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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]

Electronic and mechanical properties, and their biocompatibility, make diamond-based materials promising biomedical applications. The cost required to produce high quality single crystalline diamond films is still a hurdle to prevent them from commercial applications, but the emergence of polycrystalline diamond (PCD) films grown by chemical vapour deposition (CVD) method has provided an affordable strategy. PCD films grown on silicon wafer have been used throughout and were fully characterised by SEM, XPS, Raman spectroscopy and FTIR. The samples contain nearly pure carbon, with impurities originated from the CVD growth and the silicon etching process. Raman spectroscopy revealed it contained tetrahedral amorphous carbon with small tensile stress. The sp2 carbon content, comprised between 16.1 and 18.8%, is attributed to the diamond grain boundaries and iron-catalysed graphitisation. Antibacterial properties of PCD films were performed with two model bacteria, i.e. Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) using direct contact and shaking flask methods. The samples showed strong bacteriostatic properties against S. aureus and E. coli with the direct contact method and no influence on planktonic bacterial growth. These results suggest that the bacteriostatic mechanism of PCD films is linked to their surface functional groups (carbon radicals and –NH 2 and –COOH groups) and that no diffusible molecules or components were involved. [ABSTRACT FROM AUTHOR]

• The used big grain PCD films allow the effect of grain boundaries to be ignored. • Compact needles with high aspect ratio were obtained at a rate of 2 μm/min. • O 2 plasma etching generated trans -polyacetylene was suppressed by Cl or H ions. • Preferential etching and needles formation were investigated time-dependently. The needle-like surface morphology evolution in oxygen plasma in combination with a secondary gas (Cl 2 , CHF 3 or CF 4) by inductively coupled plasma reactive ion etching (ICP-RIE) on a free-standing polycrystalline diamond was investigated. The addition of CF 4 can produce trans -polyacetylene (t -PA), which is similar to the result when the pure O 2 etching takes place, and generate compact needle-tip particles. However, the t -PA disappears with the introduction of Cl or H ions. The optimised etching parameters for the needle-like structure formation are as following: Cl 2 /O 2 ratio 20% and RF-power (RFP) 100 W, where more compact and even nano-needles are realised with an average etching rate of 2 μm/min. The Cl 2 /O 2 plasma etching results indicate that the time-dependent etching mechanism of diamond nano-needles results from (1 1 1) crystal plane selective etching and preferential graphitisation at the twin-plane boundary and dislocation area. [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]

[Display omitted] • The La-doped Er 2 O 3 anti-reflection films was prepared by the power of magnetron sputtering. • The compound of La 2 O 3 formed along the grain boundary of the columnar crystal structure of the polycrystalline film. • The highest hardness and yield strength of the La-doped Er 2 O 3 film was two times higher than that of pure Er 2 O 3 film. • The transmittance of the La-doped Er 2 O 3 anti-reflection films only decreased 1% after erosion. The composition and microstructure consisting of anti-reflection films was obtained by the power of magnetron sputtering. X-ray photoelectron spectroscopy (XPS) and High-resolution transmission electron microscopy (HRTEM) provided evidence to support that the doping La element exists as oxide in the grain boundaries of the matrix Er 2 O 3 films. The undoped and La-doped Er 2 O 3 films show a columnar crystal structure of the main cubic (2 2 2) plane. Twinning and a large number of dislocations show up in the undoped Er 2 O 3 films due to the competitive growth of the columnar crystal. In addition, the La-doped Er 2 O 3 films show a lower roughness (RMS) value in comparison with undoped Er 2 O 3 films. The grain size of columnar crystals decreases significantly with increasing La concentration in the La-doped Er 2 O 3 films. The fine grains resulted in the La-doped Er 2 O 3 films developing high mechanical and impact resistance properties, with an increase in hardness from 12.6 ± 2.1 GPa to 26.1 ± 3.4 GPa and the eroding area rate decreasing from 38.9 % to 1.9 %. Moreover, the La-doped Er 2 O 3 anti-reflection films on the chemical vapor deposition (CVD) diamond substrate maintained 74 % transmittance in the long-wavelength infrared range of 8–12 μm after sand eroding. [ABSTRACT FROM AUTHOR]

Surface etching of single-crystal diamond (SCD) in hydrogen plasma plays a decisive role for high-quality homoepitaxy and surface conduction of diamond. The complexity of surface/subsurface condition such as defects would give rise to the distinct morphology features and even further result in the unpredictable properties. Correspondingly, the evolutionary relationship between the morphology and electrical properties of mechanically polished SCDs which have typical cleavage damage in microns depth after hydrogen plasma treatment still needs to be further completed. In this work, the chemical vapor deposited (CVD) SCDs with uniform polishing-caused subsurface cleavage were immersed in microwave hydrogen plasma for variable duration. Time-dependent morphological evolution, multi-mode etched pits (EPs) (resulting from local defects/cracks and dislocations) and associated etching mechanism were comprehensively studied. At the early stage of plasma treatment before 60 min, owing to the obvious surface roughing generated by preferential etching (with the rate of >400 nm/h) of severe mechanically damaged regions, the hole mobility was significantly deteriorated, also accompanying with the apparent drop of sheet concentration. Concurrently, the deposited surface sp 2 amorphous carbon (a -C) nanodots on diamond surface and non- sp 3 hydrogen bonds reconstruction, which arising from defect-etching produced local abundant carbon-containing radicals or possible exfoliation generated by hydrogen penetration of massive defective regions, also would play an adverse role for the conduction associated with (100) C–H surface. However, the surface roughness was reduced from the maximum 13.2 nm–4.2 nm by prolonging etching, resulting from the smoothing effect of small-angle crystal misorientation on waved height difference related to the uniform (111) cleavage and the removal of dense irregular EPs associated with polishing-induced local defects as well as the vanishing of surface a -C nanodots. In this case, the improvement of surface electrical properties together with the negative correlation of the mobility and sheet concentration were appeared by the gradual formation of (100) diamond surface and the building of uniform (100) C–H bonds. • CVD SCDs with typical subsurface damages(defects) were treated in pure hydrogen plasma. • Morphology evolution associated with polishing defects was time-dependently presented. • Surface sp2 nanodots deposition from defect-etching and CH reconstruction would affect electrical properties. [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]

The high-speed three-dimensional movement dynamic friction polishing (3DM-DFP) has been recognized as an efficient approach for ultra-smoothing single crystal diamond (SCD) surface. Continuing from the previous works focusing on the subsurface cleavage of diamond after 3DM-DFP, process optimization and surface reaction evolution mechanism as a fundamental building block is investigated, for the first time, for comprehensively understanding this fast-smoothing manner. By systematically adjusting the controlling factor, stronger load (0.3 MPa) and appropriate duration (0.5 h) as well as moderate sliding speed (in the range of 30 to 45 m s−1) is found to be able to obtain the smooth surface of SCD without uncontacted traces or break-surface cleavage. Subtle residual clues on SCD surface as a function of progressive DFP procedure indicate that Fe catalytic oxidation mainly produce Fe 2 O 3 and partial intermediate oxides Fe 1-y O. Meanwhile, the activated oxygen inserts sp 3 C C bonds could form C O or C O and C-O-V (vacancy) at existing reactive surface sites. The (100) favorable C O bonds can be rebuilt if (100) surface is reformed, although the C O bonds associated with non-(100) rough surface would replace them during DFP procedure. The formed C O C and concomitant C-O-V as well as the oxidized graphite give rise to the increase of C O proportion, and finally the covered defective graphitic phase has an approximate C O/C O ratio of 1.25. All these are endowed potential value for future upgrading of DFP technique for diamond surface smoothing. [Display omitted] • The understanding of high-speed 3DM-DFP is further built by optimally control together with previous works. • The smooth surface with roughness <1 nm was obtained without uncontacted traces and extended cleavage. • Comprehensive polishing mechanism of SCD by high-speed 3DM-DFP was discussed. • Surface carbon‑oxygen bonds evolution is carefully studied based on the polishing procedure. [ABSTRACT FROM AUTHOR]