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The interaction between the Au layer and ZrS3(001) can be analyzed using X-ray light emission spectroscopy (XPS). Angle-resolved XPS measurements show that ZrS3(001) is terminated by disulfide (S22−), while Au thickness-related XPS indicate that the observed band bending is consistent with Schottky barrier formation at the Au/ZrS3(001) interface due to low Au coverage.