Single-Crystal Diamond Needle Fabrication Using Hot-Filament Chemical Vapor Deposition

Single-crystal diamonds in the form of micrometer-scale pyramids were produced using a combination of hot-filament (HF) chemical vapor deposition (CVD) and thermal oxidation processes. The diamond pyramids were compared here with similar ones that were manufactured using plasma-enhanced (PE) CVD. The similarities revealed in the morphology, Raman, and photoluminescent characteristics of the needles obtained using the hot-filament and plasma-enhanced CVD are discussed in connection with the diamond film growth mechanism. This work demonstrated that the HF CVD method has convincing potential for the fabrication of single-crystal diamond needles in the form of regularly shaped pyramids on a large surface area, even on non-conducting substrates. The experimental results demonstrated the ability for the mass production of the single-crystal needle-like diamonds, which is important for their practical application.     

Synthesis and Characterization of Multilayered Diamond Coatings for Biomedical Implants

With incredible hardness and excellent wear-resistance, nanocrystalline diamond (NCD) coatings are gaining interest in the biomedical community as articulating surfaces of structural implant devices. The focus of this study was to deposit multilayered diamond coatings of alternating NCD and microcrystalline diamond (MCD) layers on Ti-6Al-4V alloy surfaces using microwave plasma chemical vapor deposition (MPCVD) and validate the multilayer coating's effect on toughness and adhesion. Multilayer samples were designed with varying NCD to MCD thickness ratios and layer numbers. The surface morphology and structural characteristics of the coatings were studied with X-ray diffraction (XRD), Raman spectroscopy, and atomic force microscopy (AFM). Coating adhesion was assessed by Rockwell indentation and progressive load scratch adhesion tests. Multilayered coatings shown to exhibit the greatest adhesion, comparable to single-layered NCD coatings, were the multilayer samples having the lowest average grain sizes and the highest titanium carbide to diamond ratios.     

Achieving Ultra-Low Friction with Diamond/Metal Systems in Extreme Environments

In the search for achieving ultra-low friction for applications in extreme environments, we evaluate the interfacial processes of diamond/tungsten sliding contacts using an on-line macro-tribometer and a micro-tribometer in an ultra-high vacuum. The coefficient of friction for the tests with the on-line tribometer remained considerably low for unlubricated sliding of tungsten, which correlated well with the relatively low wear rates and low roughness on the wear track throughout the sliding. Ex situ analysis was performed by means of XPS and SEM-FIB in order to better understand the underlying mechanisms of low friction and low-wear sliding. The analysis did not reveal any evidence of tribofilm or transferfilm formation on the counterface, indicating the absence of significant bonding between the diamond and tungsten surfaces, which correlated well with the low-friction values. The minimal adhesive interaction and material transfer can possibly be explained by the low initial roughness values as well as high cohesive bonding energies of the two materials. The appearance of the wear track as well as the relatively higher roughness perpendicular to the sliding indicated that abrasion was the main wear mechanism. In order to elucidate the low friction of this tribocouple, we performed micro-tribological experiments in ultra-high vacuum conditions. The results show that the friction coefficient was reduced significantly in UHV. In addition, subsequently to baking the chamber, the coefficient of friction approached ultra-low values. Based on the results obtained in this study, the diamond/tungsten tribocouple seems promising for tribological interfaces in spacecraft systems, which can improve the durability of the components.     

Unusual Dependence of the Diamond Growth Rate on the Methane Concentration in the Hot Filament Chemical Vapor Deposition Process

Although the growth rate of diamond increased with increasing methane concentration at the filament temperature of 2100 °C during a hot filament chemical vapor deposition (HFCVD), it decreased with increasing methane concentration from 1% CH₄ –99% H₂ to 3% CH₄ –97% H₂ at 1900 °C. We investigated this unusual dependence of the growth rate on the methane concentration, which might give insight into the growth mechanism of a diamond. One possibility would be that the high methane concentration increases the non-diamond phase, which is then etched faster by atomic hydrogen, resulting in a decrease in the growth rate with increasing methane concentration. At 3% CH₄ –97% H₂, the graphite was coated on the hot filament both at 1900 °C and 2100 °C. The graphite coating on the filament decreased the number of electrons emitted from the hot filament. The electron emission at 3% CH₄ –97% H₂ was 13 times less than that at 1% CH₄ –99% H₂ at the filament temperature of 1900 °C. The lower number of electrons at 3% CH₄ –97% H₂ was attributed to the formation of the non-diamond phase, which etched faster than diamond, resulting in a lower growth rate.     

Chemical Vapor Deposition of <110> Textured Diamond Film through Pre-Seeding by Diamond Nano-Sheets

Diamond films prepared by chemical vapor deposition will exhibit different surface morphologies, which are determined by the texture and the structural perfection of the deposited diamond. In general, its surface morphology can be controlled by adjusting the deposition conditions. In the present work, <110> textured diamond film was deposited on single crystalline silicon through pre-seeding by diamond nanosheets, rather than controlling the deposition conditions. The employed diamond nano-sheets were prepared by cleavage along a plane, exhibiting good crystallinity. Before chemical vapor deposition, the as-prepared diamond nano-sheets were pre-seeded on the surface of single crystalline silicon as nucleation sites for diamond growth. SEM and XRD results show that the prepared diamond films have a <110> texture. FIB observation reveals that diamonds homogeneously grow on the pre-seeded diamond nano-sheets during chemical vapor deposition, achieving the diamond film with <110> texture. Our work provides a new strategy to prepare <110> textured diamond film.     

Boron Doped Diamond for Real-Time Wireless Cutting Temperature Monitoring of Diamond Coated Carbide Tools

Among the unique opportunities and developments that are currently being triggered by the fourth industrial revolution, developments in cutting tools have been following the trend of an ever more holistic control of manufacturing processes. Sustainable manufacturing is at the forefront of tools development, encompassing environmental, economic, and technological goals. The integrated use of sensors, data processing, and smart algorithms for fast optimization or real time adjustment of cutting processes can lead to a significant impact on productivity and energy uptake, as well as less usage of cutting fluids. Diamond is the material of choice for machining of non-ferrous alloys, composites, and ultrahard materials. While the extreme hardness, thermal conductivity, and wear resistance of CVD diamond coatings are well-known, these also exhibit highly auspicious sensing properties through doping with boron and other elements. The present study focuses on the thermal response of boron-doped diamond (BDD) coatings. BDD coatings have been shown to have a negative temperature coefficient (NTC). Several approaches have been adopted for monitoring cutting temperature, including thin film thermocouples and infrared thermography. Although these are good solutions, they can be costly and become impractical for certain finishing cutting operations, tool geometries such as rotary tools, as well as during material removal in intricate spaces. In the scope of this study, diamond/WC-Co substrates were coated with BDD by hot filament chemical vapor deposition (HFCVD). Scanning electron microscopy, Raman spectroscopy, and the van der Pauw method were used for morphological, structural, and electrical characterization, respectively. The thermal response of the thin diamond thermistors was characterized in the temperature interval of 20–400 °C. Compared to state-of-the-art temperature monitoring solutions, this is a one-step approach that improves the wear properties and heat dissipation of carbide tools while providing real-time and in-situ temperature monitoring.     

Femtosecond-Laser Nanostructuring of Black Diamond Films under Different Gas Environments

Irradiation of diamond with femtosecond (fs) laser pulses in ultra-high vacuum (UHV) conditions results in the formation of surface periodic nanostructures able to strongly interact with visible and infrared light. As a result, native transparent diamond turns into a completely different material, namely “black” diamond, with outstanding absorptance properties in the solar radiation wavelength range, which can be efficiently exploited in innovative solar energy converters. Of course, even if extremely effective, the use of UHV strongly complicates the fabrication process. In this work, in order to pave the way to an easier and more cost-effective manufacturing workflow of black diamond, we demonstrate that it is possible to ensure the same optical properties as those of UHV-fabricated films by performing an fs-laser nanostructuring at ambient conditions (i.e., room temperature and atmospheric pressure) under a constant He flow, as inferred from the combined use of scanning electron microscopy, Raman spectroscopy, and spectrophotometry analysis. Conversely, if the laser treatment is performed under a compressed air flow, or a N₂ flow, the optical properties of black diamond films are not comparable to those of their UHV-fabricated counterparts.     

Impact of Methanol Concentration on Properties of Ultra-Nanocrystalline Diamond Films Grown by Hot-Filament Chemical Vapour Deposition

Diamond is a very interesting material with a wide range of properties, making it highly applicable, for example, in power electronics, chemo- and biosensors, tools’ coatings, and heaters. Due to the high demand for this innovative material based on the properties it is already expected to have, it is important to obtain homogeneous diamond layers for specific applications. Doping is often chosen to modify the properties of layers. However, there is an alternative way to achieve this goal and it is shown in this publication. The presented research results reveal that the change in methanol content during the Hot Filament Chemical Vapour Deposition (HF CVD) process is a sufficient factor to tune the properties of deposited layers. This was confirmed by analysing the properties of the obtained layers, which were determined using Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and an atomic force microscope (AFM), and the results were correlated with those of X-ray photoelectron spectroscopy (XPS). The results showed that the increasing of the concentration of methanol resulted in a slight decrease in the sp³ phase content. At the same time, the concentration of the -H, -OH, and =O groups increased with the increasing of the methanol concentration. This affirmed that by changing the content of methanol, it is possible to obtain layers with different properties.     

Silicon Nitride and Hydrogenated Silicon Nitride Thin Films: A Review of Fabrication Methods and Applications

Silicon nitride (SiNx) and hydrogenated silicon nitride (SiNx:H) thin films enjoy widespread scientific interest across multiple application fields. Exceptional combination of optical, mechanical, and thermal properties allows for their utilization in several industries, from solar and semiconductor to coated glass production. The wide bandgap (~5.2 eV) of thin films allows for its optoelectronic application, while the SiNx layers could act as passivation antireflective layers or as a host matrix for silicon nano-inclusions (Si-ni) for solar cell devices. In addition, high water-impermeability of SiNx makes it a potential candidate for barrier layers of organic light emission diodes (OLEDs). This work presents a review of the state-of-the-art process techniques and applications of SiNx and SiNx:H thin films. We focus on the trends and latest achievements of various deposition processes of recent years. Historically, different kinds of chemical vapor deposition (CVD), such as plasma enhanced (PE-CVD) or hot wire (HW-CVD), as well as electron cyclotron resonance (ECR), are the most common deposition methods, while physical vapor deposition (PVD), which is primarily sputtering, is also widely used. Besides these fabrication methods, atomic layer deposition (ALD) is an emerging technology due to the fact that it is able to control the deposition at the atomic level and provide extremely thin SiNx layers. The application of these three deposition methods is compared, while special attention is paid to the effect of the fabrication method on the properties of SiNx thin films, particularly the optical, mechanical, and thermal properties.     

Electroplating Deposition of Bismuth Absorbers for X-ray Superconducting Transition Edge Sensors

An absorber with a high absorbing efficiency is crucial for X-ray transition edge sensors (TESs) to realize high quantum efficiency and the best energy resolution. Semimetal Bismuth (Bi) has shown greater superiority than gold (Au) as the absorber due to the low specific heat capacity, which is two orders of magnitude smaller. The electroplating process of Bi films is investigated. The Bi grains show a polycrystalline rhombohedral structure, and the X-ray diffraction (XRD) patterns show a typical crystal orientation of (012). The average grain size becomes larger as the electroplating current density and the thickness increase, and the orientation of Bi grains changes as the temperature increases. The residual resistance ratio (RRR) (R_{300 K}/R_{4.2 K}) is 1.37 for the Bi film (862 nm) deposited with 9 mA/cm² at 40 °C for 2 min. The absorptivity of the 5 μm thick Bi films is 40.3% and 30.7% for 10 keV and 15.6 keV X-ray radiation respectively, which shows that Bi films are a good candidate as the absorber of X-ray TESs.     

Fabrication of Boron-Doped Diamond Film Electrode for Detecting Trace Lead Content in Drinking Water

This work aimed to fabricate a boron-doped diamond film electrode for detecting trace amounts of lead in drinking water so as to safeguard it for the public. Available detectors suffer from high costs and complex analytical processes, and commonly used electrodes for electrochemical detectors are subject to a short life, poor stability, and secondary pollution during usage. In this work, a boron-doped diamond (BDD) electrode was prepared on a porous titanium substrate, and the microstructure and electrochemical properties of the BDD electrode were systematically studied. Moreover, the stripping parameters were optimized to obtain a better signal response and determine the detection index. As a result, diamond particles were closely arranged on the surface of the BDD electrode with good phase quality. The electrode showed high electrochemical activity, specific surface area, and low charge transfer resistance, which can accelerate the stripping reaction process of Pb²⁺. The BDD electrode presented a low detection limit of 2.62 ppb for Pb²⁺ under an optimized parameter set with an enrichment time of 150 s and a scanning frequency of 50 Hz. The BDD electrode also has good anti-interference ability. The designed BDD electrode is expected to offer a reliable solution for the dilemma of the availability of metal electrodes and exhibits a good application prospect in the trace monitoring of Pb²⁺ content in drinking water.     

The Fabrication of Porous Metal-Bonded Diamond Coatings Based on Low-Pressure Cold Spraying and Ni-Al Diffusion-Reaction

A porous metal-bonded diamond grinding wheel has an excellent performance in precision grinding. In this research, a novel manufacturing process of porous metal-bonded diamond coating was presented. Firstly, the diamond/Ni/Al coatings (400–600 μm) were fabricated via low-pressure cold spraying and their microstructures were studied. The diamond particles in the feedstock had a core–shell structure. Secondly, the post-spray heat-treatments were set at 400 °C and 500 °C to produce pores in the cold-sprayed coatings via Ni-Al diffusion. The porosities of 400 °C and 500 °C heated coating were 8.8 ± 0.8% and 16.1 ± 0.7%, respectively. Finally, the wear behavior of porous heated coating was tested in contrast with cold-sprayed coating under the same condition via a ball-on-disc tribometer. The wear mechanism was revealed. The porous heated coating had better wear performance including chip space and slight clogging. The surface roughness of wear counterpart ground by the porous heated coating was smaller (Sa: 0.30 ± 0.07 μm) than that ground by cold-sprayed coating (Sa: 0.37 ± 0.09 μm). After ultrasonic clean, the average exposure height of diamond particles in the wear track of porous heated coating was 44.5% higher than that of cold-sprayed coating. The presented manufacturing process can contribute to fabricate high performance grinding wheels via cold spraying and porous structure controlling through Ni-Al diffusion–reaction.     

In Situ Laser-Induced Fabrication of a Ruthenium-Based Microelectrode for Non-Enzymatic Dopamine Sensing

In this paper, we propose a fast and simple approach for the fabrication of the electrocatalytically active ruthenium-containing microstructures using a laser-induced metal deposition technique. The results of scanning electron microscopy and electrical impedance spectroscopy (EIS) demonstrate that the fabricated ruthenium-based microelectrode had a highly developed surface composed of 10 μm pores and 10 nm zigzag cracks. The fabricated material exhibited excellent electrochemical properties toward non-enzymatic dopamine sensing, including high sensitivity (858.5 and 509.1 μA mM⁻¹ cm⁻²), a low detection limit (0.13 and 0.15 μM), as well as good selectivity and stability.     

Cyclodextrins as Supramolecular Recognition Systems: Applications in the Fabrication of Electrochemical Sensors

Supramolecular chemistry, although focused mainly on noncovalent intermolecular and intramolecular interactions, which are considerably weaker than covalent interactions, can be employed to fabricate sensors with a remarkable affinity for a target analyte. In this review the development of cyclodextrin-based electrochemical sensors is described and discussed. Following a short introduction to the general properties of cyclodextrins and their ability to form inclusion complexes, the cyclodextrin-based sensors are introduced. This includes the combination of cyclodextrins with reduced graphene oxide, carbon nanotubes, conducting polymers, enzymes and aptamers, and electropolymerized cyclodextrin films. The applications of these materials as chiral recognition agents and biosensors and in the electrochemical detection of environmental contaminants, biomolecules and amino acids, drugs and flavonoids are reviewed and compared. Based on the papers reviewed, it is clear that cyclodextrins are promising molecular recognition agents in the creation of electrochemical sensors, chiral sensors, and biosensors. Moreover, they have been combined with a host of materials to enhance the detection of the target analytes. Nevertheless, challenges remain, including the development of more robust methods for the integration of cyclodextrins into the sensing unit.     

Fabrication and Supercritical Water Corrosion Resistance of TiN/TiNC/Al2O3 Multilayer Coating on Inconel 625 Alloy by CVD Method

A TiN/TiNC/Al₂O₃ multilayer coating was deposited on an Inconel 625 alloy by the chemical vapor deposition method as a protective barrier to improve the corrosion resistance in supercritical water. The corrosion characteristics were evaluated in a reactor at 500 °C and 25 MPa for 72 h. The surface morphology of the coated samples was relatively dense with no obvious cracks or pores observed. The XRD analysis revealed that the coatings were composed of TiN, TiNC and α-Al₂O₃ phases. After exposure to supercritical water, the surface morphology of the coatings was still dense and kept integrity. The phase composition of the coatings was also not changed, with no obvious corrosion scales detected. This result demonstrates the effectiveness of TiN/TiNC/Al₂O₃ coatings as a protective coating under harsh supercritical water environments.     

Fabrication of a Micron-Scale Three-Dimensional Single Crystal Diamond Channel Using a Micro-Jet Water-Assisted Laser

Two types of a trench with conventional vertical and new reverse-V-shaped cross-sections were fabricated on single crystal diamond (SCD) substrate using a micro-jet water-assisted laser. In addition, a microwave plasma chemical vapor deposition device was used to produce multiple micrometer-sized channels using the epitaxial lateral overgrowth technique. Raman and SEM methods were applied to analyze both types of growth layer characterization. The hollowness of the microchannels was measured using an optical microscope. According to the findings, the epitaxial lateral overgrowth layer of the novel reverse-V-shaped trench produced improved SCD surface morphology and crystal quality.     

A Low Temperature Growth of Cu2O Thin Films as Hole Transporting Material for Perovskite Solar Cells

Copper oxide thin films have been successfully synthesized through a metal–organic chemical vapor deposition (MOCVD) approach starting from the copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), Cu(tmhd)₂, complex. Operative conditions of fabrication strongly affect both the composition and morphologies of the copper oxide thin films. The deposition temperature has been accurately monitored in order to stabilize and to produce, selectively and reproducibly, the two phases of cuprite Cu₂O and/or tenorite CuO. The present approach has the advantages of being industrially appealing, reliable, and fast for the production of thin films over large areas with fine control of both composition and surface uniformity. Moreover, the methylammonium lead iodide (MAPI) active layer has been successfully deposited on the ITO/Cu₂O substrate by the Low Vacuum Proximity Space Effusion (LV-PSE) technique. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM) analyses have been used to characterize the deposited films. The optical band gap (E_g), ranging from 1.99 to 2.41 eV, has been determined through UV-vis analysis, while the electrical measurements allowed to establish the p-type conductivity behavior of the deposited Cu₂O thin films with resistivities from 31 to 83 Ω cm and carrier concentration in the order of 1.5–2.8 × 10¹⁶ cm⁻³. These results pave the way for potential applications of the present system as a hole transporting layer combined with a perovskite active layer in emergent solar cell technologies.     

Nitrogen Functionalization of CVD Grown Three-Dimensional Graphene Foam for Hydrogen Evolution Reactions in Alkaline Media

Three-dimensional graphene foam (3D-GrFoam) is a highly porous structure and sustained lattice formed by graphene layers with sp² and sp³ hybridized carbon. In this work, chemical vapor deposition (CVD)—grown 3D-GrFoam was nitrogen-doped and platinum functionalized using hydrothermal treatment with different reducing agents (i.e., urea, hydrazine, ammonia, and dihydrogen hexachloroplatinate (IV) hydrate, respectively). X-ray photoelectron spectroscopy (XPS) survey showed that the most electrochemically active nitrogen-doped sample (GrFoam3N) contained 1.8 at % of N, and it exhibited a 172 mV dec⁻¹ Tafel plot associated with the Volmer–Heyrovsky hydrogen evolution (HER) mechanism in 0.1 M KOH. By the hydrothermal process, 0.2 at % of platinum was anchored to the graphene foam surface, and the resultant sample of GrFoamPt yielded a value of 80 mV dec⁻¹ Tafel associated with the Volmer–Tafel HER mechanism. Furthermore, Raman and infrared spectroscopy analysis, as well as scanning electron microscopy (SEM) were carried out to understand the structure of the samples.