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In the present study, two types of diamond films with a diameter of 123 mm were deposited by DC arc plasma jet chemical vapor deposition (CVD) operating in the gas recycling mode. These two diamond films were found to possess peculiar grain family morphologies. The fracture strengths of the samples were 182.65 and 995.58 MPa, respectively. To investigate the possible reason for the large difference in the fracture strength between the samples, the surface and fracture morphologies of the two types of diamond films as well as their grain size were characterized. The results revealed that the sample with low fracture strength suffered from a typical intergranular fracture. Weak grain boundary, impurities distributed in the boundary, and low strength of diamond grains led to a decrease in the fracture strength. However, the sample with high fracture strength mainly suffered from transgranular fracture and the columnar grain exhibited numerous voids. Owing to the impact of twinning, the voids could be occupied, thus increasing the contact area between the adjacent grains. Moreover, large grain family on the growth side contained numerous small grains and twins. These small grains, twins on growth side along with the difference of stress on surfaces inhibit fracture strength from decreasing rapidly. All these features benefitted fracture strength. Moreover, when the sample was loaded, the tips located in the voids probably resulted in increase of risk of stress concentration, which might have led to initiation of crack origin and eventual fracture. [ABSTRACT FROM AUTHOR]

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]

Y 2 O 3 anti-reflection films were deposited on freestanding chemical vapor deposited (CVD) diamond substrates by radio frequency magnetron sputtering. The effects of oxygen–argon ratio on microstructure, composition, optical property and mechanical property were analyzed by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, spectroscopic ellipsometry, Fourier transformed infrared spectroscopy, and nanoindentation. The results showed that the crystal structure of Y 2 O 3 films transformed from cubic to monoclinic with the increase of oxygen–argon ratio. Meanwhile, the degree of non-stoichiometry of the film with the monoclinic phase was higher than the film with the cubic phase. Both monoclinic and cubic Y 2 O 3 film had an anti-reflection effect on diamond in the 8–12 μm long-wavelength infrared (LWIR) range. However, the maximum transmittance of the Y 2 O 3 film-coated diamond was shifted to lower wavelengths, which were mainly attributed to the reflective indexes of the Y 2 O 3 film that decreased with the increase of the oxygen–argon ratio. The Y 2 O 3 film with a cubic phase had high resistance to abrasion and plastic deformation. Therefore, the Y 2 O 3 film with a cubic phase was much more suitable for long-wave infrared application. [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]

Abstract: The plasma treatment of rapid heating was introduced for increasing fracture strength of free-standing diamond films. The effects of plasma high temperature annealing treatment on surface morphology, internal stress, vacancy defects, impurities and fracture strength of free-standing diamond films were investigated by scanning electron microscopy (SEM), Raman, positron annihilation technique (PAT) and mechanical property testing. It showed that the fracture strength of the diamond films increases up to 70% for lower fracture diamond films with treating temperature (1500–1600°C). The graphitization in surface and interior of diamond films would be produced by high temperature treatment more than 1700°C. Fracture strengths of diamond films could be enhanced after high temperature treatment and the main factor of that was compressive stress state in diamond films induced by graphitization. The impurity of N was segregated and integrated with vacancy cluster to become [N–V]0 and [N–V]−. [Copyright &y& Elsevier]

Abstract: Highly c-axis oriented ZnO film is often deposited on diamond substrates by RF magnetron sputtering and widely used for high frequency surface acoustic wave (SAW) devices. Deposition temperature is a key factor affecting the quality of the ZnO film. Different quality polished free-standing diamond films prepared by DC Arc Plasma Jet were used as the substrates to deposit ZnO films at different temperatures. Effect of the deposition temperature and the quality of the diamond films on the properties of the ZnO films were investigated by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that highly c-axis oriented ZnO films can be much easier deposited on the optical-grade diamond films with <111> preferred orientation than the tool-grade diamond films with <220> preferred orientation. The optimal deposition temperature is 200°C for highly c-axis oriented and lower roughness ZnO films. Acoustic phase velocity of more than 10,000m/s for the SAW devices based on the ZnO/optical-grade free-standing diamond films was obtained. [Copyright &y& Elsevier]

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]

• Large scale all diamond microchannel has been fabricated by DC arc jet CVD and laser cutting. • Three methods have been carried out to modify the diamond microchannel surface to fulfill different terminations, including oxygen termination, hydrogen termination and fluorine termination. • The change of the surface properties of the diamond surface referring to the real situation flow was analyzed and explained in detail. The diamond microchannel heat sink (D-MCHS) has extremely ultra-high stability and heat transfer capacity, and the surface modification can further improve the heat dissipation capacity of D -MCHS. In this study, diamond microchannels were modified by three surface termination operations, including oxygen-terminated (OT), hydrogen (HT), and fluorine-terminated surfaces (FT). Referring to the real situation, after the treatment of heat flow, the hydrophobic properties of HT-diamond microchannels decreased and resulted in the increase of surface heat transfer coefficient by 11%. The hydrophilic properties of OT-diamond tend to be stable after being significantly reduced, and the heat transfer coefficient decreased by 7%. FT-diamond was the most stable; its hydrophobicity remained constant after a slight decrease in the initial stage, and the corresponding surface heat transfer coefficient increased by 14%. X-ray photoelectron spectroscopy (XPS) was used to evaluate the surface bonding state of different terminal treatments. The results show that although the F terminal has more stable hydrophobicity, its surface temperature is 5 °C higher than that of the hydrophilic terminal, and the heat transfer coefficient is reduced from 9500 to 6000 W/(m2K), decreasing by nearly 58%. [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]

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]

Abstract: A destroyable Ti interlayer on graphite substrate was used for fabrication of crack-free free-standing diamond films by high-power DC Arc Plasma Jet. Ti interlayer was arc ion plated on the polycrystalline graphite substrate. The thickness, morphology and composite phase of the Ti interlayer were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Titanium carbide (TiC) was detected in both sides of the interlayer, which played an important role with respect to reasonable adhesion and diamond nucleation. Semi-translucent and crack-free diamond films were obtained and characterized by SEM and Raman spectroscopy. It is shown that the diamond films so obtained have excellent Raman signature. The overall results suggest that plating Ti interlayer on graphite substrate is an effective way to obtain potentially crack-free free-standing diamond films. [Copyright &y& Elsevier]

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]

The growth process of carbon film on the surface of hydrocooling copper substrate in high-density direct current (DC) arc plasma was studied. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, nuclear magnetic resonance spectroscopy, and UV confocal Raman spectroscopy were used to analyze the structural constituents of the intermediate products generated at different growth periods. Results show that despite the remarkable heating effect of DC arc plasma to the copper substrate, one layer of cauliflower saturated carbon and double carbon bond as main component loose matter are first formed because of water-cooled copper substrate. With the increase in thickness of carbon film, the surface temperature gradually increases, the etching ability of the atomic hydrogen is enhanced and high concentration reactive units are maintained on the surface of carbon film. The cauliflower structure may effectively reduce the diamond nucleation barrier and promote the generation of nano-diamond. The diamond grains gradually grow up to the micron scale by the continuing influence of carbon-based active group and plasma. The growth pattern of carbon film on the hydrocooling copper substrate in high-density DC arc plasma may provide a new way to prepare large crack-free diamond films. [ABSTRACT FROM AUTHOR]

The addition of titanium (Ti) interlayer was verified to reduce the residual stress of diamond films. The evolution of interfacial stress during the cooling process is critical for the fabrication of large-area crack-free diamond films, so it is very worthy of further study. Variable-temperature X-ray diffraction (XRD) tests and finite element simulation were performed to evaluate the stress evolution of a diamond film. The film (with diameter of 150 mm) was prepared on a graphite substrate with Ti interlayer using DC arc plasma jet. Residual compressive stress in the diamond film is gradually increased during the cooling process. Moreover, the value and growth rate of the residual stress from the XRD tests are significantly lower than the finite element simulation results. All XRD peaks of diamond, graphite, and titanium carbide (TiC) generated on both sides of the Ti interlayer shift to a larger angle. By contrast, several XRD peaks of Ti deviate to a low angle. Elastic deformation of the Ti layer may offset the lattice contraction caused by the cooling effect. Elasticity modulus of TiC is significantly greater than that of Ti, which is more inclined to release the stress of the diamond film by self-fracturing. After the variable-temperature tests, residual compressive stress of the diamond film at room temperature is 1.1 GPa, whereas that before the tests is 1.4 GPa. These values are significantly lower than the finite element simulation results (3.05 GPa). [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]

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]

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]

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]

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-situ micro-area analysis of precisely polished polycrystalline diamond (PCD) film by high-speed three-dimensional dynamic friction polishing (3DM-DFP) is carried out in this work, continuing from the previous works focusing on the subsurface cleavage and polishing mechanism. Multi-orientational grains with variable hardness anisotropy are generally considered the reason for the surface irregularity of PCD after smoothing. The unreached surface ultra-smoothness in local region after polishing is mainly resulted from the height difference at grain boundary (GB) area (e.g. , a selected GB micro-region is of around Ra roughness of 5.7 nm and altitude intercept of 6.6 nm). However, different individual grains nearby showing (100), (110), (111) orientations are all of roughness <0.5 nm, demonstrating these places are contiguously polished. The observed local roughening at GBs region after mechanical sliding accompanying with friction heat is the major factor to cause the surface irregularity, which is affected by the inhomogeneity of crystal thermal expansion and contraction associated with the defects in multi-orientational crystals generated by mechanical process. Among multi-crystals the low-position (110) region has a Ra roughness of 0.1 nm but with great tensile stress and relatively weak distortion compared with other orientational areas. An insight of the inhomogeneous volume change associated with thermal expansion and contraction affected by defects condition was proposed to straightforwardly illuminate the rationale of GB effects on the ultra-smoothing of PCD by 3DM-DFP. [Display omitted] • A phenomenon deteriorating ultra-smoothing of PCD by high-speed 3DM-DFP was found. • In-situ micro-area analysis of PCD before and after 3DM-DFP was carried out. • The height difference at GBs is resulted from the CTE inhomogeneity associated with defects. [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]

The surface conductivity on the H-terminated diamond is still an interesting topic in the field of diamond electronics. Until now, the carrier mobility in the conductive channel has been limited to below 200cm2/Vs due to the various surface scattering mechanisms. In this paper, a high mobility conductive channel on the H-terminated diamond surface was reported. Firstly, the high quality diamond films were deposited on the commercial CVD diamond substrates. After polishing, the H-termination was obtained by hydrogen plasma treatment. The surface morphology of the H-terminated diamond was observed by atomic force microscope (AFM) and scanning electron microscope (SEM). The crystal quality on the diamond surface was characterized by Raman spectroscopy. The impurities in the crystals were tested by photoluminescence spectroscopy. The surface conductivity of H-terminated diamond was monitored comprehensively by Hall test. It can be found that the sheet resistance decreases much and the carrier mobility increases dramatically after the hydrogen plasma treatment and mechanical cleaning. The maximum mobility value is up to 365cm2/Vs with carrier density of 2.9 × 1012 cm−2, which is the highest value reported. Raman spectra of diamond surface show that a peak appears at 1121.4 cm−2 after the hydrogen plasma treatment, which corresponds to the nanocrystal diamond or carbon clusters of sp3 bonded material. The corresponding mobility enhancement mechanism on the H-terminated diamond surface was proposed. Unlabelled Image • The carrier mobility enhancement on the H-terminated diamond surface was found. • A thin carbon film on the diamond surface was observed with Raman peak at 1121 cm−1. • The H-terminated diamond surface showed high carrier mobility of 365cm2/Vs. • The corresponding mobility enhancement mechanism was proposed. [ABSTRACT FROM AUTHOR]

To unfold the promise of diamond as an advanced technical material, single-crystal diamonds (SCDs) and polycrystalline diamonds (PCDs) were smoothed by high-precision three-dimensional movement dynamic friction polishing (3DM-DFP) to achieve the ultra-smooth surface with roughness <5 nm (even 1 nm) more effectively. However, this inevitably leads to subsurface damage growth, i.e., subsurface defects evolved from nearly damage free to partial defects, and to cleavage faults beneath the SCD surface, resulting from mechanical fatigue and/or the rate of energy input by increasing the linear polishing velocity (from 12 m s−1 to 60 m s−1). In this study it was elucidated, for the first time, the subsurface uniform tile-roof-like cleavage faults and its formation mechanism of diamond after 3DM-DFP at the superhigh speed of linear sliding velocity of 60 m s−1. And the generated subsurface damage would be extended to about 10 μm in depth of the (100) SCD and manifested as micro-cleavage fault region, transition area and compressive zone. Meanwhile, two Raman peaks of 1425 cm−1 (first-order) and 2200 cm−1 (second-order) are assigned to the subsurface damage, which is the amorphous carbon (quasi sp 3 + sp 2) resulting from the cleavage along (111) crystal planes, based on the fine analysis of Raman spectroscopy and the study of subsurface defect evolution in different types of diamonds. Moreover, the assignment of concomitant peaks of 1750 cm−1 (localized defects) and 2100 cm−1 (sp 1 chains) were revealed. Unlabelled Image • SCDs and PCDs with roughness <5 nm (even 1 nm) were smoothed by 3DM-DFP. • Uniform subsurface cleavage was generated in SCD after 3DM-DFP at linear velocity of 60 m s−1. • Mechanical damage beneath the SCD (100) surface would be extended to 10 μm in depth. • Heavy subsurface damage comprises cleavage, transition and compressive regions. • Subsurface a -C consisting of quasi sp 3 + sp 2, sp 1 and C V was revealed after 3DM-DFP. [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]