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Optical erbium oxide (Er 2 O 3) films were prepared by radio frequency (RF) magnetron sputtering to improve the infrared (IR) transmittance of chemical vapor deposition (CVD) diamond. This study aims to analyze the microstructure, composition and optical properties of Er 2 O 3 anti-reflection films at various oxygen/argon ratios. Atomic force microscopy (AFM) analysis was used to detect the surface morphology of chemical oxidation CVD diamond and Er 2 O 3 films. The surface roughness of Er 2 O 3 films decreased with an increase in the oxygen/argon ratio. The crystalline structure of Er 2 O 3 films was analyzed by using X-ray diffraction. Meanwhile, a gradual decrease was observed when the crystallite size and its strain were calculated. This was due to the transformation of partial phases from monoclinic to cubic structures. The chemical composition of Er 2 O 3 films was analyzed by X-ray photoelectron spectroscopy (XPS). The surface of Er 2 O 3 films underwent a transformation from the unstable structure of nonstoichiometric Er 2 O 3-x to the stable structure of Er 2 O 3 with an increase in the level of oxygen. Defect behavior was determined by transmission electron microscopy (TEM). Specifically, dislocation and twinning were observed at a high oxygen/argon ratio, which was mainly attributed to the competitive growth of polycrystalline Er 2 O 3 films. The optical constants of Ψ and △ were shifted to lower wavelengths with increase oxygen/argon ratio. The maximum transmittance of the Er 2 O 3 /diamond film was 79% in the long-wavelength infrared (LWTR) range of 8–12 μm at an oxygen/argon ratio of 1:35. This value was significantly higher than that of the high oxygen/argon ratio. The present study concludes that a low oxygen/argon ratio promotes the growth and IR transmittance of Er 2 O 3 films. [ABSTRACT FROM AUTHOR]

Diamond has attracted increasing attention because it has high thermal conductive. Here, a freestanding diamond thermal conductive film with a diameter of about 7 in. and an average thickness of 1.54 mm was prepared by DC arc plasma jet CVD with multi-stage magnetic fields. Specifically, the thickness uniformity was ensured by adding the magnetic field during the deposition of the freestanding diamond film. The morphology, structure and thermal conductivity of the diamond film were studied. The results showed that the expansion area of the DC arc plasma approached the surface of the substrate increasing duo to add the bottom magnetic field. Structural characterization revealed that the grain of the diamond film in the arc main were coarse, affected by the shape of DC arc plasma, while in the arc center and edge were fine. The main orientation of polycrystalline structure of the diamond film was the crystalline plane of (220). The Raman peaks of diamond film in different areas moved to a higher wavelength, indicating the existence of compressive stress inside the diamond film. The coarse columnar grain and a few grain boundaries were in the arc main. Therefore, the average value of the thermal conductivity (k ⊥) of diamond film measured in the arc main was 1728.9 ± 4.9 W/(m·k). Meanwhile, the thermal conductivity of the arc center and edge area was lower than that of the arc main. [Display omitted] • A freestanding diamond thermal conductive film with a diameter of about 7 in. was prepared. • DC arc plasma jet CVD with multi-stage magnetic fields was adopted. • The average value of the thermal conductivity (k ⊥) of diamond film measured in the arc main was 1728.9 ± 4.9 W/(m·k). [ABSTRACT FROM AUTHOR]

Graphite-based metal transition-layer substrates hold great potential for preparing large-area diamond films and achieving crack-free release. In this study, a five-inch crack-free free-standing diamond film was prepared on a graphite substrate with a sacrificial Mo/Ti double-layer transition layer using direct-current arc plasma jet chemical vapor deposition (DC jet CVD). The interfacial bonding and diffusion behavior between the diamond and the transition layers were investigated. The effect of abundant metal particles and elemental diffusion between layers on film adhesion and stress release are discussed and analyzed. The surface of Ti layer prepared by the multi-arc ion-plating contains numerous metal particles that provide a template for the fine-crystalline Mo layer. Metal particles are encapsulated and embedded in the diamond and act as anchors that ensure the stability of the substrate–diamond bond during high-temperature deposition. After deposition, those metal particles act as weak points and play crucial stress-release roles. Mutual elemental diffusion occurs between the Ti, Mo, and diamond layers. Ti penetrates the Mo layer to form a continuous 140-nm-thick thin layer during the initial deposition period, facilitating diamond nucleation. Carbon from the plasma and diamond diffuses into the metal transition layer. Thermal stress generated between the diamond and the graphite substrate is released by destroying the metal transition layer with high thermal expansion coefficient and low elastic modulus during cooling from the deposition temperature. Cracks rapidly propagate along the interface between destroyable transition layers and graphite substrate, which results in the liftoff of a fully crack-free diamond film. [Display omitted] [ABSTRACT FROM AUTHOR]

Oxygen evolution reaction (OER) is critical in water splitting for green hydrogen gas production due to its sluggish kinetics; however, commercial OER catalysts commonly suffer from high cost, low catalytic activity and poor stability. Herein, we developed a C+ ion implantation method to modify single crystal diamond, and the resultant surface amorphous layer not only raised the active site number but also increased the content of the C=O group, thus significantly improving the OER activity. The C+ ion implanted high-temperature and high-pressure (C+-HTHP) and chemical vapor deposition (C+-CVD) diamonds both exhibit low OER overpotential with η 10 of 317 mV and 325 mV respectively, superior to those of HTHP diamond (360 mV), CVD diamond (395 mV) and RuO 2 (364 mV). The potentiostatic testing shows that the C+ implanted diamonds almost didn't undergo the rise of OER overpotential upon catalysis for more than 12 h at a current density of 10 mA cm−2, suggesting a high catalytic stability, owing to the strong bonding between single crystal diamond and amorphous carbon layer. For the first time, we utilized carbon ion implantation to prepare diamond-based high-performance OER catalyst, which broadens the understanding of carbon-based materials in OER catalysis. [ABSTRACT FROM AUTHOR]

Reducing the self-heating of SiC- and GaN/SiC-based high-powered devices by integrating diamond films offers promising performance enhancement of these devices. However, such a reduction strategy faces serious problems, such as diamond nucleation on SiC and stress accumulation greater than 10 GPa. In this work, a SiN x dielectric layer (∼50 nm) was coated onto the C polar face of a 4H–SiC wafer using microwave plasma chemical vapor deposition (MPCVD) to improve direct dense diamond nucleation and growth, significantly reduce the stress, and build Si–C(SiC)⋯Si⋯C(diamond) bond bridges. This SiN x thin layer, prepared by activating Si ions under Ar/N plasma during magnetron sputtering, gave rise to local Si 3 N 4 crystal features and a low effective work function (EWF) for promoting surface dipoles with electronegative carbon-containing groups. In the H plasma environment during diamond growth, the local Si 3 N 4 crystal was amorphized, and the N atoms escaped as a result of atomic H and the high temperature. At the same time, C atoms diffused into the SiN x and formed C–Si bonds (49.7% of the total C bonds) by replacing N–Si and Si–Si, thus increasing the direct nucleation density of the diamond grains. The diamond thin film grew rapidly and uniformly, with a grain size of approximately 2 μm in mixed orientation, and the stress of the 2-inch SiC-on-diamond wafer was extremely low (to ∼0.1–0.2 GPa). In comparison, partially connected diamond grains (>10 μm) on the bare SiC in the preferential (110) orientation resulted in a film with twin-grain features and significant stress, which was associated with the hexagonal lattice interface of 4H–SiC. These results are considered the material and surface/interface bases for actively controlling wafer fabrication and enhancing the heat dissipation of SiC and GaN/SiC electronics. [ABSTRACT FROM AUTHOR]

In this study, standard diamond bars were prepared using an ultra-thick diamond plate, and the bars had sizes consistent with the International Organization for Standardization (ISO) 14704:2016(E) three-point bending method for measuring the fracture strength. Ultra-thick diamond plate with dimensions of 125 mm (diameter) × 6.5 mm (thickness) were deposited using direct current arc plasma jet chemical vapour deposition. After cutting, grinding, and polishing, 12 diamond bars meeting the requirements of the ISO standard were prepared (36 mm × 4 mm × 3 mm) and tested for fracture strength using the cited ISO standard and elastic modulus using deflection measurements. The fracture strength of the ultra-thick diamond plate was found to be 580 ± 66 MPa. In addition, for comparison, the fracture strengths of standard ZnS, sapphire, and alumina were also analysed. Crucially, this is the first report of the fracture strength of standard-sized diamond plate. The effects of the defects and grain size on the crack formation and failure of the diamond film were analysed. The diamond's fracture strength was affected by the sample thickness, which caused the gradual accumulation of defects as this dimension increased, but not by its length and width. The elastic moduli of sapphire and alumina were compared. Overall, the measurement of the fracture strengths of ultra-thick diamond plate via the ISO standard is important for industrial applications. [ABSTRACT FROM AUTHOR]

Deposition of a consistent diamond coating on intricate surfaces has historically posed a difficulty. This article presents the advancement in research on depositing a uniform diamond coating on three-dimensional (3D) silicon spheres, utilizing a faraday cage within a microwave plasma chemical vapor deposition (MPCVD) reactor. A self-consistent three-dimensional multi-physics field model has been established for simulating the microwave electric field and plasma inside a reactor with or without a faraday cage. Results indicate the cage effectively reduces the discharge at the top of the silicon sphere and improves uniformity of the distribution of the microwave electric field and plasma electron density on the sphere's surface. MPCVD trials have demonstrated that a powerful discharge takes place at the apex of the silicon sphere resulting in an excessive thermal gradient if the cage is not added. The apex of the silicon sphere is covered with a blend of diamond and graphite phases. Due to the excessive internal stress of the coating, approximately 50 % of the samples experience coating detachment. After the addition of the cage, the strong discharge is transferred to the top of the cage, effectively suppressing the microwave electric field and plasma inside the cage. Improved quality, reduced internal stress, and enhanced uniformity of the polycrystalline diamond coating are achievable on the silicon spheres within the cage. Moreover, this technique offers a novel approach to coat diamond on complex 3D geometries. [Display omitted] • Three-dimensional multi-physics modeling verifies that faraday cage suppresses microwave electric field and plasma. • The Faraday cage improves the uniformity of the distribution of microwave electric fields and plasma in the internal space. • Uniform, high crystal quality, low stress diamond coating. [ABSTRACT FROM AUTHOR]

The direct-current arc plasma jet method is advantageous for the rapid deposition of large-area self-supporting diamond films. However, dark defects tend to be generated during the growth process, significantly affecting the performance of the diamond. In this study, we use the direct-current arc plasma jet method to prepare transparent and translucent samples. Subsequently, we compare their optical, thermal, and mechanical properties and analyze the differences in their performances via microstructure and defect analyses. The results indicate that the transparent diamond samples exhibit excellent optical and thermal properties, with a transmittance of 68.4 % at a wavelength of 10.6 μm and a thermal conductivity similar to that of type-IIa single crystal diamond (i.e. 2002 W/(m·K)). Meanwhile, the translucent diamond exhibits outstanding mechanical properties, with a fracture strength of 984 MPa. Characterization results based on electron backscatter diffraction and X-ray computed tomography suggest that a preferred orientation along the (220) planes is conducive to the densification growth of the samples, thereby enhancing their optical and thermal properties. However, the generation of numerous twins results in interlocking between grains, which improves sample's mechanical properties but introduces porosity and impurities, thus deteriorating its optical and thermal performance. [Display omitted] • Optical and thermal diamond films were deposited by DC-arc plasma jet CVD with growth rates >6 μm/h. • Strong (220) texture and numerous twins can improve optical transmittance and fracture strength, respectively. • X-ray CT was used to reveal defects distribution and content within diamond samples. [ABSTRACT FROM AUTHOR]

The fabrication of GaN-on-diamond structure by the process of diamond growth on GaN technology is becoming more and more attractive for high-power GaN devices. However, due to the high-temperature steps employed during the GaN epitaxial layer transfer process, significant stress accumulates in the GaN-on-diamond structure and induces the formation of cracks or deformations in the GaN layer. To improve the stress characteristics of the GaN layer, in this work, dual-sided diamond film deposition was carried out to accomplish the GaN-on-diamond structure. The surface morphology, interface microstructure and crystal quality of diamond on GaN were analyzed by using scanning electron microscopy, atomic force microscopy, transmission electron microscopy and X-ray diffraction. The results showed that the stress accumulation originating from the GaN epitaxial layer transfer process was effectively alleviated as compared with other reporteds in the literature and that the crystal quality of the GaN was only slightly altered. The stress relaxation was attributed to the low-quality diamond used as the temporary carrier during the GaN transfer process. In addition, a thin SiC transition layer in the interface is also beneficial in alleviating the mismatch between the coefficients of thermal expansion for the GaN and the diamond. [ABSTRACT FROM AUTHOR]

Slightly graphitization might be incurred on CVD diamond films when suffering instantaneous high temperature thermal shock. In this paper, phase transitions of CVD free-standing diamond films have been studied experimentally at the temperature range of 1500–1800 °C through a plasma rapid heating process. Raman spectra and X-ray photoelectron spectra (XPS) are compared and discussed for the purpose of measuring the percentage of graphitic carbon component in CVD diamond films after heat treatment at different temperatures. An obvious optical degradation took place in both visible and infrared bands with the increased treating temperature. The result indicates that graphitization is dominated along grain boundaries rather than in internal grains. In addition, the nitrogen related absorption peaks were not covered by the enhanced optical absorption background, which was caused by the opaque graphitic carbon formed at high temperature. Nitrogen concentrations have also been evaluated for these graphitized diamond films and there is no evidence to show the movement or aggregation of nitrogen atoms. [ABSTRACT FROM AUTHOR]

Polycrystalline CVD free-standing diamond films have been heat treated through a rapid heating process using a direct current (DC) arc plasma jet system within the temperature range of 1500–2000 °C. The optical transmission of the diamond film decreases when the treatment temperature exceeds 1500 °C. When the diamond film was annealed to 1800 °C for just 1 min, the infrared (IR) transmittance at λ = 10.6 μm of the film was significantly decreased from 60.5% to 4.0%, due to the transformation from diamond to graphite. Further increase of the temperature to 2000 °C leads to complete loss of optical transmittance in only 30 s, due to the detrimental occurrence of graphitization. XRD patterns indicate that graphite ultimately grows preferentially along the (0002) plane by forming disordered or turbostratic graphite as intermediate product. Raman spectra and SEM images verify that at 1500–1850 °C graphitic carbon transforms from the diamond surface in the form of protruding submicron crystallites, which were still containing a number of sp 3 C C bonds. In addition to graphitization on the external surface, the diamond-graphite phase transition also occurs along the grain boundaries and the calculated activation energy of the grain boundary graphitization process is 276 kJ·mol − 1 for the CVD diamond. [ABSTRACT FROM AUTHOR]

Lift-off is a promising method to prepare thin, high-finish, and freestanding large-area single crystal and polycrystalline diamonds. However, accurate control of the damage layer characteristic to achieve both stress release and lift-off process is difficult. In this work, high-energy C+ was implanted in single crystal diamond and polycrystalline diamond to create subsurface damage. The defect behavior and structural transformation of the ion implantation and annealing process were investigated. The homoepitaxial growth was subsequently carried out and the epitaxial layer was lifted off from the substrate by selectively etching the damaged layer. The results show that the cap layer and the substrate (below the damage layer) keep the sp3 carbon structure before and after annealing, which is confirmed by the atomic-scale electron energy loss spectroscopy (EELS). The high-resolution transmission electron microscopy (HRTEM) images show that after annealing at 1000 °C for 1 h, the damaged layer was transformed from amorphous carbon to a mixture of graphite and amorphous carbon, providing the damaged layer that could be removed by electrochemical solution. Meanwhile, the distorted diamond area was changed to a sharp interface, which ensures the low roughness of the substrate surface after the lift-off process. After etching for 30 h, a freestanding polycrystalline diamond film with a thickness of 100 μm and a surface roughness of 1.68 nm was obtained. The roughness of the lift-off substrate surface is 1.10 nm, indicating the epitaxial growth can be repeated directly without polishing. [Display omitted] • The defect behavior and structural transformation of the high-energy C+ implanted diamonds were investigated. • The stress state of the diamonds before and after ion implantation and after lift-off process were evaluated. • A 100 μm-thick freestanding polycrystalline diamond film with a surface roughness of 1.68 nm was successful obtained. [ABSTRACT FROM AUTHOR]

A plasma arc generator was used to heat treat the free-standing CVD diamond films at 1450–1900 °C. An Arrhenius curve was fit according to trends in the measured Raman peak intensity ratio of diamond to graphite as a function of heat treatment temperature, and the curve was extrapolated linearly. It was found that the extrapolation lines intersected at the Debye temperature, Θ D = 2021 K. By comparing the activation energies of diamond graphitization in literature and from different measurement modes in our study, it was found that the graphitization mechanisms were different on both sides of Debye temperature due to differences in the excited lattice vibration modes. When the heat treatment temperature was just below the Debye temperature, the graphitization process was promoted by generating vacancies or the breaking of single C C bonds, and the apparent activation energy was 366 ± 60 kJ·mol−1. When the heat treatment temperature was above the Debye temperature, the graphitization process was promoted by the simultaneous breaking of multiple C C bonds, and the apparent activation energy was 887 ± 141 kJ·mol−1. In combination with the morphology changes on the surface of the CVD diamond film after high temperature heat treatment, the mechanism of the micro-cyclic phase transition on the surface of the diamond film at temperatures lower than Debye temperature was summarized as follows. First, C C bonds on the diamond surface were activated and broken at high temperatures, and some diamond carbon atoms dissociated from solid phase sites to the gas phase by forming hydrocarbon free radicals. Then, the carbon atoms from these hydrocarbons entered the graphite lattice step by step to complete the spontaneous deposition of sp2 clusters. [Display omitted] • The morphological changes of diamond surface dependent on temperature and hydrogen plasma environment were observed. • Taking the Debye temperature as a critical point, the graphitization activation energy exhibits a significant difference. • The graphitization mechanism of CVD diamond surface was proposed based on the kinetics analysis. [ABSTRACT FROM AUTHOR]

Polycrystalline CVD diamond films were subjected to transient heat treatment at the temperature range of 1500–1900 °C in the Ar/H 2 plasma arc environment. The structural changes of the diamond grain boundaries (GB) were indirectly investigated by employing IR optical absorption, Raman spectroscopy, X-ray diffraction (XRD), and fractographic scanning electron microscopy (SEM). The graphitization difference between near-nucleation side and near-growth side is mainly due to the difference in the GBs' content. It is proposed that the bonded‑hydrogen atoms, of which a large amount remained in the diamond GBs, play an active role in the process of graphitization. We recognized the intensity evolution of a peak in Raman spectra located at 1470 cm−1, which was attributed to the trans -polyacetylene at diamond GBs. This result suggests the likelihood that the long-chain hydrocarbon precursor is involved in a mechanism for the sp3-to-sp2 transformation. As the propagation of the graphitization from diamond GB to grain interior, sp2 carbon with compressed state forms in its place due to the limited space for expansion. The graphite along GBs affects the fracture mode of the diamond films, which causes partial GBs to tear, while transgranular fracture occurs instead of directly intergranular fracture. [Display omitted] • A transient heat treatment method was employed to effectively keep the GB graphitization at an early stage. • The Graphitization model demonstrated the long-chain hydrocarbon precursor was involved in the sp3-to-sp2 transformation. • The fracture of annealed diamond was completed between transgranular and intergranular crack propagation. [ABSTRACT FROM AUTHOR]