Edge effect during microwave plasma chemical vapor deposition diamond-film:Multiphysics simulation and experimental verification

This study focused on the investigation of the edge effect of diamond films deposited by microwave plasma chemical vapor de-position.Substrate bulge height△h is a factor that affects the edge effect,and it was used to simulate plasma and guide the diamond-film deposition experiments.Finite-element software COMSOL Multiphysics was used to construct a multiphysics(electromagnetic,plasma,and fluid heat transfer fields)coupling model based on electron collision reaction.Raman spectroscopy and scanning electron microscopy were performed to characterize the experimental growth and validate the model.The simulation results reflected the experimental trends observed.Plasma discharge at the edge of the substrate accelerated due to the increase in△h(△h=0-3 mm),and the values of electron density(n_(c)),molar concentration of H(C_(H)),and molar concentration of CH_(3)(C_(CH_(3)))doubled at the edge(for the special concave sample with△h=−1 mm,the active chemical groups exhibited a decreased molar concentration at the edge of the substrate).At=0-3 mm,a high diamond growth rate and a large diamond grain size were observed at the edge of the substrate,and their values increased with.The uniformity of film thickness decreased with.The Raman spectra of all samples revealed the first-order characteristic peak of dia-mond near 1332 cm^(−1).When△h=−1 mm,tensile stress occurred in all regions of the film.When△h=1-3 mm,all areas in the film ex-hibited compressive stress.

Evaluation on residual stresses of silicon-doped CVD diamond films using X-ray diffraction and Raman spectroscopy

The effect of silicon doping on the residual stress of CVD diamond films is examined using both X-ray diffraction (XRD) analysis and Raman spectroscopy measurements. The examined Si-doped diamond films are deposited on WC-Co substrates in a home-made bias-enhanced HFCVD apparatus. Ethyl silicate (Si(OC2H5)4) is dissolved in acetone to obtain various Si/C mole ratio ranging from 0.1% to 1.4% in the reaction gas. Characterizations with SEM and XRD indicate increasing silicon concentration may result in grain size decreasing and diamond [110] texture becoming dominant. The residual stress values of as-deposited Si-doped diamond films are evaluated by both sin2ψ method, which measures the (220) diamond Bragg diffraction peaks using XRD, with ψ-values ranging from 0° to 45°, and Raman spectroscopy, which detects the diamond Raman peak shift from the natural diamond line at 1332 cm-1. The residual stress evolution on the silicon doping level estimated from the above two methods presents rather good agreements, exhibiting that all deposited Si-doped diamond films present compressive stress and the sample with Si/C mole ratio of 0.1% possesses the largest residual stress of ~1.75 GPa (Raman) or ~2.3 GPa (XRD). As the silicon doping level is up further, the residual stress reduces to a relative stable value around 1.3 GPa.

Effect of deposition parameters on micro-and nano-crystalline diamond films growth on WC-Co substrates by HFCVD

The characteristics of hot filament chemical vapor deposition（HFCVD） diamond films are significantly influenced by the deposition parameters, such as the substrate temperature, total pressure and carbon concentration. Orthogonal experiments were introduced to study the comprehensive effects of such three parameters on diamond films deposited on WC-Co substrates. Field emission scanning electron microscopy, atomic force microscopy and Raman spectrum were employed to analyze the morphology, growth rate and composition of as-deposited diamond films. The morphology varies from pyramidal to cluster features with temperature decreasing. It is found that the low total pressure is suitable for nano-crystalline diamond films growth. Moreover, the substrate temperature and total pressure have combined influence on the growth rate of the diamond films.

Enhancement of nucleation of diamond films deposited on copper substrate by nickel modification layer

A Ni layer with a thickness of about 100 nm was sputtered on Cu substrates,followed by an ultrasonic seeding with nanodiamond suspension.High-quality diamond film with its crystalline grains close to thermal equilibrium shape was deposited on Cu substrates by hot-filament chemical vapor deposition（HF-CVD）,and the sp2 carbon content was less than 5.56%.The nucleation and growth of diamond film were investigated by micro-Raman spectroscopy,scanning electron microscopy,and X-ray diffraction.The results show that the nucleation density of diamond on the Ni-modified Cu substrates is 10 times higher than that on blank Cu substrates.The enhancement mechanism of the nucleation kinetics by Ni modification layer results from two effects：namely,the nanometer rough Ni-modified surface shows an improved absorption of nanodiamond particles that act as starting points for the diamond nucleation during HF-CVD process;the strong catalytic effect of the Ni-modified surface causes the formation of graphite layer that acts as an intermediate to facilitate diamond nucleation quickly.

Effects of deposition parameters on HFCVD diamond films growth on inner hole surfaces of WC-Co substrates

Deposition parameters that have great influences on hot filament chemical vapor deposition (HFCVD) diamond films growth on inner hole surfaces of WC?Co substrates mainly include the substrate temperature (t), carbon content (φ), total pressure (p) and total mass flow (F). Taguchi method was used for the experimental design in order to study the combined effects of the four parameters on the properties of as-deposited diamond films. A new figure-of-merit (FOM) was defined to assess their comprehensive performance. It is clarified thatt,φandp all have significant and complicated effects on the performance of the diamond film and the FOM, which also present some differences as compared with the previous studies on CVD diamond films growth on plane or external surfaces. Aiming to deposit HFCVD diamond films with the best comprehensive performance, the key deposition parameters were finally optimized as:t=830 °C,φ=4.5%,p=4000 Pa,F=800 mL/min.

Preparation and characterization of diamond film on Cu substrate using Cu-diamond composite interlayer

Large area diamond films were fabricated on copper substrates by a multi-step process comprised of electroplating Cu-diamond composite layer on Cu substrate, plating a Cu layer to fix the protruding diamond particles, and depositing continuous diamond film on composite interlayer by hot-filament chemical vapor deposition （HFCVD）. The interface characteristics, internal stress and adhesion strength were investigated by scanning electron microscopy, Raman analysis and indentation test. The results show that the continuous film without cracks is successfully obtained. The microstructure of the film is a mixture of large cubo-octahedron grains grown from homo-epitaxial growth and small grains with （111） apparent facets grown from lateral second nuclei. The improved adhesion between diamond film and substrate results from the deep anchoring of the diamond particles in the Cu matrix and the low residual stress in the film.

Application of ultra-smooth composite diamond film coated WC-Co drawing dies under water-lubricating conditions

A specific revised HFCVD apparatus and a novel process combining HFCVD and polishing technique were presented to deposit the micro-and nano-crystalline multilayered ultra-smooth diamond（USCD） film on the interior-hole surface of WC-Co drawing dies with aperture ranging from d1.0 mm to 60 mm.Characterization results indicate that the surface roughness values（Ra） in the entry zone,drawing zone and bearing zone of as-fabricated USCD coated drawing die were measured as low as 25.7,23.3 and 25.5 nm,respectively.Furthermore,the friction properties of USCD films were examined in both dry sliding and water-lubricating conditions,and the results show that the USCD film presents much superior friction properties.Its friction coefficients against ball-bearing steel,copper and silicon nitride balls（d4 mm）,is always lower than that of microcrystalline diamond（MCD） or WC-Co sample,regardless of the lubricating condition.Meanwhile,it still presents competitive wear resistance with the MCD films.Finally,the working lifetime and performance of as-fabricated USCD coated drawing dies were examined under producing low-carbon steel pipes in dry-sliding and water-lubricating conditions.Under the water-lubricating drawing condition,its production significantly increases by about 20 times compared with the conventional WC-Co drawing dies.

Preparation, characterization and electrochemical properties of boron-doped diamond films on Nb substrates

A series of boron-doped polycrystalline diamond films were prepared by hot filament （HF） chemical vapor deposition on Nb substrates. The effects of B/C ratio of reaction gas on film morphology, growth rate, chemical bonding states, phase composition and electrochemical properties of each deposited sample were studied by scanning electron microscopy, Raman spectra, X-ray diffraction, microhardness indentation, and electrochemical analysis. Results show that the average grain size of diamond and the growth rate decrease with increasing the B/C ratio. The diamond films exhibit excellent adhesion under Vickers microhardness testing （9.8 N load）. The sample with 2% B/C ratio has a wider potential window and a lower background current as well as a faster redox reaction rate in H2SO4 solution and KFe（CN）6 redox system compared with other doping level electrodes.

Two Steps B Ion-Implantation of Diamond Film Grown on an n-Type Si Substrate and Its p-n Junction Effects

Polycrystalline diamond thin films are deposited on an n-type Si substrates by hot filament chemical vapor deposition,and then are implanted with boron ions in a 200keV ion implanter.In order to achieve a better distribution of the implanted element,boron ions are implanted by two steps:implanting boron ions with the energy of 70keV first,and then with the energy of 100keV.The homogeneous distribution of the B ion is gained.The current-voltage characteristics of the samples are studied.It is found that the p-n heterojunction effect is achieved in these samples.

EFFECT OF GRID BIAS ON DEPOSITION OF NANOCRYSTALLINE DIAMOND FILMS

A positive grid bias and a negative substrate bias voltages are applied to the self-made hot filament chemical vapor deposited （HFCVD） system. The high quality nanocrystalline diamond （NCD） film is successfully deposited by double bias voltage nucleation and grid bias voltage growth. The Micro-Raman XRD SEM and AFM are used to investigate the diamond grain size, microstructure, surface morphology, and nucleation density. Results show that the obtained NCD has grain size of about 20 nm. The effect of grid bias voltage on the nucleation and the diamond growth is studied. Experimental results and theoretical analysis show that the positive grid bias increases the plasma density near the hot filaments, enhances the diamond nucleation, keeps the nanometer size of the diamond grains, and improves the quality of diamond film.

Study on the Dielectric Properties of Chemical Vapor Deposited Diamond Film

Aim To study the dielectric properties of diamond film. Methods Dielectric properties (the frequency dependenCe of conductance, permittivity, and loss factor) of diamond film preped by DC are plasma jet chemical vapor deposition (CVD) were studied. Resuls Dielectric properties of CVD diamond fAn depend mainly on its polycrystalline nature, and the presence of non-diamond disordered graphitic regions and impurities between diamond grains of the film. Annealing at 500℃ leads to the removal of greater part of disordered graphitic regions, but am not remove all disordered graphitic regions and impurities. Conclusion Much work nab to be done tO prepare or post-treat diamond films before using CVD diamond as a substrate for electronic devices.

DIAMOND FILMS DEPOSITED AT LOW TEMPERATURES MICROWAVE PLASMA-ASSISTED CVD METHOD

Low-temperature deposition of diamond thin films in the range of 280￣445℃ has been successfully carried out by microwave plasma-assisted CVD method.At lower deposition temperatures (280￣445℃),the large increase in the nucleation density and great improvement in the average surfae roughness of the diamond were observed. Results of low temperature deposition and characterization of diamond thin films obtained are presented.

Amorphous SiO_2 interlayers for deposition of adherent diamond films onto WC-Co inserts

Amorphous Si O2（a-Si O2） films were synthesized on WC-Co substrates with H2 and tetraethoxysilane（TEOS） via pyrolysis of molecular precursor.X-ray diffraction（XRD） pattern shows that silicon-cobalt compounds form at the interface between a-Si O2 films and WC-Co substrates.Moreover,it is observed by transmission electron microscope（TEM） that the a-Si O2 films are composed of hollow mirco-spheroid a-Si O2 particles.Subsequently,the a-Si O2 films are used as intermediate films and chemical vapor deposition（CVD） diamond films are deposited on them.Indentation tests were performed to evaluate the adhesion of bi-layer（a-Si O2 ＋ diamond） films on cemented carbide substrates.And the cutting performance of bi-layer（a-Si O2 ＋ diamond） coated inserts was evaluated by machining the glass fiber reinforced plastic（GFRP）.The results show that a-Si O2 interlayers can greatly improve the adhesive strength of diamond films on cemented carbide inserts;furthermore,thickness of the a-Si O2 interlayers plays a significant role in their effectiveness on adhesion enhancement of diamond films.

Si-doped diamond films prepared by chemical vapour deposition

The effects of Si doping on morphology, components and structure characteristics of CVD diamond films were studied. Si-doped CVD diamond films were deposited on Si substrate by adding tetraethoxysilane （TEOS） into acetone as source of reactant gas. The morphology and microstructure of diamond films were characterized by scanning electron microcopy （SEM）. The crystalline quality of diamond films was studied by Raman spectroscopy and X-ray diffractometry （XRD）. The surface roughness of the films was evaluated with surface profilometer. The results suggest that Si doping tends to reduce the crystallite size, enhance grain refinement and inhibit the appearance of （11 I） facets. Raman spectra indicate that Si doping can enhance the formation of sp2 phase in diamond films. Moreover, Raman signal of SiC was detected, which suggests the existence of Si in the diamond films. Smooth fine-grained diamond （SFGD） film was synthesized at Si to C ratio of 1%.

Microscopic mechanical characteristics analysis of ultranano-crystalline diamond films

The microscopic mechanical characteristics of ultranano-crystalline diamond films which were prepared in four different atmospheres were investigated for the applications in microelectron-mechanical system（MEMS）.The loading-unloading curves and the change of modulus and hardness of samples along with depth were achieved through nanoindenter.The results show that the films which are made in atmosphere without Ar have the highest recovery of elasticity,hardness（72.9 GPa） and elastic modulus（693.7 GPa） among the samples.Meanwhile,samples fabricated at a low Ar content have higher hardness and modulus.All the results above demonstrate that atmosphere without Ar or low Ar content leads to better mechanical properties of nanodiamond films that are the candidates for applications in MEMS.

Numerical Analysis of Nd:YAG Pulsed Laser Polishing CVD Self-standing Diamond Film

Chemical vapor deposited （CVD） diamond film has broad application foreground in high-tech fields. But polycrystalline CVD self-standing diamond thick film has rough surface and non-uniform thickness that adversely affect its extensive applications. Laser polishing is a useful method to smooth self-standing diamond film. At present, attentions have been focused on experimental research on laser polishing, but the revealing of theoretical model and the forecast of polishing process are vacant. The paper presents a finite element model to simulate and analyze the mechanism of laser polishing diamond based on laser thermal conduction theory. The experimental investigation is also carried out on Nd：YAG pulsed laser smoothing diamond thick film. The simulation results have good accordance with the results of experimental results. The temperature and thermal stress fields are investigated at different incidence angles and parameters of Nd：YAG pulsed laser. The pyramidal-like roughness of diamond thick film leads to the non-homogeneous temperature fields. The temperature at the peak of diamond film is much higher than that in the valley, which leads to the smoothing of diamond thick film. The effect of laser parameters on the surface roughness and thickness of graphite transition layer is also carried out. The results show that high power density laser makes the diamond surface rapid heating, evaporation and sublimation after its graphitization. It is also found that the good polish quality of diamond thick film can be obtained by a combination of large incident angle, moderate laser pulsed energy, large repetition rate and moderate laser pulse width. The results obtained here provide the theoretical basis for laser polishing diamond film with high efficiency and high quality.

Effect of deposition temperature on properties of boron-doped diamond films on tungsten carbide substrate

Boron-doped diamond(BDD)films were deposited on the tungsten carbide substrates at different substrate temperatures ranging from 450 to 850°C by hot filament chemical vapor deposition(HFCVD)method.The effect of deposition temperature on the properties of the boron-doped diamond films on tungsten carbide substrate was investigated.It is found that boron doping obviously enhances the growth rate of diamond films.A relatively high growth rate of 544 nm/h was obtained for the BDD film deposited on the tungsten carbide at 650°C.The added boron-containing precursor gas apparently reduced activation energy of film growth to be 53.1 kJ/mol,thus accelerated the rate of deposition chemical reaction.Moreover,Raman and XRD analysis showed that heavy boron doping(750 and 850°C)deteriorated the diamond crystallinity and produced a high defect density in the BDD films.Overall,600-700°C is found to be an optimum substrate temperature range for depositing BDD films on tungsten carbide substrate.

Co evolutions for WC-Co with different Co contents during pretreatment and HFCVD diamond film growth processes

Systematical researches were accomplished on WC-Co with different Co contents(6%,10%and 12%,mass fraction).Based on the XPS and EDX,from orthogonal pretreatment experiments,it is indicated that the acid concentration,the time of the acid pretreatment and the original Co content have significant influences on the Co-removal depth(D).Moreover,the specimen temperature,original Co content and Co-removal depth dependences of the Co evolution in nucleation,heating(in pure H2 atmosphere)and growth experiments were discussed,and mechanisms of Co evolutions were summarized,providing sufficient theoretical bases for the deposition of high-quality diamond films on WC-Co substrates,especially Co-rich WC-Co substrates.It is proven that the Co-rich substrate often presents rapid Co diffusion.The high substrate temperature can promote the Co diffusion in the pretreated substrate,while acts as a Co-etching process for the untreated substrates.It is finally found that the appropriate Co-removal depth for the WC-12%Co substrate is 8-9μm.

Simulations of the Dependence of Gas Physical Parameters on Deposition Variables during HFCVD Diamond Films

During the growth of the hot filament chemical vapor deposition （HFCVD） diamond films, numerical simulations in a 2-D mathematical model were employed to investigate the influence of various deposition parameters on the gas physical parameters, including the temperature, velocity and volume density of gas. It was found that, even in the case of optimized deposition parameters, the space distributions of gas parameters were heterogeneous due primarily to the thermal blockage come from the hot filaments and cryogenic pump effect arisen from the cold reactor wall. The distribution of volume density agreed well with the thermal round-flow phenomenon, one of the key obstacles to obtaining high growth rate in HFCVD process. In virtue of isothermal boundary with high temperature or adiabatic boundary condition of reactor wall, however, the thermal roundflow was profoundly reduced and as a consequence, the uniformity of gas physical parameters was considerably improved, as identified by the experimental films growth.

Microwave CVD Thick Diamond Film Synthesis Using CH4/H2/H2O Gas Mixtures

Thick diamond films with a thickness of up to 1.2 mm and a area of 20 cm^2 have been grown in a homemade 5 kW microwave plasma chemical vapor deposition （MPCVD） reactor using CH4/H2/H2O gas mixtures. The growth rate, radial profiles of the film thickness, diamond morphology and quality were evaluated with a range of parameters such as the substrate temperature of 700℃ to 1100℃, the fed gas composition CH4/H2 = 3.0%, H2O/H2 = 0.0%,-2.4%. They were characterized by scanning electron microscopy and Raman spectroscopy. Translucent diamond wafers have been produced without any sign of non-diamond carbon phases, Raman peak as narrow as 4.1 cm^-1. An interesting type of diamond growth instability under certain deposition conditions was observed in a form of accelerated growth of selected diamond crystallites of a very big lateral size, about 1 mm, and of a better structure compared to the rest of the film.