DC Reactive Magnetron Sputtering 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.

Synthesis and characterization of ceramic high entropy carbide thin films from the Cr-Hf-Mo-Ta-W refractory metal system

We use reactive DC magnetron sputtering to showcase synthesis strategies for multicomponent carbides with the NaCl-type fcc structure and illustrate how deposition conditions allow controlling the formation of metallic and ceramic single phases in the Cr-Hf-Mo-Ta-W system. The synthesis is performed in argon flow and different acetylene flows from 0 to 12sccm, at ambient and elevated temperatures (700 °C), respectively, hindering/promoting the adatom diffusion. Structural and microstructural investigations reveal the formation of the bcc metallic phase (a=3.188−3.209Å) in films deposited without acetylene flow, also supported by ab initio density function theory (DFT) analysis of lattice parameters as a function of the C content. Experimentally, a bcc-to-fcc phase transition is observed through the formation of an amorphous coating. Contrarily, samples deposited in higher acetylene flow show an fcc multielement carbide phase (a=4.33−4.49 Å). The crystalline films reveal columnar morphology, while the amorphous ones are very dense. We report promising mechanical properties, with hardness up to 25±1GPa. The indentation moduli reach up to 319±6GPa and show trends consistent with DFT predictions. Our study paves the path towards the preparation of Cr-Hf-Mo-Ta-W multicomponent carbides by magnetron sputtering, showing promising microstructure as well as mechanical properties.

Titanium oxynitride thin films by the reactive sputtering process with an independent pulsing of O2 and N2 gases

Titanium oxynitride thin films are deposited by DC reactive magnetron sputtering. A pure titanium target is sputtered in a reactive atmosphere composed of argon, oxygen and nitrogen gases. The oxygen mass flow rate as well as that of the nitrogen gas are both pulsed during the deposition time using an independent and rectangular signal for each reactive gas. A constant pulsing period T = 45 s is applied for both reactive gases and a delay time δ of 34 s between N2 and O2 injection times is set for all depositions. Oxygen and nitrogen duty cycles are systematically and independently changed from 0 to 100 % of their pulsing period. From real time measurements of the Ti target potential and total sputtering pressure, it is shown that the reactive process alternates between oxidized, nitrided and elemental sputtering modes as a function of the oxygen and nitrogen injection times. The full poisoning of the Ti target surface by oxygen and/or nitrogen can be avoided for some given ranges of O2 and N2 duty cycles. Deposition rates of titanium oxynitride films are substantially enhanced and can be adjusted between that of pure Ti and TiN films with a gradual transition of their electrical conductivity and optical transmittance in the visible range. These results support that titanium oxynitride compounds exhibiting absorbent to transparent behaviors can be precisely sputter-deposited by means of a two reactive gases pulsing process.

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.

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.

Engineering electrically tunable TiN/SiO2 epsilon-near-zero metamaterials

Electrically tunable TiN/SiO2/TiN epsilon-near-zero photonic structures with various parameters were fabricated using the reactive DC magnetron sputtering approach. Effective medium approximation was used to predict the optical permittivity of a multilayered TiN/SiO2 metamaterial and guide the design/fabrication. Experimental reflectance measurements for tunable TiN/SiO2/TiN structures were obtained using the ellipsometer technique in the visible and near-infrared spectral ranges. Results show that reflectance for biased (12 V) and un-biased bulk TiN/SiO2/TiN structure changes up to ∼ 2% with the spectral shift at the ENZ spectral point ∼ 10 nm for samples with an optimal SiO2 dielectric layer (thickness d=10 nm). Reflectance measurements for multilayered tunable TiN/SiO2/TiN structures show strong variation in reflectance change for s- polarized light at epsilon-near-zero wavelengths due to applied voltage (12 V). We expect that the results of this research study of the tunable TiN/SiO2/TiN epsilon-near-zero photonic structures will potentially be useful for the photonic density of states engineering, surface sensing, and metamaterial-based super-resolution imaging.

ScxAl1-xN piezoelectric film grown at room temperature

In order to overcome the shortcomings of AlN piezoelectric thin films such as low piezoelectric coefficient and low electromechanical coupling coefficientrealize, ScxAl1−xN thin films with CMOS process compatibility were prepared by pulsed DC reactive magnetron sputtering. High performance ScxAl1−xN piezoelectric thin films were prepared at room temperature by optimizing process parameters including power, gas flow ratio, substrate temperature, seed layers and so on. The phase separation phenomenon was investigated through XRD, TEM, and XPS. We found that the phase separation is related to the appearance of rocksalt ScN and led to the degeneration of film properties. The existence of ScN phase is a key factor affecting the performance of ScxAl1−xN. The results show that the piezoelectric constant d33 of ScAlN film achieved 27.5 pC/N and the full width at half maximum (FWHM) of the rocking curve is 1.9° in room temperature when the content of Sc reaches 35%.

Influence of Ar:O2 Mixing Ratio on Characteristics of Tio2 Nanostructured Thin Films Deposited by DC Reactive Magnetron Sputtering Method

Abstract: In this paper, titanium dioxide nanostructured thin films TiO2 were deposited on unheated glass substrates by applying the DC reactive magnetron sputtering method. Three TiO2 films were deposited using argon sputtering gas with different oxygen ratios: 10%, 25%, and 50%. The resulting films had thicknesses of 200, 184, and 140 nm, respectively. The structural, morphological, optical, and electrical properties of deposited thin films were studied. X-ray diffraction (XRD) data showed that the samples exhibited an amorphous phase. It was found from atomic force microscopy (AFM) that the deposited thin films had a nanostructure, and the heights of their nanograins were 16, 24, and 30 nm, respectively. It was observed from the root-mean-square height RMS values that the films had low roughness. The UV-Vis-NIR spectroscopy showed that the films become more transparent with the increase in oxygen content. The direct band gap ranged between 3.68 and 3.88 eV, while the indirect band gap ranged from 3.3 to 3.66 eV. The highest intensity photoluminescence emission was obtained for the film deposited at 50% O2. In addition, the impedance spectroscopy showed that the films’ resistance did not change with changing oxygen content. Keywords: Magnetron sputtering, Titanium dioxide, X-ray diffraction, Absorption spectra, Atomic Force Microscopy, Photoluminescence, Impedance.

Mechanical properties of Xe-ion-irradiated high-entropy-alloy-based multilayers

In this Letter, we investigate the mechanical stability of HEA-based multilayers after Xe-ion irradiation. CrFeCoNi/TiNbZrTa metallic and nitride thin films with a bilayer thickness of 30 nm were grown by reactive dc-magnetron sputtering on Al2O3(0001) substrates for irradiation studies and on Si(100) substrates for other characterizations. The films were subjected to 3-MeV Xe-ion irradiation at room temperature (RT) and at 500 °C. The crystal structure and mechanical properties of the films before and after irradiation were studied by x-ray diffraction and nanoindentation. Before irradiation, both the metallic and nitride multilayers displayed a lower hardness (7 and 20 GPa, respectively). Annealing at 500 °C for 150 min increased the hardness of the multilayer samples, but it also induced intermixing of elements between the sublayers of the metallic multilayer. Irradiation hardening was observed only in the metallic multilayer at room temperature. When comparing the effects of irradiation damage vs the effects of annealing on the mechanical properties, it was observed that annealing the multilayers had a more pronounced effect.

Microstructure, mechanical properties and tribological behavior of (TiZrHfNbTa)Nx high entropy films deposited by magnetron sputtering

High entropy nitride (HEN) films of (TiZrHfNbTa)Nx were deposited by reactive DC magnetron sputtering, choosing 304 stainless steel and silicon wafers as the experimental substrates. The influence of nitrogen flow rate RN: N2/(N2+Ar) on the microstructure and properties of HEN films was investigated. The results showed that HEN films exhibit granular surface morphologies and internal characteristics of amorphous embedded FCC crystals, exhibiting a structure of amorphous at the lower RN (0, 2 %) and transforming to FCC crystals with preferred (111) orientation as RN increasing (6.5%–26 %), with the decrease of crystallinity and the alteration of preferred orientation from (111) to (200) at the further increase of RN at 40 %. The introduction of nitrogen led to significant improvements of film hardness (>23 GPa) and modulus (>270 GPa). When RN = 13 %, the hardness is up to 30.7 GPa, and the modulus is 340 GPa at RN = 6.5 %. The as-deposited films exhibited excellent wear resistance, and the wear rate (6.65✕10−6mm3/Nm) was the lowest when RN = 2 %.

Annealing Temperature Effect on the Physical Properties of NiO Thin Films Grown by DC Magnetron Sputtering

AbstractNickel oxide is a promising material for transparent electronics applications. This semiconductor demonstrates the possibility of modifying its physical properties depending on the method of growth and subsequent processing. Here the effects of the discharge power are reported during reactive dc magnetron sputtering, as well as the modes of subsequent annealing of NiO films, on their structural, electrical, and optical properties. NiO films are annealed at various temperatures both in an oxygen‐containing environment and under vacuum conditions. Deposited NiO films have a polycrystalline structure with a preferred orientation (200) for the low discharge power mode and (111) for the high discharge power mode. However, obtained NiO films exhibit crystallinity improvement after annealing. The presence of both Ni2+ and Ni3+ oxidation states in the deposited films is found. In addition, it is shown that the relative carrier concentration (Ni3+/Ni2+ peak area ratio) can be controlled by choosing the NiO film preparation mode. The trend in this ratio corresponds to the trend in film conductivity and the number of free‐charge carriers. The deposited films are semitransparent, and the estimated optical bandgap of NiO is in the range from 3.50 to 3.74 eV.

One-step synthesis of photoluminescent nanofluids by direct loading of reactively sputtered cubic ZrN nanoparticles into organic liquids.

ZrN nanofluids may exhibit unique optoelectronic properties because of the matching of the solar spectrum with interband transitions and localized surface plasmon resonance (LSPR). Nevertheless, these nanofluids have scarcely been investigated, mainly because of the complexity of the current synthetic routes that involve aggressive chemicals and high temperatures. This work aims to validate reactive dc magnetron sputtering of zirconium in Ar/N2 as an environmentally benign, annealing-free method to produce 22 nm-sized, highly crystalline, stoichiometric, electrically conductive, and plasmonic ZrN nanoparticles (NPs) of cubic shape and to load them into vacuum-compatible liquids of different chemical compositions (polyethylene glycol (PEG), paraffin, and pentaphenyl trimethyl trisiloxane (PTT)) in one step. The nanofluids demonstrate LSPR in the red/near-IR range that gives them a bluish color in transmittance. The nanofluids also demonstrate complex photoluminescence behavior such that ZrN NPs enhance the photoluminescence (PL) intensity of paraffin and PEG, whereas the PL of PTT remains almost invariable. Based on DFT calculations, different energetic barriers to charge transfer between ZrN and the organic molecules are suggested as the main factors that influence the observed optoelectronic response. Overall, our study provides a novel approach to the synthesis of transition metal nitride nanofluids in an environmentally friendly manner, deepens the understanding of the interactions between ZrN and organic molecules, and unveils new optoelectronic phenomena in such systems.

Synthesis and study of photoelectrochromic and photocatalytic behavior of double-layer N-doped TiO2/Co3O4 configuration via DC reactive magnetron sputtering

Synthesis and study of photoelectrochromic and photocatalytic behavior of double-layer N-doped TiO2/Co3O4 configuration via DC reactive magnetron sputtering

Fabrication and characterization of sub-micron high current density NbN Josephson junctions for large-scale digital circuits

We have developed a fabrication process based on Chemical Mechanical Polishing (CMP) for the sub-micron NbN Josephson junctions on single-crystal MgO substrates. The NbN junctions were fabricated with epitaxial NbN/AlN/NbN trilayers deposited by reactive DC magnetron sputtering. The top electrode of the junction was exposed using CMP to contact the NbN wire without opening the submicron via through the dielectric. It has produced submicron NbN junctions with areas as small as 0.09 μm2. We have fabricated NbN tunnel junctions with a wide range of critical current density Jc. The NbN junctions show excellent Josephson tunneling characteristics, the gap voltage Vg is 5.8 mV and the quality factor Rsg/Rn is 12 for the junctions with a Jc of 10.7 kA/cm2, and Vg is 5.3 mV and Rsg/Rn is 4 for the junctions with a Jc of 150.5 kA/cm2. The 1000-junction arrays were fabricated and their I-V characteristics were measured, critical current uniformity was obtained and the standard deviation is about 5%. The high Jc sub-micron NbN junctions will be helpful in developing large-scale NbN SFQ circuits with high operating frequency.

The Influence of Nitrogen Flow on the Stoichiometric Composition, Structure, Mechanical, and Microtribological Properties of TiN Coatings.

Utilizing reactive DC magnetron sputtering method, TiN coatings were deposited on the silicon substrates at different nitrogen flows and powers. A study of the X-ray phase composition of the coatings was carried out. The stoichiometric composition of the coatings was determined using energy dispersive x-ray spectroscopy. The structure of the surface, cross-section, and thickness of the coatings were determined using scanning electron (SEM) and atomic force microscopy (AFM). A significant change in the surface structure of TiN coatings was established with changes in deposition power and nitrogen flow. SEM images of cross-sections of all coated samples showed that the formation of coatings occurs in the form of a columnar structure with a perpendicular orientation relative to the silicon substrate. The mechanical properties (elastic modulus E and microhardness H) of TiN coatings of the first group demonstrate a maximum at a nitrogen flow of 3 sccm and are 184 ± 11 GPa and 15.7 ± 1.3 GPa, respectively. In the second group, the values of E and H increase due to a decrease in the size of the structural elements of the coating (grains and crystallites). In the third group, E and H decrease. Microtribological tests were carried out in 4 stages: at a constant load, multi-cycle for 10 and 100 cycles, and with increasing load. The coefficient of friction (CoF) and specific volumetric wear ω depend on the roughness, topology, and mechanical properties of the resulting coatings. Fracture toughness was determined using nanoscratch and depends on the mechanical properties of TiN coatings. Within each group, coatings with the best mechanical and microtribological properties were described: in the first group-TiN coating at 3 sccm (with (29.6 ± 0.1) at.% N), in the second group-TiN coating at 2 sccm (with (40.8 ± 0.2) at.% N), and in the third group-TiN coating at 1 sccm (c (37.3 ± 0.2) at.% N).

Growth of Highly Oriented (VNbMoTaW)S2 Layers.

Compositional tunability, an indispensable parameter for modifying the properties of materials, can open up new applications for van der Waals (vdW) layered materials such as transition-metal dichalcogenides (TMDCs). To date, multielement alloy TMDC layers are obtained via exfoliation from bulk polycrystalline powders. Here, we demonstrate direct deposition of high-entropy alloy disulfide, (VNbMoTaW)S2, layers with controllable thicknesses on free-standing graphene membranes and on bare and hBN-covered Al2O3(0001) substrates via ultra-high-vacuum reactive dc magnetron sputtering of the VNbMoTaW target in Kr and H2S gas mixtures. Using a combination of density functional theory calculations, Raman spectroscopy, X-ray diffraction, scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy, we determine that the as-deposited layers are single-phase, 2H-structured, and 0001-oriented (V0.10Nb0.16Mo0.19Ta0.28W0.27)S2.44. Our synthesis route is general and applicable for heteroepitaxial growth of a wide variety of TMDC alloys and potentially other multielement alloy vdW compounds with the desired compositions.

Fabrication of high-critical current density Nb/Al-AlN/Nb junctions with an AlN barrier deposited by DC magnetron reactive sputtering

We have developed a process to fabricate submicron Nb/Al-AlN/Nb junctions using an AlN barrier layer deposited by DC magnetron reactive sputtering, a SiO2 cap-layer and Chemical Mechanical Polishing (CMP) were introduced in the process. Junctions of designed diameters of 0.5–3.0 μm with Jc ranging from 15 to 120 kA/cm2 were fabricated. Jc·t is exponentially dependent on the deposition time (t) of AlN. Nb/Al-AlN/Nb junctions showed lower subgap leakage current than Nb/Al-AlOx/Nb junctions in the high-Jc range. The uniformity of junction parameters over whole 4-inch wafer were also presented. The results indicate that the Nb/Al-AlN/Nb junction is an excellent candidate for superconducting digital applications.

Enhancing the Extinction Efficiency and Plasmonic Response of Bimetallic Nanoparticles of Au-Ag in Robust Thin Film Sensing Platforms

The extinction efficiency of noble metal nanoparticles (NPs), namely gold (Au) and silver (Ag), are dependent on their size and surrounding dielectric. Exploiting the Localized Surface Plasmon Resonance (LSPR) phenomenon, the composition and structure of the NPs might be tailored to achieve a configuration that optimizes their response (sensitivity) to environmental changes. This can be done by preparing a bimetallic system, benefiting from the chemical stability of Au NPs and the higher scattering efficiency of Ag NPs. To enhance the LSPR sensing robustness, incorporating solid supports in the form of nanocomposite thin films is a suitable alternative. In this context, the NPs composed of gold (Au), silver (Ag), and their mixture in bimetallic Au-Ag NPs, were grown in a titanium dioxide (TiO2) matrix using reactive DC magnetron sputtering. Thermal treatment at different temperatures (up to 700 °C) tuned the LSPR response of the films and, consequently, their sensitivity. Notably, the bimetallic film with Au/Ag atomic ratio 1 exhibited the highest refractive index sensitivity (RIS), with a value of 181 nm/RIU, almost one order of magnitude higher than monometallic Au-TiO2. The nanostructural analysis revealed a wide NP size distribution of bimetallic NPs with an average size of 31 nm, covering about 20% of the overall surface area. These findings underscore the significant potential of bimetallic film systems, namely AuAg-TiO2, in LSPR sensing enhancement.

Tuning the Refractive Index Sensitivity of LSPR Transducers Based on Nanocomposite Thin Films Composed of Noble Metal Nanoparticles Dispersed in TiO2

This work reports on the development of nanoplasmonic thin films consisting of Au, Ag, or Au-Ag nanoparticles dispersed in a TiO2 matrix and the optimization of the deposition parameters to tune their optical response. The thin films were produced by reactive DC magnetron sputtering of a Ti target with Au and/or Ag pellets placed on the erosion zone. The thicknesses (50 and 100 nm) of the films, the current density (75 and 100 A/m2) applied to the target (titanium), and the number of pellets placed on its surface were the deposition conditions that were used to tailor the optical (LSPR) response. The total noble metal content varied between 13 and 28 at.% for Au/TiO2 films, between 22 and 30 at.% for Ag/TiO2 films, and 8 to 29 at% for the Au-Ag/TiO2 systems with 1:1, 1:1.5, and 1:2 Au:Ag atomic ratios. After thermal annealing at 400 and 600 °C, LSPR bands were found for all films concerning the Au-TiO2 and Au-Ag/TiO2, while for Ag/TiO2, only for thin films with 28 and 30 at.% of Ag concentration. Refractive index sensitivity (RIS) was evaluated for Au and Au-Ag/TiO2 thin films. It was found that for bimetallic nanoparticles, the sensitivity can increase up to five times when compared to a monometallic nanoplasmonic system. Using Au-Ag/TiO2 thin films can decrease the cost of fabrication of LSPR transducers while improving their sensitivity.

Effect of Substrate Bias on the Microstructure and Properties of Non-Equimolar (AlCrSiTiZr)N Films with Different Cr/Zr Ratios Deposited Using Reactive Direct Current Magnetron Sputtering

To reduce the cost of tools operated in extreme environments, we developed films with excellent corrosion/oxidation resistance. Two high-entropy nitride films, (AlCrSi0.3TiZr)N and (AlCr1.5Si0.3TiZr0.5)N, were deposited using reactive DC magnetron sputtering under different substrate biases. The films exhibited a maximum hardness of 32.5 GPa ((AlCrSi0.3TiZr)N) and 35.3 GPa ((AlCr1.5Si0.3TiZr0.5)N) when deposited at −150 V, corresponding to 27 and 142% increases compared to those deposited at 0 V. This indicates that the bias strengthened (AlCr1.5Si0.3TiZr0.5)N (higher Cr/Zr ratio) more significantly. The enhancement of the mechanical properties was highly correlated with the interstitial point defects and densification of the film microstructures. The corrosion resistance of the films deposited on 6061 Al alloy substrate under different biases was tested in 0.1 M H2SO4. (AlCrSi0.3TiZr)N and (AlCr1.5Si0.3TiZr0.5)N displayed the lowest corrosion currents of 0.75 and 0.19 μA/cm2 when deposited at −100 and −150 V, respectively. These values are two orders of magnitude lower than that of the uncoated substrate. The (AlCr1.5Si0.3TiZr0.5)N film showed better oxidation resistance than the (AlCrSi0.3TiZr)N film and remained partially oxidized after heat treatment at 1000 °C. The (AlCr1.5Si0.3TiZr0.5)N film deposited at −150 V exhibits excellent mechanical properties and corrosion/oxidation resistances, making it suitable for protecting tools operating in harsh environments.