Reactive Magnetron Sputtering Research Articles

Elevating Platinum to Volumetric Capacitance: High Surface Area Electrodes through reactive Pt sputtering.

Platinum is the most widespread electrode material used for implantable biomedical and neuroelectronic devices, motivating exploring ways to improve its performance and understand its fundamental properties. Using reactive magnetron sputtering, we prepare PtOx, which upon partial reduction yields a porous thin-film form of Platinum with favorable properties, notably record-low impedance values outcompeting other reports for platinum-based electrodes. We establish that its high electrochemical capacitance scales with thickness, in the way of volumetric capacitor materials like IrOx and poly(3,4-ethylenedioxythiophene), PEDOT. Unlike these two well-known analogs, however, we find that PtOx capacitance is not caused by reversible pseudofaradaic reactions but rather due to high surface area. In contrast to IrOx, PtOx is not a reversible valence-change oxide, but rather a porous form of platinum. Our findings show that this oxygen-containing form of Pt can place Pt electrodes on a level competitive with IrOx and PEDOT. Due to its relatively low cost and ease of preparation, PtOx can be a good choice for microfabricated bioelectronic devices. This article is protected by copyright. All rights reserved.

Enhancement of hole mobility in high-rate reactively sputtered Cu2O thin films induced by laser thermal annealing

In presented work, a reactive high-power impulse magnetron sputtering (r-HiPIMS) was used for high-rate deposition (≈ 170 nm/min) of Cu2O films. Films were deposited on a standard soda-lime glass (SLG) substrate at a temperature of 190 °C. As-deposited films exhibit poor hole mobility in the orders of ≈ 1 cm2/Vs. We have systematically studied the effect of laser thermal annealing (LTA) procedure performed using high-power infrared laser under different laser parameters (number of pulses, length of the pulse). We have found, LTA procedure could significantly enhance the hole mobility (up to 24 cm2/Vs in our case). We have also fitted the results of a temperature-dependent Hall measurement to clarify the mechanism of the reported increase in hole mobility. Moreover, we have discussed the effect of the LTA procedure on microstructure (crystallinity, surface morphology) and on the value of optical band gap.

Ultrafast UV Luminescence of ZnO Films: Sub‐30 ps Decay Time with Suppressed Visible Component

AbstractUltrafast sub‐100 picosecond luminescence is vital in many applications involving ultrafast events and time‐of‐flight systems. Materials exhibiting fast luminescence, such as barium fluoride (BaF2) and zinc oxide (ZnO), also suffer from an intrinsically slow nanosecond (ns) to microsecond (µs) luminescence. Here, 2.2 micrometer (µm)‐ to 5.7 µm‐thick undoped ZnO films on soda‐lime glass (SLG) substrates without a buffer layer by a hybrid pulsed reactive magnetron sputtering operating in the medium‐frequency range (MF magnetron) assisted by an electron cyclotron wave resonance (ECWR) plasma is deposited. The undoped ZnO films exhibited superior optical properties characterized by intense ultraviolet (UV) luminescence, unprecedented ultrafast decay times, and for the case of MF+ECWR‐deposited films, suppressed defect‐related visible luminescence. The 2.2 µm‐thick MF‐deposited film exhibited the fastest 9‐ps decay time at room temperature. The impressive properties of the films are attributed to the use of advanced deposition technology with properly tuned plasma parameters, especially a high degree of dissociation of molecular oxygen together with an increased proportion of activated zinc particles, leading to a higher deposition rate, better crystallinity, fewer defects, and a lower proportion of oxygen vacancies. These films will pave the way toward the development of time‐of‐flight detectors, high‐resolution nuclear imaging cameras, and high‐rate ultrafast timing devices.

Impact of blocking layers based on TiO2 and ZnO prepared via direct current reactive magnetron sputtering on DSSC solar cells

The optimization of dye-sensitized solar cells (DSSCs) technology towards suppressing charge recombination between the contact and the electron transport layer is a key factor in achieving high conversion efficiency and the successful commercialization of this type of product. An important aspect of the DSSC structure is the front blocking layer (BL): optimizing this component may increase the efficiency of photoelectron transfer from the dye to the semiconductor by reduction charge recombination at the TiO2/electrolyte and FTO/electrolyte interfaces. In this paper, a series of blocking layer variants, based on TiO2 and ZnO:TiO2, were obtained using the reactive magnetron sputtering method. Material composition, structure and layer thickness were referred to each process parameters. Complete DSSCs with structure FTO/BL/m-TiO2@N719/ EL-HSE/Pt/FTO were obtained on such bases. In the final results, verification of opto-electrical parameters of these cells were tested and used for the conclusions on the optimal blocking layer composition. As the conclusion, application of blocking layer consists of neat TiO2 resulted in improvement of device efficiency. It should be noted that for TiO2:ZnO/CuxO and TiO2/CuxO cells, higher efficiencies were also achieved when pure TiO2 was used as window layer. Additionally it was proven that the admixture of ZnO phase inspires Voc and FF growth, but is overall unfavorable compared to pristine TiO2 blocking layer and the reference cell, according to the final cell efficiency.

Copper tantalum nitride (CuTaN2) thin films prepared by reactive radio-frequency magnetron sputtering

RF reactive sputtering was used to deposit copper tantalum nitride (CuTaN2) films from a Cu/Ta target in an environment containing a mixture of argon and nitrogen at two different substrate temperatures: room temperature and 200 °C. The films were studied by SEM, EDS, XRD, Raman spectroscopy, spectrophotometry, and resistivity measurements. The deposition conditions significantly impacted the morphology of the films, which varied from smooth, void-free films at high nitrogen concentrations and at room temperature substrates to cauliflower-like grains with voids at low nitrogen contents and elevated substrate temperatures. Despite the target’s 1:1 Cu: Ta ratio, the stoichiometric analysis showed a lower Ta content in the deposited film. The films produced on silicon substrates were polycrystalline, whereas those deposited on glass substrates were amorphous. The band gap (0.9 eV to 1.55 eV) and film resistivity (20 kΩ-cm to 76 kΩ-cm) are strongly affected by the nitrogen fraction in the sputtering gas. Increasing the nitrogen percentage in semiconductor films results in smoother films with larger bandgaps (approximately 1.5 eV), higher resistivity, and compositions closest to those of stoichiometric CuTaN2.

Toughness enhancement in TiN/Zr0.37Al0.63N1.09 multilayer films

The hardness and fracture toughness of high-temperature wear-resistant transition metal aluminum nitride multilayer films depend largely on the constituting layer's structure, compositional modulation, morphology, and interface coherency. We present a study on 1-micron thick multilayered films consisting of stacked layers of TiN and Zr0.37Al0.63N1.09, each layer being 10 nm thick. The films were grown using ion-assisted reactive magnetron sputtering on MgO(001) and Si(001) at substrate temperatures ranging from ambient to 900°C. By increasing growth temperature, we found that the ZrAlN layers transition from near amorphous to nanocrystalline wurtzite to decomposed c-ZrN and w-AlN domains. Concurrently, the TiN layers exhibit strong fiber texture, polycrystallinity, and epitaxial growth carried by the ZrN domains. Both hardness and fracture stress, evaluated by nanoindentation and micromechanical tests, increase with temperature from H=24 GPaMgO, 23 GPaSi to 36 GPaMgO, 30 GPaSi, and σFSi= 6.1-7.7 GPa, respectively. An improved fracture toughness of KIC=2.4-2.8 MPa√m is related to different toughening mechanisms for the various microstructures. The difference in hardness between the substrates is related to compressive stress due to the deposition conditions and thermal contraction. The superior fracture stress is attributed to dense multilayers, free from macroscopic defects due to ion-assisted growth. After being deposited at 200°C, the multilayers remained thermally stable when vacuum annealed for 15 hours at 900°C, with no significant change in phase composition or hardness. The improved hardness, toughness, and temperature stability of the otherwise brittle nitrides are promising for industrial applications.

High-performance self-powered UV photodetectors using SnO2 thin film by reactive magnetron sputtering

Self-powered UV photodetector (UVPD) operates without the need for an external energy source and contributes to global energy conservation. With ongoing innovation, self-powered PDs are becoming increasingly appealing for industrial and innovation applications such as advanced environmental monitoring and communication devices. This study investigates the influence of varying working pressures (ranging from 3 to 15 mTorr) during reactive magnetron sputtering on the crystalline structure, surface morphology, and performance of SnO2 thin film photodetectors, aiming to fabricate self-powered UVPDs. The SnO2-based UVPD demonstrates exceptional self-powered UV photodetection capabilities, characterized by a sensitivity of 6.41×105%, responsivity of 0.09 mA/W, and detectivity of 2.99×1010 Jones. In addition, SnO2-based UVPD possesses a switching photo response and recovery time of 0.75 and 0.99 s. Henceforth, it was observed that 8 mTorr SnO2 thin film exhibits exceptional stability, superior photodetector performance, and remarkable repeatability, rendering them highly suitable for UVPD applications. Notably, these films demonstrate sustained functionality for approximately 100 days without necessitating encapsulation. These excellent results confirm that SnO2 thin films are suitable for fabricating future smart optoelectronics devices.

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.

Durability enhancement of all-solid-state electrochromic devices by adjusting the charge density ratio between electrochromic and counter electrode layers

Owing to an increase in global warming, smart-window devices based on charge-balanced electrochromic devices (ECDs), which exhibit high potential to increase the thermal efficiency of buildings, have gained prominence. However, studies on the fabrication and cycling stability of charge-balanced ECDs are scarce. In this study, WO3 and NiOx films were deposited on indium–tin–oxide (ITO)-coated glass substrates by reactive direct-current magnetron sputtering, and the deposition time was varied to control the thickness and charge density of the thin films. Subsequently, the NiOx/ITO/glass and WO3/ITO/glass substrates were laminated with a Li-based polymeric electrolyte to fabricate all-solid-state ECDs comprising electrochromic (EC) and counter-electrode (CE) layers in charge-density ratios of 12.6, 6.4, 2.3, and 1.1. Changes in the electrochromic properties, device-layer microstructure, crystal structure, and elemental composition of the as-constructed ECDs before and after degradation were investigated to understand the influence of the charge-density ratio of the EC and CE layers on the long-term durability of ECDs. Increasing the charge-density ratio decreased the cycling stability of the device owing to changes in the microstructure and crystal structure of the NiOx layer in the microstructural deep-trap sites. Among all the ECDs, those comprising EC and CE layers with similar charge densities showed the most stable optical modulation and highest long-term durability. Finally, based on the aforementioned results, a degradation mechanism for charge-imbalanced all-solid-state ECDs was proposed. This study is expected to open new frontiers in designing optimal-performance electrochemical devices with a wide variety of potential applications.

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.

Changes in chemical composition of TixAl1−xN coatings immersed in oxygen-saturated Lead–Bismuth Eutectic at low and moderate temperatures (250 °C ≤ T ≤ 410 °C)

Lead–Bismuth Eutectic (LBE) will serve as a liquid metal coolant in accelerator-driven systems, posing a corrosive threat to exposed materials. To address this challenge, TixAl1-xN coatings (0.38 ≤ x ≤ 0.58) were applied onto AISI 316 L austenitic stainless steel using the reactive bipolar magnetron sputtering technique. These coated samples underwent immersion in static oxygen-saturated LBE at temperatures of 250 °C and 360 °C for durations of 500 h and 1000 h, and at 410 °C for 500 h. XPS depth profiles revealed minimal oxidation at 250 °C even after 1000 h. However, at 360 °C, a mixed oxide layer of (Ti, Al)Ox was formed on the coating's surface. Exposure to LBE at 410 °C for 500 h led to the creation of an oxide bilayer comprising TiO2 (outer sublayer) and (Ti, Al)Ox depleted of Ti (inner sublayer). A model is proposed to illustrate the oxidation mechanism.

Plasma emission spectroscopy and optical properties of reactive-sputtered silicon oxynitride films

Silicon oxynitride (SiO x N y ) thin films were synthesized via reactive direct current magnetron sputtering under different reactive gas mass flow ratios (O2:N2) and discharge powers. The process was monitored by optical emission spectroscopy (OES), while spectroscopic ellipsometry was used to characterize the optical properties of the thin films and deposition rates. In this work, the plasma generated under different deposition parameters is analyzed by monitoring the emission lines of different species (Si I, Ar I, O2, and N2) and these results are then correlated with the corresponding target poisoning process and the optical properties of the grown thin films. According to the spectral analysis, the emission lines proved to be sensitive to the synthesis process as it was possible to differentiate deposition variations when other parameters remained unchanged. Furthermore, similar plasma conditions determined via the emission of different species were found to produce consistent thin film optical properties and vice versa. OES showed to be an effective method of monitoring and controlling the deposition of SiO x N y thin films with specific compositions.

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.

Deposition of Fe2O3:Sn semiconducting thin films by reactive pulsed HiPIMS + ECWR co-sputtering from Fe and Sn targets

Semiconducting Fe2O3 thin films were deposited on SnO2:F (FTO) and Pt substrates by reactive high-power impulse magnetron sputtering combined with electron cyclotron wave resonance plasma (HiPIMS + ECWR). Fe2O3 films were fabricated either by sputtering from a single Fe target or by co-sputtering from an additional Sn target. Plasma parameters during co-sputtering were measured by an RF probe system enabling the comparison between HiPIMS + ECWR and only HiPIMS conditions used for the film deposition. As deposited Fe2O3 films were post-annealed in air at 450 °C and 650 °C, respectively. It was shown that as deposited Fe2O3 films were amorphous but became crystalline after post-annealing at 450 °C. Further increase of annealing temperature to 650 °C did not improve significantly the crystalline structure of the Fe2O3 film. All post-annealed Fe2O3 films exhibited photocurrents in the anodic region; generally, hematite films annealed at 650 °C exhibited higher photocurrents than those annealed at 450 °C. Films doped by Sn co-sputtering had higher photocurrents than films only doped by Sn diffusion during post-annealing from the FTO substrate. Hematite films on Pt substrate doped by Sn co-sputtering and post-annealed at 650 °C exhibited the highest photocurrents. It was verified by XPS analysis with ion sputtering depth profiling that Pt atoms also diffuse from the Pt substrate into the Fe2O3 film during the post-annealing at 650 °C and can, similar to Sn in the case of an FTO substrate, act as a dopant.

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.

Microstructure evolution and mechanical properties of refractory high-entropy alloy nitride film

The (TiZrNbMo)Nx refractory high-entropy alloys (RHEAs) nitride films were fabricated using reactive magnetron sputtering by modifying the N2 flow rate ratio in the mixed N2 + Ar atmosphere. The incorporation of the N element induced a phase transition in the (TiZrNbMo)Nx films from body-centered cubic (BCC) to face-centered cubic (FCC) structure, accompanied by increasing in the amorphous phase. With the introduction of N2, the hardness of (TiZrNbMo)Nx films firstly increased significantly to 25.2 GPa when the N2 flow rate ratio was at 50 % and then decreased slightly to 18.5 GPa when the N2 flow rate ratio was at 75 %. Theoretical analysis shows that the doping of N element enhances the solid strengthening effect, with the formation of nitride phases and grain boundary (GB) strengthening effect significantly contributing to the enhanced hardness. Furthermore, the addition of N element can also inhibit grain rotation and GB sliding during deformation. This work provides a new insight into understanding the structure and properties of refractory high-entropy alloy films.

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.

Tailoring the mechanical and high‐temperature tribological properties of Si‐DLC films by controlling the Si content

The poor high‐temperature tribological performance of diamond‐like carbon (DLC) films severely limits their applications. To address this issue, silicon (Si) doped DLC films with Si content ranging from 0 to 11.52 at.% were synthesized utilizing the plasma‐assisted reactive magnetron sputtering technique. The influence of Si incorporation on the microstructure and mechanical properties was meticulously investigated by Raman spectroscopy, scanning electron microscope (SEM), X‐ray photoelectron spectroscopy (XPS), nanoindentation, and scratch testing. To ascertain the tribological behavior of the Si‐DLC films under elevated temperature conditions, in situ high‐temperature tests were conducted, spanning temperatures from ambient to 500°C. The findings indicated that distinct lubrication mechanisms prevail for Si‐DLC films with varying Si content across different temperature domains. As the test temperature and Si content increased, the lubrication mechanism exhibited a gradual transitions from high‐temperature induced graphitization to a particle wear regime dominated by SiC and formed SiO2 abrasive phases. The comprehensive performance of the films peaked at a Si content of 4.72 at.%, suggesting an optimal composition for high‐temperature applications. It is postulated that the in‐depth investigation presented herein holds considerable value for the design and fabrication of DLC films intended for use in high‐temperature settings, potentially unlocking their full potential in such demanding environments.

Ultrahigh-reflective optical thin films prepared by reactive magnetron sputtering with RF-induced substrate bias.

Optical thin films with high-reflectivity (HR) are essential for applications in quantum precision measurements. In this work, we propose a coating technique based on reactive magnetron sputtering with RF-induced substrate bias to fabricate HR-optical thin films. First, atomically flat SiO2 and Ta2O5 layers have been demonstrated due to the assistance of radio-frequency plasma during the coating process. Second, a distributed Bragg reflector (DBR) mirror with an HR of ∼99.999 328% centered at 1397nm has been realized. The DBR structure is air-H{LH}19-substrate, in which the L and H denote a single layer of SiO2 with a thickness of 237.8nm and a single layer of Ta2O5 with a thickness of 171.6nm, respectively. This novel coating method would facilitate the development of HR reflectors and promote their wide applications in precision measurements.