Optical properties of zirconium oxynitride films: the effect of composition, electronic and crystalline structures

tThis work is devoted to the investigation of zirconium oxynitride (ZrOxNy) films with varied opticalresponses prompted by the variations in their compositional and structural properties. The films wereprepared by dc reactive magnetron sputtering of Zr, using Ar and a reactive gas mixture of N2+ O2(17:3).The colour of the films changed from metallic-like, very bright yellow-pale and golden yellow, for low gasflows to red-brownish for intermediate gas flows. Associated to this colour change there was a significantdecrease of brightness. With further increase of the reactive gas flow, the colour of the samples changedfrom red-brownish to dark blue or even to interference colourations. The variations in composition dis-closed the existence of four different zones, which were found to be closely related with the variationsin the crystalline structure. XRD analysis revealed the change from a B1 NaCl face-centred cubic zirco-nium nitride-type phase for films prepared with low reactive gas flows, towards a poorly crystallizedover-stoichiometric nitride phase, which may be similar to that of Zr3N4with some probable oxygeninclusions within nitrogen positions, for films prepared with intermediate reactive gas flows. For highreactive gas flows, the films developed an oxynitride-type phase, similar to that of -Zr2ON2with someoxygen atoms occupying some of the nitrogen positions, evolving to a ZrO2monoclinic type structurewithin the zone where films were prepared with relatively high reactive gas flows. The analysis carriedout by reflected electron energy loss spectroscopy (REELS) revealed a continuous depopulation of thed-band and an opening of an energy gap between the valence band (2p) and the Fermi level close to 5 eV.The ZrN-based coatings (zone I and II) presented intrinsic colourations, with a decrease in brightness anda colour change from bright yellow to golden yellow, red brownish and dark blue. Associated to thesechanges, there was also a shift of the reflectivity minimum to lower energies, with the increase of thenon-metallic content. The samples lying in the two last zones (zone III, oxynitride and zone IV, oxide films)revealed a typical semi-transparent-optical behaviour showing interference-like colourations only dueto the complete depopulation of the d band at the Fermi level. The samples lying in these zones presentedalso an increase of the optical bandgap from 2 to 3.6 eV.

Thin films composed of Ag nanoclusters dispersed in TiO2: Influence of composition and thermal annealing on the microstructure and physical responses

Noble metal powders containing gold and silver have been used for many centuries, providing different colours in the windows of the medieval cathedrals and in ancient Roman glasses. Nowadays, the interest in nanocomposite materials containing noble nanoparticles embedded in dielectric matrices is related with their potential use for a wide range of advanced technological applications. They have been proposed for environmental and biological sensing, tailoring colour of functional coatings, or for surface enhanced Raman spectroscopy. Most of these applications rely on the so-called localised surface plasmon resonance absorption, which is governed by the type of the noble metal nanoparticles, their distribution, size and shape and as well as of the dielectric characteristics of the host matrix. The aim of this work is to study the influence of the composition and thermal annealing on the morphological and structural changes of thin films composed of Ag metal clusters embedded in a dielectric TiO2 matrix. Since changes in size, shape and distribution of the clusters are fundamental parameters for tailoring the properties of plasmonic materials, a set of films with different Ag concentrations was prepared. The optical properties and the thermal behaviour of the films were correlated with the structural and morphological changes promoted by annealing. The films were deposited by DC magnetron sputtering and in order to promote the clustering of the Ag nanoparticles the as-deposited samples were subjected to an in-air annealing protocol. It was demonstrated that the clustering of metallic Ag affects the optical response spectrum and the thermal behaviour of the films.