The oxide semiconductor compounds such as SnO2, In2O3, ITO, ZnO and others brought about a new attention for the metal-insulator-semiconductor structures as photovoltaic converters because of the high values of transmission and conductivity and the possibility of metal replacement in above-mentioned structures. The characteristics of the solar cells based on these oxide semiconductor compounds can be improved with conductivity increasing of the transparent semiconductor films and that is why the purpose of this paper is obtaining of F-doped tin oxide thin films, preparation of SnO2:F-Si solar cells and studying of their properties. The F-doped tin oxide thin films were prepared by spray pyrolysis technique [1–8]. This method was chosen because of the simplicity of the apparatus and relatively low cost. Aqueous solutions containing 0.1 M (TT, BTT or DTD) and 0.07 M NH4F (in the case of doping with F) have been sprayed by an atomizer on Si or glass substrates, heated up to 420 °C by maintaining the spray liquid volume, the spray time and the pressure of the carrier gas. Spray pyrolysis deposition of transparent and conductive SnO2 is a low-cost and very flexible technique applicable to solar cells. For SnO2, the drawback is that polycrystalline films are only obtained at relatively high deposition temperatures, largely above 450 °C. This constraint may cause damage to the photovoltaic junction. In the present work, it will be demonstrated that the photovoltaic parameters can be influenced by adding small amounts of hydrogen peroxide (H2O2) to the source solution.