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The current-voltage characteristics of Ni contacts with the surfaces of ZnO thin films as well as single crystal (0001) ZnO substrate are investigated. The ZnO thin film shows a conversion from Ohmic to rectifying behavior when annealed at 800°C. Similar findings are also found on the Zn-polar surface of (0001) ZnO. The O-polar surface, however, only shows Ohmic behavior before and after annealing. The rectifying behavior observed on the Zn-polar and ZnO thin film surfaces is associated with the formation of nickel zinc oxide (Ni1-xZnxO, where x = 0.1, 0.2). The current-voltage characteristics suggest that a p-n junction is formed by Ni1-xZnxO (which is believed to be p-type) and ZnO (which is intrinsically n-type). The rectifying behavior for the ZnO thin film as a result of annealing suggests that its surface is Zn-terminated. Current-voltage measurements could possibly be used to determine the surface polarity of ZnO thin films.