Herein, diode characteristics of n‐MgxZn1−xO/p‐Si heterojunctions grown by pulsed laser deposition at different oxygen ambient pressures are investigated. It is found that the heterojunctions grown at lower oxygen growth pressure of 1.0 × 10−2 mbar and below do not show rectifying diode‐like behavior, whereas those grown at higher oxygen pressures at and above 2.5 × 10−2 mbar exhibit perfect diode‐like rectifying characteristics. The diode characteristics are found to improve significantly with increasing oxygen ambient pressure during the growth of MgxZn1−xO film. The current–voltage measurements show that the n‐MgxZn1−xO/p‐Si heterojunction diode grown at a higher oxygen ambient pressure of ≈1.0 × 10−1 mbar has the lowest reverse saturation current of ≈19 nA and highest rectification ratio of ≈1.4 × 104. The capacitance–voltage measurements reveal that the depletion layer width of heterojunction diodes increases manifold with increasing oxygen ambient pressure during the growth of MgxZn1−xO, which is understood in terms of decrease in carrier concentrations in the MgxZn1−xO thin films grown at higher oxygen ambient pressures. The n‐MgxZn1−xO/p‐Si heterojunction diodes, grown at high oxygen ambient pressures, with low reverse saturation current, high rectification ratio, and large depletion width may have potential application in wide‐bandgap nanoelectronic devices and UV enhanced photodetectors.

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