Thin Solid Films, Vol.518, No.5, 1522-1526, 2009
Structure and optical properties of Zr1-xSixN thin films on sapphire
A series of zirconium silicon nitride (Zr1-xSixN) thin films were grown on r-plane sapphire substrates using reactive RF magnetron co-sputtering of Zr and Si targets in a N-2/Ar plasma. X-ray diffraction pole figure analysis, X-ray reflectivity, X-ray photoelectron spectroscopy (XPS), optical microscopy, and optical absorption spectroscopy were used to characterize the film stoichiometries and structures after growth at 200 degrees C and post-deposition annealing up to 1000 degrees C in ultra-high vacuum. The atomically clean r-plane sapphire substrates induce high quality (100) heteroepitaxy of ZrN films rather than the (111) orientation observed on steel and silicon substrates, but the addition of Si yields amorphous films at the 200 degrees C growth temperature. After the annealing treatment, films with Si content x<0.15 have compressive stress and crystallize into a polycrystalline structure with (100) fiber texture. For x>0.15, the films are amorphous and remain so even after ultra-high vacuum annealing at 1000 degrees C. XPS spectra indicate that the bonding changes from covalent to more ionic in character as Si-N bonds form instead of Zr-N bonds. X-ray reflectivity. atomic force microscopy (AFM) and optical microscopy data reveal that after post-deposition annealing the 100 nm thick films have an average roughness <2 nm, except for Si content near x=0.15 corresponding to where the film becomes amorphous rather than being polycrystalline. At this stoichiometry, evidence was found for regions of film delamination and hillock formation, which is presumably driven by strain at the interface between the film and sapphire substrate. UV-visible absorption spectra also were found to depend on the film stoichiometry. For the amorphous Si-rich films (x>0.15), the optical band gap increases with Si content, whereas for Zr-rich films (x<0.15), there is no band gap and the films are highly conductive. (C) 2009 Elsevier B.V. All rights reserved.