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This work focuses on the film deposition mechanisms in a low-pressure argon-acetylene magnetron assisted plasma via Particle-in-Cell Monte-Carlo simulation in combination with a chemical surface model including saturated and dangling bond sites to account for the film growth mechanisms involving reactive radical species. A main point of interest was to find out whether the film growth is dominated by ions, by radicals or by target sputtering. Predictions were made regarding the equilibrium coverage and the deposition profile at equilibrium for various acetylene ratios by varying the initial surface coverage of dangling bonds, fitting its evolution with time and extrapolating predictions to discharge powers. These predictions were tested against experimental a-CH film characterizations, including RBS/ERDA, XPS, Raman, and profilometer measurements. Even if high uncertainty remains, we demonstrated that films deposited on a grounded substrate facing the target have Gaussian deposition profiles which can be reproduced quantitatively for various C 2H 2 ratios. This model could be used to accelerate the search for optimal deposition parameters for more complex deposition configurations without relying on costly trial-and-errors, and to get a clearer understanding on the underlying processes which is hard to obtain with in-situ experiments for PECVD.

The electrochemical behaviour of magnetron sputtered Ti-Si-B-C nanocomposite coating on SS 304 substrate has been examined using potentiodynamic polarization and electrochemical impedance spectroscopy after long time immersion (1, 20, 40, 70 days) in 3.5 wt% NaCl solution. The surface morphology, elemental composition and surface topography of coated and uncoated surfaces have been analyzed using FESEM, EDX spectroscopy and AFM, respectively. The XRD study revealed the presence of TiB2 and TiSi2 phases in the film which were exposed to 70 days immersion test. It implies that the grains of TiB2 and TiSi2 have grown on the Ti-Si-B-C coating. The results obtained from the electrochemical measurements of sputtered coatings showed the increase of corrosion inhibition capability for Ti-Si-B-C coating compared to SS 304 as the immersion time increases in simulated marine environment.

Monolithic and multilayered W N and W–Si–N coatings were fabricated through direct current magnetron cosputtering at substrate holder rotation speeds of 0 and 5 rpm. The mechanical properties, structural evolutions, and oxidation behaviors of the W N and W–Si–N coatings were investigated through nanoindentation, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The mechanical properties of crystalline W N coatings correlated to their textures and residual stresses. The monolithic W77N23 samples located closest to the W target exhibited a high deposition rate of 18.0 nm/min, a strong (200) texture coefficient, a high nanoindentation hardness of 32.7 GPa, a high Young's modulus of 392 GPa, and a high residual stress of −3.2 GPa. The addition of Si into the W N matrix transformed the monolithic W–Si–N coating into an X-ray amorphous phase dominated structure that comprised Si3N4, W2N, and W constituents. Ion bombardment caused the formation of multilayered W78N22 samples with high residual stress and mechanical properties. The mechanical properties and residual stresses of the multilayered W–Si–N coatings decreased due to the preferential formation of Si3N4. By contrast, oxidation resistance was improved by adding Si content higher than 24 at.% with annealing at 600 °C in a 1% O2–99% Ar atmosphere.

Biodegradable electronic devices based on non-toxic materials are an emerging field, in which the key characteristic is the complete dissolution of the devices within a determined period of time. Usually, these devices are built on polymer substrates or pure metals; however they present some disadvantages such as low degradation rate. The present study reports and compares the sustainable preparation of FeMn films via electrodeposition and magnetron co-sputtering as a possible alternative to the aforementioned materials. Morphological, chemical, structural and magnetic characterization of the obtained layers was carried out and the corrosion and biocompatibility characteristics were assessed by electrochemical studies and cell viability assays. Different ratios of Mn2+:Fe2+ ions in the electrolyte leaded to metallic and oxide based FeMn layers. The electrodeposited FeMn films showed different crystalline structure depending on their nature: a bcc-Fe crystal structure when they are metallic and fcc when they are oxidized. In addition, glycine was used as complexing agent in the electrolytic bath, which leaded to less-crack films and varied the Mn content in the films (9–24 wt%). The Mn content of the magnetron co-sputtered films varied between 10 and 70 wt%. Differently to the electrodeposited films, the sputtered revealed a well-defined bcc structure that lowers its symmetry when the Mn content increases. Regarding the magnetic behavior, all obtained films showed a soft magnetic behavior. Their corrosion behavior in NaCl solutions was evaluated by electrochemical studies, observing a shift to more negative corrosion potential values when Mn content increases. In vitro cytotoxicity tests revealed highly biocompatible characteristics with a cell viability of 85% even for the Mn-richest sputtered films (70 wt%) while electrodeposited films showed a clear indication of toxicity.

Ensuring a high adhesion of amorphous carbon films to steel substrates remains a challenging task, sustaining continuous research efforts to improve the adhesion strength. Besides the interlayer system and the substrate material, surface pretreatments have a significant impact on the adhesion behavior. Within this context, the influence of the High Power Impulse Magnetron Sputtering (HiPIMS) pretreatment on the adhesion of magnetron sputtered hydrogenfree (a-C) and hydrogenated (a-C:H) amorphous carbon films with a chromium carbide (CrC) interlayer on 16MnCr5 steel is investigated. The plasma treatment consisted of 30 min Ar ion etching as well as a sequential 5 min of HiPIMS-pretreatment with a Cr cathode. Subsequently this pretreatment was compared to a procedure without utilizing the HiPIMS technique. The impact of the HiPIMS-pretreatment on the structure of the film was systematically analyzed by taking the CrC interlayer as well as the entire film structure into consideration. The adhesion strength of the a-C and a-C:H films is significantly improved by the formation of a Cr HiPIMS-nanolayer in the substrate/film interface. In scratch tests, the critical load Lc3 for a total film delamination increases from 43 ± 4 to 59 ± 3 N and from 48 ± 2 to 64 ± 3 N for the a-C and a-C:H film. The improved adhesion behavior of the carbon films is ascribed to the increased adhesion of the CrC interlayer, which did not delaminate when scratched with a load up to 159 ± 18 N. Complementary Rockwell indentation tests reveal that the HiPIMS-pretreatment improves the adhesion class from HF6 to HF4 and from HF5 to HF3 for a-C and a-C:H. The enhanced adhesion is essential to exploit the properties of a-C and a-C:H films in applications with high loads. In conclusion, the HiPIMS-pretreatment has proven to be a promising technique to increase the adhesion strength of carbon films.

High entropy alloys (HEAs) have drawn lots of attentions from researchers and industries because of their outstanding properties, such as high hardness, and good corrosion resistance. Particularly, the refractory high entropy alloy is characterized by its high temperature strength and stable thermal properties. We conducted the magnetron co-sputtering process to grow one V-Nb-Mo-Ta-W and three V-Nb-Mo-Ta-W-Cr-B refractory HEA coatings. The BCC phase of V-Nb-Mo-Ta-W HEA coating was changed into the amorphous-like structures when Cr and B elements were added into the coatings. Oxidation reactions occurred and very complex refractory metal oxides were produced on all HEA coatings when the oxidation was held at 800 °C in air for 1 h. The addition of Cr and B constituents into the V-Nb-Mo-Ta-W coating can provide good oxidation resistance and anti-corrosion performance. The highest hardness of 18.4 ± 0.5 GPa, an excellent corrosion resistance at room temperature, a high hardness of 15.9 ± 1.1 GPa and good thermal stability after 500 °C oxidation test were obtained for the V10.4Nb10.5Mo10.5Ta11.2W10.5Cr16.3B28.6 refractory HEA coating in this study.

It is of great significance to develop accident tolerant fuel claddings for enhancing the safety margin of light water reactors. Cr-Al-Si-N quaternary coatings were proposed to improve the mechanical properties and the high-temperature steam oxidation resistance of Zr-based alloys. (Cr0.6Al0.3Si0.1)xN1−x coatings with three kinds of microstructure, were prepared on Zr coupons, and then were evaluated on their mechanical properties and oxidation resistance in the high-temperature steams. The “dense & column-free” coating exhibits a combination of the best mechanical properties and the highest oxidation resistance. In comparison with the Zr coupon, its hardness H and indentation modulus E* increased by ~4 times and ~twice, respectively. After coated with the “dense & column-free” coating, the oxidation of the Zr coupon was completely suppressed in the 1000 °C steam for 15 min, and the thickness of the α-Zr(O) layer deceased by 40%–92% in the 1200 °C steam for 30 min. By contrast, the “porous & columnar” coating hardly provided any protection for the underneath Zr substrate in the high-temperature steams. The result demonstrates that the densely fine-grained or amorphous microstructure could effectively suppress inner-diffusion of O atoms and favor formation of a dense and coherent scale on surface, which would be highly desirable for the protection coatings of Zr claddings.

Magnetron co-sputtering from TiB2 and TaB2 stoichiometric targets is used to prepare AlB2-prototype ternary Ti1-xTaxB2±Δ solid solution, with x in the range from 0 to 1. Using this technique, the boron-to-metal ratio (B/Me) varies with the actual Ti and Ta content. The boron-to‑tantalum ratio can be increased by decreasing the TaB2 target voltage, which has a considerable effect on the coating structure. Coatings with B/Me > 2 reveal highly textured nanocolumnar structure, while the coatings with B/Me

Titanium diboride (TiB2) is a hard coating with a hexagonal crystal structure that maintains its high hardness and inertness at elevated temperatures, even in contact with aluminum and its alloys. Therefore, titanium diboride coatings are often used in cutting, forming, injection molding and tribological applications. While there are multiple deposition routes available for this coating, there are limitations in terms of control of the coating microstructure and internal stresses, which translate to limitations in the film properties and film integrity in industrial use. High-power impulse magnetron sputtering (HiPIMS) is a deposition technique which has recently shown promise for depositing titanium diboride films due to its intrinsic microstructural control capabilities. However, issues such as relatively low deposition rates and high compressive stresses have not been sufficiently addressed for this technique. This investigation reports on the implementation of a new HiPIMS-based TiB2 process and a high average-power process optimization from a cylindrical rotating magnetron fitted with ceramic TiB2 as the target material. By tuning the HiPIMS pulse conditions, high-hardness films were obtained at high deposition rates, while maintaining high ionization rates as determined by optical emission spectroscopy and Langmuir probe measurements. Micropillar compression and nanoindentation techniques were used to investigate the film deformation behavior. Tests at room temperature showed superior fracture strengths for the new HiPIMS coatings as compared to films deposited by traditional direct current magnetron sputtering under otherwise identical conditions. The differences in deformation are explained by a microstructural investigation by transmission electron microscopy.

WSxC(H) coatings were deposited on single crystal silicon(100) wafers by magnetron co-sputtering and reactive sputtering at various target-substrate distances. Upon increasing the distance, the stoichiometric S/W ratio increases from 0.51 to 1.89. Also, the porosity of coatings gradually augments and a columnar microstructure tends to form. Preferential sulfur resputtering rather than contaminations primarily accounts for the low S/W ratio. TEM reveals randomly oriented WS2(002) platelets in the WSxC coatings when deposited at a large distance, which is supported by XRD. The composite coatings exhibit a decreasing hardness and elastic modulus with increasing target-substrate distance. The triboperformance is strongly affected by the coating composition, the target-substrate distance and the testing environment. Cross-sectional TEM of formed tribofilms reveals an obvious reorientation of WS2(002) basal planes parallel to the plane of sliding, leading to an ultralow friction.

Titanium nitride films deposited by conventional magnetron sputtering are prone to contamination, especially residual gas species, and the composition and properties can be affected. In this work, an anode layer ion source (ALIS) is used in magnetron sputtering to deposit TiN films and the effects of the average energy Ei and ion flux density Ji on the chemical composition of the deposited films are determined. By coupling and varying the magnetron discharge current It, the ALIS can be used to control Ei to as low as 80 eV and Ji as high as 3.5 × 1016 ions cm−2 s−1. To discern the roles of Ei and Ji, the films are deposited under three different conditions of magnetron discharge It. A reduction of 95% in the oxygen concentration and an increase of 30% in the nitrogen concentration are observed by increasing Ji. X-ray photoelectron spectroscopy reveals decreased peak broadening, shifts to higher binding energies, and increase initial slope of the Ti 2p peak with larger Ji. The N 1s peak shows decreased broadening while the O 1s peak indicates less oxide-related compounds. Raman scattering reveals reduced intensity ratios of the Ti to N vibration phonon peaks (ITi/IN) indicating enhanced nitrogen-related optical phonon peaks and that the film resistivity decreases as the oxygen concentration decreases. Our experiments disclose compositional changes especially reduced oxygen incorporation with ALIS assistance during magnetron sputtering. The hybrid technique which can be scaled up readily to meet industrial demand enables control of the film composition without resorting to other parameters like high temperature, biasing, and ultrahigh vacuum that may adversely affect other film properties and add manufacturing costs.

To improve the corrosion resistance and electrical conductivity of 316L stainless steel used as a bipolar plate, TiN and ZrN coatings are deposited on the surface through magnetron sputtering in this study. Subsequently, the surface topography, composition, corrosion resistance, and interfacial contact resistance of the coated samples are characterized. The results show that the TiN and ZrN coating can significantly enhance the corrosion resistance of the 316L stainless steel. The corrosion current density of the coated 316L stainless steel with TiN and ZrN in the simulated cathodic environment of a proton-exchange membrane fuel cell (PEMFC) is 0.099 μA/cm2 and 0.209 μA/cm2, respectively, which meets the U.S. DOE 2020 target (

In this work, the effect of the deposition parameters of a magnetron sputtered Ti adhesive intermediate layer on the morphology and hydrogen absorption properties of thin Pd films of about 100 nm was investigated. The insertion of an adhesive layer between a Pd film and a rigid substrate usually suppresses or reduces hydrogen absorption. In this study, it is shown that by tuning the surface topography of the intermediate layer the morphology, crystallographic texture and hydrogen absorption properties of the Pd film can be controlled. The surface topography of the Ti layer was characterized using atomic force microscopy. The surface topography strongly depends on the Ti deposition conditions and can vary from widely spread large islands to densely packed small-grained islands depending on thickness (between 1 and 6 nm) and sputter pressure (0.4 and 3 Pa). TEM and XRD analysis led to the conclusion that rough Ti intermediate layers result in Pd films with an open columnar structure with small voids, and a weak and broad (111) texture. Smooth Ti intermediate layers promote the formation of Pd films with a dense columnar structure with fewer voids, and a strong and sharp (111) texture. Changes in the Pd adatom surface diffusion and shadowing effects are the main cause of the observed differences. Pd films with an open columnar morphology and weaker texture show better hydrogen absorption properties with respect to absorption capacity and kinetics of the films with dense columnar morphology. By tuning the surface topography of the Ti adhesive layer, Pd films with controlled morphology and texture can be prepared such that no delamination from the substrate occurs without compromising on absorption properties.

Transition metal nitrides have become a kind of promising alternative plasmonic materials. TixZr1−xNy ternary nitride films were prepared by magnetron co-sputtering method, and the effects of bias voltage and temperature on the structure and dielectric properties of the films were investigated. The experimental results show that all the films are fcc-structured, and high substrate bias and temperature can significantly improve the N and Ti content. Increasing substrate bias voltage or temperature can reduce the crossover frequency ωc at which the films transit from dielectric to metallic phase. Also, a high bias can greatly influence the energy loss of the films. Furthermore, the plasmonic quality factor can be effectively tailored by bias and temperature. Increasing bias can decrease the quality factor while high temperature (600 °C) can enhance the quality factor significantly. The study demonstrates that the TixZr1−xNy films, as one kind of alternative plamonic materials, have considerable performances, and their dielectric and plasmonic properties can be modulated by varying the bias voltage and temperature in a wide range.

Here we report the novel interlayer for the high-quality CVD diamond thin films with reduced residual stress. We used the novel sputtering technique of reactive high power impulse magnetron suttering (r-HiPIMS) which allows us to deposit high quality, void- and defect-free AlSiN interlayer films. The film based on Al-Si-N system shows fully amorphous structure at temperature of diamond film synthesis (800 °C), inertness to diamond and hard WC-Co alloy at elevated temperatures and reduction of the diamond macrostress up to −0.25 GPa for film with AlSiN interlayer. Additionally, varying the Al content in Al-Si-N film we can finely tune its mechanical properties and total stress in substrate – AlSiN – diamond system. We show that AlSiN with the combination of its properties overcomes conventionally used interlayer materials for CVD-diamond such as transition metals or their nitrides and carbides.

The fabrication of high-hardness non-hydrogenated diamond-like carbon (DLC) via standard magnetron sputtering (MS) is often hindered by the low sputtering yields and ionisation rates of carbon, therefore investigations into pulsed alternatives of MS, else sputtered species post-ionisation methods, are of particular interest. This work focuses on investigating the influence of pulsed-direct current MS (pDCMS), high power impulse magnetron sputtering (HiPIMS) and their microwave plasma-assisted (MA-pDCMS, MA-HiPIMS) variants on the properties of the fabricated DLC films. Two setups were used for the pDCMS- and HiPIMS-based methods, respectively. The films were characterised using Raman spectroscopy, nanoindentation, X-ray reflectometry and scanning electron microscopy, where the pDCMS-produced films were additionally characterised by film-stress measurements. Moreover, in situ time-resolved Langmuir probe plasma analysis was performed under HiPIMS and MA-HiPIMS conditions to analyse the influence of the magnetron and microwave plasmas on one another. For both DCMS- and HiPIMS-based procedures, it was found that the addition of microwave plasma did not facilitate attaining hardnesses beyond 30 GPa, however, it did enable modifying the morphology of the films. Furthermore, this study shows the potential of synchronised sputtering with substrate biasing, as well as the importance of microwave plasma source positioning in relation to the substrate.

The mechanical properties, microstructure, adhesion and wear resistance of a Ti0.45Al0.55N monolithic coating and Ti0.45Al0.55N/Ti0.45Al0.55 multilayer coatings were comparatively studied. The coatings were deposited on stainless steel substrates by DC magnetron sputtering. The multilayer coatings exhibited a lower hardness and reduced elastic modulus when compared to those of the monolithic coating. However, the multilayers were characterized by higher critical loads under scratch testing that testifies to their improved toughness and adherence. This resulted in the enhancement of the wear resistance of the multilayer coatings under pin-on-disk wear tests. The optimal thickness of Ti0.45Al0.55N and Ti0.45Al0.55 layers in the multilayers was determined to provide more than a three-fold decrease of the wear rate as compared with the monolithic coating. The applicability of different mechanical parameters such as the H/E⁎ ratio, plasticity index and crack propagation resistance parameter for comparative prediction of the wear resistance of the monolithic and multilayer coatings was evaluated. It was shown that the crack propagation resistance parameter is the most promising for this purpose.

Magnesium and magnesium alloys are widely used in the electronics, automobile and aerospace industry but the poor corrosion resistance has hindered some applications. In this work, a transparent fluorocarbon polymeric thin film is deposited on magnesium by magnetron sputtering and the corrosion resistance is evaluated. Potentiodynamic polarization and electrochemical impedance spectroscopy in combination with immersion experiments in 3.5 wt% NaCl reveal markedly improved corrosion resistance. The corrosion mechanism is discussed from the perspective of random defects in the fluorocarbon film.

Among the different techniques of reactive sputtering, the bipolar and high power impulse magnetron sputtering are growing in interest for the thin films research community. However, the combination of both processes in presence of a reactive atmosphere is extremely complex and the role of the sputtering parameters are key points to control the deposited material properties. In this study, we have investigated the effect of the duty cycle and the pulse frequency on the reactive bipolar sputtering efficiency of chromium in presence of nitrogen. The study has been performed on a wide range of parameters: from 12.5 to 87.5% for the duty cycle, and from 62.5 to 5000 Hz for the frequency. In situ measurements of the magnetron discharge characteristics have been performed (excitation temperature, peak target current and voltage, energy influx at substrate position) in addition to ex situ characterizations of the deposited thin films (structure, microstructure, density, composition, optical and mechanical properties). It appears that the modulation of the duty cycle allows a better control of the mechanical properties due to higher ionization level at the target, while the frequency is better adapted to tune the optical properties that are attributed to a change of texturation and density of the deposited film (confirmed by simulation). All films present a similar microstructure due to the absence of bias applied to the substrate during the deposition process, which leads to a similar energy per atom of deposited species.

Accident tolerant fuel claddings are extremely urgent to increase the safety margin of light water reactors. In this work, Cr-Al-Si ternary alloy coatings were proposed to increase high-temperature oxidation resistance of zirconium claddings. Cr62.8Al27.9Si9.3 coatings were deposited on Zr coupons by magnetron sputtering, followed by evaluation of their oxidation resistance and adhesion strength under high-temperature steam. No oxidation of the Zr coupons underneath the coatings occurred in the 1000 °C steam for 15 min. In the 1200 °C steam for 30 min, both the weight gain and the thickness of the α-Zr(O) layer decreased 40% and 50%, related to those of the uncoated coupons, respectively. Moreover, the adhesion of coating and substrate was improved after the high-temperature oxidation, with the adhesion strength of the oxidized coating – Zr substrate more than ~50 N. It was further observed that the Al and Si atoms preferentially diffused outwards the surface to form a layer of oxides, and the atoms diffused towards the Zr substrate to form a mixed interlayer. The outside barrier layer and the inter-diffused layer could contribute to the enhanced oxidation resistance and the adhension of the coated Zr coupons, which would be highly desirable for the zirconium claddings.

In this work, magnetron sputtered CrNx thin films with nitrogen concentrations ranging from 17 to 30 at.% were deposited on plasma activated ABS. Two sets of thin films were obtained by varying the N-2 flow inside the vacuum chamber (series #1) and the deposition time (series #2). The polymer samples were also subjected to plasma treatment in Ar prior to the CrNx thin films' deposition, in order to enhance the adhesion. The fundamental microstructural, chemical and physical properties, as well as the electrochemical and adhesion behavior of the CrNx thin films, were assessed by SEM, XRD, 3D profilometry, RAMAN, colorimetry, OCP measurements and cross-cut tape test. Main results show that high-quality CrNx films with a low percentage of defects were obtained. The CrNx film sputtered with 3 sccm N-2 for 20 min was considered to possess the most appropriate brightness, color, electrochemical stability and interfacial adhesion to fit the end-user requirements. Magnetron sputtering is thus a promising alternative to the hazardous chrome plating for an effective metallization of ABS., This work was developed within the scope of the project POCI-01-0247-FEDER-003493 co-financed by FEDER through the POCI program and project CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT ref. UID/CTM/50011/2013), financed by national funds through FCT and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement., info:eu-repo/semantics/publishedVersion

Samples of a Ti-46Al-8Nb (at.%) alloy with Cr-0.5Si, Cr-5Si or Cr-66Si (CrSi2) coatings deposited by magnetron sputtering were oxidised in air under thermal cycling conditions at 700 °C and 800 °C for 80 h. Mass changes over time were measured periodically to evaluate reaction progress as well as susceptibility of the coating or scale to spallation. Vickers hardness, elastic modulus and adhesion of the coatings were determined before and after oxidation. Selected samples were oxidised for up to 1500–2000 h. The nature and extent of coating degradation in each case was evaluated through systematic analyses of surfaces and cross-sections using different techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). It has been found that coatings with the composition Cr-5Si (at.%) had the most promising combination of oxidation resistance and micromechanical properties.

Nb–Si–N coatings with Si contents of 0–30 at% were fabricated through reactive direct current magnetron cosputtering. The processing parameters were various sputtering powers, substrate holder rotation speeds, and nitrogen flow ratio (N2/(N2 + Ar)). Three phase regions, namely face-centered cubic (f.c.c.) NaCl structure, X-ray amorphous, and nanocrystalline phases, were identified and related to the chemical compositions of the coatings. Low-Si-content (0–13 at%) and middle-N-content (39–45 at%) Nb–Si–N coatings exhibited an f.c.c. structure, high-Si-content (17–30 at%) and high-N-content (45–53 at%) Nb–Si–N coatings exhibited an X-ray amorphous structure, and low-Si-content (6 at%) and low-N-content (26–30 at%) Nb–Si–N coatings exhibited a nanocrystalline structure. Examining the bonding characteristics of the Nb–Si–N coatings by using X-ray photoelectron spectroscopy indicated that NbN tended to form preferentially and was followed by Si3N4, which is consistent with the laws of thermodynamics. The correlations between the mechanical properties, residual stresses, and structures of the Nb–Si–N coatings were investigated using nanoindentation, a curvature method, and X-ray diffraction. The oxidation behaviors of the Nb–Si–N coatings annealed in air at 400–600 °C were also examined.

It is known that cathodic arc deposition (CAD) has been widely used in industry for high quality thin film coatings. An extremely high current density (~1012 A/m2) was created to evaporate and ionize the target material rapidly. However, the CAD also produces macroparticles or droplets along with the deposition process leading to the degradation of the film properties. Magnetic filters with different designs were therefore adopted to reduce the macro particles or droplets. However, the macroparticles still cannot be fully eliminated. Lately, a newly developed PVD process known as high power impulse magnetron sputtering (HiPIMS) was found to have the capability of yielding highly ionized flux of both gas and sputtered materials by applying a high power in short pulses to the target. High plasma density in the order of 1017 to 1019 m−3, which is three orders of magnitude higher than that of the conventional dc magnetron sputter (dcMS), can therefore be achieved from the large fluxes of energetic ions in a HiPIMS process. As a result, a smoother and denser thin film with better adhesion to the substrate can be obtained, leading to enhanced mechanical, electrical, and optical properties. However, it was also found the deposition rate of the HiPIMS process was much slower than that of the conventional dcMS and CAD process. Therefore, a hybridized deposition system combining CAD and HiPIMS was studied in this paper. Titanium nitride (TiN) films were deposited to investigate their microstructures, physical, chemical, and mechanical properties. The macroparticles were reduced in the HiPIMS system while thin films with enhanced hardness was obtained in the CAD system.

Hard and wear resistant coatings deposited by PVD techniques have been characterized for decades for their capabilities to protect steel substrates from corrosion. In the present work the effect of Mg incorporated into TiN coatings is described in terms of the corrosion behavior as well as the mechanical and structural properties. TiN and TiMgN films with Mg contents between 10 and 35 at.% were deposited onto mirror polished 100Cr6 (1.3505) steel samples with 2.5 and 5 μm thickness by using DC magnetron sputtering. The corrosion protection capabilities of the coatings were characterized by neutral salt spray (NSS) test, considering the amounts and sizes of growth defects inherent in each coated sample as determined by a recently developed optical scan method (Large Area High Resolution mapping). The defect data were statistically analyzed for improved interpretation of NSS test results. Chosen growth defects were additionally analyzed by focused ion beam technique. Furthermore the coating composition and morphology, the hardness and the tribological behavior were characterized. Polished steel samples coated with 2.5 μm TiMgN containing about 35 at.% Mg were in the plane free of corrosion after 24 h in a NSS test. TiMgN with 10 or 20 at.% Mg only provided a slightly improved corrosion protection in relation to pure TiN coatings, which was limited to certain types of growth defects. The highest Mg containing coatings exhibited a decreased hardness down to 1200 or 1800 HV depending on type of deposition (HV 1200: Ti- and Mg-target with rotating substrate holder, 1800: Mg-plugged Ti-target with static substrate holder), but also showed a strongly improved wear resistance against Al2O3 related to pure TiN. By analyzing the NSS test results it was found that the corrosion behavior of the coated samples did not only depend strongly on the Mg content, but also on the sample individual defect concentrations. Therefore this subject is extensively discussed.

A high-power impulse magnetron sputter deposition system with feedback control using an optical emission spectrometer (OES) is used to deposit nc-WC/a-C:H thin films using a tungsten (W) target material reaction with C2H2 gas in a reactive mode. The plasma emission intensity of W+ ions at an emission wavelength of 429.6 nm is monitored, and the amount of reactive C2H2 gas is precisely controlled in order to maintain stable emission intensity during the deposition process. By controlling the input flow rate of C2H2 and using different W+ ion optical emission intensity set points, various nc-WC/a-C:H thin films are obtained at a fixed duty cycle of 2% and pulse frequency of 133 Hz between deposition temperatures of 70 °C and 75 °C. The characteristics and mechanical properties of the obtained thin films are investigated. The highest peak current and peak power density of 189 A and 706 W/cm2, respectively, are obtained at an OES set point of 10%, which corresponds to a high amount of C2H2 gas injection. When the OES set point is

In this study, pseudo-elastic Ni 50.8 at.%-Ti alloy sheets of 1000 μm thickness were coated with 10 μm thick refractory metal thin films (Mo, Ta and Nb thin films, respectively), by nonreactive d.c. magnetron sputtering. These thin films were characterized with regard to their microstructure, morphology and selected mechanical properties. Microstructural characterization of the thin films included X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. SEM images show, that Mo thin films grow in a densely packed structure with columnar grains. Pole figure analyses reveal a distinct (110) texture of the deposited Mo thin films on the NiTi substrate. The Mo thin films exhibit relatively large crystallite sizes, 290–300 nm. Ta and Nb thin films show XRD reflections of various lattice planes, i.e. polycrystalline b.c.c. structures, with preferential (110) orientation. Both of these thin films grow with much smaller crystallite size in comparison to the Mo thin films, 30–40 nm. The Young's Modulus of both the thin films and thin film/substrate composites were investigated on various scales. For this purpose, indentation experiments were performed using both nano- and microindentation techniques. A comparison of the values of the Young's Modulus of the thin film materials (in bulk, literature data) and the results obtained from nanoindentation shows a very good agreement between the measured data and bulk data. Progressive scratch tests were used to evaluate the adhesion of the thin film materials on the NiTi substrate. These scratch tests suggest that the metallic thin films undergo plastic deformation at larger normal forces. However, no thin film delamination is observed, independent of the material combinations and testing conditions applied.

The microstructural development of reactively sputter-deposited tantalum nitride thin films is investigated as a function of the N2-to-total-pressure ratio (pN2/pT) and the operating mode of the metallic tantalum cathode; by direct current magnetron sputtering (DCMS), pulsed DCMS, and high power impulse magnetron sputtering (HiPIMS). For all sputtering modes investigated, the phase evolution of the Ta-N films strongly depends on the nitrogen partial pressure, pN2, used when keeping the total pressure, pT, constant at 0.3 or 0.6 Pa. The major crystalline phases identified, with increasing the pN2/pT-ratio, are α-Ta, orthorhombic o-Ta4N, hexagonal close packed (hcp) γ-Ta2N, face-centred cubic δ-TaN, and hcp e-TaN. Their development is basically determined by the N2 partial pressure present. The deposition rate decreases slowest with increasing pN2 for the HiPIMS mode and fastest for the DCMS mode. The coatings with a dominating γ-Ta2N phase (which could be obtained for pN2 between 0.08 and 0.15 Pa) exhibit the highest hardness with 38.2 ± 4.6 GPa (HiPIMS), 38.0 ± 2.3 GPa (pulsed DCMS), and 40.0 ± 3.8 GPa (DCMS) among all samples studied. Higher pN2 lead to the formation of δ- and e-TaN phases and a reduction in hardness. Especially, the e-TaN rich coatings are comparably soft with only ~20 GPa. Based on our results we can conclude that coatings dominated by Ta-rich o-Ta4N or γ-Ta2N phases exhibit the most favourable mechanical properties, according to which the most important pN2-range is between 0.04 and 0.15 Pa, as for higher N2 partial pressures the films undergo a transformation from γ-Ta2N (plus o-Ta4N) into mixed δ- and e-TaN.

High temperature oxidation behavior during a fast self-propagating reaction is reported in binary 1Zr/1Al reactive multilayer films. Magnetron sputtered deposited freestanding Zr/Al films with different bilayer thicknesses were investigated experimentally to characterize the oxidation behavior during a self-propagating reaction, ignited by an electrical arc. X-ray diffraction (XRD) analysis of reacted film, ignited in air indicates the formation of oxides of both Zr and Al besides intermetallic compounds. In argon 4.6 atmosphere, oxidation has been reduced, but it is also evident that a very small amount of only ZrO2 forms. The temperature profiles measured by a high-speed two-color pyrometer exhibit the temperature plateau after reaching the maximum temperature. The static temperatures in plateau vary from 1475 °C to 1588 °C depending on bilayer thicknesses. This temperature plateau becomes more pronounced with increasing bilayer thickness. However, an extended time duration at high temperature plateau characterizes the significant oxidation in air during a self-propagating reaction, which can influence reaction properties and thus broaden the scope of applications.

In high power impulse magnetron sputtering (HiPIMS) process, the magnetic field and unbalance degree and pulsing configuration are key factors in controlling metal ionization rate and flux of sputtered species towards the substrate. This work reports results on the effect of pulsing configuration (pulse duration) and an auxiliary magnetic field on the deposition rate of ten technologically-relevant elemental target materials (C, Al, Ti, Mn, Ni, Cu, Zn, Mo, Ta, and W) sputtered using HiPIMS. An auxiliary magnetic field was created with a toroidal-shaped permanent magnet placed in front of a strong balanced magnetron. Deposition rates in HiPIMS assisted by this auxiliary magnetic field were compared to those obtained in direct current magnetron sputtering (dcMS) and HiPIMS without an external magnetic field, under the same experimental conditions (average power, gas pressure). It was found that in the case of HiPIMS assisted by the external magnetic field, the deposition rates were approximately 40% to 140% higher compared to HiPIMS without auxiliary magnetic field and, for some materials, even higher compared to those found in dcMS. For copper (Cu) target, total ion current, ion-to-metal flux ratio and ion energy distribution function were measured at the substrate position. Experimental results indicate that during HiPIMS operation (without external magnetic field), the ionized Cu flux fraction increases by 10 to 50% as the pulse duration decreases from 50 to 3 μs, while, in the presence of the external magnetic field, the ionized Cu flux fraction further increases, with values in the range of 40–80% higher. Beside higher deposition rates and increased metal ionization rate, the HiPIMS assisted by the external magnetic field significantly improves Cu target utilization from 20 to 32%. Therefore, deposition rate, metal ion flux towards substrate and target utilization may be optimized by using an appropriate magnetic field and pulsing design.

Cr/CrN/(Cr,N)-DLC/DLC and Cr/Cr-DLC/DLC multilayer coatings have been synthesized using DC sputtering magnetron technique to protect steel substrates from wear. The microstructure was investigated by scanning electron microscopy and the chemical structure of the DLC layers was investigated by Raman spectroscopy. The mechanical and tribological properties were evaluated by nanoindenter, scratch tester and Rockwell ‘C’ indentation test, ball-on-disk tribometer and surface profiler. A new methodology for the selection of coating performance was proposed by using a performance index based on a mix of adhesion, mechanical and tribological properties.

High performance permeation barrier coatings are usually multilayer stacks consisting of inorganic and organic layers. Besides the water vapor transmission rate, the optical properties of such layers have a high importance. This contribution focuses on the deposition of silicon oxynitride as an inorganic layer. This material attracts a widespread interest due to its varying refractive index depending on its oxygen and nitrogen content. The experiments were carried out in a roll-to-roll coating machine using a rotatable magnetron system. The layers were deposited by reactive pulse magnetron sputtering using targets of 1 m length. It was established that the ratio of oxygen to nitrogen in the layer was not only determined by the reactive gas mixture but also by the chosen set point of the closed loop control. Both the Secondary Ion Mass Spectrometry and the Glow Discharge Optical Emission Spectroscopy measurements revealed a vertically different composition of the SiOxNy layers. This could be supported by the simulation of the optical properties of the layers.

The paper presents results of elemental and structure investigations of (Ti,Cu)-oxide system thin films with gradient Ti and Cu elements distributions vs. thin film thickness. Thin films were prepared using multi-magnetron sputtering system equipped with separate Cu and Ti targets sputtered in reactive oxygen plasma. The elements gradient distribution was assured by programming three exemplary, different profiles of powering the magnetron equipped with Cu target: linearly increasing, V- and U-shape profile of the power. Investigations performed with the aid of transmission electron microscope integrated with X-ray energy dispersive attachment showed clearly that programmed three different exemplary magnetron powering profiles were very well reproduced in Cu and Ti elements distribution profiles. Detailed structure investigations allowed on observation of the microstructure evolution during the thin film growth and it was proven that at given deposition conditions it was strongly influenced by the amount of particular element in the selected areas of deposited coatings.

The deposition rate, as well as the structure of a coating for a given magnetron sputtered material are determined by the plasma properties which are significantly dependent on the type of plasma generation. Single-pulse high power impulse magnetron sputtering (s-HiPIMS), multipulse HiPIMS (m-HiPIMS) with the same energy per pulse sequence and conventional direct current magnetron sputtering (DC-MS) were employed to deposit metallic Ti coatings. Varying the number of pulses in one pulse sequence in multipulse HiPIMS operation enables us to influence the ion fluxes on the substrate and the ionisation of the sputtered titanium. The grain size for the HiPIMS-deposited coatings was in the range of 5 to 25 nm depending on the number of pulses in the pulse sequence, whereas it was 15 nm for the coating prepared by the DC-MS. By the use of multipulse HiPIMS, it was also possible to achieve coatings with a smoother surface morphology and lower roughness as well rougher coatings with larger asperities and higher roughness compared to DC-MS. The texture and the deposition rate were significantly affected by the number of pulses, too.

In this paper the results of a first attempt to ignite an inverted fireball with a magnetron sputter source are presented. The conducted measurements show that there is no inverted fireball visible to the naked eye present during the experiments. However, some features are observed that indicate at least an initial onset of such an inverted fireball with an interruption before it is fully developed. In the course of the experiments magnetron sputtered molybdenum films have been deposited inside a highly transparent gridded anode and the obtained films have been analysed. It turns out that even without a visible inverted fireball being present, the film morphology and mechanical properties such as elastic modulus, hardness and surface roughness have changed significantly compared to a setup without inverted fireball anode. Additionally, the deposition rate is elevated by up to 20% inside the inverted fireball anode compared to the reference setup, although with a nearly threefold increase in total input power (cathode power + grid anode power). This increase in deposition rate was achieved despite the fact that a mesh electrode with only about 37% transparency was used. On the other hand, it was demonstrated that the use of additional gridded electrodes in such a device triggers instabilities and non-linearities in the plasma, which might be of interest for further fundamental research.

Oxidation behavior of magnetron sputtered Ti1-x-yAlxTayN coatings (with y varied from 0.1 to 0.35) on titanium substrates was studied upon isothermal exposure in air at 850 and 950 °C in comparison with a Ti0.45Al0.55N coating. It was found that the Ti1-x-yAlxTayN coatings demonstrate substantially improved protective properties at a temperature of 850 °C while this effect is only slightly pronounced at 950 °C. The protective properties of the Ti1-x-yAlxTayN coatings at 950 °C were found to deteriorate with increasing the Ta content so that only the Ti0.41Al0.49Ta0.10N composition provided reasonably effective protection of the underlying titanium substrate.

The magnetron sputtered tantalum diboride (TaBy) coatings from stoichiometric TaB2 target are often reported to be deposited in broad B/Ta interval with diverse structure and mechanical properties. In this article, the effect of Ar neutrals reflected from TaB2 target on the B/Ta ratio is examined. Two targets with different thickness are used to influence the current-voltage characteristic of the discharge and the energy of reflected Ar neutrals. In addition, external magnetic field from Helmholtz coils is applied to influence the plasma density in the substrate region. It is demonstrated that the reflected Ar neutrals have a significant effect on B/Ta ratio reduction from 1.9 to 1.4. While decreasing the B/Ta ratio, preferred TaBy crystal orientation changes from (0001) to ( 10 1 ¯ 1 ) . Intense Ar bombardment results in loss of crystallinity exemplified by diffraction maxima broadening. The variation of B/Ta ratio is accompanied by change of hardness and Young's modulus in range from 48 GPa to 32 GPa and from 532 GPa to 390 GPa, respectively. The coatings with B/Ta ratio

We describe our work on tungsten disilicide film deposition by planar magnetron sputtering at low operating gas pressure (down to 0.08 Pa). The sputter target was a tungsten disilicide composite with diameter 125 mm, and the DC magnetron current 0.1–1 A. We have explored the dependence of film homogeneity over the 100 mm diameter substrate on substrate temperature and distance from the magnetron, and the spatial distribution of ion current density and the effect of operating pressure on the roughness and resistivity of the films.

In this study, magnetron sputtered tungsten oxide (W3O) thin films were deposited on stainless steel 316L substrates followed by annealing treatment at different temperatures (200 to 800 °C). The synthesized films were characterized and thereafter investigated for their corrosion resistance behavior, in both 3.5% NaCl and 0.5 M H2SO4 environments, using electrochemical corrosion techniques. FESEM, XRD, and XPS analyses revealed that the oxygen content increases with annealing temperature, which then results in morphological and microstructural changes from cubic nanorods to monoclinic nanoplatelets and nanopyramids, composing of mixed oxidation states (WO2.72 and WO2.92). Electrochemical impedance and potentiodynamic measurements showed that in the chloride-containing solution the resistance increases with the annealing temperature until an optimum temperature of 400 °C. Similarly, the as-deposited and the films annealed at temperatures up to 400 °C demonstrated better protectiveness that exceeds 95%, in the acidic environment. The passive current densities and the pitting potentials of the films were likewise improved in both environments. Findings in this investigation suggest that an annealing temperature of 400 °C induced optimum protective barrier properties to the film.

The present work investigates the microstructure-property relations of Mo-O thin films synthesised by non-reactive dc magnetron sputter deposition from ceramic MoO x targets with compositions ranging from x = 2.5 to 2.8. Two series of films with different deposition powers, 150 and 450 W, were synthesised. The O content in the films is ~ 10% lower than in the target due to element-specific scattering of the sputtered species during the transport from the target to the substrate. The evolution of microstructure and chemical bonds was studied by X-ray photoelectron spectroscopy, X-ray diffraction and Raman spectroscopy. The structure of the films is dominated by the thermodynamically stable phases MoO 2 and MoO 3 , as well as the intermediate phases Mo 4 O 11 and Mo 9 O 26 . The films exhibit high absorbance of up to 75% and reflectance below 12% with electrical resistivity values in the range of 10 − 2 to 1 Ωcm. In general, the use of oxide targets in dc magnetron sputter deposition of Mo-O films offers an efficient and reliable alternative to films sputtered reactively from metal targets and might thus enable their use in a wide range of opto-electronic applications.

WS2/a-C coatings with various carbon contents (0-65 at.%) were deposited on silicon wafers by magnetron co-sputtering under different Ar flow rates. Increasing the argon flow rate increases the chemical stoichiometric S/W ratio, but the coating gradually becomes porous and columnar-like. The S/W stoichiometry is less influenced by the variation in carbon concentration. TEM and XRD confirm well crystallized basal (002) planes in the sputter deposited pure WS2 or low-carbon WS2/a-C coatings. The hardness of the composite coatings increases with increasing carbon content or decreasing Ar flow rate. The coating at 40 at.% C exhibits the highest hardness (10.6 GPa). Tribotests show that, together with a ultralow wear rate of 10(-7) mm(3) m(-1) N-1, the coefficient of friction can be as low as 0.02 in dry air (5% R-H) and around 0.15 in moisture (55% R-H) and remains stable within a sliding distance of 1000 rn. The wear resistance is strongly affected by the carbon concentration, deposition pressure and the testing atmospheres.

Thin oxinitride films of Zn–Sn–O–N and Si–Al–O–N were deposited on glass and on low emissivity thin film-on-glass coatings by reactive magnetron sputtering at various nitrogen-to-oxygen ratios. Oleophobic properties were improved by the films deposited, and optimal composition of oxygen to nitrogen was found to be equal O 2 :N 2 ≈ 2:1. Correlation between surface morphology and oleophobic properties was analyzed. Mechanical wet sheening, Taber abrasion tests, and sclerometry scratching demonstrated good mechanical wear resistivity of the coatings. Surface stratometry before and after acid bath diving demonstrated good chemical resistivity. Chemical and mechanical resistivity of the oleophobic films was found to be stable after storage at various temperatures, air humidity, and time.

Ta Si N coatings with a Si content of 19–21 at.% were fabricated through reactive direct current magnetron cosputtering; the sputter power was set at 100 W for each target, and the coatings were X-ray amorphous in the as-deposited state. The N contents of the Ta Si N coatings increased from 31 to 47 at.% as the N 2 /(N 2 + Ar) flow ratio was increased from 0.1 to 0.4; additionally, nanoindentation hardness decreased from 20 to 14 GPa, and the Young's modulus decreased from 220 to 196 GPa. The oxidation resistance of the Ta Si N coatings was evaluated through annealing at 600 °C and 800 °C in ambient air, which revealed notable oxidation resistance related to the TaN coatings. The oxidation behavior of the X-ray amorphous Ta Si N coatings was examined through transmission electron microscopy and X-ray photoelectron spectroscopy.

The article reports on the effect of the energy delivered into the growing film by bombarding ions ℰbi and/or fast neutrals ℰfn on its structure, microstructure and mechanical properties, and resistance to cracking. The effect of the total delivered energy ℰ = ℰbi + ℰfn on the film properties is demonstrated on the Ti(Al,V)Nx films deposited by reactive magnetron sputtering. The films were sputtered onto Si(111) and Mo substrates in a mixture Ar + N2 gases by a dual magnetron with closed magnetic field and equipped with TiAlV (6 at.% Al, 4 at.% V) alloy targets. It was shown that (1) The energy ℰ is a key parameter controlling the physical and mechanical properties, and the resistance to cracking of sputtered Ti(Al,V)Nx films, (2) The structure of Ti(Al,V)Nx films varies from TiN(200) to TiN(220) with increasing energy ℰ, (3) The Ti(Al,V)Nx films with high ratio H/E⁎ ≥ 0.1, high elastic recovery We ≥ 60% and dense voids-free microstructure exhibit an enhanced resistance to cracking and can be produced only in the case when a sufficient energy ℰ is delivered into the growing film either by bombarding ions or by bombarding fast neutrals and (4) The energy ℰfn makes it possible to sputter crystalline films onto dielectric substrates held at a floating potential Us = Ufl.

Tribological behaviors of a magnetron sputtered CrSiN coating with 12.5 at.% Si were studied by ball-on-plate sliding tests in three environments, including ambient air, deionized water, and 3.5 wt% NaCl water. Then in-situ microscopic examinations on the wear tracks were followed by the combination of scanning electron microscopy (SEM), Energy Dispersive X-ray spectrometry (EDX), and a focused ion-beam system (FIB). Under air ambient the coating exhibited a friction coefficient of ~ 0.47 and a specific wear rate of 1.2 × 10 − 16 m 3 /N m, corresponding to a mild wear mainly dominated with tribo-oxidation. The tribological behavior of the coating appeared similar features under the deionized water and the 3.5 wt% NaCl water. The friction coefficients were lower (~ 0.24) and the specific wear rates increased almost an order of magnitude, which might be attributed to more tribochemical reactions occurred under the wet conditions. No or little corrosive effect was observed in the coating-substrate system during the 2.16 × 10 4 sliding cycles under the 3.5 wt% NaCl water. The microscope characterization indicated that the reactive agents could not diffuse to the substrate, since the cracks with limited lengths were not throughout the whole coating.

Ag/TiN-Ag composite multilayers were deposited on Si and Ti-6Al-4V substrates using a multi-target magnetron co-sputtering system. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the Ag/TiN-Ag composite multilayers exhibited a weaker TiN textures with the smaller modulation period (Λ), which proved the smaller Λ can block the growth of columnar grain and particle, inducing a smoother surface and smaller roughness parameters (R a : 0.82 nm; R q : 1.2 nm). Ag existence in the surrounding TiN in top TiN-Ag composite layer and Ag layer insertion into TiN layer prohibited the emergence and propagation of cracks and prevented the growth and dislocation slip of defects, thus limited TiN grain size in a nanoscale size (5–10 nm), which enhanced the hardness and adhesion strength of the multilayers with smaller Λ. The hardness, elastic modulus and critical load reached 35.983 GPa, 426.937 GPa and 38 mN, respectively, when Λ was 10 nm. The population of living cells growing on the composite multilayers with Λ = 10 nm was far higher than those of other tested groups. This work proved the Ag/TiN-Ag composite multilayer with smaller Λ was beneficial for improvement of hardness, adhesion strength and living cells growth.

Ti–Al–N thin films are well established due to their outstanding thermo-mechanical properties. Nevertheless, this system is still a subject of many research activities to further enhance their oxidation resistance and thermal stability. The addition of reactive elements, such as Cerium, can significantly improve especially the oxidation resistance of various materials. Therefore, we study in detail the impact of Ce (2 at.% alloyed to powder metallurgically prepared Ti 0.50 Al 0.50 targets) on growth processes, structure, mechanical properties, thermal stability, and oxidation resistance of magnetron sputtered Ti 1 − x − y Al x Ce y N coatings prepared with DC bias potentials of U bias = − 25, − 50, − 75, and − 100 V. The deposition rate is significantly increased by a factor of ~ 1.75 (U bias = − 25 V) to 1.45 (U bias = − 100 V) when using Ti 0.49 Al 0.49 Ce 0.02 instead of Ti 0.50 Al 0.50 targets. Furthermore, also the hardness of the resulting single phase face centered cubic Ti 0.43 Al 0.55 Ce 0.02 N is with ~ 35 GPa above that of Ti 0.42 Al 0.58 N with ~ 34 GPa, for coatings on polycrystalline Al 2 O 3 and U bias = − 50 V. All temperature dependent characteristics of Ti 0.42 Al 0.58 N are improved significantly by the addition of Cerium. Wurtzite-structured AlN formation within Ti 0.43 Al 0.55 Ce 0.02 N can only be detected at T a = 1100 °C, about 200 °C higher as for Ti 0.42 Al 0.58 N. Their peak-hardness, due to spinodal decomposition of the supersaturated cubic phase is ~ 37.0 GPa with T a = 900 °C, as compared to 34.6 GPa with T a = 800 °C for Ti 0.42 Al 0.58 N. Additionally, even after exposure to ambient air at 950 °C for 3 h, still > 50% of the Ti 0.43 Al 0.55 Ce 0.02 N coating is intact (below the ~ 1.2 μm thin oxide scale), whereas Ti 0.42 Al 0.58 N is already fully oxidized. Based on our results we can conclude, that Ce-doping improves the deposition characteristics and mechanical properties as well as thermal stabilities (incl. oxidation resistance) of Ti–Al–N, to be used as protective coatings for a wide range of high-demanding applications.

The effects of multilayer designs in ternary films on self-propagating exothermic reaction properties were reported. The magnetron sputtered deposited ternary reactive films with two different multilayer arrangements of Ti/Si/Ti/Al and Si/Ti/Al/Si with the identical bilayer of 29 ± 5 nm and total thickness of 6 μm were investigated. The reaction properties in terms of reaction heat, temperature and reaction velocity were characterized for these two types of multilayer constructions. The reaction heat was calculated by using the thermodynamic simulation. As-deposited and reacted foils were characterized by using electron microscopes. After an electric ignition, the exothermic reaction front propagates in the films. The propagation velocity and temperature were measured by using a high speed camera and a two-color pyrometer. Reaction products were analyzed by means of X-ray diffraction (XRD) analysis. The steady state reaction fronts propagate through Ti/Si/Ti/Al films with the reaction velocity of 9.1 ± 2 m/s and the maximum reaction temperature of 1768 ± 41 °C. Moreover, both steady state and unsteady propagation modes were observed in Si/Ti/Al/Si reactive foil. This film shows a maximum reaction velocity of 2.7 ± 0.8 m/s. Compared to this film, Ti/Si/Ti/Al films exhibit higher reaction temperature and propagation velocity. Here, experimental results suggest the dependency of the reaction properties on the multilayer arrangement. Although both ternary films have similar reactant types and morphology, different reactant interfaces introduce the distinct interfacial reactions and local atomic mixing rates, which influence on the reaction characteristics. This research also shows a new opportunity to design nanoscale reactive films with different multilayer arrangements to control reaction propagation besides existing technology.

For pre-treatment of dielectric and conductive products planetary rotating inside a process vacuum chamber and beam-assisted deposition on the products of magnetron sputtered coatings, a closed cylindrical grid is placed inside the planetary rotation system. When magnetron targets are disconnected from power supplies, the chamber is filled with plasma of glow discharge at argon pressure of 0.2–1 Pa. Application to the grid of negative voltage up to 3 kV results in production of fast neutral argon atoms with energy up to 3 keV, which bombard the rotating products heating and etching them. When magnetrons are switched on, and high-voltage pulses are applied to the grid, mixing by high-energy gas atoms of the product and coating atoms results in appreciable improvement of adhesion and other properties of the coatings.

The article focuses on the study of growth conditions for metal coatings during the operation of magnetron sputtering systems with a liquid-phase target. It also discusses the trends of coating properties formation (in terms of copper example) depending on the growth conditions. The data of the experiments and calculations confirm that the appearance of intensive evaporation on the target surface allows increasing more than 10 times the deposition rate and deposited particles flux density in comparison to conventional sputtering with a cooled solid target at the same magnetron power. In the case of the magnetron sputtering system with a liquid-phase target, energy fluxes and particles ones towards the substrate during the coating growth and the substrate heating rate are much greater than at conventional magnetron deposition with a solid target. The combination of calculations and experiments have made it possible to reveal the structure of energy and particles fluxes towards the substrate during the operation of the magnetron sputtering system with a liquid-phase target. The contribution of these fluxes formed by different mechanisms in a wide range of magnetron power has also been found out. The analysis of structural and mechanical properties of copper films being deposited at different energy and particles fluxes ratio towards the substrate has been carried out. It has been found that at intensive evaporation the coating surface is smooth and uniform, and the size of grains decreases. The mechanical properties of coatings (adhesion and microhardness) have got higher values compared to the cases related to only sputtering.