device particularly useful as a photovoltaic device such as a solar cell comprises a heterojunction formed between a first layer of semiconductor material exhibiting one type of electronic conductivity (N or P) and a second layer of a compositionally different material exhibiting the other type of electronic conductivity (P or N), which second layer has an energy bandgap relatively wider than that of the semiconductor material and an electron affinity less than or equal to the electron affinity of the semiconductor. Preferably, the wider bandgap material is a glassy amorphous material which possess or is doped to possess a low resistivity below about 10.sup.7 ohm-cm. In devices employing N-type wider bandgap layers, the conduction band energy level of the wider bandgap material is preferably at substantially the same energy level as the conduction band energy level of the narrower bandgap material at electrical neutrality.