Many interesting materials in a broad range of applications have in their composition the coexistence of zinc and iron. Their characterization by XPS should identify and quantify both elements. The most intense regions for these elements Zn 2p and Fe 2p are, therefore, used to accomplish that purpose. By using sphalerite as an example of a material where Zn and Fe may coexist and using XPS with two different X radiation sources to study them, it is demonstrated that the Fe 2p region, when the iron is the minor component, may be seriously affected by the Auger Zn L3M1M23 structure. The sphalerite (Zn1−xFexS) here studied has x ≈ 0 and is a good example to show how an XPS spectrum obtained with the X-ray Al Kα, the most used radiation in monochromatic equipment, leads to a wrong assignment of the structures existing in the binding energy region of Fe 2p. The simultaneous use of Mg Kα radiation showed that the Fe 2p is below the XPS detection in this specific sample of sphalerite. Its attested absence reveals that the structure detected, when using Al Kα in the “Fe 2p” region, is assigned to a zinc Auger multiple peak and not to the expected 2p photoelectron doublet peak of iron.
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