Reactive Magnetron Sputtering Process Research Articles

Oxygen plasma treatment WO3 nanorods for Improvement H2S gas sensing

Herein, the oxygen (O2) plasma has been used to post-treat tungsten oxide (WO3) nanorods to improve the sensing performance of the H2S gas sensor. The reactive DC magnetron sputtering process with the glancing-angle deposition (GLAD) technique was used to prepare the WO3 nanorods. After deposition, the WO3 nanorod thin films were treated with O2 plasma at different treatment power from 100 – 200 W. The physical structure of as-deposition and treated WO3 nanorod thin films was investigated crystal structure and morphology by grazing incident X-ray diffraction (GIXRD), field-emission scanning electron microscope (FE-SEM), and high-resolution transmission electron microscope (HRTEM). The result indicated that the WO3 nanorod structure transformed to the monoclinic polycrystalline phase. FE-SEM and HRTEM observed slight changes in the shape of the WO3 nanorods. The H2S sensing properties were measured at 10 ppm at 150 – 350°C operating temperatures. At an operating temperature of 200 °C, the response to H2S of O2 plasma treated WO3 nanorods is increased by a factor of 5 – 15, and the maximum response to H2S is 15. The results showed that the O2 plasma treatment process improved the sensing response of the WO3 nanorods.

In-situ hydrogenated V2O5 thin films: Study of the structural dynamics and their behavior as Li-ion batteries cathode

This investigation focuses on a one-step preparation method to produce hydrogenated V2O5 thin films by controlling the atmosphere of the DC reactive magnetron sputtering process. An increasing hydrogen flux during the film deposition promotes the formation of defects such as oxygen vacancies and hydroxyl sites in the oxide matrix. The hydrogenated samples were tested as cathodes in Li-ion batteries and exhibited lower charge capacities but superior stability to cycling compared to pristine V2O5 film. These results pave the way to prepare hydrogenated transition metal oxide thin films by a simple route without further thermal procedures and affordable conditions.

Analysis of the Inhomogeneous Growth of Sputtered Black TiO2 Thin Films.

Black titanium dioxide (B-TiO2) is a highly active photoelectrochemical material compared to pure titanium dioxide due to its increased light absorption properties. Recently, we presented the deposition of thin-film B-TiO2 using an asymmetric bipolar reactive magnetron sputter process. The resulting samples exhibit excellent photoelectrochemical properties, which can be fine-tuned by varying the process parameters. In this article, results of morphological, electrical, and photoelectrochemical measurements are discussed to better understand the surprisingly high electrochemical activity of the films. In order to study the influence of the dynamic process on film formation, we use static sputtering with a fixed substrate covering the entire chamber area in front of the two targets. This allows the material composition of the sputtered film to be analyzed depending on its relative position to the targets. The results lead to the conclusion that the asymmetric bipolar sputtering mainly produces two phases, a transparent, nonconductive crystalline phase and a black, conductive amorphous phase. As a consequence, the dynamically sputtered samples are multilayers of these two materials. We discuss that the significantly better electrical and photoelectrochemical properties emerge from the inhomogeneous nature of the laminates, like also found in core-shell nanoparticles of B-TiO2.

NO2 gas sensing performance of Ag−WO3−x thin films prepared by reactive magnetron sputtering process

NO2 gas sensing performance of Ag−WO3−x thin films prepared by reactive magnetron sputtering process

Photocatalytical and corrosion behavior of sputtered zirconium oxynitride thin films doped with titanium

ZrTiON coatings were deposited by reactive magnetron sputtering process of a single Zr target, while Ti was added by placing Ti ribbons on the erosion track of the Zr sputtering target. The variation of parameters such as the number of Ti ribbons, the applied sputtering current, and the reactive gas flow led to obtaining different sample configurations. The coatings were analyzed in terms of chemistry (chemical composition and chemical states) by X-ray Photoelectron Spectroscopy, morphology by Atomic Force Microscopy, surface energy, photodegradation tests, electrochemical studies, and accelerated corrosion tests. It was found that the coatings show features of oxides, nitrides, and oxynitrides, depending on the deposition conditions applied. The photodegradation efficiency regarding methylene blue solutions under visible light varies between 58% and 96%, depending on the type of illuminant and the sample characteristics, while the lowest corrosion rate was exhibited by the reference samples deposited without the addition of Ti. The samples doped with Ti and deposited with 1.5 A sputtering current exhibited a more efficient photodegradation effect, compared to the reference ZrON sample. The accelerated corrosion tests showed that the coatings deposited with an applied current of 2 A behaved significantly better than the ones deposited with 1.5 A sputtering current after 8 h of exposure to the water vapor and sulfur dioxide gas atmosphere.

Tweaking the mechanical stability of Al1−xWxN ternary nitride alloys for hard coating applications, and study on their structural, photoluminescence and surface chemical analysis

This study focuses on the synthesis and achievement of ternary Al1−xWxN nitride films as hard coating materials. A dual-target DC reactive magnetron sputtering process was used to coat Al1−xWxN thin films on Si (100), glass, and transparent quartz substrates. The elemental analysis of the films was calculated by energy dispersion spectroscopy and the corresponding value of x changes from 0 to 1. The X-ray diffraction data showed a-axis orientation of the AlN films with hexagonal phase and amorphous nature for Al0.78W0.22N and Al0.58W0.42N films. Atomic force microscopy analysis showed that the surface morphology of Al0.78W0.22N films was better than that of AlN and Al0.3W0.7N films, as evidenced by the significantly lower root-mean-square roughness value of 1.79 nm compared to 5.78 and 13.9 nm, respectively. The resistivity of Al1−xWxN films was determined by a four-probe method and resulted in a record low value of 4.08 × 10−5 Ω-m for WN films. The photoluminescence emission spectra showed distinct peaks in the visible region at different wavelengths, and the deconvoluted blue emission peak was attributed to the native defects in the Al1−xWxN films. X-ray absorption spectroscopy data showed an increase in feature-a from Al0.78W0.22N to Al0.58W0.42N films, indicating stronger hybridization of N 2p with Al 3p and W 5d orbitals due to π * -resonance. The oxygen content calculated by X-ray photoelectron spectroscopy was 34.6, 35.39, and 19.74 at% on the surface of AlN, Al0.58W0.42N, and WN films, respectively. The surface oxidation of AlN films triggered the transfer of charge from nitrogen to oxygen on the surface of AlN films. The nanoindentation results showed that the Al0.3W0.7N films have hardness and elastic modulus of 17.84 GPa and 196.96 GPa, which are higher than those of the other Al1−xWxN films, while the AlN films have higher fracture toughness due to the reduction of contact pressure.

Characterization of Structural, Optical, Corrosion, and Mechanical Properties of HfO2 Thin Films Deposited Using Pulsed DC Magnetron Sputtering.

Various properties of HfO2, such as hardness, corrosion, or electrical resistance, depend on the method and the conditions of deposition. In this work, a thorough comparison of scarcely investigated mechanical properties of HfO2 thin films deposited with different conditions of reactive magnetron sputtering process is presented. Four thin films were sputtered in processes that varied in plasma ignition method (continuous or sequential) and target-substrate distance. The structural characteristics of the HfO2 thin films were examined using Raman spectroscopy and X-ray diffraction measurements. Furthermore, the optoelectronic properties were determined based on transmittance and current-voltage characteristics. The mechanical properties of the HfO2 thin films were determined using nanoindentation and scratch test. In turn, the corrosion properties were determined by analyzing the voltametric curves. The transparent HfO2 thin films deposited in the continuous process are characterized by better corrosion resistance than the same layer formed in the sequential process, regardless of the target-substrate distance (8 cm or 12 cm). Furthermore, these samples are also characterized by the highest value of Young's modulus and scratch resistance. The combination of good corrosion and scratch resistance could contribute to the new application of HfO2 as a corrosion protective material.

Evidence of 1000 eV positive oxygen ion flux generated in reactive HiPIMS plasma

The arrival of highly energetic (near 1000 eV) positive atomic oxygen ions at the substrate region has been detected in a unipolar reactive high-power impulse magnetron sputtering process operated with an uncooled copper target in argon–oxygen mixtures. Examination of the ion fluxes from discharge plasma was performed with a magnetic sector mass-spectrometer and an electrostatic energy analyzer. The energy of fast positive O+ ions is close to the value of eV d (e—elementary charge, V d—discharge voltage), which indicates their connection to the well-studied fraction of negative O− ions, which undergo acceleration in the cathode sheath. After switching the oxygen gas supply off, the flux of energetic O+ species decreases gradually as the poisoned target surface layers become depleted of oxygen due to sputtering in pure argon. Presumably, the observed energetic O+ ions originate as a result of low-angle scattering of fast negative O− ions from other charged or neutral species in the plasma followed by electron detachment, ionization, or charge exchange.

Materials Based on Amorphous Al2O3 and Composite W-Al2O3 for Solar Coatings Deposited by High-Rate Sputter Processes

In parabolic trough technology, the development of thermally and structurally stable solar coatings plays a key role in determining the efficiency, durability, and economic feasibility of tube receivers. A cermet-based solar coating is typically constituted by a thin film stratification, where a multilayer graded cermet is placed between an infrared metallic reflector and an antireflection filter. This work reports the realization of materials based on Al2O3 and W characterized by high structural and chemical stability in vacuum at high temperature, obtained through the optimization of high-deposition-rate processes. Al2O3 material, employed as the antireflection layer, was deposited through a reactive magnetron sputtering process at a high deposition rate. Cermet materials based on W-Al2O3 were deposited and employed as absorber layers by implementing reactive magnetron co-sputtering processes. An investigation into the stability of the realized samples was carried out by means of several material characterization methods before and after the annealing process in vacuum (1 × 10−3 Pa) at high temperature (620 °C). The structural properties of the samples were evaluated using Raman spectroscopy and XRD measurements, revealing a negligible presence of oxides that can compromise the structural stability. Spectrophotometric analysis showed little variations between the deposited and annealed samples, clearly indicating the high structural stability.

High-performance p-type transparent conducting CuI–Cu2O thin films with enhanced hole mobility, surface, and stability

We employed reactive magnetron sputtering and iodination process at room temperature to deposit CuI–Cu2O films with enhanced hole mobility, surface, and stability.

Enhancing ultraviolet response of NiO/Si heterojunction by high temperature anneal

In this work, NiO/Si heterojunction is fabricated by direct current reactive magnetron sputtering process and the effect of post anneal temperature on ultraviolet response of the heterojunction is investigated. The results indicate that the dark current is decreased and the light current is increased with annealing temperature increasing in the fabricated NiO/Si heterojucntion. When illuminated under 365 nm UV light with an intensity of 1.0 mW/cm2, the light to dark switch ratio of the fabricated NiO/Si heterojunction annealed at 800 °C is about 486.1. The corresponding ultraviolet response is enhanced by about 83.8 times compared to the heterojucntion without anneal. The switch-on and switch-off time of the 800 °C annealed NiO/Si heterojunction illuminated under 365 nm UV light are about 100 μs and 180 μs, respectively. It is expected that the NiO/Si heterojunction has enormous potential in multi-wavelength light detecting application.

Analysis of TihxOy Films Produced by Physical Vapor Deposition Method

For decades, partially oxidized hydrides were commonly considered as undesirably contaminated phases and were avoided by scientists. Nevertheless, more recently, it was realized that in some hydrides and oxides, partial substitution of dissimilar H− and O2− anions allows one to obtain unique optical and electrical properties that might have appealing applications in commercial products. It was determined that specific properties of so called oxyhydride materials strongly depend on the used synthesis methods; therefore, there is a great interest in exploring various variants of oxyhydride formation. In the current study, TiHxOy films were deposited by a reactive magnetron sputtering process in Ar-O2-H2 gas mixtures. Color, transparency and crystal phase composition of the films coherently reacted to the Ar:O2:H2 gas ratio. Namely, the rise in partial hydrogen pressure promoted the formation of anatase phase TiO2 structure and darkening of the films. Interestingly, this had only minimal impact on the band gap values, but had a relatively strong negative effect on the photocatalytic activity of the films. The unaccustomed results stressed the difference between the partially reduced TiO2 with a significant amount of oxygen vacancies and synthesized TiHxOy films where some O2− ions are implicitly substituted by H− ions.

High Rate Deposition of Piezoelectric AlScN Films by Reactive Magnetron Sputtering from AlSc Alloy Targets on Large Area.

This paper reports on the deposition and characterization of piezoelectric AlXSc1-XN (further: AlScN) films on Si substrates using AlSc alloy targets with 30 at.% Sc. Films were deposited on a Ø200 mm area with deposition rates of 200 nm/min using a reactive magnetron sputtering process with a unipolar–bipolar hybrid pulse mode of FEP. The homogeneity of film composition, structural properties and piezoelectric properties were investigated depending on process parameters, especially the pulse mode of powering in unipolar–bipolar hybrid pulse mode operation. Characterization methods include energy-dispersive spectrometry of X-ray (EDS), X-ray diffraction (XRD), piezoresponse force microscopy (PFM) and double-beam laser interferometry (DBLI). The film composition was Al0.695Sc0.295N. The films showed good homogeneity of film structure with full width at half maximum (FWHM) of AlScN(002) rocking curves at 2.2 ± 0.1° over the whole coating area when deposited with higher share of unipolar pulse mode during film growth. For a higher share of bipolar pulse mode, the films showed a much larger c-lattice parameter in the center of the coating area, indicating high in-plane compressive stress in the films. Rocking curve FWHM also showed similar values of 1.5° at the center to 3° at outer edge. The piezoelectric characterization method revealed homogenous d33,f of 11–12 pm/V for films deposited at a high share of unipolar pulse mode and distribution of 7–10 pm/V for a lower share of unipolar pulse mode. The films exhibited ferroelectric switching behavior with coercive fields of around 3–3.5 MV/cm and polarization of 80–120 µC/cm².

Growth of Highly c-Axis Oriented AlScN Films on Commercial Substrates.

In this work, we present a method for growing highly c-axis oriented aluminum scandium nitride (AlScN) thin films on (100) silicon (Si), silicon dioxide (SiO2) and epitaxial polysilicon (poly-Si) substrates using a substrate independent approach. The presented method offers great advantages in applications such as piezoelectric thin-film-based surface acoustic wave devices where a metallic seed layer cannot be used. The approach relies on a thin AlN layer to establish a wurtzite nucleation layer for the growth of w-AlScN films. Both AlScN thin film and seed layer AlN are prepared by DC reactive magnetron sputtering process where a Sc concentration of 27% is used throughout this study. The crystal quality of (0002) orientation of Al0.73Sc0.27N films on all three substrates is significantly improved by introducing a 20 nm AlN seed layer. Although AlN has a smaller capacitance than AlScN, limiting the charge stored on the electrode plates, the combined piezoelectric coefficient d33,f with 500 nm AlScN is only slightly reduced by about 4.5% in the presence of the seed layer.

Modeling current–voltage characteristics of DC reactive magnetron discharges and its application to superconducting NbTiN film deposition

A numerical model for simulating current–voltage characteristics (IVCs) of reactive magnetron discharges is developed. The model is built on the basis of equilibrium equations describing the steady state of reactive magnetron sputtering processes. This modeling technique allows an analytical expression of IVCs with a pair of parametric equations, which are computationally convenient. This approach is self-contained because some critical parameters that are not available from direct measurement can be determined by model fitting of measured IVCs. By using this IVC model, the dependence of various physical quantities on the discharge current and voltage can be systematically investigated. In addition, the conditions leading to hysteresis in IVCs are analyzed and clarified with this model. This modeling method is applied to a realistic case of superconducting NbTiN film deposition, and the simulation results suggest helpful guidance to the optimization of the plasma process for desired film quality and provide insight into the experimental phenomena.

Measurement of negative ion fluxes during DC reactive magnetron sputtering of Ti in Ar/O2 atmosphere using a magnetic-filtering probe

The flux of negative oxygen ions in a dc reactive magnetron discharge has been measured using a specially developed magnetic-filtering probe. The gridded probe which operates as a retarding field analyzer has a magnetic filter attached to the front entrance to suppress plasma electrons entering the device. As a result, the fluxes of unmagnetized negative ions with energies of higher than ~10 eV can arrive to an ion collector and contribute to the detected probe current. During the oxide mode of Ti–Ar/O2 magnetron sputtering discharge, the measured negative ion flux is considered to be contributed by the sputtered O− ions generated at the target surface and the plasma O− ions created in the discharge volume. However, in specific discharge conditions, the sputtered ions are likely to dominate in the measured flux signal. As a result, the yield of the sputtered O− ions and associated energy flux can be examined. The magnetic-filtering probe could potentially be employed as a real-time diagnostic tool to monitor the sputtered O− flux as well as the oxide state of the target surface during reactive magnetron sputtering processes.

Demonstration of lateral epitaxial growth of AlN on Si (1 1 1) at low temperatures by pulsed reactive sputter epitaxy

We present a pulsed reactive magnetron sputter process for high quality AlN on Si (111) beneficially avoiding any high-temperature growth. Initially, metallic aluminium with a nominal thickness of about one monolayer is deposited at a substrate temperature around 850 °C in an Ar plasma followed by sputtering in an Ar/N plasma. For 250 nm thick AlN layers a surface roughness below 0.2 nm rms is obtained as determined by atomic force microscopy (AFM). Using an Al nucleation step prior to AlN growth substantially improves the crystalline properties of AlN. The FWHM values of the AlN (0 0 0 2) and the AlN (1 0 1 0) diffraction peaks with 0.45° and 0.86°, respectively, are comparable to state-of-the-art AlN on Si layers grown by metalorganic vapour phase epitaxy (MOVPE). Two different N-precursor gases, namely N2 and NH3, lead to distinct layer qualities as revealed by atomic force microscopy and transmission electron microscopy. Only with NH3 substantial lateral growth can be achieved at T = 850 °C which is mandatory to obtain smooth surface morphologies. In MOVPE such lateral AlN growth is typically only achieved at high growth temperatures (T > 1000 °C).

High-temperature tribological performance of the Si-gradually doped diamond-like carbon film

Silicon containing diamond-like carbon films is of value for engineering applications operating at the temperature above 200 °C. This work presents a Si-gradually doped diamond-like carbon film with increasing the Si content from outer layer to inner layer deposited by plasma-assisted reactive magnetron sputtering process. The microstructure, chemical bonding state and temperature-dependence tribological properties upto 500 °C of the film are investigated by using focused ion beam/transmission electron microscope (FIB/TEM), X-ray photoelectron spectroscopy (XPS) techniques and ball-on-disk tribometer, respectively. The results show that the as-deposited Si-gradually doped DLC film exhibit amorphous structure. The wear track tested at 500 °C are composed of carbon, SiO2 and silicon oxide. High-temperature tribological tests show that the friction coefficient values are 0.05 ± 0.01, 0.02 ± 0.004 and 0.09 ± 0.04, while the wear rates are 1.17 × 10−7 mm3/N·m, 1.65 × 10−7 mm3/N·m and 1.4 × 10−6 mm3/N·m at 300 °C, 400 °C and 500 °C, respectively. It is proposed that the improved high-temperature tribological properties of the Si-gradually doped DLC film benefit from its special composition structure that the inner layer with high Si content provides the required mechanical properties and the outer layer with low Si content reduces the friction coefficient as well as the wear rate.

Nitride formation during reactive sputter deposition of multi-principal element alloys in argon/nitrogen mixtures

Nitrides based on multi-principal element alloys have been deposited by reactive magnetron sputtering from powder targets. All deposited nitrides were based on alloys of which the majority of the constituent metals have a low chemical affinity to molecular nitrogen (Co, Cu, Fe, Ni, Mn, and Zn). Some more reactive metals (Al, Cr, Ti, Mo, and V) were also added. The nitrogen incorporation in these alloys was investigated based on two different approaches. The incorporation efficiency is calculated based on the chemical composition of the deposited layer, and the metal flux towards the substrate. The calculations are based on a previous published model to simulate the reactive magnetron sputtering process. The observed trends are compared with results obtained from (energy resolved) mass spectrometry measurements. Both methods proof that the nitrogen incorporation is dominated by sputtered nitrogen from the (partially) poisoned target. The composition weighted electronegativity average of the alloy constituent elements is used to asses the target poisoning level. It is shown that this electronegativity average correlates with the incorporation efficiency. The nitrogen incorporated in these alloys is mainly atomic nitrogen which affects the texture development. In contrast to nitrides based on highly reactive metals such as Ti which exhibit a cubic 〈111〉 fiber texture, a cubic 〈001〉 fiber texture is observed for the studied alloys.

Filament-assisted reactive magnetron sputter deposition of VSiN films

Many vapor deposition techniques utilize ion irradiation during growth of transition metal nitride-based films to obtain low porosity and to control nanostructural evolution, phase content, and crystallographic texture. In this study, V1-xSixN films (0.18 ≤ x ≤ 0.30) were deposited by a reactive magnetron sputtering process in which a heated filament was used to enhance growth temperature and ion bombardment. Filament discharge current (0.0 A ≤ ID ≤ 2.6 A) and sputter target powers (PV = 500 W,250 W, PSi = 180 W,90 W) were varied among depositions. With filament-assistance, substrate current densities doubled relative to the current densities achieved without the filament. Atomic force microscopy, scanning electron microscopy, and electrical resistivity measurements indicated that the use of the hot filament reduced the porosity present in the deposited films. X-ray diffraction revealed that all VSiN films contained a single crystalline phase with a crystal structure and lattice spacing similar to NaCl-type VN. Texture coefficient calculations showed that increases in filament discharge current initially enhanced (111) texturing until, at the maximum filament discharge current, a mixed (111)/(200) texture was obtained. Film hardness and elastic modulus were measured using nanoindentation and found to scale with filament discharge current to maximum values of 16 GPa and 218 GPa, respectively. Rockwell indentation tests revealed that film adhesion decreased with increases in filament discharge current and film deposition rate. Telephone cord blisters were observed in films deposited at the highest filament discharge currents confirming that the ion irradiation conditions generated compressive residual stresses.