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.     

氧化铝基体表面预处理对金刚石薄膜生长的影响

采用微波等离子体化学气相沉积方法,在经不同预处理的氧化铝衬底上沉积金刚石薄膜.用X射线衍射仪、激光拉曼光谱仪、扫描电镜(SEM)对所得薄膜的成分、物相纯度和表面形貌进行表征,比较不同的预处理方式对金刚石薄膜生长的影响.结果表明,基体表面经过熔融碱腐蚀后形成薄膜的膜基结合良好且膜材质量最佳,但表面平整度较低;而基体只经金刚石微粉乙醇悬浊液超声处理则在沉积时金刚石容易成膜,且结构要更为致密;在经过酸腐蚀的基体上沉积金刚石薄膜时,容易在薄膜与基体之间先形成过渡层,而后才进行金刚石薄膜的沉积.所得结果表明熔融碱腐蚀处理是获得电学应用氧化铝基金刚石薄膜复合材料的最适宜的基体表面预处理.     

Effect of microwave power and nitrogen addition on the formation of {100} faceted diamond from microcrystalline to nanocrystalline

In this work, we report {100} multi-faceted diamond from large grained micro- to nano-crystalline obtained by microwave plasma chemical vapor deposition (MPCVD). The diamond samples were grown using different microwave power 2000 and 3200 W with a small amount of nitrogen and oxygen addition into conventional methane and hydrogen plasma in a 5 kW MPCVD reactor. Scanning electron microscopy (SEM), micro-Raman spectroscopy and X-ray diffraction (XRD) were used to characterize the morphology, crystalline quality and orientation or texture of the diamond samples. SEM micrographs clearly evidence various diamonds of distinct morphologies consisting of smooth square {100} facets from micrometer or nanometer size. Especially novel morphology, large {100} faceted nanocrystalline diamond balls of high growth rate 17.0 μm/h were obtained. The effect of microwave power and temperature and the role of nitrogen addition on diamond growth rate and the formation of different types of {100} faceted diamond from micro- to nanocrystalline is discussed. These results shed light into the specific growth mechanism of CVD diamond upon nitrogen perturbation.     

Study of the moderate-temperature growth process of optical quality synthetic diamond films on quartz substrates

Growth of undoped and boron-doped diamond films on quartz substrates at moderate temperature of 500 °C by microwave plasma chemical vapor deposition method was studied in terms of growth rate, surface roughness and optical transmittance. Similar density of diamond seed particles on quartz surfaces seeded mechanically before the deposition process and diamond grains within diamond films grown on those substrates is observed. The growth rate is found similar to that reported for diamond deposited on silicon substrates in the same plasma deposition system, although with substantially higher activation energy. Furthermore, increased level of dopant concentration in the gas mixture resulted in a decrease of the growth rate, while a gradual reduction of the surface roughness occurred at high dopant levels. Overall, the highest measured regular optical transmittance of the undoped diamond film on quartz was 45% at 1100 nm (including quartz absorption), whereas that of boron-doped diamond peaked 5% at 700 nm (tail absorption of boron centers).     

Growth behavior of CVD diamond films with enhanced electron field emission properties over a wide range of experimental parameters

In this study, diamond films were synthesized on silicon substrates by microwave plasma enhanced chemical vapor deposition (CVD) over a wide range of experimental parameters. The effects of the microwave power, CH₄/H₂ ratio and gas pressure on the morphology, growth rate, composition, and quality of diamond films were investigated by means of scanning electron microscope (SEM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). A rise of microwave power can lead to an increasing pyrolysis of hydrogen and methane, so that the microcrystalline diamond film could be synthesized at low CH₄/H₂ levels. Gas pressure has similar effect in changing the morphology of diamond films, and high gas pressure also results in dramatically increased grain size. However, diamond film is deteriorated at high CH₄/H₂ ratio due to the abundant graphite content including in the films. Under an extreme condition of high microwave power of 10 kW and high CH₄ concentration, a hybrid film composed of diamond/graphite was successfully formed in the absence of N₂ or Ar, which is different from other reports. This composite structure has an excellent measured sheet resistance of 10–100 Ω/Sqr. which allows it to be utilized as field electron emitter. The diamond/graphite hybrid nanostructure displays excellent electron field emission (EFE) properties with a low turn-on field of 2.17 V/μm and β = 3160, therefore it could be a promising alternative in field emission applications.     

Effects of Homo-buffer Layer on Properties of Sputter-deposited ZnO Films

Two-step growth regimes were applied to realize a homoepitaxial growth of ZnO films on freestanding diamond substrates by radio-frequency(RF)reactive magnetron sputtering method.ZnO buer layers were deposited on freestanding diamond substrates at a low sputtering power of 50 W,and then ZnO main layers were prepared on this buffer layer at a high sputtering power of 150 W.For comparison,a sample was also deposited directly on freestanding diamond substrate at a power of 150 W.The effects of ZnO buffer layers...     

新型MPCVD装置在高功率密度下高速沉积金刚石膜

使用自行研制的新型MPCVD装置,以H2-CH4为气源,在输入功率为5kW,沉积压力分别为13.33、26.66kPa和不同的甲烷浓度下制备了金刚石膜。利用等离子体发射光谱法对等离子体中的H原子和含碳的活性基团浓度进行了分析。用扫描电镜、激光拉曼谱对金刚石膜的表面和断口形貌、金刚石膜的品质等进行了表征。实验结果表明,使用新型MPCVD装置能够在较高的功率密度下进行金刚石膜的沉积;提高功率密度能使等离子体中H原子和含碳活性基团的浓度明显增加,这将提高金刚石膜的沉积速度,并保证金刚石膜具有较高的质量。     

无支撑、光学级MPCVD金刚石膜的研制

利用引进的6 kW微波等离子体化学气相沉积设备,进行了无支撑金刚石膜工艺的初步研究。在800~1050℃的基片温度范围内,金刚石膜都呈(111)择优取向;基片相对位置对沉积较大面积、光学级金刚石膜至关重要。制出0.25 mm厚Φ50 mm的无支撑金刚石膜。拉曼光谱和X射线衍射分析表明,合成的金刚石膜晶体结构完整,sp2含量极低;透过率测试结果说明了优良的光学性能:截止波长225 nm,光学透过率(λ≥2.5μm)≥70%。     

Stress and phase purity analyses of diamond films deposited through laser-assisted combustion synthesis

Diamond films were deposited on silicon and tungsten carbide substrates in open air through laser-assisted combustion synthesis. Laser-induced resonant excitation of ethylene molecules was achieved in the combustion process to promote diamond growth rate. In addition to microstructure study by scanning electron microscopy, Raman spectroscopy was used to analyze the phase purity and residual stress of the diamond films. High-purity diamond films were obtained through laser-assisted combustion synthesis. The levels of residual stress were in agreement with corresponding thermal expansion coefficients of diamond, silicon, and tungsten carbide. Diamond-film purity increases while residual stress decreases with an increasing film thickness. Diamond films deposited on silicon substrates exhibit higher purity and lower residual stress than those deposited on tungsten carbide substrates.     

Growth and characterization of diamond particles,diamond films,and CNT-diamond composite films deposited simultaneously by hot filament CVD

It is important to understand the growth of CNT-diamond composite films in order to improve the inter-link between two carbon allotropes, and, in turn, their physical properties for field emission and other applications. Isolated diamond particles, continuous diamond thin films, and thin films of carbon nanotubes (CNTs) having non-uniformly distributed diamond particles (CNT-diamond composite films) were simultaneously grown on unseeded, seeded, and catalyst pre-treated substrates, respectively, using a large-area multi-wafer-scale hot filament chemical vapor deposition. Films were deposited for four different growth durations at a given deposition condition. The changes in surface morphology and growth behavior of diamond particles with growth duration were investigated ex situ using field emission scanning electron microscopy and 2D confocal Raman depth spectral imaging, respectively. A surface morphological transition from faceted microcrystalline nature to nanocrystalline nature was observed as a function of growth duration in the case of isolated diamond particles grown on both unseeded and catalyst pre-treated substrates. However, such a morphological transition was not observed on the simultaneously grown continuous diamond thin films on seeded substrates. 2D confocal Raman depth spectral imaging of diamond particles showed that the local growth of CNTs did not affect the growth behavior of neighboring diamond particles on catalyst pre-treated substrates. These observations emphasize the importance of surface chemical reactions at the growth site in deciding sp² or sp³ carbon growth and the final grain size of the diamond films.     

基片预处理对MWPCVD金刚石薄膜的影响

利用自行研制的石英钟罩式微波等离子体化学气相沉积金刚石薄膜装置，研究了硅基片的不同预处理方式对沉积结果的影响。通过扫描电子显微镜形貌观察和喇曼谱分析表明，基片预处理能提高形核密度；用于预处理的金刚石研磨膏的粒度不同，影响金刚石薄膜沉积时的形核密度、晶形和薄膜的质量；表面划痕对沉积金刚石薄膜的影响具有双重性。     

微波等离子体刻蚀处理对金刚石薄膜涂层刀具附着力和切削性能的影响

用HFCVD法在硬质合金（YG6）刀具衬底上沉积金刚石薄膜,用氢微波等离子体刻蚀的方法对衬底进行表面预处理,研究了该预处理技术对WC硬质合金衬底表面成分的影响,进一步探讨了所沉积金刚石薄膜的表面形貌和附着力,并通过难加工材料实际切削试验。研究了所制备的金刚石薄膜涂层刀具的切削性能。试验结果表明,Ar-H2微波等离子体刻蚀脱碳处理是提高金刚石薄膜附着力和改善涂层刀具切削性能的有效预处理方法。     

Diamond film synthesis in high-alternating-current glow discharge

Results of experiments with the deposition of polycrystalline diamond films onto silicon, titanium, and molybdenum substrates in a specially designed ac glow discharge system are presented. The phase composition and morphology of deposited films have been studied using the atomic force microscopy and X-ray diffraction techniques. It is established that the obtained diamond films possess high purity and degree of crystallinity. Inclusions of non-diamond carbon phases are absent. The rate of diamond film growth in the proposed system is 6–7 μm/h.     

Cyclic voltammetry and impedance studies of undoped diamond films

The undoped, polycrystalline diamond films were deposited on tungsten wire substrates by hot filament chemical vapor deposition (HF CVD), using a precursor gas mixture of methanol with excess of hydrogen. The morphology and quality of the as-deposited films were monitored by scanning electron microscopy (SEM) and Raman spectroscopy. The surface morphology analyzed by SEM resembles a continuous and well faceted diamond film. Raman results showed essential differences in qualities of diamond films grown at different hydrocarbon concentrations. The electrochemical properties of diamond electrodes were examined with cyclic voltammetry (CV) and the electrochemical impedance spectroscopy (EIS). The CV experiments revealed a large chemical window (>～4.3 V) of undoped diamond. Analysis of the ferrocyanide-ferricyanide couple at a diamond electrode suggests some extent of electrochemical quasi-reversibility, but the rates of charge transfer across the diamond substrate interface vary with diamond quality.     

微波CVD金刚石热沉片的制备研究

采用化学气相沉积法（CVD）制备的金刚石薄膜具有接近于天然金刚石的导热性能,是目前最为理想的热沉材料。利用微波等离子体化学气相沉积法（MPCVD）制备了金刚石热沉片,并在此基础上研究了不同沉积工艺对金刚石热沉片散热性能的影响。采用扫描电子显微镜（SEM）和激光拉曼光谱（Raman）检测了薄膜的表面形貌及纯度,金刚石热沉片的导热性能则通过测量封装LED后薄膜的散热效果来进行表征。结果表明,在其他条件不变的情况下,提高生长过程中的微波输出功率、降低反应气压以及增加基片温度有利于制备出散热性能更佳的金刚石热沉片。     

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.     

采用MPCVD法在硅衬底上选择性生长金刚石膜

采用微波等离子体化学气相沉积（MPCVD）法在附有SiO2掩摸的硅衬底上选择性沉积出了金刚石膜。采用扫描电子显微镜（SEM）和Raman光谱仪对金刚石膜的表面形貌和结构进行了表征。并讨论了衬底温度对金刚石薄膜选择性沉积的影响。得出了较佳的沉积条件。     

水冷反应室式MWPCVD制备金刚石膜装置研制

微波等离子体化学气相沉积(MWPCVD)是制备金刚石膜的一种重要方法.为了获得金刚石膜的高速率大面积沉积,研制成功了水冷反应室式MWPCVD制备金刚石膜的装置.装置在微波输入功率为3.0 kW时能长时间稳定运行,并在硅衬底上沉积出金刚石膜.     

Characterization of hypervelocity impact craters on chemical vapour-deposited diamond and diamond-like carbon films

Microwave plasma chemical vapour-deposited (CVD) process has been used to grow polycrystalline diamond films over silicon substrates. Diamond-like carbon (DLC) thin films were grown over silicon substrates using a microwave plasma disc reactor. Reactant gases of CH4 and H2 were used in both CVD processes. Some preliminary feasibility tests were performed on the possible applicability of diamond and diamond-like carbon thin films for space-protective applications against artificially simulated electrically actuated plasma drag hypervelocity impact of olivine particles. As-deposited films were analysed by Raman for their chemical nature. The morphology and dimensions of hypervelocity impact craters in diamond and DLC films was also studied by scanning electron microscopy (SEM) and optical microscopy. The velocity of debris particles was determined by high-speed photography using a streak camera. The size of the impact particles was determined by measuring the size of the holes formed in the mylar sheet mounted just above the target diamond and DLC film/silicon and coordinates of the impact sites were determined using the same apparatus. This revised version was published online in November 2006 with corrections to the Cover Date.     

表面波激发等离子体合成类金刚石薄膜的实验研究

用表面波等离子体装置进行了类金刚石薄膜的合成实验,研究了微波功率、基底负偏压和气体组成等条件对成膜的影响.用拉曼光谱和扫描电子显微镜对薄膜结构和表面形貌进行了分析,得出在100Pa的工作气压下,使用CH4放电,大功率和高偏压有利于生成质量较好的薄膜.