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In this work we have studied the interfacial reactions between chromium and an Al2O3(11‐02) surface with X‐ray photoelectron spectroscopy and Auger electron spectroscopy. The results reveal that, at room temperature, the interfacial reactions are dominated by the interaction of Cr atoms with the oxygen anions on the Al2O3 substrate forming a Cr–O–Al complex oxide. Annealing the Cr‐covered sample to high temperature, additional interfacial reactions occur, involving the formation of chromium oxide and metallic Al, indicating the interfacial reactions have a strong temperature dependence. The results also show that the relative Auger peak‐to‐peak height (APPH) of the Cr LMM group peaks is very sensitive to the change of the valence band structure, therefore, it can be used as an index to identify the oxidation state of chromium at the Cr/Al2O3 interface.

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