Physical Vapor Deposition Research Articles

Nanosized curing catalyst via nano-templated plasma PVD for attaining superior low-cure powder coating films

The addition of curing catalysts into powder coating is a key method to fabricate low-temperature curing powder coating for reducing energy consumption and expanding its applications to heat-sensitive substrates. However, the heterogeneous dispersion of the unmodified catalysts in powder coatings results in inconsistent catalysis of resin crosslinking, thus leading to compromised surface smoothness and gloss. Utilizing nanosized catalysts is an efficient solution to such problems. In this paper, we propose a nano-templated dielectric barrier discharge (DBD) plasma-assisted physical vapor deposition (PVD) strategy to fabricate the nanosized catalysts. The curing catalyst, 2-ethylimidazole (2-elm), is successfully vaporized and deposited on nano-carrier SiO2 (SiO2-NPs) in the DBD plasma reactor at atmospheric pressure, producing 2-elm@SiO2-NPs. The mechanical strength and chemical resistance of finishes of powder coating incorporated with the 2-elm@SiO2-NPs remained at low curing temperature (170 °C for 15 min) and fast curing condition (190 °C for 8 min). In addition, their surface qualities are comparable to that of the original powder coating, with up to 100 % gloss retention, successfully eliminating the issue of more than 25 % gloss attenuation of the powder coating with unmodified 2-elm. This study provides an effective, solvent-free strategy for fabricating nanosized curing catalysts and achieving high-quality film finishes.

Development of thermal barrier coating on single crystal superalloy CMSX-4 by two-source evaporation EB-PVD and hot corrosion performance of the coating in a simulated aero-engine environment

Superalloys are crucial in high-temperature applications, particularly in the gas turbine industries. With the development of high-temperature superalloy materials, efforts are still being made to improve the turbine entry temperature (TET), which will ultimately raise the efficiency of gas turbines. In this research, a second-generation single-crystal superalloy CMSX-4 based on nickel was prepared. The surface was coated by thermal barrier coating (TBC) with a bond coat of NiCoCrAlY with vacuum plasma spray (VPS) and a top coat with Yttria Stabilized Zirconia (YSZ) by Electron Beam Physical Vapor Deposition (EB-PVD) with a minimal current of 2.3 A with two sources compared to the conventional high-current that has been currently employed. These CMSX-4 specimens, both the as-cast and TBC coated, were used to test the effects of cyclic oxidation and hot corrosion at 1000 °C, simulating an aircraft engine. Also, a hot corrosion test using salt compositions (Wt%) of 60Na2SO4 - 40NaCl was performed simulating an aviation engine environmental condition. A FE-SEM/EDS analysis was used to examine the surface and cross-section microstructures of oxidized, hot-corroded as-cast, and hot-corroded TBC-coated CMSX-4 and its corrosion products. Using the XRD technique, the phases that were found in the oxidized and hot-corroded samples were identified. The outcome demonstrated that the EB-PVD TBC-coating on CMSX-4 with beam switching technique and a lower electron beam current has adequate protection without any damage to the coatings at 1000 °C.

Van der Waals Epitaxially Grown Molecular Crystal Dielectric Sb2O3 for 2D Electronics.

Two-dimensional (2D) semiconducting materials have attracted significant interest as promising candidates for channel materials owing to their high mobility and gate tunability at atomic-layer thickness. However, the development of 2D electronics is impeded due to the difficulty in formation of high-quality dielectrics with a clean and nondestructive interface. Here, we report the direct van der Waals epitaxial growth of a molecular crystal dielectric, Sb2O3, on 2D materials by physical vapor deposition. The grown Sb2O3 nanosheets showed epitaxial relations of 0 and 180° with the 2D template, maintaining high crystallinity and an ultrasharp vdW interface with the 2D materials. As a result, the Sb2O3 nanosheets exhibited a high breakdown field of 18.6 MV/cm for 2L Sb2O3 with a thickness of 1.3 nm and a very low leakage current of 2.47 × 10-7 A/cm2 for 3L Sb2O3 with a thickness of 1.96 nm. We also observed two types of grain boundaries (GBs) with misorientation angles of 0 and 60°. The 0°-GB with a well-stitched boundary showed higher electrical and thermal stabilities than those of the 60°-GB with a disordered boundary. Our work demonstrates a method to epitaxially grow molecular crystal dielectrics on 2D materials without causing any damage, a requirement for high-performance 2D electronics.

Bismuth tri-iodide – Graphene 2D material

In recent years, a multitude of 2D materials has been extensively studied, and new ones continue to emerge. Among these, bismuth tri-iodide-graphene material has been reported in both theoretical and experimental studies, displaying intriguing properties. These findings suggest potential photovoltaic applications for BiI3 layers and van der Waals superstructures. In this context, the present work explores the growth of van der Waals superstructures BiI3–graphene, obtained through physical vapor deposition. These structures are achieved by nucleating BiI3 and allowing it to grow on graphene-covered TEM grids and ultra-flat silicon substrates.When the structures are directly grown on grids and substrates covered with graphene, twisted BiI3 structures are formed, leading to Moiré interference, indicating the presence of two or more BiI3 layers and non-uniformity. However, when the structures are grown on grids pre-treated with UV/O3, and then subjected to annealing and post-growth, they become more uniform and aligned, without observable twisting. Structures obtained on substrates with this treatment and post-growth result in thinner layers, as thin as 7.59 ± 0.16 nm, with a roughness of 0.435 ± 0.018 nm. As the thickness decreases, the position of the (003) reflection peak in the diffraction pattern shifts to lower values and broadens, indicating an expansion of the cell along the c-axis. The obtained bandgap values, ranging from 1.55 ± 0.04 to 1.62 ± 0.04 eV, closely align with theoretical predictions. The obtained structures become part of the 2D universe of other similar materials, such as TMDs-graphene, and open up exciting possibilities for new properties and applications.

2D Free-Standing GeS1-xSex with Composition-Tunable Bandgap for Tailored Polarimetric Optoelectronics.

Germanium-based monochalcogenides (i.e., GeS and GeSe) with desirable properties are promising candidates for the development of next-generation optoelectronic devices. However, they are still stuck with challenges, such as relatively fixed electronic band structure, unconfigurable optoelectronic characteristics, and difficulty in achieving free-standing growth. Herein, it is demonstrated that two-dimensional (2D) free-standing GeS1-xSex (0 ≤ x ≤ 1) nanoplates can be grown by low-pressure rapid physical vapor deposition (LPRPVD), fulfilling a continuously composition-tunable optical bandgap and electronic band structure. By leveraging the synergistic effect of composition-dependent modulation and free-standing growth, GeS1-xSex-based optoelectronic devices exhibit significantly configurable hole mobility from 6.22 × 10-4 to 1.24 cm2V-1s⁻1 and tunable responsivity from 8.6 to 311 AW-1 (635nm), as x varies from 0 to 1. Furthermore, the polarimetric sensitivity can be tailored from 4.3 (GeS0.29Se0.71) to 1.8 (GeSe) benefiting from alloy engineering. Finally, the tailored imaging capability is also demonstrated to show the application potential of GeS1-xSex alloy nanoplates. This work broadens the functionality of conventional binary materials and motivates the development of tailored polarimetric optoelectronic devices.

Metallization of polypropylene substrates through surface functionalization and physical vapor deposition of chromium coatings

Physical vapor deposition (PVD) of chromium coatings represents an interesting alternative to electroplating to obtain metallized plastic parts for a variety of manufacturing sectors. This process is however hampered by the limited adhesion of the metallic layer on the underlying polymeric substrates. Within this context, PVD metallization of polypropylene substrates has so far been particularly challenging given the low surface energy and poor wettability of this commodity plastics. To address this issue, a comprehensive approach is proposed here to enable the production of PVD-metallized PP substrates with excellent and stable interlayer adhesion. The adhesive properties of the PP substrate are modified by a selective UV-induced photografting process in which vinyl-, glycidyl- or 2-hydroxyethyl methacrylate species are covalently attached to the PP surface, as confirmed by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and surface wettability measurements. Based on the chemistry of the photografted functionality, different resin systems are selected and investigated for use as primers to enable subsequent chromium deposition, including acrylic, epoxy and polyurethane systems. The effect of the photografting process on the adhesion between PP and the primers is systematically assessed by means of pull-off tests, highlighting a significant improvement of the adhesion force after surface functionalization with appropriate grafting agents. Finally, functionalized PP substrates are chromated through PVD, obtaining homogeneous and crack-free chromium surfaces upon judicious selection of suitable primer-grafting agent combinations. This also led to outstanding interlayer adhesion and micromechanical performance. This work provides the first demonstration of chromium-metallization of PP substrates via PVD for metallized plastic components with excellent surface characteristics, and paves the path for the design of mechanically durable and aesthetically-compliant PVD-metallized PP components.

Correlation between structural, morphological, and electrical transport properties of nano-dimensional Tellurium thin film by low energy ion beam irradiation

Tellurium (Te), an emerging semiconductor material, exhibits intriguing physical properties in low-dimensional forms. This study investigates the structural, morphological, and transport properties of low-dimensional Te thin film deposited by physical vapor deposition after 400 keV Kr2+ ion irradiation with varying fluences of 1 × 1013, 5 × 1013, and1 × 1014 ions-cm−2. The X-ray diffraction (XRD) pattern reveals the hexagonal phase of pristine Te. As ion fluence increases, intensity of the XRD peaks decreases and the full-width half maxima (FWHM) increases, indicating a reduction in crystallinity. The intensity of the Raman peak decreases upon irradiation, resulting in a red shift in the spectra of the irradiated sample. The evolution of morphology at different fluences has been examined with atomic force microscopy (AFM) measurements. The results indicate the segregation of grains and an increase in root mean square (RMS) roughness from 2.59 pm to 5.11 pm with ion fluence up to 5 × 1013 ions-cm−2. At the highest fluence, i.e., 1 × 1014 ions-cm−2, there is an agglomeration of grains, and hence a decrease in RMS roughness to 3.92 pm is observed. The DC resistivity measurement indicates the semiconducting nature of all films. Additionally, this measurement signifies the rapid decrease in activation energy at both band-to-band conduction and nearest neighbour hopping (NNH) conduction. Following irradiation, Hall measurement demonstrates a decrease in the concentration of charge carriers and an increase in resistivity due to scattering originating from grain boundaries. However, when the fluence is increased to 1 × 1014 ions-cm−2, there is a reduction in resistivity and an increase in carrier concentration with enhanced Hall mobility in comparison to pristine Te. Therefore, this study showcases that low-energy ion irradiation has a significant impact on the modification of the structure, morphology, and electrical transport properties of semiconducting Te thin film.

Study of MoN gate impact on GaN high electron mobility transistor

AbstractIn this letter, molybdenum nitride (MoN) gate AlGaN/GaN HEMT has been investigated with MoN developed in various physical vapour deposition (PVD) conditions. The Schottky gate is studied through forward and reverse characteristics with different processed MoN, which is compared with the standard Ni gate. Similar DC and radio frequency (RF) performances are obtained with MoN and Ni gate, while MoN demonstrated higher reliability than Ni gate through RF aging test.

Nodular defects aggravated tribocorrosion failure mechanism in Cr/GLC multilayer coatings for marine applications

Amorphous carbon coatings by various physical vapor deposition (PVD) have been widely attempted for enhancing both anti-wear and corrosion resistance of bulk materials used in harsh marine environments. However, PVD coatings are apt to be worn due to the existence of growth defects mostly like macro-size nodular particles. In this work, we deliberately fabricated the SiO2 nanoparticles with a size of 200 nm as nodular defects in Cr and graphite-like carbon (Cr/GLC) multilayer coatings, and the dependence of tribocorrosion behavior of coating on the nodular defects was focused by the comprehensively tribological and electrochemical tests. The results showed that introducing SiO2 nodular particles could not degrade the mechanical properties of Cr/GLC coating, but significantly accelerated both the abrasive wear in early sliding-stage under dry friction and the corrosive failure in chloride solution. Particularly, once the tribocorrosion tests in 3.5 wt.% NaCl solution were conducted for the Cr/GLC coating with nodular defects, the distinct ploughing damage originated from abrasive wear promoted the localized spallation of coatings, which thereafter enabled the easy water wedging along spallation for the substantial catastrophe of coatings. The present observations could evident the importance to fabricate the defect-free protective coatings required for harsh tribocorrosion applications.

Properties of silicon dioxide coatings obtained by nano physical vapor deposition (PVD) method on the titanium 13‐niobium 13‐zirconium alloy

AbstractSurface modification techniques play an important role in adjusting the physicochemical properties of titanium and its alloys. To reduce the penetration of alloying element ions into the body, various types of oxide coatings are used to protect it from the corrosive environment. Another important issue related to the surface layer requirement is ensuring an appropriate set of mechanical properties. Accordingly, in this study, the mechanical and electrochemical properties of the silicon dioxide layers formed by the deposition of nano physical vapor deposition on the surface of titanium and titanium 13‐niobium 13‐zirconium alloy samples were investigated. To evaluate the mechanical properties of the layers produced by this method, hardness tests were carried out, as well as tests on the adhesion of these layers to the metal substrate. On the other hand, electrochemical properties were studied using potentiodynamic measurements to assess the resistance to pitting corrosion, followed by impedance measurements to interpret the processes and phenomena occurring at the silicon dioxide layer/electrolyte interface. The data obtained showed different mechanical and electrochemical properties of the silicon dioxide layers generated with varying process parameters.

Large nonlinear optical absorption and refraction of β-In2Se3 thin film from above to below bandgap excitation

Nonlinear optical materials, especially two-dimensional materials, are anticipated to reveal broadband optical nonlinearity for future miniaturized photonic applications. Herein, we report a physical vapor deposition method to produce β-In2Se3 thin film and investigate the broadband nonlinear absorption (β) and refraction (n2) characteristics. The β-In2Se3 semiconductor shows an excellent optical nonlinearity with large β in 102 cm GW−1 scale and n2 in 10−12 cm2 W−1 scale from visible to NIR wavelengths, which are superior to those of metal carbides and nitrides (MXenes) and metal-organic frameworks. This excellent optical nonlinearity makes β-In2Se3 a promising candidate for advanced nanophotonic devices and beyond.

Performance and Degradation of Electrolyte Supported SOECs with Advanced Thin-Film Gadolinium Doped Ceria Barrier Layers in Long-Term Stack Test

Electrolyte supported Solid Oxide Cells (ESCs) with advanced thin-film Gd-doped ceria diffusion barrier layers between electrolyte and electrodes were assembled and electrochemically investigated in steam electrolysis mode in a so-called “rainbow” stack with 30 repeat units (RUs). The barrier layers were deposited onto the electrolyte supports via electron-beam physical evaporation deposition (EB-PVD) method at 600 °C. In this paper, the investigation mainly focuses on the electrochemical characteristics of RUs containing the EB-PVD thin-film GDC layers. At the initial stage of the SOEC operation, the stack reached a high performance with an electrical efficiency of 99.65% at 75% steam conversion and a total power input of 1.98 kW. A long-term stack test was performed in SOEC mode for over 5000 h and demonstrated a low voltage degradation of approx. +11.3 mV·kh–1 per RU (+0.9% kh–1). The RUs with EB-PVD GDC thin-films revealed similar initial performance and degradation rate to the state-of-the-art cells with screen printed GDC layers.

Nanoscale speckle patterning for combined high‐resolution strain and orientation mapping of environmentally sensitive materials

AbstractScanning electron microscopy‐based high‐resolution digital image correlation (HRDIC) is now an established technique, providing full‐field strain and displacement measurement at the microscale. Techniques for generating speckle patterns for sub‐micron strain mapping can often be either substrate dependent or rely on applying aggressive conditions which may alter the microstructure of interest or damage the substrate in highly sensitive materials. We detail a modification of a methodology successfully applied in the literature to allow its use with metallic materials that are particularly sensitive to the corrosive media, such as copper‐base alloys. Nanometre‐thick silver films, applied with physical vapour deposition, are remodelled using NaBr in non‐aqueous isopropanol, replacing the aqueous solution of NaCl in the original method, forming a uniform dispersion of silver islands highly suitable for digital image correlation (DIC) measurement. The entire procedure is performed at ambient temperature. We find that the DIC pattern is suitably electron transparent to allow electron backscatter diffraction (EBSD) measurements without pattern removal, producing diffraction patterns of sufficient quality for cross‐correlation based high‐angular resolution EBSD. This property facilitates simultaneous EBSD and DIC mapping experiments, providing deeper insights into the kinematics of plastic deformation in crystalline materials. Sub‐100 nm islands are achieved through control of the sputter coating parameters, resulting in DIC cross‐correlation subwindows of 140 nm with a 50% overlap. This resolution is sufficient to capture the fine detail of strain localisation phenomena during plastic deformation, demonstrated here with a case study in CuCrZr, a precipitation‐hardened heat sink material for application in nuclear fusion components. Here, we extract full‐field displacement data with DIC and corresponding orientation information using EBSD without the need for pattern removal.

Autonomous Synthesis of Thin Film Materials with Pulsed Laser Deposition Enabled by In Situ Spectroscopy and Automation.

Autonomous systems that combine synthesis, characterization, and artificial intelligence can greatly accelerate the discovery and optimization of materials, however platforms for growth of macroscale thin films by physical vapor deposition techniques have lagged far behind others. Here this study demonstrates autonomous synthesis by pulsed laser deposition (PLD), a highly versatile synthesis technique, in the growth of ultrathin WSe2 films. By combing the automation of PLD synthesis and in situ diagnostic feedback with a high-throughput methodology, this study demonstrates a workflow and platform which uses Gaussian process regression and Bayesian optimization to autonomously identify growth regimes for WSe2 films based on Raman spectral criteria by efficiently sampling 0.25% of the chosen 4D parameter space. With throughputs at least 10x faster than traditional PLD workflows, this platform and workflow enables the accelerated discovery and autonomous optimization of the vast number of materials that can be synthesized by PLD.

Robust Self‐powered Optoelectronic Synapses Based on Epitaxial InSe/GaN Heterojunction with Interfacial Charge‐Trapping Layer

AbstractNeuromorphic devices that parallelize perception, preprocessing, and computation functions are expected to play a significant role in future non‐von Neumann architecture computers. Herein, a new retina‐inspired broadband self‐powered optoelectronic synaptic device based on 2D/3D heterojunction of epitaxial InSe on GaN(0001) is reported. Few‐layer n‐type InSe is grown on p‐type GaN by physical vapor deposition in an ultra‐high vacuum (UHV) environment. The devices are fabricated using a shadow mask assisted UHV electrode deposition technique. High‐resolution transmission electron microscopy images reveal that an atomically thin amorphous layer, which induces highly efficient charge trapping, is formed at the InSe/GaN interface. The photoresponse spans from visible to near‐infrared, and the response time is prolonged to 103 ms owing to the deep trapping levels. Thus, synaptic functions, including excitatory postsynaptic current, paired‐pulse facilitation with a high index of up to 170%, short‐term plasticity, and high‐pass filtering characteristics, are realized. Additionally, the synapses demonstrated the merit of realizing image sharpening and arithmetic operations on the same device under infrared and visible light illumination. This study provides a new platform of 2D/3D heterostructures for robust optoelectronic synapses that may find applications in post‐Moore era neuromorphic vision systems.

Photocatalytic degradation of methylene blue by TiO2/Nd2O3 composite thin films

To improve the photocatalytic property of TiO2 thin films, the composite thin films of TiO2/Nd2O3 structure were fabricated by electron-beam physical vapor deposition method, and the photocatalytic property of the fabricated films was experimentally studied in the present work. The XRD and Raman analyses show that the TiO2/Nd2O3 films are mainly hexagonal crystalline phase of Nd2O3. The XPS analysis for the chemical state changes of Ti, O and Nd of the basic elements in the films is confirming the electron flow in the internal electric field which generated in the TiO2/Nd2O3 films. The surface morphology shows the lattice distortion which affects the changes in the energy band structure. Moreover, the formation of n-n homojunctions improved the separation efficiency of electrons and holes, and enhanced the catalytic activity. The photocatalytic performance for the methylene blue target dye shows that the sample with TiO2 thickness of 20–25 nm has better performance, high degradation efficiency and high reaction rate.

Enhanced fatigue resistance of ferroelectric Al0.65Sc0.35N deposited by physical vapor deposition

Enhanced fatigue resistance of ferroelectric Al0.65Sc0.35N deposited by physical vapor deposition

Review on Preparation of Perovskite Solar Cells by Pulsed Laser Deposition

Pulsed laser deposition (PLD) is a simple and extremely versatile technique to grow thin films and nanomaterials from a wide variety of materials. Compared to traditional fabrication methods, PLD is a clean physical vapour deposition approach that avoids complicated chemical reactions and by-products, achieving a precise stochiometric transfer of the target material onto the substrate and providing control over the film thickness. Halide perovskite materials have attracted extensive attention due to their excellent photoelectric and photovoltaic properties. In this paper, we present an overview of the fundamental and practical aspects of PLD. The properties and preparation methods of the halide perovskite materials are briefly discussed. Finally, we will elaborate on recent research on the preparation of perovskite solar cells by PLD, summarize the advantages and disadvantages of the PLD preparation, and prospect the all-vacuum PLD-grown solar cells in a full solar cell structure.

Effect of Electrode Shape on the Performance of ZnO-Based Ethanol Sensor

This paper reports the deposition of Zn on glass substrates using the physical vapor deposition (PVD) method, followed by an annealing process to grow ZnO for gas-sensing applications. Surface morphologies were characterized using scanning electron microscopy, which revealed nanowire shape. The diameter of the wire was about 35 nm. In addition, X-ray diffraction analysis demonstrated that the ZnO nanowire possessed a wurtzite structure with an orientation of (002). Three types of resistive gas sensors with a spiral-square and two-comb electrode geometries were designed, fabricated, and tested for their ethanol vapor-sensing properties. The experimental results show that the sensor with square-spiral electrode has the sensitivity of 43% for 2,000 ppm of ethanol vapor at 200°C, while the sensor with a comb electrode shows the sensitivity of 32% at the same conditions. Also, two sensors with different dimensions of comb-shaped electrodes showed the same sensitivity, as both the width and the distance between the fingers change simultaneously in the larger comb-shaped electrode. The response time for the comb electrode is shorter than the square-spiral type, and the recovery time is almost independent of the electrode geometry. Therefore, the optimal structure should be selected based on the application.

Stable DC vacuum arc plasma generation from a 100 mm TiB2 cathode

Titanium diboride exhibits outstanding properties for hard and wear resistant coatings. However, efficient physical vapor deposition (PVD) processing through DC vacuum arc, with a deposition rate unreachable for any other PVD technique, is comparatively unexplored for TiB2 thin films due to challenges associated with the film synthesis process. In this work, we used an industrial scale arc plasma source having a plane cathode of 100 mm in diameter and a permanent magnet on its back side. We present analysis of the cathode surface, plasma generation/composition, as well as analysis of collected macroparticles. The cathode weight loss and the amount of generated macroparticles were measured as a function of process parameters (arc current and pressure, in both Ar and N2 gas). Plasma analysis shows average ion energies around 120 and 25 eV for Ti and B, respectively, and plasma ion composition of approximately 50 % Ti and 50 % B. The cathode weight loss was around 0.3–0.5 g/min, of which at least 25 % is estimated to be macroparticles. Notably, the intensity of the macroparticle generation was reduced with an increase in N2 pressure. Altogether, the results show a stable and reproducible plasma generation process and a high potential for the use of the cathodic arc as an efficient and useful method for deposition of metal borides.