Bonding structure and morphology of chromium oxide films grown by pulsed-DC reactive magnetron sputter deposition

Chromium oxide (CrOx) thin films were grown by pulsed-DC reactive magnetron sputter deposition in an Ar/O2 discharge as a function of the O2 fraction in the gas mixture (ƒ) and for substrate temperatures, Ts, up to 450 °C. The samples were analysed by Rutherford backscattering spectrometry (RBS), spectroscopic ellipsometry (SE), atomic force microscopy (AFM), scanning (SEM) and transmission (TEM) electron microscopy, X-ray diffraction (XRD), and X-ray absorption near-edge structure (XANES). On unheated substrates, by increasing ƒ the growth rate is higher and the O/Cr ratio (x) rises from ∼2 up to ∼2.5. Inversely, by increasing Ts the atomic incorporation rate drops and x falls to ∼1.8. XRD shows that samples grown on unheated substrates are amorphous and that nanocrystalline Cr2O3 (x = 1.5) is formed by increasing Ts. In amorphous CrOx, XANES reveals the presence of multiple Cr environments that indicate the growth of mixed-valence oxides, with progressive promotion of hexavalent states with ƒ. XANES data also confirms the formation of single-phase nanocrystalline Cr2O3 at elevated Ts. These structural changes also reflect on the optical and morphological properties of the films.