Selective growth of diamond by hot filament CVD using patterned carbon film as mask

Selected-area deposition (SAD) of diamond films was achieved on silicon substrates with carbon film mask by hot filament chemical vapor deposition.Needle tip scraped lines were used to grow diamond films.Scanning electron microscope (SEM) investigation demonstrates that highly selective and sharp edged diamond films were produced.The results also demonstrate that the proper substrate temperature is very important for diamond selective growth in this deposition process.Since the enhancement of diamond growth was not observed on the needle tip scraped area of Si wafer with diamond powder scratching,the selective growth was considered to be closely correlated to silicon carbide formed during carbon film deposition and the residual carbon in the scraped area.

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.

Influence of intermittently etching on quality of CVD diamond thin films

A new method, called growing-etching repetitional process based on hot filament chemical vapor deposition, was proposed to improve the quality of diamond film. During the deposition carbon source was intermittently closed letting hydrogen etch the surface of the diamond film from time to time. In order to find whether it is helpful to the films’ quality, a series of experiments were done. The results show that the new method can enhance the orientation of the chemical vapor deposition diamond films, reduce the graphite phase and increase the film’s surface resistivity.

<100> Textured Diamond Film on Silicon Grown by Hot Filament Chemical Vapor Deposition

The <100> textured growth of diamond film on HF eroded silicon wafer has been studied by HFCVD. The evolution of grain size and sudece morphology vs deposition time is presented and the <100> textured thick diamond film (80μm) with smooth surface, desirable for practical application in many fields is obtained

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.

Structural and Electrical Properties of Sulfur-Doped Diamond Thin Films

We report our observations on the higher carrier mobility and higher conductivity of sulfur-doped n-type diamond thin films synthesized by the hot filament chemical vapor deposi- tion （HFCVD）. The structural and electrical characterizations of the films are measured by X-ray diffraction （XRD）, Raman spectroscopy, scanning electron microscope （SEM）, energy dispersion X-ray spectra （EDX）, and Hall effect measurements. It is found that the sulfur atoms are in- corporated into the polycrystalline diamond films. The n-type conductivity of the films increases with the H2S concentration, and a conductivity of the films as high as 1.82 ^-l.cm-1 is achieved. The results show that the sulfur atom plays an important role in the structural and electrical properties of sulfur-doped diamond thin films.

Investigation of a Hot Filament Diamond Deposition by in situ Infrared Absorption

In situ infrared absorption spectroscopy has been measured for a hot filament diamond growth process. Absorption of CH4 and C2H2 species at 3050 cm-1 and 730 cm-1 were detected respectively. The absorption intensity of CH4 decreases while that of C2H2 increases as filament temperature is raised. The correlation between infrared absorption intensity and diamond growth rate or diamond film quality was found. High C2H2 or low CH4 concentration in the reaction region leads to high quality diamond film growth and high growth rate.

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.

Annealing effect and irradiation properties of HFCVD diamond films

The post-growth treatment of a [100]-oriented diamond film was performed to improve the film quality. The characteristic of post-growth film was investigated by using the RAMAN spectrum and the capacitance-frequency curve. The results show that the resistivities and frequency response enhance after the post-treatments in solution of H2SO4 and H2O2 and an annealing under N2 atmosphere at 500 ℃ for 60 min. Under a bias voltage of 100 V, the net photocurrent is obtained under 55Fe(5.9 keV) X-rays and 241Am (5.5 MeV) α particles radiation, respectively. The photocurrent increases rapidly at first and becomes stable for the “pumping” effect with the radiation time.

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.

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%.

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.

Fabrication and application of nanocrystalline diamond films

Nanocrystalline diamond films were deposited on Co-cemented carbide substrates using acetone/ H2/Ar gas mixture by bias-enhanced hot filament chemical vapor deposition（HFCVD） technique.The evidence of nanocrystallinity,smoothness and purity was obtained by characterizing the sample with scanning electron microscopy（SEM）,X-ray diffraction（XRD）,Raman spectroscopy,atomic force microscopy （AFM ）,and field emission transmission electron microscopy（FE-TEM ）.The results show that nanocrystalline diamond films consists of nanocrystalline diamond grains with sizes range from 20 to 80 nm and contain a large amount of grain boundaries.The surface roughness of the films is measured as Ra【50nm.The Raman spectroscopy,XRD pattern,and FE-TEM image of the films indicate the presence of nanocrystalline diamond.A new process is used to deposit composite diamond coatings by a two-step chemical vapor deposition procedure,including first the deposition of the rough polycrystalline diamond and then the smooth fine-grained nanocrystalline diamond film.Such composite diamond coatings not only display good adhesion and wear resistant properties,but also have smooth surfaces that are liable to polishing.This coating technology can not only meet the requirement of the adhesion of diamond coatings,but also reduce surface roughness of diamond coatings effectively,thus remove the obstacles for the industrialization of CVD diamond coatings.The diamondcoated dies with these composite coatings show obvious effect in the practical application.

Study of filament performance in heat transfer and hydrogen dissociation in diamond chemical vapor deposition

Hot-filament chemical vapor deposition ( HFCVD) is a promising method for commercial production of diamond films. Filament performance in heat transfer and hydrogen decomposition in reactive environment was investigated. Power consumption by the filament in vacuum, helium and 2% CH4/H2 was experimentally determined in temperature range 1300℃-2200℃. Filament heat transfer mechanism in C-H reactive environment was calculated and analyzed. The result shows that due to surface carburization and slight carbon deposition, radiation in stead of hydrogen dissociation, becomes the largest contributor to power consumption. Filament-surface dissociation of H2 was observed at temperatures below 1873K, demonstrating the feasibility of diamond growth at low filament temperatures. The effective activation energies of hydrogen dissociation on several clean refractory flaments were derived from power consumption data in literatures. They are all lower than that of thermal dissociation of hydrogen revealing the nature of catalytic dissociation of hydrogen on filament surface. Observation of substrate temperature suggested a weaker role of atomic hydrogen recombination in heating substrates in C-H environment than in pure hydrogen.

Formation and Transport of Atomic Hydrogen in Hot-Filament Chemical Vapor Deposition Reactors

In this paper we focus on diamond film hot-filament chemical vapor deposition reactors where the only reactant is hydrogen so as to study the formation and transport of hydrogen atoms. Analysis of dimensionless numbers for heat and mass transfer reveals that thermal conduction and diffusion are the dominant mechanisms for gas-phase heat and mass transfer, respectively. A simplified model has been established to simulate gas-phase temperature and H concentration distributions between the filament and the substrate. Examination of the relative importance of homogeneous and heterogeneous production of H atoms indicates that filament-surface decomposition of molecular hydrogen is the dominant source of H and gas-phase reaction plays a negligible role. The filament-surface dissociation rates of H2 for various filament temperatures were calculated to match H-atom concentrations observed in the literature or derived from power consumption by filaments. Arrhenius plots of the filament-surface hydrogen dissociation rates suggest that dissociation of H2 at refractory filament surface is a catalytic process, which has a rather lower effective activation energy than homogeneous thermal dissociation. Atomic hydrogen, acting as an important heat transfer medium to heat the substrate, can freely diffuse from the filament to the substrate without recombination.

CVD金刚石膜研究进展

金刚石由于其优异的声、光、电、热和力学性能,是重要的功能材料之一。金刚石的制备方法主要有高温高压方法和低压化学气相沉积方法。化学气相沉积法因制备得到的样品质量高、面积大,设备简单、可规模化等特性,是合成金刚石膜的重要方法。为了实现低合成压力条件下的金刚石膜的均匀、快速、大尺寸、高质量生长,目前研究人员在金刚石低压生长的控制方面做出了深入的研究。文章综述了近年来化学气相沉积法(包括热丝CVD法、离子体增强CVD法、燃烧火焰CVD法)生长金刚石膜的研究进展,包括金刚石膜的生长机理、关键设备、关键工艺参数等。此外,还详细讨论了生长过程中的关键工艺参数与金刚石膜生长速率和质量的关系,这些对化学气相沉积制备金刚石膜的研究、生产至关重要。

热丝CVD大面积金刚石薄膜的生长动力学研究

在传统工业型热丝化学气相沉积(HFCVD)反应腔内,相关工艺参数取模拟计算优化值的条件下,采用XRD,SEM及Ram an光谱等分析手段研究了单晶S i(100)上较大面积金刚石薄膜的动力学生长行为,讨论了晶格取向的变化规律。结果表明:优化工艺参数条件下,在模拟计算的衬底温度和气体温度分布均匀的区域内,沉积的金刚石薄膜虽存在一定的内应力,但整体薄膜连续、均匀,几何晶形良好,质量较高,生长速率达1.8μm/h。薄膜生长过程中晶形显露面受衬底温度和活性生长基团浓度的影响较大。

CVD金刚石涂层拉丝模的研制与应用

:以市售大孔径 (>2mm)硬质合金拉丝模为衬底 ,经酸腐蚀去钴、研磨和还原处理后 ,以氢气和丙酮为原料 ,用穿孔直拉热丝CVD法制备了金刚石涂层。利用扫描电镜和喇曼谱图对涂层均匀性进行了评估。初步应用试验表明 ,金刚石涂层的附着力能满足实际拉伸要求 ,涂层拉丝模的工作寿命可提高 3～ 5倍。