The versatility of hot-filament activated chemical vapor deposition

In the field of activated chemical vapor deposition (CVD) of polycrystalline diamond films, hot-filament activation (HF-CVD) is widely used for applications where large deposition areas are needed or three-dimensional substrates have to be coated. We have developed processes for the deposition of conductive, boron-doped diamond films as well as for tribological crystalline diamond coatings on deposition areas up to 50 cm × 100 cm. Such multi-filament processes are used to produce diamond electrodes for advanced electrochemical processes or large batches of diamond-coated tools and parts, respectively. These processes demonstrate the high degree of uniformity and reproducibility of hot-filament CVD. The usability of hot-filament CVD for diamond deposition on three-dimensional substrates is well known for CVD diamond shaft tools. We also develop interior diamond coatings for drawing dies, nozzles, and thread guides.Hot-filament CVD also enables the deposition of diamond film modifications with tailored properties. In order to adjust the surface topography to specific applications, we apply processes for smooth, fine-grained or textured diamond films for cutting tools and tribological applications. Rough diamond is employed for grinding applications. Multilayers of fine-grained and coarse-grained diamond have been developed, showing increased shock resistance due to reduced crack propagation.Hot-filament CVD is also used for in situ deposition of carbide coatings and diamond-carbide composites, and the deposition of non-diamond, silicon-based films. These coatings are suitable as diffusion barriers and are also applied for adhesion and stress engineering and for semiconductor applications, respectively.     

Implementation of the time-modulated process to produce diamond films using microwave-plasma and hot-filament CVD systems

A newly developed process called time-modulated chemical vapour deposition (TMCVD) was employed to deposit smooth polycrystalline diamond films onto silicon substrates using both microwave plasma CVD (MPCVD) and hot-filament CVD (HFCVD) systems. The distinctive feature of the TMCVD process, which separates it from the conventional diamond CVD process, is that it pulses methane (CH₄) at different flow rates for different time durations into the vacuum reactor during the entire diamond CVD process. Generally, both MPCVD and HFCVD systems produced results that displayed similar trends, except that the growth rate results obtained using the two CVD systems were conflicting. In comparison to the conventional CVD diamond films, the time-modulated films, deposited using both MPCVD and HFCVD techniques, were generally found to be (i) smoother, (ii) consisted of smaller diamond crystallites and (iii) displayed approx. similar film quality. The diamond-carbon phase purity of the as-grown films was assessed using Raman spectroscopy. In addition, the surface roughness, Ra, values of the deposited films were obtained using surface profilometry.     

Nucleation behaviour of diamond particles on silicon substrates in a hot-filament chemical vapour deposition

Diamond films and particles have been deposited on a silicon substrate using a hot-filament chemical vapour deposition (CVD) method in order to study the effect of hydrogen on the behaviour of diamond nucleation. The nucleation density of diamond was affected by both hydrogen treatment prior to deposition and filament temperature,T _f. The nucleation density was decreased markedly with increasing hydrogen-treatment time. The nucleation density also changed with increasingT _f, which increased initially and then reached a maximum at 2100°C and decreased thereafter. Etching of the substrate surface was observed and enhanced with both increasing hydrogen-treatment time and increasingT _f. The changes in nucleation behaviour were related closely to the etching of substrate surface. These results are explained in terms of the etching of nucleation sites.     

Effect of methane concentration on physical properties of diamond-coated cemented carbide tool inserts obtained by hot-filament chemical vapour deposition

Diamond-coated tools can greatly improve the productivity of machining highly abrasive materials such as high silicon–aluminium alloys used in the automotive industry. Cemented-carbide diamond-coated tool inserts have not become an off-the-shelf product owing to several difficulties including insufficient adhesion of diamond to the substrate and questionable reproducibilty in their machining performance in the manufacturing. In order to overcome these difficulties, a better understanding of the effects of the chemical vapour deposition (CVD) conditions such as methane concentration, reactor pressure and substrate temperature is important. In this work, cemented tungsten carbide tool inserts with 6 wt% Co (WC–Co) were coated with diamond films deposited at five different methane concentrations (1–9 vol%). Here we present preliminary results of the effect of methane concentration variation on the following physical properties of the diamond coating: surface morphology; crystal structure; chemical quality; surface roughness; residual stress. The results indicate that the best physical properties of diamond-coated tool inserts using hot-filament CVD are achieved with diamond coatings deposited at methane concentrations ranging from 1 to 3%.     

Pulsed ion beam characterization of CVD diamond surfaces under thin film deposition conditions

Diamond and diamond-like carbon have properties which in principle make them ideally suited to a wide variety of thin-film applications. The widespread use of diamond thin films, however, has been limited for a number of reasons related largely to the lack of understanding and control of the nucleation and growth processes. Real-time, in-situ studies of the surface of the growing diamond film are experimentally difficult because these films are normally grown under a relatively high pressure of hydrogen, and conventional surface analytical methods require an ultrahigh vacuum environment. Pulsed ion beam based analytical methods with differentially pumped ion sources and particle detectors are able to characterize the uppermost atomic layer of a film during growth at ambient pressures in the range 0.7–27 Pa (4–6 orders of magnitude higher than other surface-specific analytical methods). We describe here a system which has been developed for the purpose of determining the hydrogen concentration and bonding sites on diamond surfaces as a function of sample temperature and ambient hydrogen pressure under hot-filament chemical vapor deposition (CVD) growth conditions. It is demonstrated that as the hydrogen partial pressure increases the saturation hydrogen coverage of the surface of a CVD diamond film increases, but that the saturation level depends on the atomic hydrogen concentration and substrate temperature. At the highest temperatures studied (700 °C), it was found that the surface hydrogen concentration did not exceed 1/4 monolayer.     

铁基底上扩散感应的CVD金刚石成核

在硅和铁基底上同时进行ＣＶＤ 金刚石的沉积,利用硅基底上的金刚石成核感应金刚石在铁基底上直接成核。研究表明,硅和铁基底上不同的沉积过程导致了铁基底上碳原子表面扩散的加强,从而促成了ＣＶＤ 金刚石在铁基底上的直接成核。表面扩散对ＣＶＤ 金刚石成核有重要影响。     

Effect of carbon concentration on the optical properties of nanocrystalline diamond films deposited by hot-filament chemical vapor deposition method

With reducing diamond grain size to nano-grade, the increase of grain boundaries and non-diamond phase will result in the change of the optical properties of chemical vapor deposition (CVD) diamond films. In this paper, the structure, morphology and optical properties of nanocrystalline diamond (NCD) films, deposited by hot-filament chemical vapor deposition (HFCVD) method under different carbon concentration, are investigated by SEM, Raman scattering spectroscopy, as well as optical transmission spectra and spectroscopic ellipsometry. With increasing the carbon concentration during the film deposition, the diamond grain size is reduced and thus a smooth diamond film can be obtained. According to the data on the absorption coefficient in the wavelength range from 200 to 1100 nm, the optical gap of the NCD films decreases from 4.3 eV to 3.2 eV with increasing the carbon concentration from 2.0% to 3.0%. From the fitting results on the spectroscopic ellipsometric data with a four-layer model in the photon energy range of 0.75-1.5 eV, we can find the diamond film has a lower refractive index (n) and a higher extinction coefficient (k) when the carbon concentration increases.     

低压气相生长金刚石薄膜

在低压下,以甲烷和氢的混和气为原料,应用热丝 CVD 法,在 Si 基片上生长出了金刚石薄膜。经 X 射线衍射、激光刺曼光谱和扫描电子显微镜分析,生长产物呈多晶金刚石结构。探讨了金刚石薄膜的生长机理。     

The effects of oxygen on diamond synthesis by hot-filament chemical vapor deposition

The effects of oxygen addition on the synthesis of diamond are extensively studied by using the hot-filament chemical vapor deposition (HFCVD) method, in which it is simple and easy to control the deposition parameters independently. Diamond films are deposited on silicon wafers under the conditions of substrate temperature 530–950 C; total reaction pressure 700–8000 Pa; and methane concentration 0.4–2.4% in both CH₄–H₂ and CH₄–H₂–O₂ systems.At deposition conditions of low substrate temperature, high CH₄ concentration or high total pressure, soot-like carbon and/or graphite are deposited without oxygen addition. When even a small amount of oxygen (about 0.6%) is added, well-faceted diamond films are observed in scanning electron microscopy micrographs and a sharp diamond peak in the Raman spectra appears. The range of deposition parameters for high-quality diamond syntheses are extended by oxygen addition (low substrate temperature, high methane concentration and high reaction pressure).     

Deposition and characterization of smooth ultra-nanocrystalline diamond film in CH4/H2/Ar by microwave plasma chemical vapor deposition

The smooth ultra-nanocrystalline diamond (UNCD) films were prepared by microwave plasma chemical vapor deposition (MWCVD) using argon-rich CH₄/H₂/Ar plasmas with varying argon concentration from 96% to 98% and negative bias voltage from 0 to −150 V. The influences of argon concentration and negative bias voltage on the microstructure, morphology and phase composition of the deposited UNCD films are investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD), atom force microscopy (AFM), and visible and UV Raman spectroscopy. It was found that the introduction of argon in the plasma caused the grain size and surface roughness decrease. The RMS surface roughness of 9.6 nm (10 micron square area) and grain size of about 5.7 nm of smooth UNCD films were achieved on Si(100) substrate. Detailed experimental results and mechanisms for UNCD film deposition in argon-based plasma are discussed. The deposited highly smooth UNCD film is also expected to be applicable in medical implants, surface acoustic wave (SAW) devices and micro-electromechanical systems (MEMS).     

Simultaneous fabrication of nanocrystalline and {100} textured large-grained diamond films

In this work, we report the simultaneous synthesis of both nanocrystalline and {100} textured large-grained diamond films in one deposition run performed in a 5-kW microwave plasma chemical vapor deposition (MPCVD) reactor. This was achieved by employing the coupled effect of nitrogen addition in the gas phase and substrate temperature on the growth of diamond films. In one deposition run, different substrate surface temperatures were obtained by a novel substrate arrangement, nanocrystalline diamond of high growth rate around 3 μm/h was formed at low temperature, while {100} textured large-grained diamond of much higher growth rate about 11 μm/h was grown at high temperature. This new method opens way for mechanical and tribological applications of both nano-diamond and {100} textured diamond in industrial level. This result indicates that distinct growth modes or growth mechanisms were involved at different substrate temperatures with a certain amount of nitrogen addition. The coupled effect of nitrogen addition and temperature on the growth of CVD diamond films and the involved growth mechanism is briefly discussed from the point of view of gas phase chemistry and surface reactions.     

Adhesion improvement of diamond films on cemented carbides with copper implant layer

The deposition of diamond films on cemented carbides is strongly influenced by the catalytic effect of cobalt under typical deposition conditions. Decreasing the content of Co on the surface of the cemented carbide is often used for the diamond film deposition. But the leaching of Co from the WC-Co substrate leads to a mechanical weak surface, often causing poor adhesion. In this paper we adopt a copper implant layer to improve the mechanical properties of the Co leached substrate. The copper implant layer is prepared with vaporization. The diamond films are grown by microwave plasma chemical vapor deposition from the CH₄/H₂ gas mixture. The morphology and the quality of the diamond films have been characterized by scanning electron microscopy and Raman spectroscopy. A Rockwell apparatus has evaluated the adhesion of the diamond on the substrate. The results indicate that the diamond films have good adhesion to the cemented carbide substrate due to the recovery of the mechanical properties of the Co depleted substrate after the copper implantation and less graphite formation between the substrate and the diamond film.     

基体预处理对氧化铍基金刚石膜性能的影响

通过改变氧化铍基体的预处理方法,研究了热丝化学气相沉积系统中金刚石薄膜与氧化铍基体的结合情况,及其对导热性能的影响.分别利用金相显微镜和扫描电镜观察薄膜的剥落程度和其表面形貌,利用激光热物性测试仪测量基体和金刚石膜/氧化铍复合体的热扩散系数,并计算其热导率.实验结果表明:水磨砂纸研磨和氢氟酸处理均能有效提高金刚石薄膜与基体的结合情况;氢氟酸处理时间10min时可得到致密连续、表面均匀的金刚石薄膜,此时复合体的热导率较原来的氧化铍基体可提高31.4%.     

Diamond deposition on copper: studies on nucleation, growth, and adhesion behaviours

This paper presents a systematic study on diamond growth on copper by microwave plasma chemical vapour deposition (MPCVD). It includes the following four main parts. 1. Effect of substrate pre-treatment on diamond nucleation. 2. Effect of deposition conditions on diamond nucleation and growth. 3.Preparation of free-standing diamond films using copper substrate. 4. Adherent diamond coating on copper using an interlayer. In the first part we show that diamond nucleation on copper is strongly affected by the substrate pre-treatment. The residues of abrasives left in the surface of the copper substrate play an important role in the diamond nucleation. In the second part we show that the diamond growth rate increases with microwave power and gas pressure. The effect of the microwave power is mainly an effect of substrate temperature. Increasing methane concentration results in a higher nucleation density and higher growth rate, but at the cost of a lower film quality. Gas flow rate has little influence on the diamond nucleation density and growth rate. In the third part we demonstrate the possibility of preparing large area free-standing diamond films using copper substrate, which has nearly no carbon affinity and usually leads to weak adhesion of the diamond films. The normally observed film cracking phenomenon is discussed and a two-step growth method is proposed for stress release. In the fourth part we show that adherent diamond coating on copper can be obtained using a titanium interlayer. Residual stress in the films is evaluated by Raman spectroscopy. It is found that with increase in the film thickness, the diamond Raman line shifts from higher wave numbers to lower, approaching 1332 cm–1. The stress variation along the depth of the film is also analysed using Airy stress theory.     

CATALYST EFFECT FOR DIAMOND NUCLEATION IN THE LOW PRESSURE PROCESS

The fundamental study of diamond nucleation on several kinds of substrates using the hot-filament CVD method, was carried out. To investigate the diamond nucleation density, the substrate which coated with the catalytic materials by the vacuum deposition was utilized. Diamond particles scarcely grew on a normal Si wafer, but a catalytic material promoted the growth of diamond on the Si substrate. The catalytic material increases the diamond nucleation density as compared with any other substrates with a surface treatment. The particles grown on the substrates have been examined by means of x-ray diffraction and scanning electron microscopy, and identified as diamond.     

电镀铬-金刚石复合过渡层提高金刚石膜/基结合力

在铜基体上沉积铬-金刚石复合过渡层, 用热丝CVD系统在复合过渡层上沉积连续的金刚石涂层. 用扫描电镜(SEM)、X射线(XRD)、拉曼光谱及压痕试验对所沉积的镶嵌结构界面金刚石膜的相结构及膜/基结合性能进行了研究. 结果表明, 非晶态的电镀Cr在CVD过程中转变成Cr₃C₂, 由于金刚石颗粒与Cr₃C₂的相互咬合作用, 金刚石膜/基结合力高; 在294 N载荷压痕试验时, 压痕外围不产生大块涂层崩落和径向裂纹, 只形成环状裂纹.     

Growth of nanocrystalline diamond films in CCl4/H2 ambient

We investigated the growth characteristics of the nanocrystalline diamond films using CCl₄/H₂ as gas sources in a hot-filament chemical vapor deposition (CVD) reactor. Successful growth of nanocrystalline diamond at typical growth condition of 1.5-2.5% CCl₄ and 550-730 °C substrate temperature has been demonstrated. Glancing angle X-ray diffraction (XRD) clearly indicated the formation of diamond in the films. Typical root-mean-square surface roughness of 10-15 nm and an optimal root-mean-square surface roughness of 6 nm have been achieved. Transmission electron microscopy (TEM) analyses indicated that nanocrystalline diamond film with an average grain size in the range of 10-20 nm was deposited from 2.5% CCl₄/H₂ at 610 °C. Effects of different source gas composition and substrate temperature on the grain nucleation and grain growth processes, whereby the grain size of the nanocrystalline film could be controlled, were discussed.     

Effects of the grain size of CVD diamond films on the detector performance

Although the unique properties of CVD diamond films have made it a candidate material for radiation detectors, the detector performance is strongly dependent on the film quality. In this paper, three CVD diamond films with different grain size were grown by using a hot-filament chemical vapor deposition (HFCVD) technique and the ratio of the grain size to the film thickness is high to 50%. 5.9 keV ⁵⁵Fe X-rays measured the photocurrents and the pulse height distributions (PHDs) of these CVD diamond detectors. The detector performance is improved with the grain size increasing. The dark-current of 16.0 nA and the photocurrent of 15.9 nA are obtained at an electrical field of 50 kV⋅cm⁻¹ and the PHD peak is well separated from the noise pedestal.     

Polishing of polycrystalline diamond by hot nickel surface

A microwave plasma technique has been employed to deposit polycrystalline diamond film over a molybdenum substrate button using a gas mixture of hydrogen and methane at a substrate temperature of 851°C. A CVD diamond coated molybdenum substrate button was mounted with a load against hot nickel plate and rotated for 3.45 h in a hydrogen ambient. Hot tungsten filament was used as a heat source to maintain the temperature of the nickel block and CVD diamond coated molybdenum button at 848°C. This experiment has reproducibly shown the successful polishing of polycrystalline CVD diamond by hot nickel. A Tencor profilometer and scanning electron microscope have been used to evaluate the surface smoothness and morphology before and after polishing the polycrystalline diamond thin films.     

Chemical vapour deposition of microdrill cutting edges for micro- and nanotechnology applications

Conventional cemented tungsten carbide-cobalt (WC-Co) microdrills generally have a low cutting efficiency and short lifetime mainly because they operate at very high cutting speeds. Since it is relatively expensive to make microtools it is highly desirable to improve their lifetime and in-service performance. Microtools used to make microelectronic and mechanical systems (M.E.M.S) devices with sharp cutting edges, such as milling or drilling tools need protective coating in order to extend life and improve performance. One method of achieving this objective is to use a suitable surface engineering technology to deposit a hard wear resistant coating, such as diamond. Diamond has excellent mechanical properties, such as ultra-high hardness and a low friction coefficient. One of the most promising surface treatment technologies for depositing diamond onto complex shaped components is chemical vapour deposition (CVD). However, CVD of diamond coatings onto the cemented WC-Co tool has proved to be problematic. Binder materials such as cobalt can suppress diamond nucleation resulting in poor adhesion between the coating and substrate. In this paper the effects of pre-treated substrate material on the coating structure are reported. The morphology and the crystallinity of the as-grown films was characterised by using scanning electron microscopy (SEM). Raman spectroscopy was used to assess the carbon-phase purity and give an indication of the stress levels in the as-grown polycrystalline diamond films. The diamond coated tools have potential applications in micro- and nanomachining of micro- and nano-sized components used in M.E.MS.