The iron-doped amorphous carbon films (a-C: Fe) and Al2O3 films were deposited on n-type silicon substrates using pulsed laser deposition to form (a-C: Fe)/Al2O3/Si solar cells in a pulsed laser deposition (PLD) system. The microstructure of the films was investigated by Raman scattering spectroscopy. The electrical properties of the films were characterized by room temperature electrical conductivity (σ) and the activation energy (Ea). The results show that the Fe-doped amorphous homogeneous structure is formed by Fe diffused into a-C films after annealing treatment. The a-C: Fe films are disordered graphitized carbon system and are rich in sp2. The (a-C: Fe) /Al2O3 /Si junction has good rectifying properties and remarkable Photovoltaic effect.