An Accurate Quantitative X-ray Photoelectron Spectroscopy Study of Pure and Homogeneous ZrN Thin Films Deposited Using BPDMS

A quantitative X-ray Photoelectron Spectroscopy (XPS) study has been undertaken on different experimental data sets of ZrN thin films deposited using reactive Bipolar Pulsed Dual-Magnetron Sputtering (BPDMS) on silicon/stainless steel substates, to obtain dense, pure and homogeneous coatings, free from morphological defects. Zirconium nitride (ZrN) occupies a central role within the class of transition metal nitrides (TMN) for its excellent properties, such as high hardness, low resistivity and chemical/thermal stability when its stoichiometric ratio is 1:1. Many deposition techniques, reported in the literature, tried to obtain oxygen-free and defect-free structures, but they proved a hard task. In this paper it has been demonstrated, using quantitative XPS, that stoichiometric, pure and homogeneous ZrN films have been grown at certain deposition conditions, optimized also via optional accessories mounted on the deposition apparatus. Almost all the films considered for microanalytical characterization resulted as completely oxygen-free, pure (with a lowest-detection limit of 1%) and homogeneous. Apart from these features, a stoichiometric ratio (N/Zr) close to one was calculated for six samples of the ten investigated, with a precision of ± 0.01. In this frame XPS, widely known for being a highly surface-sensitive technique (average depth resolution of 20–30 Å), and powerful for characterizing the chemical composition of materials, has been extensively employed to extract information both in the surface regions and in depth. A cluster ion beam Ar+ 2500 facility on our main XPS chamber has not proved adequate for depth-profiling acquisitions. Therefore, Ar+ ion sputtering was performed instead. To the best of our best knowledge, the results achieved in the present paper possess a level of accuracy never reached before. Rigorous calibration procedures before and during experimental spectrum acquisitions and a careful and scrupulous data processing using software CasaXps v.2.3.24PR1 were carried out to ensure a low percentage error. Progress has also been made for shake-up satellite extraction and interpretation from Zr 3d high-resolution spectra with the help of the literature milestones reported in the text. The total absence of oxygen inside most of the films prevented the formation of zirconium oxide compounds during deposition, which are generally resonant with the binding energy of the shake-up satellite peaks and hide them. A little summary about the experimental shake-up satellite peaks revealed and extracted from the Zr 3d region, after Shirley background subtraction and data processing, will be presented in the last subparagraph of the “Results” section for the ZrN samples analyzed. Figures of Zr 3d deconvoluted spectra for in-depth area analysis have been reported. The quantitative satellite contribution to the Zr 3d total area would not be included in stoichiometric calculations.