A method for manufacturing a heterojunction structure based solar cell includes preparing an n-type or p-type semiconductor substrate; forming a p-type or n-type non-oxide semiconductor material layer on the n-type or p-type semiconductor substrate to form a p-n junction; forming a transition metal oxide film on the non-oxide semiconductor material layer; and forming a front electrode and a rear electrode. The transition metal oxide layer protects the surface of the non-oxide semiconductor and improves charge extraction.