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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]

The demand of small-angle x-ray scattering (SAXS) windows for in-situ characterization of materials nano-structures in a heated vacuum environment has been increased dramatically. High-quality diamond prepared by chemical vapor deposition (CVD) has become the preferred window material due to its excellent optical and mechanical properties. However, impurities and defects in diamonds may lead to the strong X-ray scattering especially in the heating process, affecting the testing accuracy of the object. In this work, single-crystal diamond (SCD) and polycrystalline diamond (PCD) films with different quality were prepared, and their SAXS properties were investigated at room temperature and heating under vacuum. The results show that the scattering intensity of the undoped high-quality SCD is small and uniform, while that of the SCD window doped with a small amount of nitrogen increases, mainly due to the nitrogen atoms and vacancy clusters scattering. While for the PCDs, the grain boundaries and the dark features lead to strong scattering background. As the temperature rises from room temperature to 280 °C, although the phonon vibration of diamonds exhibits the obvious temperature dependence, the coherent scattering of diamonds with X-ray hardly changes, indicating no new scatterers with the changed gyration radius were generated in the heating process. SCD and PCD windows were successfully applied in an in-situ heating SAXS cell. [ABSTRACT FROM AUTHOR]

The CVD diamond films at different growth stages were prepared on the same substrate by DC arc plasma jet CVD. The surface morphologies and residual stress of diamond films were characterized by scanning electron microscope and Raman spectroscopy. The intrinsic stress of diamond films were obtained by subtracting thermal stress from residual stress. The results showed that the intrinsic compress stress was 0.42 GPa for the precoalescence stage due to the sp 2 carbon inclusions in diamond islands. With the diamond islands growing up and even snapping together to form grain boundary at the coalescence stage the intrinsic compress stress was 0.06 GPa. Eventually, the diamond islands coalesced into a continuous polycrystalline film, the intrinsic compress stress vanished and converted to tensile stress, the intrinsic tensile stress reached 1.41 GPa due to the number of grain boundaries increasing. The evolution of intrinsic stress during diamond film initial growth was mainly attributed to the surface free energy of diamond islands changed to the free energy of grain boundaries which was consistent with the Nix-Clemens model. [ABSTRACT FROM AUTHOR]

Diamond radiation detector is an ideal choice for the next-generation radiation detection in harsh environments, due to its small size, high irradiation resistance and fast response. However, high-purity single crystal diamond is hard to be prepared at the high growth rate due to the inevitable impurity incorporation. In this paper, based on the high-quality high-temperature/high-pressure (HPHT) single crystal diamond substrate, detector-grade single crystal diamonds material with high purity and low defect density were epitaxially grown at growth rate of about 4 μm/h by using plasma environment purification technology. It showed that the full width at half maximum of X-ray rocking curve of high-quality single crystal diamond could reach 0.007°, there was no nitrogen related impurity in PL spectrum, and the substitutional nitrogen content estimated by UV absorption spectrum was less than 10 ppb. After metallization and packaging process, the diamond detectors were prepared and the detector response under irradiation with 241Am α-particles was realized. For the sample with fewer dislocations, the charge collection efficiency and energy resolution of this detector were 86.8 % and 7.85 % for electrons, and 96.7 % and 2.48 % for holes. The product of mobility and lifetime of electrons and holes were 1.7 × 10−4 cm2V−1 and 3.7 × 10−4 cm2V−1, respectively. The high performances of the detector indicate that the current diamond detector can meet the application requirements of commercial diamond detectors. [Display omitted] • Detector-grade diamond was prepared by plasma environment purification technology. • The high-purity single crystal diamond was grown at growth rate of about 4 μm/h. • The diamond detector with charge collection efficiency of 96.7 % was realized. • The products of mobility and lifetime of electrons and holes were 1.7 × 10−4 and 3.7 × 10−4 cm2V−1. [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]

In order to realize the practical use of diamond as a semiconductor material, large-area single-crystal diamond wafers with uniform quality are required. Mosaic growth is an effective method to produce inch-grade single-crystal diamonds. However, the quality of the wafer is limited by the junction interface seriously, because cracking occurs easily due to the high internal stress. In this paper, the repetition growth method was adopted to grow mosaic splicing single-crystal diamond without polycrystalline diamond interface. The high-quality single crystal diamond slices were reduplicated by microwave plasma chemical vapor deposition (MPCVD). The substrates were obtained by cutting a piece of CVD diamond along a plane perpendicular to 〈001〉 (with a (100)-oriented surface). The evolution of the growth characteristics around the junction of the substrates at different stages was studied. The results show that the surface of the epitaxial layers gradually evolves from blurry terraces to a regular well-ordered step flow. When the substrates have the same deviation direction and the off-direction angles are within 3°, the junction of the substrates can connect smoothly. Raman mapping shows that there is a mixture of tensile stress and compressive stress near the junction. As the thickness of the epitaxial layer increases from 280 μm to 560 μm, the range of tensile stress near the joint area expands from 85 μm to 150 μm, the maximum tensile stress increases from 0.08 GPa to 0.16 GPa. In addition, the value of FWHM in the X-ray rocking curve is less than 2.80 cm−1 around the junction, which indicates good crystal quality. [Display omitted] • The evolution of growth characteristics around the junction in the mosaic diamond was studied. • The mosaic boundary evolved from blurry terraces to a well-ordered step flow and finally connected. • The lowest value of tensile stress near the joint area was reported as the film thickness increased. • The larger FWHM of Raman peak around the junction is caused by the increased tensile stress. • The "inherit" effect of NV content of the epitaxial layer was observed for the corresponding substrate. [ABSTRACT FROM AUTHOR]

In the present investigation, a nitrogen-doped multilayer homoepitaxial single crystal diamond is synthesized on a high-pressure high temperature (HPHT) Ib-type diamond substrate using the microwave plasma chemical vapor deposition (MPCVD) method. When 0.15 sccm of nitrogen was added in the gas phase, the growth rate of the doped layer was about 1.7 times that of the buffer layer, and large conical and pyramidal features are formed on the surface of the sample. Raman mapping and photoluminescence imaging of the polished cross sectional slice shows a broadband emission, with a characteristic zero phonon line (ZPL) at 575 nm in the doped layers, and large compressive stress was formed in the nitrogen-doped layers. X-ray topography shows that the defects at the interface can induce dislocation. The pyramid feature is formed at the defect, and more nitrogen-related defects are formed in the pyramid region. Thin nitrogen-doped multilayers were successfully prepared, and the thickness of the nitrogen-doped and buffer layers was about 650 nm each. The indentation measurements reveal that the thin nitrogen-doped multilayers are ultra-tough (at least ~22 MPa m1/2), compared to the Ib-type HPHT seed substrate (~8 MPa m1/2) and the unintentionally doped chemical vapor deposition (CVD) single crystal diamond (~14 MPa m1/2). [ABSTRACT FROM AUTHOR]