Reactive Sputtering Research Articles

Effect of Reactive Magnetron Sputtering Modes (DCMS, HIPIMS, and DC + HIPIMS) on the Properties of Copper Oxide Films

Effect of Reactive Magnetron Sputtering Modes (DCMS, HIPIMS, and DC + HIPIMS) on the Properties of Copper Oxide Films

Studies on high quality GaN/AlN deposited on glass substrates by radio-frequency reactive sputtering

Studies on high quality GaN/AlN deposited on glass substrates by radio-frequency reactive sputtering

Design and Scalable Synthesis of Thermochromic VO2-Based Coatings for Energy-Saving Smart Windows with Exceptional Optical Performance.

We report strongly thermochromic YSZ/V0.855W0.018Sr0.127O2/SiO2 coatings, where YSZ is Y-stabilized ZrO2, prepared by using a scalable deposition technique on standard glass at a low substrate temperature of 320 °C and without any substrate bias voltage. The coatings exhibit a transition temperature of 22 °C with an integral luminous transmittance of 63.7% (low-temperature state) and 60.7% (high-temperature state) and a modulation of the solar energy transmittance of 11.2%. Such a combination of properties, together with the low deposition temperature, fulfills the requirements for large-scale implementation on building glass and has not been reported yet. Reactive high-power impulse magnetron sputtering with a pulsed O2 flow feedback control allows us to prepare crystalline W and Sr codoped VO2 of the correct stoichiometry. The W doping of VO2 decreases the transition temperature, while the Sr doping of VO2 increases the luminous transmittance significantly. A coating design utilizing second-order interference in two antireflection layers is used to maximize both the integral luminous transmittance and the modulation of the solar energy transmittance. A compact crystalline structure of the bottom YSZ antireflection layer further improves the VO2 crystallinity, while the top SiO2 antireflection layer provides also the mechanical and environmental protection for the V0.855W0.018Sr0.127O2 layer.

Electrochemical Behavior of Tantalum Nitride Protective Layers for PEMFC Application

Proton Exchange Membrane Fuel Cells (PEMFCs) are promising technology to convert chemical energy from dihydrogen in electrical energy. HT-PEMFCs are working at high temperatures (above 120 °C) and with doped orthophosphoric acid H3PO4 PBI membranes. In such devices, bipolar metallic plates are used to provide reactive gas inside the fuel cell and collect the electrical current. The metallic elements used as bipolar plates, end plates, and interconnectors in acid electrolyte and gaseous fuel cells are severely damaged by a combination of oxidation (due in particular to the use of oxygen, whether pure or contained in the air) and corrosion (due in particular to acid effluents from the electrolyte). This degradation rapidly leads to the loss of the electrical conductivity of the metallic elements and today requires the use of very specific alloys, possibly coated with pure gold. The solution investigated in the present study is the use of a protective coating based on single-phase nitrides obtained by reactive magnetron sputtering or reactive HiPIMS (High-Power Impulse Magnetron Sputtering). The influence of the microstructure on the physical–chemical properties was studied. The electrochemical properties were quantified following two approaches. First, the corrosion current of the developed coatings was measured at room temperature and at higher temperatures using the Linear Sweep Voltammetry (LSV) technique. Then, Electrochemical Impedance Spectroscopy (EIS) measurements were performed to better identify and evaluate their corrosion-resistance performances.

Enhancing Conductivity of Nickel Oxide to Achieve Scalable Preparation for High-Efficiency Perovskite Solar Modules

NiOx, prepared via the sputtering method, exhibits low conductivity and energy level mismatch with the perovskite layer, thereby limiting further enhancements in the performance of perovskite solar modules (PSMs). Unlike traditional methods that enhance the performance of NiOx through reactive sputtering or directly doping NiOx targets with metal ions, both of which incur high costs and low efficiency, we employ an evaporation method using LiF to achieve efficient and low-cost doping of NiOx. Compared to the pristine NiOx, the incorporation of LiF significantly increases the conductivity of NiOx. Additionally, the incorporation of LiF enhances the quality of the deposited perovskite films, as well as the energy level alignment and symmetry between NiOx and the perovskite, effectively improving the hole extraction and transport capabilities between NiOx and the perovskite. As a result, the PSM (active area of 57.30 cm²) fabricated in air achieves an impressive efficiency of 19.54%. Furthermore, the unencapsulated PSM retains 80% of its initial efficiency after 700 h of continuous illumination, whereas the NiOx-based PSM drops to 80% after only 150 h. This study provides a simple and low-cost method for doping NiOx, which is of great significance for the further industrialization of PSMs.

Technological solutions for applying special coatings to increase wear resistance of machine parts and components

Subject of research: technology for applying alloyed diamond-like coating (DLC), the influence of the atmosphere of the working area on the results of work. Purpose of research: search for the optimal alloyed diamond-like coating for loaded parts of a car transmission in order to ensure the required service life of the unit. Methods of research: all coatings, the research results of which are described in this article, were obtained by reactive magnetron sputtering. Main results of research: an analysis of the structural-phase state of a number of coatings is provided: containing chromium, titanium and silicon, obtained by magnetron sputtering in argon-acetylene-nitrogen atmospheres. Data are presented on the phase composition and size of coherent scattering regions, as well as the relationship between the structure and mechanical properties of the APP. A basic scheme for tribological testing of coatings has been determined, and the obtained nanocomposite structures of the APP are analyzed.

Photocatalysis, wettability and optical properties of N-doped Cu2O/CuO thin films for smart coating applications

Abstract Undoped and nitrogen (N)_doped Cu2O/CuO thin films were deposited via reactive DC magnetron sputtering. The deposition was carried out by sputtering the Cu targets under various Ar/N2/O2 gas flow ratios. The structural, optical, wettability, and photocatalytic performance of the deposited films were investigated. A simple cubic Cu2O crystallographic phase is observed for the undoped film, whereas mixed cubic Cu2O and monoclinic CuO phases (Cu2O/CuO) are observed for the N_doped films. EDAX revealed that as the N2 flow rate increased the amount of nitrogen incorporated into the film increased. The transmittance and reflectance are affected by the incorporation of nitrogen into the films. The transmittance values decreased with increasing N2 flow rate, whereas the reflectance values increased. Both the refractive index and extinction coefficient almost increased with increasing N2 flow rate. A noticeable optical band gap narrowing from 2.55 eV to 2.39 eV was detected upon increasing the N2 flow from 0.0 to 190 sccm. The photoluminescence spectrum of the undoped sample contains five distinct bands at 518, 612, 654, 714 and 825 nm. These five maxima are attributed to the radiative decay of bound and free excitons, and oxygen vacancies (VO) After nitrogen incorporation, the photoluminescence intensity decreases and then increases again with increasing N2 flow rate. A reduction in the water contact angle was observed with increasing N2 flow rate. Upon Vis-light illumination, the N_doped Cu2O/CuO films reached superhydrophilicity faster than the undoped film did. The photocatalytic performance of the deposited Cu2O/CuO films was strongly enhanced with a small amount of N doping. The deposited films are promising for self-cleaning and photocatalytic degradation of organic wastes.

Enhancing the Wear Performance of 316L Stainless Steel with Nb2O5 Coatings Deposited via DC Sputtering at Room Temperature under Varied Environmental Conditions

Niobium-based oxides have garnered increased attention in recent years for their remarkable enhancement of corrosion resistance, as well as biofunctional properties of various metallic materials, including 316L SS. However, the mechanical properties of these promising coatings have not been fully elucidated. This study investigated how much the environmental conditions (air, artificial saliva, and NaCl solution) impact the wear performance of 316L SS without and with Nb2O5 coatings deposited via the reactive sputtering technique. The results exhibited a notable decrease in friction coefficient (55% in air, 18% in artificial saliva, 10% in 0.9 wt% NaCl solution), wear area (46% in air, 36% in AS, 17.5% in 0.9 wt% NaCl solution), and wear rate (44.0% in air, 19.5% in AS, 12.0% in 0.9 wt% NaCl solution). Ultimately, the results obtained in the present study elucidate the synergistic mechanisms of corrosion and wear in 316L SS containing Nb2O5 coatings, highlighting its significant potential for applications in the biomedical sector.

Acoustoelectric Effect due to an In-Depth Inhomogeneous Conductivity Change in ZnO/Fused Silica Substrates

The acoustoelectric (AE) effect induced by the absorption of ultraviolet (UV) light at 365 nm in piezoelectric ZnO films was theoretically and experimentally studied. c-ZnO films 4.0 µm thick were grown by the RF reactive magnetron sputtering technique onto fused silica substrates at 200 °C. A surface acoustic wave (SAW) delay line was fabricated with two split-finger Al interdigital transducers (IDTs) photolithographically implemented onto the ZnO-free surface to excite and reveal the propagation of the fundamental Rayleigh wave and its third harmonic at about 39 and 104 MHz. A small area of a few square millimeters on the surface of the ZnO layer, in between the two IDTs, was illuminated by UV light at different light power values (from about 10 mW up to 1.2 W) through the back surface of the SiO2 substrate, which is optically transparent. The UV absorption caused a change of the ZnO electrical conductivity, which in turn affected the velocity and insertion loss (IL) of the two waves. It was experimentally observed that the phase velocity of the fundamental and third harmonic waves decreased with an increase in the UV power, while the IL vs. UV power behavior differed at large UV power values: the Rayleigh wave underwent a single peak in attenuation, while its third harmonic underwent a further peak. A two-dimensional finite element study was performed to simulate the waves IL and phase velocity vs. the ZnO electrical conductivity, under the assumption that the ZnO layer conductivity undergoes an in-depth inhomogeneous change according to an exponential decay law, with a penetration depth of 325 nm. The theoretical results predicted single- and double-peak IL behavior for the fundamental and harmonic wave due to volume conductivity changes, as opposed to the AE effect induced by surface conductivity changes for which a single-peak IL behavior is expected. The phenomena predicted by the theoretical models were confirmed by the experimental results.

Performance evaluation of p-type Cr2O3 thin films grown by reactive DC magnetron sputtering for Schottky diode applications

Abstract In this study, we present a comprehensive investigation into the impact of combined oxygen and argon flow rates on the physical properties of Cr2O3 thin films produced via reactive DC magnetron sputtering. Additionally, we explore the influence of oxygen flow rate on various aspects, including structural, morphological, optical, chemical, and electrical characteristics of the sputtered Cr2O3 thin films. Our analysis, based on XRD results, reveals the polycrystalline nature of the films. Surface morphology was examined through scanning electron microscopy. Optical analysis indicates a band gap ranging from 2.70 eV to 2.99 eV for the films. X-ray photoelectron spectroscopy analysis shows the splitting of Cr 2p core spectra into Cr 2p3/2 and Cr 2p1/2 domains within the range of 573 eV to 585 eV, alongside the presence of satellite peaks. Moreover, extracted electrical properties reveal the p-type conductivity of the deposited Cr2O3 thin film under various oxygen flow rates. Furthermore, we fabricate and characterize an ITO/p-Cr2O3/Al Schottky diode to provide additional insights into p-Cr2O3/Al Schottky diodes. Overall, this study contributes valuable insights and enhances our understanding of Cr2O3 thin film properties, particularly in the context of semiconductor devices like Schottky diodes.

Impact of Deposition Temperature on Structural and Electrical Properties of Sputtered AlN/ Si (111) for CMOS compatible MEMS

Aluminium nitride (AlN) thin films are grown by reactive sputtering on Silicon (Si) with (111) orientation at low temperature (< 450 °C) for piezoelectric-based micro-electromechanical systems (MEMS). The grown AlN thin films were polycrystalline wurtzite hexagonal structure with a high texture coefficient for the (002) plane of orientation. The leakage current density by the current-voltage (I-V) measurement was found to be as low as 1.6 ×10-6Acm−2 in the grown films. The trapped charges are crucial in controlling these electrical characteristics, and low interface trap density (6.72 ×1010cm−2 eV) was observed for the sputtered AlN grown at a substrate temperature of 300 °C. This study on the structural and electrical properties of AlN/Si (111) at low substrate temperature is compatible with the complementary metal oxide semiconductor (CMOS) process for constructing piezoelectric-based MEMS devices for various applications.

Enhancement of optoelectronic properties of Vanadium nitride/porous silicon heterojunction photodetector prepared by electrochemical etching and reactive DC sputtering

Enhancement of optoelectronic properties of Vanadium nitride/porous silicon heterojunction photodetector prepared by electrochemical etching and reactive DC sputtering

Compositional changes between metastable SnO and stable SnO2 in a sputtered film for p-type thin-film transistors

p-Type tin(II) oxide (SnO (Sn2+)) formation using radiofrequency (RF) reactive magnetron sputtering and post-deposition annealing (PDA) processes was investigated. The as-grown SnOx film deposited from an SnOx (SnO:Sn = 60:40) target by RF sputtering at an oxygen partial pressure (PO2) of 0 Pa consisted of 2 % Sn (Sn0), 42 % Sn2+, and 56 % SnO2 (Sn4+). However, compared with the Sn2+ fraction observed after PDA under N2 and low-vacuum (∼1 Pa) conditions, that after PDA at 300 °C under high vacuum (< 5 × 10−4 Pa) (HVPDA) increased substantially to greater than 62 %. This result was attributed to the transformation from SnO2 to SnO during HVPDA. A staggered bottom-gate thin-film transistor with an SnO channel (10 nm), which was fabricated by HVPDA at 300 °C, exhibited p-type properties, including a relatively high on-current/off-current (Ion/Ioff) ratio of 5.1 × 104 and a hole field-effect mobility (µFE) of 1.8 cm2/(V·s).

Oxygen plasma-assisted magnetron sputtering deposition of non-stoichiometric Y2O3 films: Influence of oxygen vacancies on etching resistance

Yttrium oxide (Y2O3) films are widely used to protect equipment in plasma etching, a crucial technique in semiconductor processing, due to their exceptional resistance to plasma etching. Since oxygen vacancy affects the performance of Y2O3 and may impact physical etching resistance, the internal relationship necessitates further investigation. In this article, Y2O3 films with varying oxygen vacancy concentrations are prepared by reactive magnetron sputtering with the assistance of oxygen plasma. The formation and development of oxygen vacancies in cubic Y2O3 films and their impact on the physical etching resistance were investigated. The experiment results indicate that the accumulation of oxygen vacancies causes non-stoichiometry and the etching rate is significantly reduced. Combined with density-functional theory, it is revealed that oxygen vacancy distorts the lattice, which increases covalent YO bonding and the formation energy of atoms. Moreover, the vacancy line defects resulting from diffusion and aggregation of oxygen vacancies exert a similar influence on the adjacent yttrium and oxygen layers. The enhancement of physical etching resistance is attributed to the strengthened internal YO bonds led by increasing oxygen vacancy concentration in the cubic Y2O3 films without inducing phase transition. The discovery enriches the understanding of how plasma interacts with Y2O3, and the etching mechanism.

Low-loss and low-temperature Al2O3 thin films for integrated photonics and optical coatings

Amorphous aluminum oxide (Al2O3) is a key material in optical coatings due to its notable properties, including a broad transparency window (ultraviolet to mid-infrared) and excellent durability. Moreover, its higher refractive index contrast relative to silica cladding layers and high solubility of rare-earth ions make it well suited for optical waveguides and the development of various functionalities in integrated photonics. In many coatings and integrated photonics applications, the substrates are temperature and stress sensitive, while relatively thick (∼1 μm) alumina layers are required; thus, it is crucial to fabricate low optical loss alumina thin films at low deposition temperatures, while maintaining high deposition rates. In this study, plasma-assisted reactive magnetron sputtering, operated in an alternating current mode, is investigated as a reliable, straightforward, and wafer-scale compatible technique for the deposition of high optical quality and uniform Al2O3 thin films at low temperature. One-micrometer-thick amorphous Al2O3 planar waveguides, deposited at 150 °C and a rate of 23.3 nm/min, exhibit optical losses below 1 dB/cm at 638 nm and as low as 0.1 dB/cm in the conventional optical communication band.

Influence of nitrogen and niobium incorporation in bcc-chromium coatings on microstructure and mechanical properties

Stoichiometric CrN and Cr:N with different nitrogen (N) content are of interest for hard coating applications. In the Cr-N material system, bcc-Cr rich coatings, containing a few percent of diluted N, provide tunability in microstructure and mechanical properties. Additionally, the incorporation of Nb into the CrNx coatings may further tailor the materials properties. In this work, bcc-CrNx and CrNbNx coatings were deposited by reactive magnetron sputtering, and their mechanical and microstructural characteristics were investigated as a function of N content. Depending on the N content, the phases observed by X-ray diffractometry (XRD) varied from metallic bcc-Cr, mixed bcc-Cr/h-Cr2N, to h-Cr2N/CrN. X-ray reflectivity (XRR), and scanning electron microscopy (SEM) measurements show that a dense and nearly columnar-free bcc-CrNx coatings was obtained at ~13–25 at.% of N, while CrNbNx coatings composed of dense, column-free, and featureless microstructure at a N content of ~10–20 at.%. The dense and nearly column-free microstructure composed of dispersion of Cr2N grains into the bcc-Cr matrix for both CrNx and CrNbNx coatings, as shown by high resolution transmission electron microscope analysis (HRTEM). Nanoindentation revealed a hardening of the coatings due to the grain refinement, solid solution strengthening, and variation in phase content.

Floating potential probes for process control during reactive magnetron sputtering

Long term deposition of aluminum oxide by reactive magnetron sputtering results in a drift of the discharge voltage. A similar drift of the floating potential is observed. The latter observation is further investigated and it is shown that the change of the floating potential can be linked to a change of the electric properties of the vacuum chamber walls. Optimization of the floating potential probe is performed to use the difference between the discharge voltage and the floating potential as a parameter for process control. The best results were obtained with a planar probe sufficiently far positioned opposite to the magnetron, and close enough to the chamber wall facing the magnetron. This choice can be understood in terms of the ability of the probe to sense the discharge while being protected from deposition. The usage of the aforementioned difference to control the process is demonstrated with the measurement of process curves, more specifically IV-characteristics and hysteresis experiments. The shown reproducibility of these measurements opens a pathway for more precise quantification of reactive sputter deposition simulations and enhanced process control.

Thermochromic properties and surface chemical states of reactive magnetron sputtered vanadium oxide thin films at various deposition pressures

Vanadium oxide thin films were prepared using reactive magnetron sputtering method, varying the deposition pressures from 4 to 10 mTorr while maintaining the other sputtering parameters constant. Our investigations revealed sensitive dependence of deposition pressure, chemical states of the V and O atoms, crystal phases, and thermochromic (TC) optical modulation. Specifically, the film deposited at 8 mTorr displayed distinct TC characteristics with a prevalent monoclinic m-VO2 phase according to X-ray diffraction (XRD), supported by X-ray photoelectron spectroscopy (XPS). Optical transmittance modulation and electrical property measurements revealed a metal–insulator transition (MIT), confirming the intimate connection between TC characteristics and presence of the m-VO2 phase. Films deposited at pressures lower or higher than 8 mTorr exhibited typical semiconductor behavior without TC characteristics, further supported by in situ XRD, where (110) plane shifted to lower angle upon heating above τC. Chemical state analysis by XPS revealed a clear correlation between V−O peaks and the presence of a VO2 phase, with the film deposited at 8 mTorr displaying relatively large peak fitted area indicative of the VO2 phase. These findings highlight the critical and sensitive dependence of the deposition conditions in tailoring the properties of vanadium oxide thin films and provide valuable insights for potential applications in chromogenic films.

Systematic approach for high piezoelectric AlN deposition

Aluminum nitride (AlN) is a wide band gap semiconductor with interesting piezoelectric properties for many applications, including micromechanical systems (MEMS), acoustic wave sensors or energy harvesting devices. The influence of DC reactive magnetron sputtering (DCRMS) deposition parameters on the structural, crystalline, and piezoelectric properties of AlN thin films are presented. The systematic approach of Design of Experiments (DoE) has been used to evaluate the role of magnetron power, nitrogen and argon flows on the deposition process and the film properties. Magnetron power and argon flow have resulted to be the parameters causing the most significant effects on the deposition rate. AlN films have been deposited with a high crystal quality, showing low values of FWHM (0.28) and c-axis orientation parallel oriented respect to the growth direction, as evidenced by X-ray diffraction (XRD) analysis and high-resolution transmission electron microscopy (HRTEM). These samples also showed a high piezoelectric coefficient (d33) of 5 pC/N for AlN thin films. This work highlights the importance of deposition parameters on the properties of the film and the important role that DoE play for its optimization with a minimum number of depositions.

Analysis of pulsed direct current reactive magnetron sputtering on a silicon target

Reactive sputtering is a very useful technique, particularly, for producing inhomogeneous interference filters, where the refractive index changes smoothly during deposition. In such a context, precise control of deposition parameters is crucial for replicating the desired optical properties. This study employed a pulsed DC power source to investigate the influence of a duty cycle on target poisoning, sputtering plasma characteristics, electric signals, and optical and morphological properties of synthesized films. Reactive pulsed DC magnetron sputtering was characterized by analyzing the behavior of plasma emission via optical emission spectroscopy and voltage-current signals, while modulating parameters such as the oxygen content within the vacuum chamber. A set of thin films was coated on glass substrates under different system conditions. These films underwent characterization employing spectroscopic ellipsometry to ascertain their optical constants, atomic force microscopy for surface morphology analysis, and x-ray diffraction for the determination of crystalline structures. The results indicate that longer duty cycles required higher oxygen levels to poison the target. Additionally, a detailed analysis of electrical signals revealed nonsquare waveforms, whose characteristics were influenced by both the duty cycle and the oxygen content within the sputtering chamber, resulting in higher effective voltages during the on-time of the voltage pulse. Grown films via reactive pulsed DC magnetron sputtering were also compared to films grown via conventional DC magnetron sputtering at equivalent conditions of target poisoning.