X-ray absorption spectroscopy study of granular Fe / Si₃N₄ systems

[Fe (t^Fe) / Si₃N₄ (3 nm)] multilayers were prepared by sequential magnetron sputtering. The Fe layer thickness has been varied for every sample. Magnetic properties show a gradual evolution from a ferromagnetic state for samples with larger metal thickness to a granular behaviour for the samples with the smallest Fe layer thickness. Microstructural features such as average thickness and granularity, as well as the local order around Fe atoms, were studied by x-ray reflectometry and x-ray absorption spectroscopy, respectively. X-ray reflectometry suggests that the formation of discontinuous metal-insulator multilayers is produced at t^Fe ≤ 1.3 nm. Extended x-ray absorption fine structure (EXAFS) analysis shows a reduction, of the Fe-Fe coordination shell as the metal layer thickness decreases. Moreover, a new phase emerges, and it is visible at the samples with t^Fe ≤ 1.3 nm. This coordination shell is attributed to the formation of Fe-N bonds likely placed at the interface regions. X-ray absorption near edge spectroscopy (XANES) at the Fe K-edge shows as well the evolution from the metallic spectrum to a combined contribution of 2 phases as the metal layer thickness decreases. XANES calculations performed within the real-space multiple-scattering formalism of two nanometric phases for metal bcc Fe and tetrahedral FeN in zinc-blende structure provide a successful explanation of the XANES spectral evolution. The appearance of a new phase linked to the interface regions obtained by X-ray absorption analysis suggests the granular morphology of samples with t^Fe ≤ 1.3 nm.