High Sputtering Research Articles

Effects of anode geometry on DC magnetron sputtering of copper oxide films deposition

Abstract Effects of anode shape are examined in a custom-made DC magnetron sputtering system. Polycrystalline copper-oxide (CuO) films are deposited using wedge, ring and disc shaped anodes. Current–voltage (I-V) characteristics of the discharge were fitted with models of plasma discharge. Above 700 V a notable rise in average plasma impedance, from approximately 2kΩ to 7kΩ was observed. Scanning electron microscope (SEM) images reveal uniform and porous film growth. The deposition increased significantly with increasing the anode surface area due to decrease in gas density in cathode sheath. For all the anode shapes tested, the deposition rates were higher in magnetron sputtering compared to DC sputtering mode. X-ray diffraction (XRD) of the films deposited with the disk anode revealed polycrystalline films with predominant CuO phase. With increasing sputtering power, average crystallite size vary from 11 nm to 21 nm, dislocation density vary from approximately 8.4×〖10〗^(-3) nm-2 to 2.3×〖10〗^(-3) nm-2 and micro strain from approximately 3.3×〖10〗^(-3) to 1.7×〖10〗^(-3). This indicate that higher sputtering at higher powers produce higher quality films. Atomic force microscopy revealed that the rms roughness of the samples is about 4 nm.

Morphology and Magnetic Properties of Ni Nanowires in Thin Film Anodic Alumina Templates

The features of the morphology and magnetic properties of Ni nanowire arrays have been studied. Aluminum oxide matrices are used as a template for electrolytic deposition of nanowires. The matrices are obtained by anodizing the aluminum films with a thickness of 2 μm that are formed on glass substrates by high frequency ion sputtering. Electrochemical deposition of the metal is carried out using direct and alternating currents. Morphology and microstructure studies show that the nanowire arrays are polycrystalline and have a branched dendritic structure due to the morphological features of aluminum oxide matrices. A relationship between the magnetization reversal patterns and the modes of electrodeposition of Ni nanowire arrays is established. The process of magnetization reversal of an array of this kind of structures is simulated.

Structural, mechanical, corrosion, and early biological assessment of tantalum nitride coatings deposited by reactive HiTUS

This study examined microstructure, mechanical, corrosion properties and initial biological evaluation of the tantalum nitride (Ta-xN, where x – nitrogen flow rate during deposition) coatings prepared by reactive High Utilization Sputtering (HiTUS) at various nitrogen flow rates (x = 0, 2, 4, 6, and 8 sccm). Coatings were deposited on a novel Mg alloy (Mgbal.-Zn0.9-Y2.05-Al0.25 at. %) containing long-period stacking ordered (LPSO) phases. The coatings' structure was analyzed using a combination of SEM/FIB/TEM techniques, while XRD determined the phase composition. The mechanical parameters investigated included hardness, indentation modulus, and scratch behavior. The corrosion resistance of the coatings with respect to the bare substrate was evaluated in chloride-containing solutions. The wettability and early biological assessment of the coatings were also examined. The phase evolution strongly influenced the hardness and indentation modulus. The Ta-xN coatings made at x = 2 sccm nitrogen corresponding to HCP-Ta2N exhibited the highest hardness and indentation modulus. An increase in nitrogen flow rates resulted in the formation of FCC structure with slightly reduced hardness and indentation modulus. In addition, Ta-xN coatings (x ≥ 4sccm) showed superior corrosion resistance compared to BCC structured α-Ta, enhancing the corrosion performance of the Mg-LPSO bulk substrate. Finally, at the early incubation stage (24 h), L929 fibroblasts exhibited better cell attachment to the Ta-6N coating than to the bare Mg-LPSO substrate.

Application of Hipims Coatings to Enhance the Durability and Performance of Structural Components of PEM Electrolyzer Anodes

Porous transport layers (PTL) and bipolar plates (BPP) are structural elements that transport water, gases, electrons as well as heat within the electrolysis cells. On the anode side, the state-of-the-art material for BPP and PTL is titanium due its higher corrosion resistance under the operating conditions of electrolysis (high electrochemical potential, acidic and oxidizing environment) compared to other materials [1]. However, titanium components tend to form an oxide layer that rises the interfacial contact resistance (ICR) and leads to a poor performance since metal oxides are semiconductors or insulators. This issue is usually addressed by applying precious metal coatings, such as platinum or gold. In this work, we present the potential of high power sputtering techniques (HiPIMS) to manufacture ultra-low loading Pt coatings (<20 nm) with good homogeneity and high performance at an industrial scale. The influence of HiPIMS parameters on coating-substrate interface, as well as the coating properties have been evaluated. SEM, AFM and HRTEM microscopy have been used to evaluate the coating thickness and morphology. XRD analysis has been carried out to evaluate the influence of the HiPIMS parameters on the growth mode of Pt coatings, tailoring the coating texture from [200] to [111]. HiPIMS technique also provide enhanced density compared with other coating techniques due to the higher ionization achieved in the plasma [2]. The deposition of denser and defect-free coatings by HiPIMS enables the application of stainless steel components. HiPIMS prevents the formation of columnar structures and reduces oxygen diffusion. In this work, Nb- and Ti-based protective coatings have been deposited by HiPIMS on stainless steel 316L. A comparative between coated Ti Gr2 and SS316L has been set, showing the potential to reduce costs in the next generation of PEMWE structural components.

A comparative study on the structure and properties of TiAlSiN coatings deposited by FCVA and HiPIMS

The TiAlSiN coating has garnered significant interest due to its exceptional hardness, high oxidation resistance temperature, robust film-substrate bond strength, excellent wear resistance, and superior thermal stability. The energetic ion beam technology has emerged as a potent method for fabricating thin films. In this study, TiAlSiN films were deposited utilizing magnetic filtered cathode vacuum arc (FCVA) and high power pulsed magnetron sputtering (HiPIMS), and their respective structures and properties were meticulously investigated and contrasted. Upon comparative analysis, it was observed that the elemental composition of the FCVA films underwent a pronounced change with the same. Depending on the desired film thickness, the deposition rate of the FCVA system was found to be superior over the same duration. The crystallographic structure of the films fabricated by both systems predominantly featured an fcc-(Ti,Al)N phase. Notably, at an N2 flow rate of 40 sccm, the film deposited via HiPIMS demonstrated remarkable hardness (27.04 GPa), an elevated H/E* ratio (0.103), and superior wear resistance (7.24×10−6 mm3/N∙m). The films produced by these two deposition methods exhibited discernible differences and clear trends in hardness, adhesion strength, and tribological properties. This research provides a valuable reference for selecting the most appropriate deposition process and parameters based on the desired attributes of the coatings.

Effect of plasma discharge pulse length for GaN film crystallinity on sapphire substrate by high density convergent plasma sputtering device

Effect of plasma discharge pulse length for GaN film crystallinity on sapphire substrate by high density convergent plasma sputtering device

Self-Organizing Sub-μm Surface Structures Stimulated by Microplasma Generated Reactive Species and Short-Pulsed Laser Irradiation.

Catalysts are critical components for chemical reactions in industrial applications. They are able to optimize selectivity, efficiency, and reaction rates, thus enabling more environmentally friendly processes. This work presents a novel approach to catalyst functionalization for the CO2 reduction reaction by combining the reactive species of an atmospheric pressure plasma jet with the electric fields and energy input of a laser. This leads to both a nanoscale structuring as well as a controllable chemical composition of the surface, which are important parameters for optimizing catalyst performance. The treatment is conducted on thin copper layers deposited by high power pulsed magnetron sputtering on silicon wafers. Because atomic oxygen plays a key role in oxidizing copper, two photon absorption fluorescence is used to investigate the atomic oxygen density in the interaction zone of the COST plasma jet and a copper surface. The used atmospheric pressure plasma jet provides an atomic oxygen density at the surface in a distance of 8 mm to the jet nozzle of approximately or a flux of . Pulsed laser-induced dewetting is used to form nanoparticles from the deposited copper layer to enhance catalytic performance. Varying the layer thickness allows control of the size of the particles. A gas flow directed on the sample during the combined treatment disturbs the particle formation. This can be prevented by increasing the laser energy to compensate for the cooling effect of the gas flow. Investigating the surface using X-ray photoemission spectroscopy reveals that the untreated copper layer surface consists mostly of metallic copper and Cu(I) oxide. Irradiating the sample only with the laser did not change the composition. The combination of plasma and laser treatment is able to produce Cu(II) species such as CuO, whose concentration increases with treatment time. The presented process allows the tuning of the ratio of C2O/CuO, which is an interesting parameter for further studies on copper catalyst performance.

The dependence on displacement rate and temperature of near-surface void-denuding in self-ion irradiated pure polycrystalline and single-crystal iron

Pure iron has been irradiated with Fe2+ ions in a series of studies to identify neutron-atypical physical processes that influence the depth dependence of void swelling, focusing especially on suppression effects arising from injected interstitials and surface proximity. One paper in this series examined the surface influence in single-crystal Fe irradiated to 50 and 100 peak dpa over a range of temperature (425–525 °C) and ion energy (1.0, 2.5, 3.5, 5.0 MeV) while keeping the peak damage rate at 1.2 × 10–3 dpa/s, although the surface dpa rate was lower but increasing with decreasing ion energy, providing a small range of surface dpa rate. The observed denuded width Δx was modified to incorporate sputtering loss. The activation energy governing the denuding process was found to be EΔx4=1.65±0.03eV, higher than the vacancy migration energy EVm known to be 0.67 eV. This difference was attributed to the effect of dissolved carbon (103 appm) which reduces the effective vacancy mobility and thereby increases the effective migration energy.Since the previous study involved a factor of only 2.83 in near-surface dpa rate it is important to confirm that the dependence of EΔx4 on dpa rate is maintained over a larger range of damage rates. In this study polycrystalline Fe with 140 appm carbon was irradiated with 5 MeV Fe2+ ions to 50, 100 and 150 dpa over a range of peak dpa rates (2.0 × 10–4, 1.2 × 10–3, 6.0 × 10–3 dpa/sec) and temperatures (425, 475, 525 °C). At very high dpa levels sputtering and void growth lead to loss of voids via shrinkage, limiting the upper dose level where this technique can be applied. It was found that the single-crystal and polycrystal specimens yielded essentially identical behavior with EΔx4 = 1.65 eV, validating the application of this activation energy over a wider range of dpa, dpa rate, temperature, and crystal form.

Controllable Preparation and Mechanism Study of Easy‐Peel High‐Density and Vertically Aligned Carbon Nanotube Forests

The stripping of carbon nanotube forests (CNTF) is an urgent problem in terms of its application in thermal management and semiconductor devices. The easy‐peel and vertically aligned CNTF is prepared in a two‐step process of high vacuum magnetron sputtering and chemical vapor deposition. Based on the thick alumina buffer layer, CNTF with heights of 100 μm, 300 μm, and 500 μm was prepared by adjusting the magnetron sputtering power. Through SEM observation and calculation, the corresponding densities were 2.5 × 109 cm−2, 6.4 × 109 cm−2, and 1.21 × 1010 cm−2, with an average curvature of 1.64 × 102 m−1, 1.35 × 102 m−1 and 0.53 × 102 m‐−1, respectively. The TEM, XPS, Raman, and TGA were used to investigate the growth mechanism of CNTF. The experimental results show that the catalyst particles annealed under high sputtering power refined with high density can grow a low‐defect, well‐oriented, and high‐density CNTF, and confirm the tip growth route. Further analysis shows that the easy‐peel properties of CNTF depend on the thickness of the alumina layer, the tip growth route, and the tight entanglement between the nanotubes. This paper provides technical guidance and support for the preparation, stripping, and application of monolithic CNTF.

Discovering tungsten-based composites as plasma facing materials for future high-duty cycle nuclear fusion reactors

Despite of excellent thermal properties and high sputtering resistance, pure tungsten cannot fully satisfy the requirements for plasma facing materials in future high-duty cycle nuclear fusion reactions due to the coupled extreme environments, including the high thermal loads, plasma exposure, and radiation damage. Here, we demonstrated that tungsten-based composite materials fabricated using spark-plasma sintering (SPS) present promising solutions to these challenges. Through the examination of two model systems, i.e., tungsten-zirconium composite for producing porous tungsten near the surface and dispersoid-strengthened tungsten, we discussed both the strengths and limitations of the SPS-fabricated materials. Our findings point towards the need for future studies aimed at optimizing the SPS process to achieve desired microstructures and effective control of oxygen impurities in the tungsten-based composite materials.

Segregation effects of doped VN and ZrN on magnetic and microstructural characteristics of FePt-based films

Segregants are essential materials for forming the complexation or granular microstructure in thin films for magnetic recording media. One such film, FePt-BN, has a metallic L10 FePt main phase as its matrix, in addition to having BN and C segregants at the grain boundaries. Amorphous BN has sufficient mechanical strength to support the columnar growth of FePt grains, however, it has a lower deposition rate resulting in columnar grains with a nonuniform aspect ratio. Moreover, some B diffuses in the interstitial site of FePt lattices. To overcome these limitations, this study added the transition nitride VN and ZrN with equal volume percentages to replace some BN segregants in FePt(BN, Ag, C) films: substantially different segregation behaviors were observed. Microstructural imaging mapping revealed that although VN segregated the FePt grains boundary, ZrN was diffused in the lattice. The FePt-BN-ZrN film thus had more disordered grains contributing to a higher in-plane magnetization and wider hard axis magnetic hysteresis loops than did FePt-BN-VN. The FePt-BN-VN film has the highest perpendicular magnetic anisotropy constant (Ku= 2.17 × 106 J/m3) and coercivity (Hc= 4 T); moreover, parallel remanence magnetization was minimal with a linear in-plane magnetization loop. The FePt-BN-VN film was sputtered directly on MgO(100) but depositing the FePt-BN-ZrN film required a 2-nm-thick FePt nucleation layer. The high atomic number of Zr and high sputter yield ratio (YN/Ymetal) of ZrN may increase the sites occupied by N, potentially affecting ZrN segregation.

European effort to improve highly charged heavy ion beam capabilities with ECR ion sources (invited)

The European Electron Cyclotron Resonance Ion Source (ECRIS) community has more than 20 years of experience working together in various EU-funded projects. In the recent project, called ERIBS (European Research Infrastructure – Beam Services), the community will focus on improving ion beam services for the EURO-LABS (European-Laboratories for Accelerator Based Sciences) research infrastructures. The EURO-LABS is a four-year project funded by the Horizon Europe program of the European Commission for years 2022 - 2026. In the ERIBS collaboration the best expertise, know-how and practices of the ECRIS community will be exploited and transferred between the partners to take full advantage of the European ion source infrastructure. The aim is to extend the beam variety available for the European user community by developing beam production methods and techniques. This development includes further improvement of technologies related to high temperature ovens, axial sputtering and MIVOC method for all the participating laboratories. We will also aim to improve both short- and long-term plasma and beam stability, as well as methods for online monitoring of these conditions. This can be realized, for example, by optical emission spectroscopy, identifying kinetic plasma instabilities by means of hard x-ray detection and using online beam current monitoring systems. An example of the recent developments is the new collaboration proposed by the CNRS-IPHC team to synthesize enriched MIVOC compounds for the other ERIBS partners. For example, the team successfully prepared an enriched chromocene compounds, which were needed to produce intensive 54Cr and 50Cr beams for the JYFL and GANIL nuclear physics programs, respectively.

Si-enabled self-lubrication and wear resistance of CrCoNiSi medium-entropy alloy films

High- or medium-entropy alloys have gained attention in coatings attributed to high wear resistance, with the formation of an amorphous phase. However, tailoring the crystal structure has limitations in improving both friction and wear characteristics due to the uncertain influence of amorphization on friction coefficients. In this respect, Si, known to increase glass-forming ability, can reduce the friction coefficient as a self-lubricating tribo-film formed by tribochemical reactions. However, tailoring Si content also affects crystal structures, defects, and mechanical properties, which require systematical investigations. Therefore, in this study, CrCoNiSi alloy films are fabricated with controlling Si content (0–13 at%) and sputtering power (5.8–13.7 W/cm2). The increase in Si content and sputtering power both produce identical microstructural evolutions, shifting from a crystalline towards an amorphous phase. In an amorphous film of high sputtering power, the high SiO2 fraction leads to dominant adhesive wear with delamination, thus contributing to the increase in wear rate. However, the Si addition alters the Si ion fraction of post-wear, forming Si-induced tribo-film, retaining abrasive wear, and consequently reducing the friction coefficient and wear rate. This Si addition would offer control over crystal structure and self-lubricating properties, enabling tailored mechanical and tribological properties.

Sputtering of silver nanoparticles bombarded with 3–100 keV Ar ions

Rutherford backscattering spectrometry and scanning electron microscopy were applied to obtain sputtering yields of Ag nanoparticles (5–30 nm in diameter) under 3–100 keV Ar+ ion irradiation. For low-energy ion irradiation, the diameter dependence of the sputtering yield was approximately 1.5 times higher than that of the bulk at diameters of a few nanometers, and then approached the bulk value at larger diameters. Under high-energy ion irradiation, especially for 100 keV Ar+ irradiation, the sputtering yields of Ag nanoparticles with diameters as small as a few nanometers were extremely higher than those predicted by the theoretical calculations. We concluded that such high sputtering yield originated in Ag cluster emission.

Influence of Cr + Si content variation on cutting behavior of TiAlCrSiN HPPMS coatings

As high power pulse magnetron sputtering (HPPMS) technology is becoming popular in cutting tool industry, the development of nanocomposite coating systems such as TiAlCrSiN with this technology presents a new research avenue. Here, the combined effect of Cr and Si contents on properties and cutting behavior of high Al content TiAlCrSiN HPPMS coatings needs further investigation. For this purpose, three HPPMS coatings with Al/Ti ratio x = 1.4–1.5 and varying Cr + Si content, namely (Ti28Al40Cr16Si16)N, (Ti30Al43Cr17Si10)N and (Ti36Al54Cr5Si5)N, were deposited on cemented carbide substrates. In addition to basic characterization, the fracture behavior of the coatings was characterized by scratch tests. The cutting behavior of the coated inserts was exemplarily investigated during dry cutting of normalized medium carbon steel C45 with cutting speed vc = 80 m/min, feed rate f = 0.12 mm and cutting depth ap = 0.8 mm. The tool damage over the cutting time of tc = 35–40 min, as per the tool condition, was observed using light microscopy. Moreover, the damage mechanisms were analyzed in detail at the end of the cutting test using scanning electron microscopy. All coatings showed comparable indentation hardness HIT and indentation modulus EIT. However, an increased Cr + Si content amplified the brittle fracture of the coating under sliding load of scratch test. Moreover, the workpiece material C45 showed a higher adhesion tendency to cutting insert with high Cr + Si content TiAlCrSiN coatings during cutting tests. The tool wear and built-up edge formation increased due to the combined effect of workpiece adhesions and amplified brittle fracture of the coating at considered cutting speed. On the other hand, the inserts with low Cr + Si content coating exhibited better cutting performance and reduced built-up edge formation based on the improved fracture behavior of the coating and lower adhesion tendency of workpiece material to the corresponding coated insert.

Optimization of TiN/TiOxNy Laminated Electrode Films for High-Performance Gene Sequencing Chip

With continuous advancement of the fourth generation nanopore gene sequencing technology, the requirements for performance of the electrode films in gene sequencing chips are increasing. This study utilized the high vacuum reactive magnetron sputtering method to examine the impact of working pressure on the electrical, electrochemical, crystal structure, chemical composition, and surface morphology of TiOxNy thin films in detail. The findings revealed that the TiN thin film deposited at 0.4 Pa exhibited the lowest resistivity of 391.9 μΩ·cm. Additionally, the TiOxNy thin film deposited at 1.6 Pa demonstrated the highest volumetric specific capacitance of 35.37 mF·cm−2·μm−1 at 5 mV·s−1. Utilizing the optimal parameters, TiOxNy laminated electrode thin films were in situ grown. Through measurements and analysis, it was found that the TiOxNy electrode thin film effectively achieves a 29.35% improvement in specific capacitance compared to the single layer TiOxNy electrode thin film. The integration of a TiN current collector with low resistivity effectively reduced the internal resistance of the electrode system and decreased the response time to 0.038 s. The features of low impedance and high specific capacitance of TiOxNy laminated thin films offer promising prospects for the preparation of gene sequencing chip with high throughput.

Nanostructure and Optical Property Tailoring of Zinc Tin Nitride Thin Films through Phenomenological Decoupling: A Pathway to Enhanced Control.

This work addresses the need for precise control of thin film sputtering processes to enable thin film material tailoring on the example of zinc tin nitride (ZTN) thin films deposited via microwave plasma-assisted high power reactive magnetron sputtering (MAR-HiPIMS). The applied in situ diagnostic techniques (Langmuir probe and energy-resolved time-of-flight mass spectrometry) supported monitoring changes in the deposition environment with respect to microwave (MW) power. During MAR-HiPIMS, the presence of nitride ions in the gas phase (ZnN+, ZnN2+, SnN+, SnN2+) was detected. This indicates that the MW plasma facilitated their production, as opposed to pure R-HiPIMS. Additionally, MW plasma caused post-ionisation of sputtered atoms and reduced the overall energy-per-charge range of incoming charged species. By varying the MW power and substrate biasing, films with comparable chemical compositions (approximately Zn0.92Sn1.08N2) but different structures, ranging from polycrystalline to preferentially textured, were successfully produced. The application of density functional theory (DFT) further enabled the relationship between the lattice parameters and the optical properties of ZTN to be explored, where the material's optical anisotropy nature was determined. It was found that despite considerable differences in crystallinity, the changes induced in the lattice parameters were subangstrom, causing only minor changes in the final optical properties of ZTN.

A Coaxial Nozzle Attachment Improving the Homogeneity of the Gas Flow Sputtering

The Hollow Cathode Gas Flow Sputtering (GFS) provides special plasma conditions and is of extensive interest as a more affordable alternative to the high vacuum sputtering techniques. In the case of the tubular cathode a circular outlet symmetry stipulates homogeneity issues for both metallic and reactive deposition regimes. Using the results of Direct Simulation Monte Carlo (DSMC), we propose an external coaxial attachment which is manufactured and examined in a nozzle and a diffuser positioning. The impact on the homogeneity of Ti and TiO2 films is examined using profilometry and spectral ellipsometry. Our results demonstrate that the use of the nozzle attachment significantly enhances film homogeneity from about 3 cm2 to more than 12 cm2. It also secures better process control in terms of oxygen stoichiometry and film thickness. Some crucial general issues of the reactive GFS process are discussed.

Exceptional Performance of Room Temperature Sputtered Flexible Thermoelectric Thin Film Using High Target Utilisation Sputtering Technique

AbstractThe High Target Utilisation Sputtering technique (HiTUS) is of interest for industrial processes, including in roll‐to‐roll manufacturing. This study marks the first application of HiTUS to thermoelectric materials, exemplified by bismuth telluride. The HiTUS technique separates the sputtering power into the plasma power and the target power, with additional kinetic energy in the sputtering particles from the applied electrical field, thus enabling a much wider sputter parameter space to modify the film performance. This study investigates how plasma power, target power, and substrate bias in HiTUS intricately influence crystal orientation/size, elemental composition, surface morphology, and other film properties. These factors subsequently affect carrier density/mobility, and consequently the thermoelectric performance of the bismuth telluride film. These deposited films reach a power factor of 6.5 × 10−4 W m−1 K−2 with a figure of merit ≈0.14 at room temperature, the highest value for room‐temperature sputtered un‐doped bismuth telluride. Subsequent post‐deposition annealing significantly enhances the crystallinity of the film (highly polycrystalline), further improving the power factor to 23.5 × 10−4 W m−1 K‐2, with a figure of merit ≈0.45 at room temperature. The excellent performance of the HiTUS fabricated thermoelectric film opens opportunities for the large‐area manufacture of thin‐film thermoelectric materials and devices.

Cutting performance of TiAlN-based thin films in micromilling high-speed steel AISI M3:2

Micromilling high-speed steel offers high precision in shape and geometry. However, the service life greatly depends on the wear resistance of protective thin films. In comparison to TiAlN, TiAlSiN and TiAlTaN thin films offer enhanced wear resistance for difficult-to-machine materials. Employing a hybrid process that combines direct current magnetron sputtering (dcMS) and high power pulsed magnetron sputtering (HiPIMS) enhances the properties of these films. In cutting tests, it is demonstrated that TiAlSiN and TiAlTaN outperform TiAlN in micromilling of high-speed steel AISI M3:2. Notably, dcMS/HiPIMS-TiAlSiN stands out by having the lowest reduction in cutting forces combined with reduced wear.