Cu Based Dilute Alloys for Tuning the C2+ Selectivity of Electrochemical CO2 Reduction.

Electrochemical CO2 reduction is a promising technology for replacing fossil fuel feedstocks in the chemical industry but further improvements in catalyst selectivity need to be made. So far, only copper-based catalysts have shown efficient conversion of CO2 into the desired multi-carbon (C2+) products. This work explores Cu-based dilute alloys to systematically tune the energy landscape of CO2 electrolysis toward C2+ products. Selection of the dilute alloy components is guided by grand canonical density functional theory simulations using the calculated binding energies of the reaction intermediates CO*, CHO*, and OCCO* dimer as descriptors for the selectivity toward C2+ products. A physical vapor deposition catalyst testing platform is employed to isolate the effect of alloy composition on the C2+/C1 product branching ratio without interference from catalyst morphology or catalyst integration. Six dilute alloy catalysts are prepared and tested with respect to their C2+/C1 product ratio using different electrolyzer environments including selected tests in a 100-cm2 electrolyzer. Consistent with theory, CuAl, CuB, CuGa and especially CuSc show increased selectivity toward C2+ products by making CO dimerization energetically more favorable on the dominant Cu facets, demonstrating the power of using the dilute alloy approach to tune the selectivity of CO2 electrolysis.

Structural Health Monitoring of Fiber Reinforced Composites Using Integrated a Linear Capacitance Based Sensor.

The demand for fiber-reinforced polymers (FRPs) has significantly increased in various industries due to their attributes, including low weight, high strength, corrosion resistance, and cost-efficiency. Nevertheless, FRPs, such as glass and Kevlar fiber composites, exhibit anisotropic properties and relatively low interlaminar strength, rendering them susceptible to undetected damage. The integration of real-time damage detection processes can effectively mitigate this issue. This paper introduces a novel method for fabricating embedded capacitive sensors within FRPs using a coating technique. The study encompasses two types of fibers, namely glass and Kevlar fiber/epoxy composites. The physical vapor deposition (PVD) technique is employed to coat bundle fibers with conductive material, thus creating embedded electrodes. The results demonstrate the uniform distribution of nanoparticles of gold (Au) along the fibers using PVD, resulting in a favorable resistance of approximately ≈100 Ω. Two sensor configurations are explored: axial and lateral embedding of the coated yarn (electrodes) to investigate the influence of load direction on the coating yarn. Axial-sensor configuration specimens undergo tensile testing, showcasing a linear response to axial loads with average sensitivities of 1 for glass and 1.5 for Kevlar fiber/epoxy composites. Additionally, onset damage is detected in both types of fiber composites, occurring before final fracture, with average stress at the turning point measuring 208 MPa for glass and 144 MPa for Kevlar. The lateral-sensor configuration for glass fiber-reinforced polymer (GFRP) exhibits good linearity towards strain until failure, with average gauge factors of 0.25 and -2.44 in the x and y axes, respectively.

The Influence of Temperature on the Photoelectric Properties of GeSe Nanowires.

Using physical vapor deposition (PVD) technology, GeSe nanowires were successfully fabricated by heating GeSe powder at temperatures of 500 °C, 530 °C, 560 °C, 590 °C, and 620 °C. The microstructure, crystal morphology, and chemical composition of the resulting materials were thoroughly analyzed employing methods like Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), plus Raman Spectroscopy. Through a series of photoelectric performance tests, it was discovered that the GeSe nanowires prepared at 560 °C exhibited superior properties. These nanowires not only possessed high crystalline quality but also featured uniform diameters, demonstrating excellent consistency. Under illumination at 780 nm, the GeSe nanowires prepared at this temperature showed higher dark current, photocurrent, and photoresponsivity compared to samples prepared at other temperatures. These results indicate that GeSe nanomaterials hold substantial potential in the field of photodetection. Particularly in the visible light spectrum, GeSe nanomaterials exhibit outstanding light absorption capabilities and photoresponse.

Advances in physical vapor deposited silicon/carbon based anode materials for Li-ion batteries.

This paper explores the latest developments in physical vapor deposition (PVD) techniques for fabricating silicon-carbon (Si/C) based thin films as anodes of Lithium-Ion batteries (LiBs). Properties of Si/C based materials, such as high thermal stability, electrical conductivity and mechanical strength, have addressed the critical challenges associated with the use silicon as anode material for LiBs, including as volume expansion during lithiation, structural stability and electrode degradation. The review article aims to provide recent advances in the use of Si/C-based thin film materials deposited via PVD processes as anodes for LiBs. PVD deposition processes provide numerous benefits including the precise control over the structure, thickness, morphology, as well as the design of deposited thin-film materials, and this article provides an in-depth analysis on the design and synthesis of Si/C thin films, as well as its electrochemical performance and stability when used as anode for LiBs. The primary aim of this paper is to underscore the advantages provided by PVD processes in overcoming challenges associated with using pure silicon as anode material for LiBs, or in improving the electrochemical performance of Si/C-based anode materials through the design of several Si/C films, covering both multilayer and nanocomposite Si/C film configurations outlined in sections 2 and 3, respectively. Insights into the mechanisms governing lithium-ion insertion/extraction processes within the Si/C matrix are provided, offering an understanding of the material's behavior during battery cycling.

Vibration Sensors on Flexible Substrates Based on Nanoparticle Films Grown by Physical Vapor Deposition.

Flexible electronics have gained a lot of attention in recent years due to their compatibility with soft robotics, artificial arms, and many other applications. Meanwhile, the detection of acoustic frequencies is a very useful tool for applications ranging from voice recognition to machine condition monitoring. In this work, the dynamic response of Pt nanoparticles (Pt NPs)-based strain sensors on flexible substrates is investigated. the nanoparticles were grown in a vacuum by magnetron-sputtering inert-gas condensation. Nanoparticle sensors made on cracked alumina deposited by atomic layer deposition on the flexible substrate and reference nanoparticle sensors, without the alumina layer, were first characterized by their response to strain. The sensors were then characterized by their dynamic response to acoustic frequency vibrations between 20 Hz and 6250 Hz. The results show that alumina sensors outperformed the reference sensors in terms of voltage amplitude. Sensors on the alumina layer could accurately detect frequencies up to 6250 Hz, compared with the reference sensors, which were sensitive to frequencies up to 4250 Hz, while they could distinguish between two neighboring frequencies with a difference of no more than 2 Hz.

Gas-Phase Fabrication and Photocatalytic Activity of TiO2 and TiO2-CuO Nanoparticulate Thin Films.

CuO-loaded TiO2 nanomaterials have applications in pollutant degradation via photocatalysis. However, the existing methods of fabricating these nanomaterials involve liquid-phase processes, which require several steps and typically generate liquid waste. In this study, TiO2 and TiO2-CuO nanoparticulate thin films were successfully fabricated through a one-step gas-phase approach involving a combination of plasma-enhanced chemical vapor deposition and physical vapor deposition. The resulting films consisted of small, spherical TiO2 nanoparticles with observable CuO on the TiO2 surface. Upon annealing in air, the TiO2 nanoparticles were crystallized, and CuO was completely oxidized. The photocatalytic activity of TiO2-CuO/H2O2, when introduced into the rhodamine 6G degradation system, was substantially enhanced under both ultraviolet and visible light irradiation. Moreover, this study highlights the influence of pH on the photocatalytic activity; TiO2-CuO/H2O2 exhibited the highest photocatalytic activity at pH 13, with a reaction rate constant of 0.99 h-1 cm-2 after 180 min of visible light irradiation. These findings could facilitate the development of nanoparticulate thin films for enhanced pollutant degradation in wastewater treatment.

Nano multi-layered HfO2/α-Fe2O3 nanocomposite photoelectrodes for photoelectrochemical water splitting.

This study marks a significant stride in enhancing photoelectrochemical (PEC) water splitting applications through the development of a type II nano-heterojunction comprising HfO2 and α - Fe2O3. Fabricated via Physical Vapor Deposition/Radio Frequency (PVD/RF) sputtering, this nano-heterojunction effectively addresses the efficiency limitations inherent in traditional α - Fe2O3photoanodes. The integration of HfO2 leads to a substantial increase in photocurrent density, soaring from 62 µA/cm2 for pure α - Fe2O3 to 1.46 mA cm-2 at 1.23 V versus the Reversible Hydrogen Electrode (RHE). This enhancement, a 23-fold increase, is primarily attributed to the improved absorption of photons in the visible range and the facilitation of more efficient charge transfer. The enhanced performance and long-term stability of the HfO2/α - Fe2O3 nano-heterojunction, validated through XRD, XPS, Raman Spectroscopy, EDS, SEM, EIS, and UPS analyses, demonstrate its potential as a promising and cost-effective solution for PEC water splitting applications, leveraging renewable energy sources.

Short-Time Magnetron Sputtering for the Development of Carbon-Palladium Nanocomposites.

In recent nanomaterials research, combining nanoporous carbons with metallic nanoparticles, like palladium (Pd), has emerged as a focus due to their potential in energy, environmental and biomedical fields. This study presents a novel approach for synthesizing Pd-decorated carbons using magnetron sputter deposition. This method allows for the functionalization of nanoporous carbon surfaces with Pd nano-sized islands, creating metal-carbon nanocomposites through brief deposition times of up to 15 s. The present research utilized direct current magnetron sputtering to deposit Pd islands on a flexible activated carbon cloth substrate. The surface chemistry, microstructure, morphology and pore structure were analyzed using a variety of material characterization techniques, including X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectroscopy, gas sorption analysis and scanning electron microscopy. The results showed Pd islands of varying sizes distributed across the cloth's carbon fibers, achieving high-purity surface modifications without the use of chemicals. The synthesis method preserves the nanoporous structure of the carbon cloth substrate while adding functional Pd islands, which could be potentially useful in emerging fields like hydrogen storage, fuel cells and biosensors. This approach demonstrates the possibility of creating high-quality metal-carbon composites using a simple, clean and economical method, expanding the possibilities for future nanomaterial-based applications.

Sputtered Silicon-Coated Graphite Electrodes as High Cycling Stability and Improved Kinetics Anodes for Lithium Ion Batteries.

Amorphous Si thin films with different thicknesses were deposited on synthetic graphite electrodes by using a simple and scalable one-step physical vapor deposition (PVD) method. The specific capacities and rate capabilities of the produced electrodes were investigated. X-ray diffraction, scanning electron microscopy, Raman spectroscopy, profilometry, cyclic voltammetry, galvanostatic techniques, and in situ Raman spectroscopy were used to investigate their physicochemical and electrochemical properties. Our results demonstrated that the produced Si films covered the bare graphite electrodes completely and uniformly. Si-coated graphite, Si@G, with an optimal thickness of 1 µm exhibited good stability, with an initial discharge capacity of 628.7 mAhg-1, a capacity retention of 96.2%, and a columbic efficiency (CE) higher than 99% at C/3. A discharge capacity of 250 mAh g-1 was attained at a high current rate of 3C, which was over 2.5 times that of a bare graphite electrode, thanks to the high activated surface area (1.5 times that of pristine graphite) and reduced resistance during cycling.

I-GLAD: a new strategy for fabricating antibacterial surfaces.

The paper uses inverted glancing angle deposition (I-GLAD) for creating antibacterial surfaces. Antibacterial surfaces are found in nature, such as on insect wings, eyes, and plant leaves. Since the bactericidal mechanism is purely physical for these surfaces, the antimicrobial resistance of bacteria to traditional chemical antibiotics can be overcome. The technical problem is how to mimic, synthesize, and scale up the naturally occurring antibacterial surfaces for practical applications, given the fact that most of those surfaces are composed of three-dimensional hierarchical micro-nano structures. This paper proposes to use I-GLAD as a novel bottom-up nanofabrication technique to scale up bio-inspired nano-structured antibacterial surfaces. Our innovative I-GLAD nanofabrication technique includes traditional GLAD deposition processes alongside the crucial inverting process. Following fabrication, we explore the antibacterial efficacy of I-GLAD surfaces using two types of bacteria: Escherichia coli (E. coli), a gram-negative bacterium, and Staphylococcus aureus (S. aureus), a gram-positive bacterium. Scanning electron microscopy (SEM) shows the small tips and flexible D/P (feature size over period) ratio of I-GLAD nanoneedles, which is required to achieve the desired bactericidal mechanism. Antibacterial properties of the I-GLAD samples are validated by achieving flat growth curves of E. coli and S. aureus, and direct observation under SEM. The paper bridges the knowledge gaps of seeding techniques for GLAD, and the control/optimization of the I-GLAD process to tune the morphologies of the nano-protrusions. I-GLAD surfaces are effective against both gram-negative and gram-positive bacteria, and they have tremendous potentials in hospital settings and daily surfaces.

Impact of Intermittent Deposition on Spontaneous Orientation Polarization of Organic Amorphous Films Revealed by Rotary Kelvin Probe.

The control of the molecular orientation and resultant polarization is essential for improving the performance of organic optoelectronic devices. Conventionally, the substrate temperature and deposition rate are tuned to control the molecular orientation of vapor-deposited films. In this study, we proposed a novel method, referred to as "intermittent deposition", in which the polarization direction and magnitude are controlled by introducing intervals during physical vapor deposition. The rotary Kelvin probe measurement of the Alq3 and TPBi films clearly showed a time-dependent decrease in the surface potential owing to the surface relaxation of the molecular orientation immediately after deposition. Through a series of intermittent depositions, in which the deposition shutter is repeatedly opened and closed at certain intervals, a relaxed surface layer was built up, and we could control the polarization magnitude. For the Alq3 film, even the polarization direction was switched. The proposed new deposition method is applicable to general organic molecules, not limited to polar molecules, thereby potentially tuning the conduction properties of organic devices and fabricating novel devices.

CMOS-Compatible Ultrathin Superconducting NbN Thin Films Deposited by Reactive Ion Sputtering on 300 mm Si Wafer.

We report a milestone in achieving large-scale, ultrathin (~5 nm) superconducting NbN thin films on 300 mm Si wafers using a high-volume manufacturing (HVM) industrial physical vapor deposition (PVD) system. The NbN thin films possess remarkable structural uniformity and consistently high superconducting quality across the entire 300 mm Si wafer, by incorporating an AlN buffer layer. High-resolution X-ray diffraction and transmission electron microscopy analyses unveiled enhanced crystallinity of (111)-oriented δ-phase NbN with the AlN buffer layer. Notably, NbN films deposited on AlN-buffered Si substrates exhibited a significantly elevated superconducting critical temperature (~2 K higher for the 10 nm NbN) and a higher upper critical magnetic field or Hc2 (34.06 T boost in Hc2 for the 50 nm NbN) in comparison with those without AlN. These findings present a promising pathway for the integration of quantum-grade superconducting NbN films with the existing 300 mm CMOS Si platform for quantum information applications.

Preparation and Characteristics of High-Performance, Low-Density Metallo-Ceramics Composite.

By applying the physical vapour deposition method, hollow ceramic microspheres were coated with titanium, and subsequently, they were sintered using the spark plasma sintering technique to create a porous ceramic material that is lightweight and devoid of a matrix. The sintering process was carried out at temperatures ranging from 1050 to 1200 °C, with a holding time of 2 min. The samples were subjected to conventional thermal analyses (differential scanning calorimetry, thermogravimetry, dilatometry), oxidation resistance tests, and thermal diffusivity measurements. Phase analysis of the samples was performed using the XRD and the microstructure of the prepared specimens was examined using electron microscopy. The titanium coating on the microspheres increased the compressive strength and density of the resulting ceramic material as the sintering temperature increased. The morphology of the samples was carefully examined, and phase transitions were also identified during the analysis of the samples.

Investigation of the Dislocation Density of NiCr Coatings Prepared Using PVD-LMM Technology.

Micron-sized coatings prepared using physical vapor deposition (PVD) technology can peel off in extreme environments because of their low adhesion. Laser micro-melting (LMM) technology can improve the properties of the fabricated integrated material due to its metallurgical combinations. However, the microstructural changes induced by the high-energy laser beam during the LMM process have not been investigated. In this study, we used the PVD-LMM technique to prepare NiCr coatings with a controlled thickness. The microstructural changes in the NiCr alloy coatings during melting and cooling crystallization were analyzed using molecular dynamics simulations. The simulation results demonstrated that the transition range of the atoms in the LMM process fluctuated synchronously with the temperature, and the hexagonal close-packed (HCP) structure increased. After the cooling crystallization, the perfect dislocations of the face-centered cubic (FCC) structure decreased significantly. The dislocation lines were mainly 1/6 <112> imperfect dislocations, and the dislocation density increased by 107.7%. The dislocations in the twinning region were affected by the twin boundaries and slip surfaces. They were plugged in their vicinity, resulting in a considerably higher dislocation density than in the other regions, and the material hardness increased significantly. This new technique may be important for the technological improvement of protective coatings on Zr alloy surfaces.

Low-Vacuum Catalyst-Free Physical Vapor Deposition and Magnetotransport Properties of Ultrathin Bi2Se3 Nanoribbons.

In this work, a simple catalyst-free physical vapor deposition method is optimized by adjusting source material pressure and evaporation time for the reliable obtaining of freestanding nanoribbons with thicknesses below 15 nm. The optimum synthesis temperature, time and pressure were determined for an increased yield of ultrathin Bi2Se3 nanoribbons with thicknesses of 8-15 nm. Physical and electrical characterization of the synthesized Bi2Se3 nanoribbons with thicknesses below 15 nm revealed no degradation of properties of the nanoribbons, as well as the absence of the contribution of trivial bulk charge carriers to the total conductance of the nanoribbons.

A Microshutter for the Nanofabrication of Plasmonic Metal Alloys with Single Nanoparticle Composition Control.

Alloying offers an increasingly important handle in nanomaterials design in addition to the already widely explored size and geometry of nanostructures of interest. As the key trait, the mixing of elements at the atomic level enables nanomaterials with physical or chemical properties that cannot be obtained by a single element alone, and subtle compositional variations can significantly impact these properties. Alongside the great potential of alloying, the experimental scrutiny of its impact on nanomaterial function is a challenge because the parameter space that encompasses nanostructure size, geometry, chemical composition, and structural atomic-level differences among individuals is vast and requires unrealistically large sample sets if statistically relevant and systematic data are to be obtained. To address this challenge, we have developed a microshutter device for spatially highly resolved physical vapor deposition in the lithography-based fabrication of nanostructured surfaces. As we demonstrate, it enables establishing compositional gradients across a surface with single nanostructure resolution in terms of alloy composition, which subsequently can be probed in a single experiment. As a showcase, we have nanofabricated arrays of AuAg, AuPd, and AgPd alloy nanoparticles with compositions systematically controlled at the level of single particle rows, as verified by energy dispersive X-ray and single particle plasmonic nanospectroscopy measurements, which we also compared to finite-difference time-domain simulations. Finally, motivated by their application in state-of-the-art plasmonic hydrogen sensors, we investigated PdAu alloy gradient arrays for their hydrogen sorption properties. We found distinctly composition-dependent kinetics and hysteresis and revealed a composition-dependent contribution of a single nanoparticle response to the ensemble average, which highlights the importance of alloy composition screening in single experiments with single nanoparticle resolution, as offered by the microshutter nanofabrication approach.

PVD for Decorative Applications: A Review.

Physical Vapor Deposition (PVD) is a widely utilized process in various industrial applications, serving as a protective and hard coating. However, its presence in fields like fashion has only recently emerged, as electroplating processes had previously dominated this reality. The future looks toward the replacement of the most hazardous and toxic electrochemical processes, especially those involving Cr(VI) and cyanide galvanic baths, which have been restricted by the European Union. Unfortunately, a complete substitution with PVD coatings is not feasible. Currently, the combination of both techniques is employed to achieve new aesthetic features, including a broader color range and diverse textures, rendering de facto PVD of primary interest for the decorative field and the fashion industry. This review aims to outline the guidelines for decorative industries regarding PVD processes and emphasize the recent advancements, quality control procedures, and limitations.

Low-Dimensional and High-Crystallinity Carbonyl Cathodes Prepared by Physical Vapor Deposition for Green Aluminum Organic Batteries.

We report a low-cost, high theoretical specific capacity π-conjugated organic compound (PTCDA) with C═O active centers as the cathode material in aluminum organic batteries. In addition, in order to improve the electron transport rate of PTCDA, a new method is proposed in this paper, which uses physical vapor deposition (PVD) method to make PTCDA recrystallize and grow on stainless steel and quartz glass substrates to improve its crystallinity. The increase of crystallinity expands the PTCDA π-π-conjugated system, making electrons more delocalized, which is beneficial to the transmission rate of electrons and ions, thereby enhancing the conductivity of the material. The experimental results show that compared with pristine PTCDA, PTCDA(Ss) and PTCDA(G) with higher crystallinity have better cycling stability and rate capability. The DFT (density functional theory) results indicated that the electron-deficient carbonyl group in the PTCDA molecule could reversibly coordinate/dissociate with the positively charged Al complex ions (AlCl2+). This research work provides insights into the rational design of low-dimensional, high-crystallinity, high-performance cathode materials for green aluminum organic batteries.

Structure and Frictional Properties of Ultrahard AlMgB14 Thin Coatings.

This paper presents the results of studies on AlMgB14-based ceramic coatings deposited on WC-Co hard alloy substrates using RF plasma sputtering. The aim of this work is to study the structure, phase composition, and mechanical properties of AlMgB14-based coatings depending on the sputtering mode. According to the results of the microstructural study, the bias voltage applied to the substrate during the sputtering process significantly contributed to the formation of the coating morphology. Based on the results of compositional and structural studies by energy dispersive X-ray spectroscopy, X-ray diffraction, and Raman spectroscopy, it was found that the coatings are composed of nanocrystalline B12 icosahedrons distributed in an amorphous matrix consisting of Al, Mg, B, and O elements. The nanohardness of the coatings varied from 24 GPa to 37 GPa. The maximum value of the hardness together with the lowest coefficient of friction (COF) equal to 0.12 and wear resistance of 7.5 × 10-5 mm3/N·m were obtained for the coating sputtered at a bias voltage of 100 V. Compared with the COF of the original hard alloy substrate, which is equal to 0.31, it can be concluded that the AlMgB14-based coatings could reduce the COF of WC-based hard alloys by more than two times. The hardness and tribological properties of the coatings obtained in this study are in good agreement with the properties of AlMgB14-based materials obtained by other methods reported in the literature.

Comparison to Micro Wear Mechanism of PVD Chromium Coatings and Electroplated Hard Chromium.

Electroplated hard chromium (EPHC) has been widely used in industry due to its excellent mechanical properties, but the development of this technology is limited by environmental risks. The physical vapor deposition (PVD) process has shown promise as an alternative to EPHC for producing chromium-based coatings. In this research, we investigate the microstructure and wear resistance of pure chromium coatings using two PVD techniques, namely, magnetron sputtering ion plating (MSIP) and micro-arc ion plating (MAIP), which are compared to EPHC. To assess wear resistance, we evaluated factors such as hardness, coating base bonding force, wear rate and friction coefficient via friction and wear experiments. The results show that, in terms of microstructure, while the EPHC coating does not exhibit a strong preferred growth orientation, the PVD coatings exhibit an obvious preferred growth orientation along the (110) direction. The average grain size of the EPHC coating is the smallest, and the PVD chromium coatings show a higher hardness than the EPHC coating. The results of pin-on-disk tests show that there is little difference in friction coefficients between EPHC and MAIP chromium plating; however, the MAIP chromium coating showed an excellent specific wear rate (as low as 1.477 × 10-13 m3/Nm). The wear condition of the MAIP chromium coating is more stable than that of the EPHC coating, indicating its potential as a replacement for EPHC.