Study of columnar growth, texture development and wettability of reactively sputter-deposited TiN, ZrN and HfN thin films at glancing angle incidence

Abstract

In this work, TiN, ZrN and HfN thin films fabricated using glancing angle deposition (GLAD) technique are studied both experimentally and by numerical simulations. The films (1 µm thickness) were deposited by reactive magnetron sputtering at 0.3 Pa and 300°C on Si substrates inclined at α=85° with respect to the target. The film morphology and crystal structure were characterized by scanning electron microscopy, atomic force microscopy and Xray diffraction (XRD), including pole figure measurements. The wettability of these coatings was investigated using the sessile drop method with three different liquids. It is shown that TiN, ZrN and HfN films have a cubic, NaCl-type crystal structure with a [111] out-of-plane orientation and exhibit a biaxial texture. XRD pole figures reveal that the crystal habit of the grains consists of {100} facets constituting triangular-base pyramids. The films develop columnar microstructures, with typical column widths of ~ 100 nm. The tilt angle β of the columns is found to increase from 24.5, 31.5 to 34° for TiN, ZrN and HfN films, respectively. Atomistic computations of the growth of these nitrides at glancing angle using a kinetic Monte Carlo model reveal that the growth morphology and variation in column tilt angle is well reproduced by considering the difference in the angular distribution of the sputtered particles.This study also shows that GLAD films are hydrophilic comparatively to the same films deposited at near-normal incidence, and among the three nitrides, TiN is the more wettable coating.

Self-Assembled Dichroic Plasmonic Nitride Nanostructures with Broken Centrosymmetry for Second-Harmonic Generation

“…The difference in the morphology of the produced TiN and ZrN nanostructures, i . e ., quite smooth NWs vs arrays of granular NWs, respectively, may be assigned to a variety of reasons, such as differences in the angular and energy distributions of sputtered atoms reaching the substrate at a glancing angle and the reduced mobility of Zr adatoms on the active growing surface. , The reported morphological features do not change after the deposition of the homogeneous 5 nm ultrathin SiN x capping layer over the TiN or ZrN nanostructures (Figure a, step 4). When the GLAD of TiN or ZrN and the sputter deposition of the homogeneous SiN x capping layer are repeated three times, in order to produce triple arrays of nanostructures and increase their linear as well as nonlinear plasmonic response, the surface morphology of the top array of nanostructures is less organized and coherent as it is shown in the Supporting Information (Figure S2).…”

“…The difference in the morphology of the produced TiN and ZrN nanostructures, i.e. quite smooth NWs vs arrays of granular NWs, respectively, may be assigned to a variety of reasons, such as differences in angular and energy distribution of sputtered atoms reaching the substrate at glancing angle, and the reduced mobility of Zr adatoms on the active growing surface [57,58]. The reported morphological features do not change after the deposition of the homogeneous 5 nm ultrathin SiNx capping layer over the TiN or ZrN nanostructures (Fig.…”

Synthesis, microstructural characterization and nanoindentation of Zr, Zr-nitride and Zr-carbonitride coatings deposited using magnetron sputtering

“…Over the years, various properties of Zr-nitride coatings have been investigated for a range of applications. It has been evaluated for its microhardness, adhesion and wear resistance in tribological applications and as a barrier material in integrated circuits [1] , [2] , [3] , [4] , [5] , [6] , [7] , [8] , [9] , [10] , [11] , [12] , [13] , [14] , [15] , [16] , [17] , [18] , [19] , [20] , [21] , [22] , erosion protection for turbine and compressor blades [23] , [24] , [25] , biocompatibility [26] , optical and electrical properties [27] , [28] , nuclear fuel element compatibility [29] , [30] , [31] , and orientation dependence, microstructure, composition and corrosion [32] , [33] , [34] , [35] , [36] , [37] , [38] , [39] , [40] . Influence of synthesis parameters on coating properties have also been investigated [41] , [42] , [43] , [44] , [45] , [46] .…”

An experimental analysis of the influence of electrolyte compositions, current density and duration of the micro­arc oxidation process on the structural­phase state and properties of VT3­1 titanium alloy

“…The greatest effect of improving the properties when using this approach was the creation of ceramic-like coatings on the surface. Such coatings with high properties are based on nitrides [9,10], borides [11,12] and oxides [13,14] of transition metals, both in the form of single-layer [15,16] and multilayer [17,18] composites.…”