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X-ray photoelectron spectroscopy has been used to characterize the oxidation states in Ta/NiOx/Ni81Fe19/Ta magnetic multilayers prepared by rf reaction and dc magnetron sputtering. The exchange coupling field and the coercivity of NiOx/Ni81Fe19 are studied as a function of the ratio of Ar to O2 during the deposition process.The chemical states of Ni atoms in the interface region of NiOx/NiFe have also been investigated by x-ray photoelectron spectroscopy and the peak decomposition technique. The results show that the ratio of Ar to O2 has a great effect on the chemical states of nickel in NiOx films. Thus the exchange coupling field and the coercivity of Ta/NiOx/Ni81 Fe19/Ta are seriously affected. Also, the experiment shows that x-ray photoelectron spectroscopy is a powerful tool in characterizing magnetic multilayers.