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In this study, Cr−Mo−N thin films with different Mo contents were synthesised via closed field unbalanced magnetron sputtering ion plating. The effects of Mo content on the microstructure, chemical bonding state, and optical properties of the prepared films were investigated by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy, and ultraviolet-visible spectrophotometry. XRD results determined the face centered cubic (fcc) structure of pure CrN film. The incorporation of molybdenum (Mo) in the CrN matrix was confirmed by both XRD and XPS analyses. The CrMoN coatings demonstrate various polycrystalline phases including CrN, γ-Mo2N, Cr with oxides layers of MoO3, CrO3, and Cr2O3. Microstructural results of the Cr-Mo-N coatings show that the grain size increased with an increase in Mo content due to the formation of MoN phase, in which the Mo atoms interact with N atoms around the grain boundaries of the CrN phase. XPS investigations confirmed the presence of Cr, Mo, N, C and O elements in the studied coatings. The optical results revealed that the synthesised coatings exhibit low reflection magnitudes in the visible region of the solar spectrum indicating good antireflection surfaces. Mo doped thin coatings improve the solar absorptance by ~76% in the wavelength range of 200–800 nm with a low thermal emittance of ~ 20% in the infrared range (up to 4000 nm). Furthermore, by applying density functional theory, the computational simulation provides similar trends as the experimental finding of absorption coefficient in the wavelength range.

In the present study, molybdenum doped chromium nitride coatings deposited onto silicon substrates via unbalanced magnetron sputtering, in as-deposited and annealed conditions, at 500–800 °C in steps of 100 °C, were studied to reveal their temperature dependent structural, morphological, optical and mechanical behaviors. An analysis of these features was carried out using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), ultraviolet visible (UV–Vis) spectroscopy, nanoindentation and finite element modeling (FEM) techniques. XRD results exhibited a significant improvement in the crystallinity of the Molybdenum (Mo)-doped chromium nitride (CrN) coatings along (111) and (200) diffraction planes, as the annealing temperatures increased. The lattice parameters gradually decreased from 4.20 to 4.12 Å as the temperature increased. The same tendency was also observed for lattice microstrains and residual stresses. Smooth grain-like surfaces were observed by FESEM imaging techniques. At an annealing temperature of 700 °C, the spectral absorptance of Mo:CrN films attained its peak value (86%), whereas the energy band-gaps were reduced from 2.48 to 1.14 eV. The other optical parameters such as complex dielectric constants, Urbach energy values, and steepness parameters of these coatings were also discussed. The hardness and elastic modulus of the as-deposited Mo:CrN films were estimated to be 18.4 and 287 GPa, respectively. At a film thickness of 1.0 μm, the highest stress of 20 GPa was evaluated, via FEM studies, at the interface between the film and the substrate. As the film thickness was enhanced, the stress level decreased. At higher annealing temperatures, both the mechanical hardness (H) and the elastic modulus (E) of Mo-doped CrN coatings dwindled.

Ce/Ti mixed metal oxide thin films have well known optoelectrical properties amongst several other physio-chemical properties. Changes in the structural and mechanical properties of magnetron sputtered Ce/Ti oxide thin films on Si (100) wafers with different Ce:Ti ratios are investigated experimentally and by modelling. X-ray Photoemission Spectroscopy (XPS) and X-ray diffraction (XRD) confirm the primary phases as trigonal Ce2O3 and rutile form of TiO2 with SiO2 present in all prepared materials. FESEM imaging delivers information based on the variation of grain size, the mixed Ce/Ti oxides providing much smaller grain sizes in the thin film/substrate composite. Nanoindentation analysis concludes that the pure cerium oxide film has the highest hardness value (20.1 GPa), while the addition of excess titanium oxide decreases the hardness of the film coatings. High temperature in-situ XRD (up to 1000 °C) results indicate high thermal phase stability for all materials studied. The film with Ce:Ti = 68%:32% has a new additional minor oxide phase above 800 °C. Contact angle experiments suggest that the chemical composition of the surface is insignificant affecting the water contact angle. Results show a narrow band of 87.7–95.7° contact angle. The finite element modelling (FEM) modelling of Ce/Ti thin film coatings based on Si(100); Si(110); silica and steel substrates shows a variation in stress concentration.

The influence of the reaction gas composition during the DC magnetron sputtering process on the structural, chemical and optical properties of Ce-oxide thin films was investigated. X-ray diffraction (XRD) studies confirmed that all thin films exhibited a polycrystalline character with cubic fluorite structure for cerium dioxide. X-ray photoelectron spectroscopy (XPS) analyses revealed that cerium is present in two oxidation states, namely as CeO2 and Ce2O3, at the surface of the films prepared at argon-oxygen flow ratios between 0–7%, whereas the films are completely oxidized into CeO2 as the aforementioned ratio increases beyond 14%. Various optical parameters for the thin films (including an optical band gap in the range of 2.25 – 3.1 eV) were derived from the UV-Vis reflectance. A significant change in the band gap was observed as the oxygen pressure was raised from 7% to 14% and this finding is consistent with the high-resolution XPS analysis of Ce 3d that reports a mixture of Ce2O3 and CeO2 in the films. Density functional theory (DFT+U) implemented in the Cambridge Serial Total Energy Package (CASTEP) was carried out to simulate the optical constants of CeO2 clusters at ground state. The computed electronic density of states (DOSs) of the optimized unit cell of CeO2 yields a band gap that agrees well with the experimentally measured optical band gap. The simulated and measured absorption coefficient (α) exhibited a similar trend and, to some extent, have similar values in the wavelength range from 100 to 2500 nm. The combined results of this study demonstrate good correlation between the theoretical and experimental findings.

Chromium nitride (CrN) coatings were deposited by magnetron sputtering onto Si(100) substrates. The coatings were then annealed at different temperatures (500–800 °C in steps of 100 °C) in air for 1 h. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), UV–Vis spectroscopy, nanoindentation tests and finite element modeling (FEM) were conducted in order to investigate their structural, morphological, optical and mechanical properties. XRD patterns show that the crystallinity of the CrN phase increases with the rise in annealing temperatures together with its preferred orientations along (111) and (200) diffraction planes. The lattice constants were slightly reduced from 4.19 to 4.11 nm at 800 °C. The lattice micorstrains and residual stresses were also reduced as the annealing temperatures rose as a result of reduced defects, dislocations and vacancies. Smooth grain-like surfaces with grain sizes ranging between ∼50 and 250 nm were confirmed by FESEM micrographs. XPS studies indicated the existence of Cr and N on the coating systems. Optical studies showed that with the rise in annealing temperature of up to 700 °C, the solar absorptance of CrN coatings is increased from 61% to 89% and slightly decreased at 800 °C, while the optical band-gap energy dropped from 2.62 to 1.38 eV and slightly increased to 1.48 eV at 800 °C. A gradual increase of dielectric constants of CrN films were realized with the subsequent annealing progression. Nanoindentation results indicated that as the annealing progresses, the hardness and elastic modulus values are lowered.

Cr1−xAlxN coatings, synthesised by an unbalanced magnetic sputtering system, showed improved microstructure and mechanical properties for ∼14–21% Al content. In situ SR-XRD analysis indicated various crystalline phases in the coatings that included: CrN, AlN, α-Cr with small amounts of AlO2 and Al2O3 over the 25–700 °C range. Al doping improves resistance to crystal growth, stress release and oxidation resistance of the coatings. Al doping also enhances the coating hardness (H) from 29 to 42 GPa, elastic modulus (E) from 378 to 438 GPa and increased the resistance to deformation. First-principles and quasi-harmonic approximation (QHA) studies on bulk CrN and AlN were incorporated to predict the thermo-elastic properties of Cr1−xAlxN thin film coatings in the temperature range of 0–1500 °C. The simulated results at T = 1500 °C give a predicted hardness of H = ∼41.5 GPa for a ∼21% Al doped Cr1−xAlxN coating.

Transition metal nitride TixM1−x−yNy (M = Al or AlSi) based thin films are evaluated as solar selective surfaces by correlating their spectral selective features with their crystal structure and chemical bonding state including mechanical strength. Ti0.5N0.5, Ti0.25Al0.25N0.5, and Ti0.25Al0.2Si0.05N0.5 films were synthesized on AISI M2 steel substrates via closed field unbalanced magnetron sputtering technology. These were investigated using XRD, SEM, XPS, UV-Vis, FTIR and nanoindentation techniques. Analysis of the optical properties showed the solar absorptance, in the visible range, of the TixM1−x−yNy films improved significantly from 51% to 81% with AlSi-doping and an increase of solar absorptance of up to 66% was recorded from films doped with Al. Moreover, the Al doping can reduce the thermal emittance in the infrared range from 6.06% to 5.11%, whereas doping with AlSi reduces the emittance to ca. 3.58%. The highest solar selectivity of 22.63 was achieved with TiAlSiN films. Mechanical studies showed enhanced hardness by ∼32%; enhanced yield strength by ∼16% and enhanced plastic deformation by ∼110% of Al and AlSi doped TiN matrix.

Quaternary sputtered TiAlSiN coatings were investigated for their high temperature structural stability, surface morphology, mechanical behaviors, surface chemical bonding states, solar absorptance and thermal emittance for possible solar selective surface applications. The TiAlSiN films were synthesized, via unbalanced magnetron sputtered technology, on AISI M2 steel substrate and annealed at 500 °C - 800 °C temperature range. SEM micrographs show nanocomposite-like structure with amorphous grain boundaries. Nanoindentation analyses indicate a decrease of hardness, plastic deformation and constant yield strength for the coatings. XPS analysis show mixed Ti, Al and Si nitride and oxide as main coating components but at 800 °C the top layer of the coatings is clearly composed of only Ti and Al oxides. Synchrotron radiation XRD (SR-XRD) results indicate various Ti, Al and Si nitride and oxide phases, for the above annealing temperature range with a phase change occurring with the Fe component of the substrate. UV-Vis spectroscopy, FTIR spectroscopy studies determined a high solar selectivity, s of 24.6 for the sample annealed at 600 °C. Overall results show good structural and morphological stability of these coatings at temperatures up to 800 °C with a very good solar selectivity for real world applications.

Chromium nitride (CrN)-based materials display broad applications as protective coatings for automotive, power generation and aerospace industries, in which surfaces are often subjected to wear and corrosion. By using an appropriate choice of dopant, one can further increase the mechanical hardness, corrosion and oxidation resistance of these coatings. In order to identify the effect of dopants on the structural evolution and surface electronic properties of CrN coatings, Cr1-z(Al/Si)zN coatings were prepared by magnetron sputtering and then characterized via X-ray diffraction (XRD) and soft X-ray synchrotron radiation Near-edge X-ray Absorption Fine Structure (NEXAFS) studies around N K-edge. Higher degree of crystallinity of the coatings were identified through XRD studies. The bonding structure, of the doped CrN coating, was analyzed by Near-edge X-ray Absorption Fine Structure (NEXAFS) measurements performed around the N K-edge (390–450 eV) in the Auger electron yield (AEY) and total fluorescence yield (TFY) modes. NEXAFS analysis revealed Cr3d(Al3p/Si3p)N2p hybridizations in Cr1-z(Al/Si)zN compositions and complex structure splitting via spin–orbit interaction of the Cr3d levels.

CrN has widespread applications as protective coatings, for example, in aircraft jet engines whereby their high hardness and good oxidation resistance render metal components resistant to harsh operating conditions. Alloying elements are commonly incorporated (doped) into the coatings to further enhance their thermomechanical properties. However, the effect of dopants on the electronic properties and their roles in modifying the grain boundary configurations remain unclear. Lack of such critical knowledge has hindered the development of design strategies for high performance CrN-based coatings. To address this challenging issue, in the present study near-edge X-ray absorption fine structure (NEXAFS) investigations of Cr1–yNiyN coatings at the Cr L3,2-edge (570–610 eV), Ni L3,2-edge (840–890 eV), and N K-edge (380–450 eV) regions were conducted using synchrotron radiation soft X-ray (SXR) spectroscopy in both Auger electron yield (AEY) and total fluorescence yield (TFY) modes. The chemical states in CrNiN were found to change with the increase of Ni content, manifested as a small chemical shift and moderate change of shapes of various absorption edges. The CrN grain size also became smaller with increasing Ni concentration. These findings help improve our understanding of local bonding structures, which could potentially lead to improved coating designs for highly demanding applications.

One of the toughest challenges that hinders the application of ceramic coatings is their poor damage tolerance. Addressing this problem requires the development of novel micro- or nanostructures that would impart to these coatings both high hardness and high toughness. In this paper, CrAlN coatings, with varying Al contents up to 30 at.%, were engineered onto steel substrates using the magnetron sputtering technique. Whilst the addition of Al does not significantly alter the columnar microstructure, it does change the preferred grain orientation and increase the compressive residual stress. Moreover, the hardness, elastic strain to failure (H/E) and plastic deformation resistance (H 3/E 2) of the resultant CrAlN coating with the highest Al content were found to increase ∼47, ∼29 and ∼140%, respectively, as compared to CrN. Evidence collected from transmission electron microscopy and X-ray photoelectron spectroscopy experiments shows that AlN, existing in an amorphous state at the columnar CrN grain boundaries, has a crucial role in providing the unusual combination of high hardness and exceptional damage resistance. The results provide a new pathway to developing durable ceramic coatings suitable for applications involving severe loading conditions.

Nanocomposite TiSiN coatings were deposited on tool steels. Detailed mechanisms that govern the corrosion of these coated steels were revealed, following immersion tests in a 70% nitric acid solution. Pitting originated preferentially from coating defect sites and expanded with increasing immersion time. Both Young’s modulus and hardness measured by nanoindentation decreased as the corrosion damage intensified. A thin oxide layer formed from the thermal annealing of the as-deposited samples at 900 °C was found to be effective against corrosive attack. In addition, compressive residual stress was noted to suppress the propagation of corrosion-induced cracks. The role of residual stress in controlling the corrosion resistance of these ceramic-coated steels is clarified by finite element analysis.

The effects of introducing thin-TiN sublayers into TiSiN nanocomposite coatings on the deformation mechanisms imparted by both uni-axial indentation and scratch contacts were evaluated by examining cross-sections of the deformed samples. Nanoindentation testing shows that the monolithic TiSiN coating is much harder than the monolithic TiN. The indentation hardness of the multilayer samples increased with the thickness of the TiSiN sublayer in the TiSiN/TiN multilayer coatings. The density of catastrophic cracks in the coatings was largely reduced when relatively ductile TiN sublayers were introduced to form the TiSiN/TiN multilayers, as a larger portion of deformation is accommodated within them. It was observed that some of the TiN grains extended into the neighboring TiSiN sublayers. The orientation of these grains helped to inhibit the growth of cracks. To summarize, the TiN sublayers helped to maintain the structural integrity by reducing the degree of catastrophic damage in the harder TiSiN sublayers.