Non-reactive Sputtering Research Articles

Strategic lattice manipulation in transition metal nitrides for improved solubility

In this study, we propose a new concept for achieving metastable ternary transition metal nitride solid solutions, focusing on face centered cubic (fcc) structured Ti(N,B) as a model system. Combining non-reactive magnetron sputtering with computational analysis, we develop a microalloying strategy to manipulate the metallic sublattice, thereby influencing the solubility of B in the non-metal sublattice. We show that imposed tensile strain on the fcc-TiN lattice facilitates the solubility of B, with a 1.5 % strain enabling the incorporation of ∼28.5 at.% B at the non-metal sublattice. Conversely, compressive strain hinders the formation of the fcc-Ti(N,B) solid solution, highlighting the importance of lattice manipulation in controlling solubility. At the same time, our experimental findings reveal that adding larger atoms, such as Zr, to the metal sublattice enhances the solubility of B in fcc-TiN more effectively (∼2 at.% Zr proves to be sufficient to solute 10 at.% B in the fcc-TiN lattice) than smaller atoms, like Cr or similar-sized Ti atoms. The size effect of the alloying atoms on the B solubility is further supported by radial distribution function analysis, showing lower local lattice distortions for Zr compared to Cr.

New nanoscale multilayer magnetron sputtered Ti-DLC/DLC coatings with improved mechanical properties

Two sets of nanoscale multilayer Ti-DLC/DLC coatings, with similar chemical composition but different periods between consecutive layers (0.4 and 5.5 nm), were deposited by non-reactive direct current magnetron sputtering using different rotational speeds of the substrate holder (12 and 1 rpm, respectively) in this work. The results show that the overall Ti content in the coatings varied from ≈ 2.9 to ≈ 8.2 at. % in both cases. Significant fluctuations in the Ti concentration between the middle points of the DLC and Ti-DLC layers were observed for the coatings deposited at 1 rpm. All the coatings deposited were mainly amorphous, presenting a columnar structure and a cauliflower-like granular surface morphology. The sp2/sp3 ratio increased as the concentration of Ti rose. The coatings deposited at 1 rpm demonstrated better mechanical properties (up to 33 % improvement in hardness and up to 25 % improvement in the elastic modulus) when compared to the equivalent coatings deposited at 12 rpm. The multilayer titanium doped coating (deposited at 1 rpm) with 5.9 at. % Ti presented the most significant improvement in mechanical properties when compared to pure DLC and monolayer coatings deposited at 12 rpm. The results confirmed that it is possible to tune the performance of this type of coatings by depositing alternating layers of pure DLC and Ti-doped DLC.

Elemental distribution and fracture properties of magnetron sputtered carbon supersaturated tungsten films

The combination of strength and toughness is a major driving force for alloy design of protective coatings, and nanocrystalline tungsten (W)-alloys have shown to be promising candidates for combining strength and toughness. Here we investigate the elemental distribution and the fracture toughness of carbon (C) alloyed W thin films prepared by non-reactive magnetron sputtering. W:C films with up to ~4 at.% C crystallize in a body-centered-cubic structure with a strong 〈hh0〉texture, and no additional carbide phases are observed in the diffraction pattern. Atom probe tomography and X-ray photoelectron spectroscopy confirmed the formation of such a supersaturated solid solution. The pure W film has a hardness ~13 GPa and the W:C films exhibit a peak hardness of ~24 GPa. In-situ micromechanical cantilever bending tests show that the fracture toughness decreases from ~4.5 MPa·m1/2 for the W film to ~3.1 MPa·m1/2 for W:C films. The results show that C can significantly enhance the hardness of W thin films while retaining a high fracture toughness.

Electrochemical Performance of Biocompatible TiC Films Deposited through Nonreactive RF Magnetron Sputtering for Neural Interfacing.

The efficacy of neural electrode stimulation and recording hinges significantly on the choice of a neural electrode interface material. Transition metal carbides (TMCs), particularly titanium carbide (TiC), have demonstrated exceptional chemical stability and high electrical conductivity. Yet, the fabrication of TiC thin films and their potential application as neural electrode interfaces remains relatively unexplored. Herein, we present a systematic examination of TiC thin films synthesized through nonreactive radio frequency (RF) magnetron sputtering. TiC films were optimized toward high areal capacitance, low impedance, and stable electrochemical cyclability. We varied the RF power and deposition pressure to pinpoint the optimal properties, focusing on the deposition rate, surface roughness, crystallinity, and elemental composition to achieve high areal capacitance and low impedance. The best-performing TiC film showed an areal capacitance of 475 μF/cm2 with a capacitance retention of 93% after 5000 cycles. In addition, the electrochemical performance of the optimum film under varying scanning rates demonstrated a stable electrochemical performance even under dynamic and fast-changing stimulation conditions. Furthermore, the in vitro cell culture for 3 weeks revealed excellent biocompatibility, promoting cell growth compared with a control substrate. This work presents a novel contribution, highlighting the potential of sputtered TiC thin films as robust neural electrode interface materials.

On the dielectric properties and conduction mechanism in cuprous oxide thin films grown on (111)-oriented MgO substrates by means of non-reactive DC magnetron sputtering

On the dielectric properties and conduction mechanism in cuprous oxide thin films grown on (111)-oriented MgO substrates by means of non-reactive DC magnetron sputtering

Carbon defect induced evolution of structural and mechanical properties in substoichiometric (HfMoNbZr)Cx films

Substoichiometric (HfMoNbZr)Cx films with varied carbon content were synthesized using non-reactive magnetron sputtering. Findings reveal that the (HfMoNbZr)Cx film predominantly exhibits a single-phase FCC structure, which transforms to a dual-phase structure consisting of FCC and Hex. phases at higher carbon content. This behavior arises from the segregation of group VB (Nb) and VIB (Mo) elements from the FCC lattice. The film hardness (H) and elastic modulus (E) increases with rising carbon content accompanied by a decrease of coefficient of friction (COF). However, the wear rate is not decreased despite the increased H and reduced COF of the as-deposited films. This phenomenon is explained by examining the differences in the wear mechanisms between (HfMoNbZr)Cx films with single- and dual- phase structures.

Thin films of silicon nitride deposited at room temperature by non-reactive magnetron sputtering: radiofrequency power and deposition time influence on the formation of α-Si3N4 and its optical properties

Silicon nitride’s excellent electronic and optical properties have positioned it as an indispensable element in silicon-based photonic platforms and photonic quantum computing. Chemical Vapor Deposition (CVD) and Plasma Enhanced CVD (PECVD) techniques predominate in high-performance silicon nitride thin film manufacture. Unfortunately, Chemical Vapor Deposition and Plasma Enhanced CVD are expensive techniques that use hazardous gases and very high substrate temperatures. In this work, we used the sputtering technique to grow α-Si3N4 thin films at room temperature. We identified that by applying radiofrequency powers between 30 and 50 W combined with deposition times below 120 min, we could achieve the growth of silicon nitride (SiNX) films with uniformly distributed crystalline particles, limited formation of clusters, and minimal alterations in atomic ordering. The Volmer-Weber model governs the film’s growth, which favors its continuity and surface roughness. The optical bandgaps of our SiNX films ranged from 2.3 to 3.9 eV, and their RMS roughness never exceeded 4 nm. We observed a quasi-linear deposition rate concerning radiofrequency power and deposition time, whereby we were able to grow SiNX films controllably and reproducibly with thicknesses ranging from 45 to 500 nm.

Structure and Properties of Thin Magnetron Films of Cadmium Arsenide on Various Substrates

Purpose of the study. Synthesis of cadmium arsenide magnetron films on various substrates and study of their structure, composition, optical and electrical properties.Methods. The deposition of thin films of cadmium arsenide was carried out by the method of non-reactive highfrequency magnetron sputtering in an argon atmosphere. The structure and composition of the films were studied using X-ray phase analysis, scanning electron microscopy, energy dispersive analysis, and small-angle X-ray diffractometry. Optical studies were performed using Raman spectroscopy. The results of a study of the electrical properties of thin films of cadmium arsenide are presented.Results. On silicon, sapphire, and strontium titanate substrates, thin films of the Dirac semimetal, cadmium arsenide, were obtained with a thickness of about 40 nm. A study of their structure and composition showed a significant effect of annealing in an argon atmosphere following deposition on the crystallinity of the film. After annealing, regardless of the crystal structure of the substrate, partial orientation of the film with the (112) texture axis. The films closest to the stoichiometric composition were obtained by deposition followed by annealing onto an oriented strontium titanate substrate, and to the crystal structure of cadmium arsenide single crystals of a film on a sapphire substrate. Annealing also leads to a smoothing of the film surface, a decrease in structural defects, and the transition of the fractal dimension of its topology to two-dimensional from close to three-dimensional immediately after deposition. The optical properties after annealing also change, which indicates their transition from a polycrystalline (amorphous) state to a single-crystal (textured).Conclusion. Experimental studies of the structure and properties performed by various methods made it possible to establish that single-crystal or textured cadmium arsenide films suitable for studying the manifestation of topological properties can be obtained by controlled annealing.

Unraveling the superlattice effect for hexagonal transition metal diboride coatings

Superlattice structures enable the simultaneous enhancement in hardness (H) and fracture toughness (KIC) of ceramic-like coatings. While a deeper understanding of this effect has been gained for fcc-structured transition metal nitrides (TMN), hardly any knowledge is available for hexagonal diborides (TMB2). Here we show that superlattices can—similarly to nitrides—increase the hardness and toughness of diboride films. For this purpose, we deposited TiB2/WB2 and TiB2/ZrB2 superlattices with different bilayer periods (Λ) by non-reactive sputtering. Nanoindentation and in-situ microcantilever bending tests yield a distinct H peak for the TiB2/WB2 system (45.5 ± 1.3 GPa for Λ = 6 nm) but no increase in KIC related to a difference in shear moduli (112 GPa). Contrary, the TiB2/ZrB2 system shows no peak in H, but for KIC with 3.70 ± 0.26 MPa∙m1/2 at Λ = 4 nm originating from differences in lattice spacing (0.14 Å), hence causing coherent stresses retarding crack growth.

Preparation of Discontinuous Cu/SiO2 Multilayers—AC Conduction and Determining the Measurement Uncertainty

This paper presents a test stand for testing alternating current electrical parameters of Cu-SiO2 multilayer nanocomposite structures obtained by the dual-source non-reactive magnetron sputtering method (resistance, capacitance, phase shift angle, and dielectric loss angle tangent δ). In order to confirm the dielectric nature of the test structure, measurements in the temperature range from room temperature to 373 K were carried out. The alternating current frequencies in which the measurements were made ranged from 4 Hz to 7.92 MHz. To improve the implementation of measurement processes, a program was written to control the impedance meter in the MATLAB environment. Structural studies by SEM were conducted to determine the effect of annealing on multilayer nanocomposite structures. Based on the static analysis of the 4-point method of measurements, the standard uncertainty of type A was determined, and taking into account the manufacturer's recommendations regarding the technical specification, the measurement uncertainty of type B.

Non-reactive HiPIMS deposition of NbCx thin films: Effect of the target power density on structure-mechanical properties

The exceptional mechanical properties of transition metal carbide coatings are known to be governed by the carbon content and its morphological distribution. Here, we verify the influence of the target peak power density on the chemical composition, microstructure, and mechanical properties of NbCx coatings grown by non-reactive high-power impulse magnetron sputtering (HiPIMS). By tuning the pulse parameters, the power density can be increased from 0.11 to 1.48 kW/cm2 leading to a decrease in the C/Nb ratio from 1.52 to 0.99 within the films – proven by combined elastic backscattering and time-of-flight elastic recoil detection analysis. This decrease in the C/Nb ratio is accompanied by microstructural changes from nanocomposite morphologies with an average grain size of 6.6 ± 2.5 nm at 0.13 kW/cm2 into more columnar structures with an average column width of 65.2 ± 18.7 nm at 1.48 kW/cm2. Independent from the C/Nb ratio, all films exhibit a single face-centered cubic structure. The mechanical properties correlate with the enhanced growth behavior dominated by ions at higher peak power densities and the varied C/Nb ratios. A maximum in hardness and fracture toughness of H = 38.7 ± 3.6 GPa and KIc = 2.78 ± 0.13 MPa∙m1/2 (at 3.2 GPa residual compressive stress), is obtained for the nearly stoichiometric NbC coating exhibiting C/Nb ratio of 1.06.

Structure, Mechanical, and Micro-Scratch Behavior of Ta-Hf-C Solid Solution Coating Deposited by Non-Reactive Magnetron Sputtering.

The TaC, HfC, and Hf-Ta-C coatings are successfully prepared by non-reactively DC magnetron sputtering. The effects of working pressure and deposition temperature on the structure and mechanical properties of Ta-Hf-C coating are analyzed. The scratch performance of the Ta-Hf-C coating deposited on 304 stainless steel and tungsten substrates are investigated. Results show the hardness and elastic modulus of Ta-Hf-C solid solution coating both increase to 37.8 ± 1.1 GPa and 435.8 ± 13.8 GPa due to the solid solution strengthening effect. Plastic deformation resistance H3/E2 of Ta-Hf-C coating can reach 0.285, which is more than twice that of binary coating. Furthermore, the scratch performance and failure mechanism show that Ta-Hf-C coating has a weaker plastic deformation resistance on soft substrate and low friction characteristic (0.01) on hard substrate, which implies that Ta-Hf-C coating is a good protective coating that can be applied to cutting tools.

AC conductivity of amorphous and polycrystalline Cd3As2 films on single crystal substrates of Al2O3

In this work, we present first AC conductivity measurements of both amorphous and polycrystalline Cd3As2 thin films ( ∼50nm) in the frequency range 25–106Hz and temperature range 10–300 K. Cd3As2 thin films were grown by non-reactive AC magnetron sputtering. Both samples show a strong frequency dependence of the total conductivity in the order of 104Ω−1 cm−1. It was found that the DC conductivity, deduced from the total conductivity of Cd3As2 thin films, increases with increasing temperature. The experimental results indicate exponent values s>1 and s>2, which contradicts the universal dynamic response. In Cd3As2 films is observed a crossover of metal–semiconductor type at low temperatures, which is characteristic of topological materials. The results show a clearly frequency dependence of the mechanism of AC conductivity of Cd3As2 films in a wide range of temperatures.

Development of deposition technology and AC measurement of copper ultrathin layers

In this paper, the transport properties of discontinuous 4 nm copper layers obtained by dual-source non-reactive magnetron sputtering in the presence of argon are presented. The value of resistance and capacitance of the current parallel to the plane of these layers can be adjusted independently by changing the nominal thickness of the metallization. The influence of frequency on the conductivity of the obtained structures in the range from 4 Hz to 8 MHz was studied. Additionally, in order to compare the non-oxidized and oxidized layers, some of them were heated at 500 °C. Based on the results obtained, the mechanism of electric charge transfer was determined, the knowledge of which is essential for planning further experiments based on this sputtering method and potential selection of future application of the structures. Statistical measurements at room temperature will serve as a reference for the conductivity and resistivity values obtained by mathematical calculations from measurements of resistance, capacitance, phase shift angle, and dielectric loss tangent as a function of temperature from 20 K to 375 K, which are expected in further studies on the obtained structures. The work is an introduction to the technology of obtaining multi-layer metal-dielectric structures.

Tungsten-Based Cost-Effective Gas Sensors for H2S Detection

Tungsten trioxide thin films were deposited on silicon substrates by non-reactive RF sputtering from a WO3 target at room temperature. The WO3 films were post-annealed at two different temperatures, 400 °C and 500 °C. The morphological and microstructural properties of these films were analyzed by using atomic force microscopy and X-ray diffraction. X-ray diffraction patterns only show WO3 oxide phases. The AFM images show different morphologies with smaller grains for the film annealed at 400 °C. WO3 sensing films and W heating elements were embedded in commercial cases for the fabrication of cost-effective gas sensors. The sensitivity and dynamic response of the sensors were analyzed under various concentrations of H2S, from 20 to 100 ppm, at SIMTRONICS SAS (3M Company, Saint Paul, MN, USA). A good sensitivity G/G0 of about 6.6 under H2S 100 ppm was obtained with the best sensor. An interesting dynamic response was observed in particular with a short response time. Additionally, the evolution of the sensitivity was studied, and a conduction model was proposed for explaining the conduction mechanism under H2S exposition.

Features in low-temperature electrical resistivity of amorphous Cd3As2 films due to hopping conductivity with changing activation energy

Amorphous Cd3As2 films were deposited on single-crystalline SrTiO3 substrate by high-frequency non-reactive magnetron sputtering. Electrical resistivity of the film, measured within 3-75 K range, increases at cooling. Below ∼70 K, negative transverse magnetoresistance observed. Features in electrical resistivity and magnertoresistance can be attributed to variable-range hopping conductivity of the Mott type with local activation energy, which is temperature-dependent. Two temperature ranges in the hopping conductivity observed. Appearing two ranges is in qualitative accordance with the Mott-Davis energy-band model developed for amorphous semiconductors. High temperature range of the hopping conductivity is attributed to electron hops between localized states, positioned inside band tails, whereas electron hops between localized states, positioned inside Fermi-peak, can be responsible for low-temperature range. At taking into account temperature dependences of local activation energy, universal expression for various mechanisms of the hopping conductivity could be successfully applied to analyze the experimental data.

Structure and mechanical properties of reactive and non-reactive sputter deposited WC based coatings

During the growth of WC based thin films, carbon can be introduced by either a non-reactive or reactive deposition route. In this study, we compare the influence of the carbon origin on the coating properties, sputtering three different target materials – a ceramic WC, a ceramic WC including a conventional cobalt binder, and a metallic tungsten (W) target – in reactive (acetylene, C2H2) as well as non-reactive (pure Ar) atmospheres. The morphology changes, independently to the target type and atmosphere used, from crystalline (hex-W2C rich to pure fcc-WCx) to a nanocomposite (fcc-WCx nanometre sized grains embedded in an amorphous matrix) structure, up to amorphous coatings, only dominated by the prevalent C/W ratio. The cobalt binder however leads to a preferred amorphization of the coatings. The highest hardness is obtained for predominantly fcc structured WC0.67 (WC ceramic target), H = 40 ± 1.7 GPa, exhibiting also an excellent intrinsic fracture toughness of KIC = 3.3 ± 0.33 MPa·m1/2 obtained by micro-mechanical testing. Furthermore, the bonding nature of carbon is distinctly affected by the reactive carbon source, leading to more pronounced π-bonded carbon peak with increasing C2H2/Ar flow rates.

Phase formation and mechanical properties of reactively and non-reactively sputtered Ti-B-N hard coatings

In the field of hard protective coatings, nano-crystalline Ti-B-N films are of great importance due to the adjustable microstructure and mechanical properties through their B content. Here, we systematically study this influence of B on Ti-B-N during reactive as well as non-reactive DC magnetron sputtering. The different deposition routes allow for an additional, very effective key parameter to modify bond characteristics and microstructure. Plasma analysis by mass spectroscopy reveals that for comparable amounts of Ti + , Ti 2+ , Ar + , and Ar 2+ ions, the count of N + ions is about 2 orders of magnitude lower during non-reactive sputtering. But for the latter, the N + /N 2 + ratio is close to 1, whereas during reactive sputtering this ratio is only 0.1. This may explain why during reactive deposition of Ti-B-N, the B N bonds dominate (as suggested by X-ray photoelectron spectroscopy), whereas the B B and Ti B bonds dominate for non-reactively prepared Ti-B-N. Chemically, reactively versus non-reactively sputtered Ti-B-N coatings follow the TiN-BN versus TiN-TiB 2 tie line, respectively. Detailed X-ray diffraction and transmission electron microscopy studies reveal, that up to 10 at.% B can be dissolved in the fcc-TiN lattice when prepared by non-reactive sputtering, whereas already for a B content of 4 at.% a BN-rich boundary phase forms when reactively sputtered. Thus, we could not only observe a higher hardness (35 GPa instead of 25 GPa) as well as a higher indentation modulus (480 GPa instead of 260 GPa), but also a higher fracture energy (0.016 instead of 0.009 J/m during cube-corner indentations) for Ti-B-N coatings with 10 at.% B, when prepared non-reactively. • Major differences in plasma species between reactive and non-reactive sputtering • The elemental composition also varies with the deposition route. • Significant differences in mechanical properties at higher boron contents

Cu 4O3 thin films deposited by non-reactive rf-magnetron sputtering from a copper oxide target

Copper oxide thin films deposited by sputtering are frequently formed by using metal copper targets in reactive atmospheres. In this report, paramelaconite (Cu4O3) thin films were deposited by non-reactive rf magnetron sputtering. The target used for sputtering was a copper oxide disk fabricated by oxidation of metal copper at 1000 °C for 24 h in airatmosphere. X-ray diffraction (XRD) results showed that the copper oxide target was mainly composed of cupric oxide (CuO) and cuprous oxide (Cu2O) crystals. Raman analyses suggested that the surface of the copper oxide disk is composed by a (CuO) layer. XRD measurements performed to the copper oxide thin films deposited by non-reactive rf magnetron sputtering showed that the film is composed of (Cu4O3) crystals. However,Raman measurements indicated that the Cu4O3 thin films are also composed by amorphous CuO and Cu2O.

Electrical and Structural Properties of Non-Reactive Dual Magnetron Sputter Deposited W–C Thin Films for MOSFET Gates

Electrical and Structural Properties of Non-Reactive Dual Magnetron Sputter Deposited W–C Thin Films for MOSFET Gates