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A thin-film ZnO(n)/Si(p+) heterojunction diode is demonstrated. The thin film ZnO layer is deposited by Atomic Layer Deposition (ALD) at different temperatures on a p-type silicon substrate. Atomic force microscopy (AFM) AC-in-Air method in addition to conductive AFM (CAFM) were used for the characterization of ZnO layer and to measure the current-voltage characteristics. Forward and reverse bias n-p diode behavior with good rectification properties is achieved. The diode with ZnO grown at 80°C exhibited the highest on/off ratio with a turn-on voltage (VON) ∼3.5 V. The measured breakdown voltage (VBR) and electric field (EBR) for this diode are 5.4 V and 3.86 MV/cm, respectively.