X-ray photoelectron spectroscopy and powder X-ray diffraction studies of diluted magnetic semiconducting alloys Zn_{1-x}Co_{x}S, in the composition range 0 ≤ x ≤ 0.18, were performed. The analysis of XPS spectra has shown that admixture of Co into ZnS lattice does not affect the shape and position of Zn 2p core level, whereas certain modification of the S 2p peak shape was observed. The detected binding energy of Co indicated similarity between Co-S and Co-O bond structure. Significant contributions of Co 3d^{7} electrons to the valence band density of states were revealed.
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