Magnetron Sputter Ion Plating Research Articles

Multicoated Flexible Indium Tin Oxide Electrodes Fabricated Using Magnetron Sputtering and Arc Plasma Ion Plating for Flexible Perovskite Solar Cells.

High-performance flexible Sn-doped In2O3 (indium tin oxide, ITO) electrodes were fabricated using a multicoating process on colorless polyimide (CPI) substrates for flexible perovskite solar cells (FPSCs). The effects of different coating sequences on the electrical, optical, and mechanical properties of the flexible ITO electrodes were thoroughly investigated after preparing them with direct-current magnetron sputtering (DMS) and arc plasma ion plating (APIP). Although both the sputtered ITO (SITO)/arc ion-plated ITO (AITO) film and the AITO/SITO film showed similarly low sheet resistance (18.69-25.29 Ω/sq) and high optical transmittance (94.96-96.85%), the coating sequence significantly affected the mechanical flexibility of the multicoated ITO films. The 120 nm-thick SITO/AITO electrode exhibited small outer and inner critical bending radii (3 mm and 3 mm, respectively) compared to the AITO/SITO electrode (4 and 5 mm, respectively). Owing to better adhesion of the arc-ion-plated ITO bottom layer and the amorphous structure of the top SITO layer, the SITO/AITO electrode exhibited excellent mechanical flexibility and durability. In addition, an FPSC using the SITO/AITO electrode achieved a higher power conversion efficiency (15.09%) than that with the AITO/SITO electrode (13.22%). This improvement was attributed to its high transmittance, low sheet resistance, smooth surface morphology, and enhanced hole collection efficiency. These findings highlight the efficacy of the combined DMS and APIP multicoating process for fabricating high-quality flexible ITO electrodes for high-performance FPSCs.

Comparative Performance Evaluation of Magnetron Sputtered TiN, AlCrN, and TiAlCrN Coatings

This study presents a comparative performance evaluation of magnetron-sputtered TiN, AlCrN, and TiAlCrN coatings on tool steel substrates. Coatings play a pivotal role in enhancing the durability of engineering components exposed to harsh conditions. TiN is known for outstanding hardness and durability, AlCrN for superior wear resistance, and TiAlCrN for exceptional thermal stability and oxidation resistance. The substrate (EN 1.2363) underwent PVD coating using a closed-field unbalanced magnetron sputter ion plating (CFUBMSIP) process in a water-cooled stainless-steel vacuum chamber with four magnetron ports, operating for 3 hours per batch followed by 12 hours of natural convection cooling, utilizing TiN, AlCrN, and TiAlCrN films deposited for 180 minutes in an Ar and nitrogen atmosphere. X-ray diffraction (XRD) revealed distinctive crystal structures, with all coatings exhibiting a common preferred orientation of the (111) plane and TiAlCrN showing a ternary nitride phase. Scanning electron microscopy (SEM) images displayed the compact nature of TiAlCrN with finer grains, while TiN exhibited a densely compacted with no evidence of delamination and AlCrN showed denseness with smaller grains. Nano-indentation test was conducted to assess the coatings' hardness and elastic modulus. TiAlCrN exhibited the highest hardness (3091±243 HV), highest elastic modulus (369.86±54.19 GPa), and the best wear rate (0.1887 x 10-4 mm3/Nm-1) suggesting potential suitability for applications demanding superior rigidity and wear resistance. The study provides valuable insights for materials scientists and engineers in optimizing coating selection for specific applications.

Effect of phase composition on the corrosion behavior of Ti-xMo alloy films

The corrosion behavior of Ti-xMo alloy films was investigated by preparing a series of Ti-xMo (x = 0, 4, 11, 20 wt%) alloy films using non-equilibrium magnetron sputtering ion plating technology. XRD and TEM results show that these films have obvious phase composition, which are single α phase, α + β phase and single β phase, respectively. The composition of passivation film of alloy thin films is analyzed by XPS analysis method. The passivation film can be divided into inner passivation film and outer passivation film. The corrosion behavior of Ti-xMo alloy films in a 3.5 wt% NaCl solution was investigated through the electrochemical impedance spectroscopy (EIS). The findings suggest that the corrosion resistance of Ti-xMo alloy films is not only influenced by the Mo content but also governed by the composition of phases. Due to the absence of α/β interfaces in its structure and higher Mo content, the Ti-20Mo alloy film with a single β phase exhibits superior corrosion resistance compared to Pure-Ti film with a single α phase and Ti-4Mo and Ti-11Mo alloy films with an α + β phase.

Photocatalytic degradation of methylene blue by anatase TiO2 coating

AbstractPhotocatalytic coatings have the potential to contribute to the purification of water via an advanced oxidation process (AOP). A commonly used method for analyzing the mechanism of the photocatalytic performance of a given reactor type is to document the degradation behavior in a solution containing methylene blue. However, since methylene blue is rather unstable, the degradation results should be viewed critically. In this work, the degradation behavior of a test solution with methylene blue on quartz glass surfaces coated with photocatalytic titanium dioxide (TiO2) of the anatase modification was investigated through a variety of different light sources. The coating was deposited by physical vapor deposition (PVD) with the reactive pulsed DC magnetron sputtering ion plating (MSIP) method described in the study by Desch and Lake, while the quartz glasses were coated with a 100 nm thick TiO2 coating on the outside. The same glasses were used for all experiments with TiO2. In the determination of the degradation rate, additional experiments were performed using pure quartz glass without any coating, which made it possible to examine the influence of different light sources on the degradation rate of methylene blue in general. Three different light sources, namely UV‐A, UV‐C, and simple fluorescent lamps were used in this study. The concentration of methylene blue was recorded by photo spectrometer in 10‐min increments throughout the experiment and the experiments were performed for 24 h in all cases. Our data indicates that the methylene blue test is a poor method because the degradation rate is not clearly differentiable due to the low stability of the test substance. Without including reference testing in the absence of a catalyst, data may be subject to misinterpretation.

A comprehensive performance study of NiCrCN coated 316L stainless steel as bipolar plates for proton exchange membrane fuel cell

NiCrCN coatings are deposited on the surfaces of 316 L stainless steel (SS316L) substrates via closed field unbalanced magnetron sputtering ion plating (CFUMSIP) to improve the corrosion resistance and electrical conductivity of proton exchange membrane fuel cell (PEMFC) bipolar plates. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results show that CrN, Cr2N, Ni, and Cr7C3 phases exist in NiCrCN coatings. As the Cr target current grows from 2 A to 6 A, the Cr7C3 content in the carbon compounds increases from 3.39% to 11.46%, and the interfacial contact resistance (ICR) value is reduced from 18.0 mΩ cm2 to 11.2 mΩ cm2. When the Cr target current reaches 4 A, the NiCrCN coating shows the most intensive cross-sectional growth pattern by cold-field scanning electron microscopy (CFSEM) results, and the current density after prolonged polarization (0.11 μA cm−2) is much lower than that of SS316L (1.86 μA cm−2).

Investigation of corrosion protection with conductive chromium-aluminum carbonitride coating on metallic bipolar plates

To further enhance the performance of metal bipolar plates, the CrAlCN coating with high corrosion resistance and conductivity was deposited on the SS316L substrate by using Closed Field Unbalanced Magnetron Sputter Ion Plating (CFUMSIP) technique. Meanwhile, the inexpensive acetylene gas (C2H2) was utilized as a carbon source. XRD and XPS results indicate that the proportion of carbides in the coating increase with increasing carbon contents. Electrochemical measurements show that the C-doped coating significantly improves the corrosion resistance of the SS316L bipolar plates. The C doping enhances the conductivity of the CrAlN coating, and the C-doped sample obtains the lowest ICR value (2.94 mΩ cm2, before corrosion), which is well below the DOE target (≤10 mΩ cm2). The excellent conductivity and hydrophobicity of C-doped coating increase the power density of a single cell. This study demonstrates that the CrAlCN coatings have great application prospects in the bipolar plates field.

Formation of pure anatase TiO2 using the reactive pulsed dc magnetron sputtering method for controlling the target poisoning state

AbstractThe use of pulsed dc‐sputtering sources for reactive magnetron sputtering with oxygen offers a possibility to suppress the negative effects of target poisoning (such as arcing). This results in a wide process range for the selection of a desired operating point. The control of target poisoning plays a major role in maintaining constant coating properties and affects the stoichiometry of the reactive coating, as well as the coating rate and the economic impact of the coating process. In a hysteresis, the target poisoning during the reactive sputtering of titanium under oxygen addition proceeds nonlinearly. Without the use of a suitable target poisoning control technique, the sputtering process can abruptly change to an unstable state. As a result, variations of stoichiometry can occur during the deposition process. A proven method for maintaining a stable reactive sputtering process is the control of oxygen flow with the input variable target voltage. By determining the typical oxygen hysteresis at constant target power and constant argon flow, an operating point for the control loop is derived. The desired target voltage then serves as the input variable for the control loop of the target poisoning. The controlling technique for target poisoning is a basic requirement for the production of the photolytic active anatase phase of titanium dioxide (TiO2) using reactive magnetron sputtering. The photocatalytic equipment of surfaces with a titanium dioxide coating in the anatase phase can be realized with the reactive pulsed dc magnetron sputter ion plating process (DC‐MSIP). The pulsed DC‐MSIP process facilitates coating a variety of surfaces at temperatures below 200°C in an environmentally friendly manner.

Comparison to Micro Wear Mechanism of PVD Chromium Coatings and Electroplated Hard Chromium

Electroplated hard chromium (EPHC) has been widely used in industry due to its excellent mechanical properties, but the development of this technology is limited by environmental risks. The physical vapor deposition (PVD) process has shown promise as an alternative to EPHC for producing chromium-based coatings. In this research, we investigate the microstructure and wear resistance of pure chromium coatings using two PVD techniques, namely, magnetron sputtering ion plating (MSIP) and micro-arc ion plating (MAIP), which are compared to EPHC. To assess wear resistance, we evaluated factors such as hardness, coating base bonding force, wear rate and friction coefficient via friction and wear experiments. The results show that, in terms of microstructure, while the EPHC coating does not exhibit a strong preferred growth orientation, the PVD coatings exhibit an obvious preferred growth orientation along the (110) direction. The average grain size of the EPHC coating is the smallest, and the PVD chromium coatings show a higher hardness than the EPHC coating. The results of pin-on-disk tests show that there is little difference in friction coefficients between EPHC and MAIP chromium plating; however, the MAIP chromium coating showed an excellent specific wear rate (as low as 1.477 × 10-13 m3/Nm). The wear condition of the MAIP chromium coating is more stable than that of the EPHC coating, indicating its potential as a replacement for EPHC.

Microstructure, mechanical and tribological properties of gradient CrAlSiN coatings deposited by magnetron sputtering and arc ion plating technology

Three CrAlSiN coatings with gradient concentrations of Al and Si ascending from the transitional layer to the surface were prepared by a combined method of direct current magnetron sputtering and arc ion plating using linearly increasing sputtering power. Microstructure, mechanical and tribological properties of the three gradient coatings were studied. Results show that all coatings possess face-centered cubic CrN phase with small amounts of hexagonal close packed AlN phase. The preferential orientation of the gradient coatings evolves from (111) to (220) crystal plane as the linear ultimate power is enlarged from 1.2 kW to 2.8 kW. The hardness increases gradually with the linear ultimate power, while the adhesion strength and wear resistance of the three coatings decrease gradually. For all the three gradient coatings, slight oxidation occurs at the boundaries of the wear track. Abrasive wear is the main failure mode for the CrAlSiN coating with linear ultimate power of 1.2 kW and 2.0 kW, while exfoliation resulting from low crack resistance is the primary cause for the highest wear rate of the CrAlSiN coating with linear ultimate power of 2.8 kW.

Comparative study on the initial oxidation behavior of conventional and nanocrystalline MCrAlY coatings - effect of microstructure evolution and dynamic mechanisms

Two MCrAlY coatings with the same nominal composition but different microstructures are prepared by magnetron sputtering (MS) and arc ion plating (AIP). Their oxidation at 1000°C led to very different results. The relatively coarse grained AIP coating formed a duplex-layer scale, consisting of external θ-Al2O3 and internal α-Al2O3, with small amounts of NiCr2O4. Severe surface undulation was accompanied by the development of numerous cracks and voids. Aluminum depletion transformed the AIP coating from β to γ, causing volume shrinkage, promoting scale spallation and leading to premature failure. In contrast, the nanocrystalline MS coating was less degraded due to its columnar crystal structure and high-density of grain boundaries which provided rapid Al diffusion. Oxidation of this coating was characterized by a faster θ-Al2O3 to α-Al2O3 transformation and formation of an exclusive α-Al2O3 scale, protecting the surface.

Effect of Negative Bias of HiPIMS and AIP Hybrid Deposition on Microstructure, Mechanical and Anti-Corrosive Properties of Cr2N/TiN Multilayer Coatings

Multi-layered nitride coatings have been widely applied to improve the mechanical and anti-corrosive of metals and/or alloys. Cr2N/TiN multilayer coatings were prepared by the combination of high-power pulsed magnetron sputtering (HiPIMS) and arc ion plating (AIP). The Cr2N layer was co-deposited by HiPIMS and AIP, while the TiN layer was deposited by a single HiPIMS. With increasing the negative bias voltage (Vs) on substrate up to −100 V, the number and size of the droplets decreased; the average grain size of the coatings decreased from 9.4 to 7.5 nm and the hardness increased from 21.5 to 25.1 GPa, and the level of the adhesion of the coatings has reached HF1. The coatings obtained at Vs = −100 V present the best corrosion resistance in NaCl aqueous solution based on the anodic polarization curves and EIS spectroscopy.

Investigation of corrosion properties with Ni–P/TiNO coating on aluminum alloy bipolar plates in proton exchange membrane fuel cell

Aluminum alloy bipolar plates have unique application potential in proton exchange membrane fuel cell (PEMFC) due to the characteristics of lightweight and low cost. However, extreme susceptibility to corrosion in PEMFC operation condition limits the application. To promote the corrosion resistance of aluminum alloy bipolar plates, a Ni–P/TiNO coating was prepared by electroless plating and closed field unbalanced magnetron sputter ion plating (CFUMSIP) technology on the 6061 Al substrate. The research results show that Ni–P interlayer improves the deposition effect of TiNO outer layer and increase the content of TiN and TiOxNy phases. Compared to Ni–P and TiNO single-layer coatings, the Ni–P/TiNO coating samples exhibited the lowest current density value of (1.10 ± 0.02) × 10−6 A·cm−2 in simulated PEMFC cathode environment. Additionally, potential cyclic polarization measurements were carried out aiming to evaluate the durability of the aluminum alloy bipolar plate during the PEMFC start-up/shut-up process. The results illustrate that the Ni–P/TiNO coating samples exhibit excellent stability and corrosion resistance.

Study on Corrosion Resistance and Conductivity of TiMoN Coatings with Different Mo Contents under Simulated PEMFC Cathode Environment.

TiMoN coatings with different Mo contents on a SS316L substrate are deposited by using closed field unbalanced magnetron sputtering ion plating (CFUMSIP) technology to enhance the corrosion resistance and durability of stainless steel (SS) bipolar plates (BPs) in proton exchange membrane fuel cell (PEMFC) during the start-up/shut-down process. The electrochemical test results illustrate that TiMoN-4A coating has extremely good corrosion resistance compared to other coatings. The potentiostat polarization (+0.6 VSCE) tests indicate that the corrosion current density (Icorr) of TiMoN-4A coating is 5.22 × 10−7A cm−2, which meets the department of energy 2020 targets (DOE, ≤1 × 10−6 A cm−2). Otherwise, TiMoN-4A coating also exhibits the best corrosion resistance and stability in potentiostatic polarization, electrochemical impedance spectroscopy (EIS), and high potential (+1.2VSCE) polarization tests. The interfacial contact resistance (ICR) measurement results show that TiMoN-4A coating has the minimum ICR of 9.19 mΩ·cm2, which meets the DOE 2020 targets (≤10 mΩ·cm2).

Influence of substrate bias on the scratch, wear and indentation response of TiSiN nanocomposite coatings

TiSiN coatings were synthesised onto AISI M42 tool steel substrates via closed field unbalanced magnetron sputtering ion plating , using bias voltages of −40 and −50 V. The aim of this study is to investigate the underlying deformation mechanisms of TiSiN coatings, prepared at two different substrate bias voltages, following scratching, wear and indentation tests . A graded columnar microstructure evolved in these coatings. A hardness value of ~30.2 GPa was determined in the coating prepared at the lower bias voltage (i.e., −40 V), which was correlated to the fine nanocomposite structure and the presence of a high compressive residual stress. Of note, for the coating deposited at −40 V enhanced scratch adhesion strength , i.e., higher critical loads (L c1 and L c2 ) against cohesive and adhesive failure were determined with the higher H/E r and H 3 /E r 2 values. The improved scratch resistance was ascribed to the hierarchical structure that hindered crack propagation in the TiSiN coatings during progressive loading. An approximately 21% decrease in wear rate was obtained at the lower bias voltage, which was attributed to the slightly lower Si concentration (~8.3 at.%) and, in turn, higher hardness. Deformation behaviour under indentation loading was dominated by shear sliding along the columnar grain boundaries. • ~20% increase in L c1 was found in the TiSiN coating with the lower Si content. • The scratch resistance was enhanced by the coating's hierarchical structure. • ~21% reduction in wear rate was achieved in the coating with the lower Si content. • Indentation deformation was governed by columnar shear sliding.

Investigation of high potential corrosion protection with titanium carbonitride coating on 316L stainless steel bipolar plates

In order to improve the durability of stainless steel bipolar plates at high potential during the start-up/shut-down process of proton exchange membrane fuel cell (PEMFC), TiN and TiCN coatings with different C element contents are deposited on the 316L stainless steel substrates by using Closed Field Unbalanced Magnetron Sputter Ion Plating. The electrochemical test results show that the TiCN-2sccm sample possesses excellent corrosion resistance compared to other samples. The results of interfacial contact resistance (ICR) measurements show that the minimum ICR value of the TiCN-2sccm sample is 10 mΩ cm2, which meets the Department of Energy targets.

TiN versus TiSiN coatings in indentation, scratch and wear setting

The indentation response, scratch behaviour and wear performance of binary TiN and ternary TiSiN coatings under a variety of loading conditions were comparatively studied. The coatings were fabricated onto M42 steel substrates via closed field unbalanced magnetron sputtering ion plating. A maximum hardness value of ~40 GPa was obtained for one of the TiSiN coatings as compared to ~28 GPa for TiN. This was attributed to the nanocomposite structure, grain refinement, solid solution hardening and the higher compressive residual stress in the ternary coatings. The damage resistance of both the TiN and TiSiN coatings under indentation loading was governed by the dampening effects of sliding or shearing of the columnar grains along the grain boundaries coupled with the coatings’ respective mechanical characteristics. Improved scratch adhesion properties (i.e., higher LC1, LC2 and CPR values) were also observed for the TiSiN coatings that were underlain by their superior mechanical properties along with the graded structure, promoting the capacity to resist crack formation and delamination. Lower wear rates for the TiSiN coatings during dry sliding were found to be consistent with their higher H/Er, H3/Er2 and We values.

Microstructure and High-Temperature Friction and Wear Properties of CrAlMoN Film

Closed-field unbalanced magnetron sputtering ion plating was used to form CrAlMoN films on the surface of single-crystal silicon and tool steel. The composition and morphology of the films were determined through energy-dispersive X-ray spectroscopy, scanning electron microscopy, and transmission electron microscopy. High-temperature friction and wear properties of CrAlMoN films were assed using a friction and wear tester and by studying the film cross-sections. The hardness of CrAlMoN films was determined using a nanoindenter. Results showed that CrAlMoN films have a nanomultilayer structure, with the same fcc structure as CrN. At room temperature, the hardness and wear resistance of CrAlMoN films are greater than that of CrAlN films. The friction properties of CrAlMoN films varied widely with an increase in the temperature. At 600 °C, the friction performance of CrAlMoN films degrades rapidly, and the degree of film wear is significantly increased. In contrast, CrAlN films retain high wear resistance at 600 °C.

Сравнительная оценка триботехнических характеристик твердосмазочных покрытий, нанесенных методом замкнутого поля несбалансированного магнетронно-ионного распыления, для различных условий функционирования

This paper presents a comparative assessment of the tribotechnical characteristics of friction pairs with solid lubricant coatings (SLC) based on the MoS2 suspension application of VNII NP 212 and SLCCFUBMSIP deposited by the closed field unbalanced magnetron sputter ion plating (CFUBMSIP) of combined compositions MoS2+Ti, MoS2+Zr, MoS2+Cr , MoS2+W. It was established that under normal atmospheric conditions in the friction modes corresponding to the contact friction temperature of 157 °С, the life of SLCCFUBMSIP was 42.1% higher, and the coefficient of friction (ffr) was on average 2 times lower than that of SLC VNII NP 212. The average value of the life reduction coefficient for SLCCFUBMSIP during the transition from normal atmospheric conditions to water was 2.98. Under normal atmospheric conditions and in water, the SLCCFUBMSIP coefficient of friction was in the range of 0.02–0.04, and in an oil environment it ranged from 0.03 to 0.08. SLCCFUBMSIP based on pure MoS2 in normal atmospheric conditions, in water and oil was practically unusable.

Enhancing the adhesion strength and wear resistance of nanostructured NiCrN coatings

NiCrN coatings, with varying Ni contents, were deposited on AISI M2 tool steel substrates using closed field unbalanced magnetron sputtering ion plating (CFUMSIP) where the NiCr target current (INiCr) was varied. An evolution of the graded columnar structures was found in these coatings, where increased incorporation of nickel induced grain refinement, as well as a reduction in values of both hardness (H), elastic modulus (Er) and elastic recovery (We). The influence of variations in the microstructure and mechanical properties on the adhesion behaviour and tribological performance of these NiCrN coatings was investigated. Scratch test results demonstrated that higher critical loads (Lc1 and Lc2) suppressed both cohesive and adhesive failure in coatings which exhibited higher values of H/Er, H3/Er2 and We. The failure mode under progressive scratch loading was controlled by the hierarchical design of the NiCrN coatings that enhanced adhesion and prevented crack propagation through the coating. For the coatings with lower Ni contents improved wear resistance was ascribed to not only higher H/Er, H3/Er2 and We values of these coatings, but also the graded interlayers that delocalised the stress distribution during dry sliding.

Harmonizing mechanical responses of nanostructured CrN coatings via Ni additions

CrN coatings are often brittle and prone to abrupt failure. Incorporation of Ni is known to have significant effects on the chemical composition, microstructure and mechanical behaviour of chromium nitride coatings synthesised by PVD, and thus imparting toughness. In this study, a series of NiCrN coatings, with varying Ni concentrations, were deposited onto AISI M2 tool steel substrates through closed-field unbalanced magnetron sputtering ion plating (CFUMSIP). The phase compositions, microstructure, mechanical properties and deformation behaviour of the coatings were characterised by XRD, AFM, FIB, TEM/EDS and indentation testing. Residual stresses of these as-prepared coatings were measured by the XRD-sin2ψ method. A columnar structure was observed in all coatings, although grain refinement at higher NiCr target currents was noted. High hardness values of ~20 GPa were found in the coatings with the lower Ni (~5–14 at%) contents, associated with the effects of solid solution hardening, high compressive residual stress and grain refinement. Moreover, significant damage-tolerance, coupled with good hardness values (greater than ~12 GPa), was found in the NiCrN coatings deposited at INiCr ≥ 2 A. The presence of a metallic nickel-rich phase, together with nanoscale porosity, may contribute to stress dissipation and help maintain structural integrity.