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.

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.

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.

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.

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.

STUDY ON DIAMOND LIKE CARBON THIN FILM BY FILTERED VACUUM ARC DEPOSITION

Diamond like carbon thin film is successfully deposited on silicon, titanium and stainless steel substrate at low temperature in a filtered vacuum arc deposition system. Arc discharges are established on a graphite cathode in the system with a toroidal macroparticle filter. A cathode activating magnetic field and a filtered magnetic field to collimate the plasma beam are applied. Ion current convected by the plasma beam is measured with a negatively biased probe. It is shown that the magnetic field of the coils located on the plasma duct has a strong influence on cathode spot behavior. Orthogonally the designed experiments are carried out to optimize the deposition parameters of arc stability. Finally, the diamond like carbon thin films are studied by scanning electron microscope (SEM) and Raman spectrum.

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%.

沉积温度对不同Co含量WC-Co/SiC/Diamond界面结合性能的影响

本文构建了Co质量分数分别为6%、8%、10%和12%的WC-Co/SiC/Diamond金刚石涂层硬质合金界面模型,利用分子动力学方法模拟了不同沉积温度对其界面结合强度的影响,从黏附功及键长分布两个方面进行具体分析。黏附功分析结果表明,与其他三种Co含量界面模型相比,WC-6%Co/SiC/Diamond界面模型在七个沉积温度下所包含的两种界面的黏附功值均为最高值,并且在不同沉积温度下,WC-6%Co/SiC/Diamond界面模型所包含的WC-6%Co/SiC界面、SiC/Diamond界面的黏附功分别在1123、1173 K时最大,为2.468、5.394 J/m^(2)。键长分布概率分析结果表明,与其他三种Co含量界面模型相比,在任一沉积温度下,WC-6%Co/SiC/Diamond界面模型各界面处键长分布范围的最大值较小,且在1123 K时在WC-6%Co基体上沉积SiC中间层,在1173 K时在SiC中间层上沉积Diamond涂层后,该界面模型界面处的键长最短,键能最大,界面结合性能最好。

Deposition of tungsten-titanium carbides on surface of diamond by reactive PVD

The coatings of W-Ti carbides on the surface of diamond was obtained by using physical vapor deposition (PVD), during which WO3 powders pre-treated with hydrofluoric acid were reduced by titanium hydride in vacuum at 850 ℃. The resistance of diamond to corrosion at high-temperature was investigated. The formation of W-Ti carbides on the surface of diamond was verified by X-ray diffraction analysis, the interface state between diamond and matrix in metaLbase diamond composite was observed by scanning electron microscope. The results showed that the carbide coating is easy to be formed at low deposition temperature on the surface of diamond, while the resistance of diamond to corrosion at highutemperature and the strength of bonding between diarnond and metal matrix are effectively improved.

Fabrication of TiN/cBN and TiC/diamond coated particles by titanium deposition process

Cubic boron nitride particles coated by titanium nitride (TiN/cBN) as well as diamond particles coated by titanium carbide (TiC/diamond) were prepared by Ti molten salt deposition followed by heat-treatment process. cBN or diamond particles were mixed separately with Ti powders and molten salts (KCl, NaCl and K2TiF6). The mixture was heated at 900 °C under argon atmosphere. The produced particles were heat-treated under hydrogen at 1000 °C. The morphologies and chemical compositions of the produced particles were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and focused ion beam (FIB). The results show that the cBN and the diamond particles are coated by nano-sized Ti layers. By heat-treatment of the Ti/cBN and TiC/diamond coated particles under hydrogen atmosphere, the deposited Ti layers were interacted by the in-situ transformation reaction with the surfaces of cBN and diamond particles and converted to titanium compounds (TiN and TiC), respectively.

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.

Microwave Plasma Chemical Vapor Deposition of Diamond Films on Silicon From Ethanol and Hydrogen

Diamond films with very smooth surface and good optical quality have been deposited onto silicon substrate using microwave plasma chemical vapor deposition (MPCVD) from a gas mixture of ethanol and hydrogen at a low substrate temperature of 450 ℃. The effects of the substrate temperature on the diamond nucleation and the morphology of the diamond film have been investigated and observed with scanning electron microscopy (SEM). The microstructure and the phase of the film have been characterized using Raman spectroscopy and X-ray diffraction (XRD). The diamond nucleation density significantly decreases with the increasing of the substrate temperature. There are only sparse nuclei when the substrate temperature is higher than 800 ℃ although the ethanol concentration in hydrogen is very high. That the characteristic diamond peak in the Raman spectrum of a diamond film prepared at a low substrate temperature of 450 ℃ extends into broadband indicates that the film is of nanophase. No graphite peak appeared in the XRD pattern confirms that the film is mainly composed of SP3 carbon. The diamond peak in the XRD pattern also broadens due to the nanocrystalline of the film.

Deposition of crackless freestanding diamond films on Mo substrates with Zr interlayer

The Mo substrate with Zr interlayer,namely composite substrate,was employed to solve the problem of crack formation in the freestanding diamond film deposition.Freestanding diamond films deposited on the composite substrates by the direct current arc plasma jet chemical vapor deposition（CVD） method were investigated with scanning electron microscopy（SEM）,X-ray photoelectron spectroscopy （XPS）,X-ray diffraction（XRD）,and Raman spectroscopy.In addition,the stress distribution during the large area freestanding diamond film deposition on the composite substrate was analyzed based on the finite element model ANSYS.The results reveal that Zr interlayer can be easily destroyed during the post-deposition cooling process,which is helpful for stress release and crack avoiding in diamond films.

Effect of Substrate Temperature on the Selective Deposition of Diamond Films

Selective deposition of diamond film on patterned Si (100) substrates has been achieved by using microwave plasma chemical vapor deposition (MPCVD) method. The films have been characterized by scanning electron microscope (SEM) and Raman spectrum. The influence of substrate temperature on the nucleation behavior of diamond was discussed in detail and the optimized deposition condition has been obtained.

Friction Behaviors of the Hot Filament Chemical Vapor Deposition Diamond Film under Ambient Air and Water Lubricating Conditions

The friction behavior of the hot filament chemical vapor deposition（HFCVD） diamond film plays a critical role on its applications in mechanical fields and largely depends on the environment. Studies on the tribological properties of HFCVD diamond films coated on Co-cemented tungsten carbide （WC-Co） substrates are rarely reported in available literatures, especially in the water lubricating conditions. In this paper, conventional microcrystalline diamond（MCD） and fine-grained diamond（FGD） films are deposited on WC-Co substrates and their friction properties are evaluated on a reciprocating ball-on-plate tribometer, where they are brought to slide against ball-bearing steel and copper balls in dry and water lubricating conditions. Scanning electron microscopy（SEM）, atomic force microscopy（AFM）, surface profilometer and Raman spectroscopy are adopted to characterize as-deposited diamond films; SEM and energy dispersive X-ray（EDX） are used to investigate the worn region on the surfaces of both counterface balls and diamond films. The research results show that the friction coefficient of HFCVD diamond films always starts with a high initial value, and then gradually transits to a relative stable state. For a given counterface and a sliding condition, the FGD film presents lower stable friction coefficients by 0.02-0.03 than MCD film. The transferred materials adhered on sliding interface are supposed to have predominate effect on the friction behaviors of HFCVD diamond films. Furthermore, the effect of water lubricating on reducing friction coefficient is significant. For a given counterpart, the stable friction coefficients of MCD or FGD films reduce by about 0.07-0.08 while sliding in the water lubricating condition, relative to in dry sliding condition. This study is beneficial for widespread applications of HFCVD diamond coated mechanical components and adopting water lubricating system, replacing ofoil lubricating, in a variety of mechanical processing fields to implement the green production process.

Morphology Analysis of Nickel-boron/diamond Eleetroless Deposition

The influences of mass concentration of nickel chloride hexahydrate, sodium borohydride, ethylenediamine, pH value, bath temperature on deposition rate were studied with orthogonal experiments by a series of pre-treatments on micro-diamond particle, and the optimized parameters were obtained. Both the morphology and the composition of original diamond and the diamond with Ni-B coating were analyzed by SEM and XRD respectively. The SEM image shows that the spherical Ni-B particle is coated upon diamond. XRD pattern shows that the coating compositions are Ni and Ni2B.

Deposition and Boron Doping of Nano-Crystalline Diamond Thin Films on Poly-Crystalline Diamond Thick Films

Boron-doped nano-crystalline diamond （NCD） thin films have been successfully deposited on well-polished poly-crystalline diamond （PCD） thick films in a microwave plasma enhanced chemical vapor deposition （MPCVD） reactor for the first time. Different surface pretreatment techniques are carried out under different gas conditions （CH4, H2, Ar, and CH4/H2） to eliminate the effect of grain boundaries on the growth of a smooth NCD intrinsic layer. Well doped NCD films have been fabricated in CH4/H2/B2H6 plasma by varying the atomic ratio of B/C and the substrate temperature. Atomic force microscopy （AFM） results show that pretreatment in pure CH4 plasma at 1000℃ is most effective for NCD growth, while hydrogen containing plasma is harmful to the surface smoothness of NCD thin fihns. Doping research indicates that the optimum parameters for the boron-doping of high-quality NCD thin films are B/C=300 ppm （10-6） and 800℃.

FABRICATION OF DIAMOND TUBES IN BIAS-ENHANCED HOT-FILAMENT CHEMICAL VAPOR DEPOSITION SYSTEM

Deposition of diamond thin films on tungsten wire substrate with the gas mixture of acetone and hydrogen by using bias-enhanced hot filament chemical vapor deposition（CVD）with the tantalum wires being optimized arranged is investigated.The self-supported diamond tubes are obtained by etching away the tungsten substrates.The quality of the diamond film before and after the removal of substrates is observed by scanning electron microscope（SEM）and Raman spectrum.The results show that the cylindrical diamond tubes with good quality and uniform thickness are obtained on tungsten wires by using bias enhanced hot filament CVD.The compressive stress in diamond film formed during the deposition is released after the substrate etches away by mixture of H2O2 and NH4 OH.There is no residual stress in diamond tube after substrate removal.

Effect of nitrogen on deposition and field emission properties of boron-doped micro-and nano-crystalline diamond films

In this paper,we report the effect of nitrogen on the deposition and properties of boron doped diamond films synthesized by hot filament chemical vapor deposition.The diamond films consisting of micro-grains(nano-grains) were realized with low(high) boron source flow rate during the growth processes.The transition of micro-grains to nano-grains is speculated to be strongly(weekly) related with the boron(nitrogen) flow rate.The grain size and Raman spectral feature vary insignificantly as a function of the nitrogen introduction at a certain boron flow rate.The variation of electron field emission characteristics dependent on nitrogen is different between microcrystalline and nanocrystalline boron doped diamond samples,which are related to the combined phase composition,boron doping level and texture structure.There is an optimum nitrogen proportion to improve the field emission properties of the boron-doped films.