Si-ZnO n-n heterojunction diodes were prespared by r.f diode sputtering of the sintered ZnO target on n-type Si single crystal wafers and their structures and electrical properties were studied. The films were grown orientedly with the c-axis of crystallites perpendicular to the substrate surface at low r.f. powder and grown to polycrystalline films with random orientation at high r. f. powder. The crystallite size increased with the increasing substrate temperture The oriented texture films only were used to prepare the photovoltaic diodes and these didoes showed the photovoltaic effect veing positive of the ZnO side for the photons in the wavelength range of 380-1450nm. The sign reversal of phootovoltage which is the property os isotype heterojunction was not observed because of the degeneration of the ZnO films. The diode showed the forward rectification when it was biased with the ZnO side positive. The current-voltage characteristics exhibited the thermal-current type relationship J∝exp(qV/nkT) with n=1.23 at the low forward bias voltage and the tunnelling-current type relationship J∝exp($alpha$V) where $alpha$ was constant independent of temperature at the high forward bias voltage. The crystallite size of ZnO films were influenced largely on the photovoltaic properties of diodes ; The diodes with the films of the larger crystallites showed the poor photovoltaic properties. This reason may be cosidered that the ZnO films with the large crystallites could not grow to the electrically continuous films because the thickness of films was so thin in this experiment.