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In this paper, we fabricated the ultrathin ZnO p-n homojunctions, which modulated by ZnMgO asymmetrical double barriers (ADB). The ADB p-n homojunctions displays step-like curve in the absorption spectrums, this is the first time that quantum confinement effect has been observed in the absorption spectrums at room temperature (RT). The Hall-effect data confirm there is 2-dimensional electron gas in the interface of the ZnMgO ADB p-n junctions. The quantum confinement effect enhances the hall-mobility μ to 103 cm2V −1s−1 based on the polarity of the films. There was no rectification property in the ZnO homojunctions with thickness of 250nm, however, when the ADB was added in the n-type layer of the homojunctions, it displays a typical Zener diode rectification property in the I-V curve.