High thermal conductivity diamond coated graphite by microwave plasma chemical vapour deposition

Diamond film was grown on high thermal conductivity graphite substrate using microwave plasma chemical vapour deposition method. Nanodiamond particles were uniformly seeded on the substrate to generate high nucleation density by a spray gun. The continuous and high purity diamond film was obtained, and growth rate was up to 2.7 μm h^??1. The thickness, surface morphology, quality and composite phase of the film were analysed by SEM, Raman and X-ray diffraction. It was shown that graphite coated with diamond presented a higher thermal conductivity (520?W?m^??1 k^??1) than copper. Furthermore, this coated material with high thermal conductivity, good strength and non-conductive surface will make it possible to be widely used in thermal management field.     

Formation and characterization of diamond crystals synthesized by microwave plasma CVD system

Abstract

Diamond crystals have been successfully synthesized on (100) Si wafer using microwave plasma CVD. The growth was conditioned in a flowing system in which the parameters, such as CH₄/H₂ ratio, pressure, temperature and microwave power were varied. Cubo‐octahedra or tetrakaidecahedra are the equilibrium shape of diamond single crystals obtained under all conditions and are therefore the basic unit for the formation of polycrystalline diamond films, mostly through repetitive twinning and secondary growth of diamond crystals on {100} habit planes of cubo‐octahedra. Both X‐ray diffraction and Raman spectroscopy were used to facilitate the analysis of the diamond crystallinity and purity. These qualities are similar to those of natural diamonds.     

等离子热丝化学气相沉积金刚石膜工艺参数研究

采用等离子热丝化学气相沉积(PHFCVD)装置进行了金刚石薄膜的制备实验。实验条件为：氢气流量为200sccm,甲烷流量为2～12sccm,基体温度为700～900℃,偏压为0～400V,真空室压力为4kPa。通过实验得出了甲烷含量、基体温度和偏压对沉积金刚石膜的影响,并运用扫描电子显微镜(SEM)、原子力显微镜(AFM)和X射线衍射(XRD)等测试方法对金刚石薄膜进行了观察分析。     

系统压强对微波等离子体化学气相沉积金刚石成核的影响

为了在氧化铝上制备（100）定向织构的金刚石薄膜,必须先提高金刚石的成核密度,在微波等离子体化学气相沉积（MPCVD）系统中,采用低压成核的方法,在氧化铝陶瓷上沉积出高成核密度的金刚石薄膜,扫描电镜显示其成核密度可达10^8cm^-2。在此基础上,沉积出（100）织构的金刚石薄膜。     

Linear antenna microwave plasma CVD deposition of diamond films over large areas

Diamond thin films were grown by linear antenna microwave plasma CVD process over large areas (up to 20 × 10 cm²) from a hydrogen based gas mixture. The influence of the gas composition (H₂, CH₄, CO₂) and total gas pressure (0.1 and 2 mbar) on the film growth is presented. For CH₄/H₂ gas mixtures, the surface crystal size does not show dependence on the methane concentration and total pressure and remains below 50 nm as observed by SEM. Adding CO₂ (up to 10%) significantly improves the growth rate. However, still no significant change of morphology is observed on films grown at 2 mbar. The crucial improvement of the diamond film purity (as detected by Raman spectroscopy) and crystal size is found for deposition at 0.1 mbar. In this case, crystals are as large as 500 nm and the growth rate increases up to 38 nm/h.     

化学气相沉积法制备超纳米金刚石薄膜

采用微波等离子体化学气相沉积法,利用CH4、SiO2和Ar的混合气体在单晶硅片基底上制备出高质量的超纳米金刚石薄膜.表征结果显示,制备的薄膜致密而均匀,晶粒平均尺寸约7.47nm,表面粗糙度约15.72nm,并且其金刚石相的物相纯度相对较高,是质量优异的超纳米金刚石薄膜材料.     

直流热阴极PCVD法间歇生长模式制备金刚石膜

采用直流热阴极PCVD(Plasma chemical vapor deposition)法间歇生长模式制备金刚石膜,通过加入周期性的刻蚀阶段清除金刚石膜在一定生长期中形成的石墨和非晶碳等杂质,实现了金刚石膜生长的质量调控。间歇式生长过程分为沉积阶段和刻蚀阶段,两个阶段交替进行。采用Raman光谱、SEM和XRD对所制金刚石膜的品质进行了表征,并与同样生长条件下连续生长模式制备的金刚石膜样品进行了比较。结果表明,当单个生长周期为30 min(沉积时间为20 min、刻蚀时间为10 min)时,直流热阴极PCVD法间歇生长模式制备的金刚石膜中的非金刚石相杂质含量低于连续间歇生长模式制备的金刚石膜。     

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).     

微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石

研究了衬底温度、核化密度、衬底表而预处理等工艺参数对微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石的影响.采用扫描电镜、X-射线衍射、喇曼光谱和红外光谱对样品进行了表征.结果表明:从高核化密度生长的金刚石膜中探测不到碳化硅;不论对硅衬底进行抛光预处理还是未抛光预处理,从低核化密度牛长的金刚石厚膜中总能探测到碳化硅.碳化硅生长在硅衬底上未被金刚石覆盖的地方,或者是在金刚石晶核之间的空洞处.碳化硅形成和金刚石生长是同时发生的两个竞争过程.此研究结果为制备金刚石和碳化砟复合材料提供了一种新的方法.     

微波功率对掺氮纳米金刚石薄膜组成、结构及性能的影响

以CH4和CO2作生长金刚石薄膜的反应气体,以Ar作载气将三聚氰胺甲醇饱和溶液带入沉积室内作氮掺杂源,用微波等离子体化学气相沉积法在单晶硅衬底上制备出掺氮纳米金刚石薄膜。通过拉曼光谱、原子力显微镜、霍尔效应研究了掺氮纳米金刚石薄膜的组成、结构和导电性能,重点研究了微波输入功率对薄膜特性的影响。结果表明,制备的掺氮纳米金刚石薄膜具有良好的电子导电性,且随着激发等离子体微波功率的增大,其晶粒尺寸、晶界宽度、表面粗糙度和电导率增大,在最佳微波功率条件下制备出电子电导率高、材料质量好的纳米金刚石薄膜。     

Chemical vapour deposition (CVD) diamond coated tools performance in machining of PEEK composites

This paper presents a study about the chemical vapour deposition (CVD) diamond coated tool performance in machining unreinforced PEEK and composite PEEK CF30 (reinforced with 30% of carbon fibres).

The experimental procedure consisted of turning operations, during which cutting forces and surface roughness obtained in composite workpieces were measured.

The obtained results showed a best cutting performance for CVD diamond coated tool in machining PEEK composites, particularly in terms of cutting forces and power consumption, when compared with polycrystalline diamond (PCD) and cemented carbide (K10) cutting tools. This fact is very important due to the minor production costs of CVD diamond coated tools in comparison with PCD tools.     

两段成长法改善微波电浆辅助化学气相沉积多晶金刚石之品质

以化学气相沉积法成长多晶金刚石薄膜时,薄膜的品质会受到成长时间、成长压力、反应气体比例、偏压与否及成核的机制等因素影响.研究采用微波电浆辅助化学气相沉积(MPECVD)法,以甲烷(CH4)和氢气(H2)作为反应气体原料,在P型(111)硅基板沉积多晶金刚石薄膜.典型沉积多晶金刚石薄膜的制程可分为四个阶段:抛蚀表面阶段、渗碳阶段、偏压增强成核(BEN)阶段及成长阶段.研究将成长阶段划分为两个阶段,第一阶段压力较低(成长Ⅰ阶段),第二阶段压力较高(成长Ⅱ阶段).结果表明:第一阶段可大大改善金刚石薄膜的品质,所获多晶金刚石薄膜的晶粒具有明确的颗粒边界、较低的碳化物或缺陷,电导率急剧降低,显现出本徵金刚石半绝缘的性质.可以认为金刚石薄膜品质的改善完全为低压成长所致.实验发现在成长Ⅰ阶段或成长Ⅱ阶段施加偏压时,只会降低多晶金刚石薄膜的品质.     

直流热阴极CVD金刚石薄膜生长特性研究

为了获得高质量的金刚石薄膜,采用直流热阴极化学气相沉积系统分别在不同基片温度和不同碳源气体含量条件下生长金刚石薄膜,利用Raman光谱、SEM和XRD检测方法研究了基片温度和碳源气体含量对金刚石薄膜生长特性的影响.结果表明,金刚石薄膜与基片Mo之间有Mo2C的过渡层存在;1000℃的温度能够促进金刚石晶体的生长,抑制其他碳杂质的形成,CH4体积分数为2%适于快速生长高纯度的金刚石薄膜.     

Characteristics of nano-crystalline diamond films prepared in Ar/H2/CH4 microwave plasma

Characteristics of nano-crystalline diamond (NCD) thin films prepared with microwave plasma chemical vapor deposition (CVD) were studied in Ar/H₂/CH₄ gas mixture with a CH₄ gas ratio of 1-10% and H₂ gas ratio of 0-15%. From the Raman measurements, a pair of peaks at 1140 cm^− 1 and 1473 cm^− 1 related to the trans-polyacetylene components peculiar to nano-crystalline diamond films was clearly observed when the H₂ gas ratio of 5% was added in Ar/H₂/CH₄ mixture. With an increase of H₂ gas content up to 15%, their peaks decreased, while a G-peak at roughly 1556 cm^− 1 significantly increased. The degradation of NCD film quality strongly correlates with the decrease of C₂ optical emission intensity with the increase of hydrogen gas contents. From the surface analysis with atomic force microscopy (AFM), it was found that grain sizes of NCD films were typically of 10-100 nm in case of 5% H₂ gas addition.     

红外光学材料硫化锌衬底上沉积金刚石膜的研究

采用微波等离子体化学气相沉积法,在预镀陶瓷过渡层的硫化锌衬底上沉积金刚石膜。在以前的实验中,我们发现在陶瓷过渡层上沉积金刚石膜极其困难,但采用金刚石诱导形核方法后,我们已经在过渡层／硫化锌试样表面获得了很小面积（约1mm宽的环状区域）的金刚石形核。本文对前期的诱导形核工作进行了一定改进,目前已经使形核生长范围大大增加,沉积面积超过原来10倍。此外,本文对金刚石／过渡层／硫化锌试样的红外透过特性以及金刚石膜质量等进行了评价。     

HFCVD diamond deposition parameters optimized by a Taguchi Matrix

A Taguchi Matrix was used for the experimental design to study the CVD diamond deposition parameters in a cold-wall HFCVD reactor. Gas composition, total gas pressure, total mass flow and substrate temperature were considered as controllable factors, and three levels for each of these factors were selected, in an L9 orthogonal array. A new Figure-of-Merit (FOM) is proposed to assess the best combination of film properties: grain size, residual stress, structural quality and growth rate. Substrate temperature affects mostly grain size and diamond quality, while methane content mostly determines residual stresses and the growth rate. The latter is also mainly affected by the total pressure as well as is grain size, while total gas flow has a neutral effect. Under the limits of deposition conditions, the best FOM is obtained at the highest total gas pressure and mass flow, average CH₄ content, and lowest substrate temperature.     

Electrochemical studies of nano-structured diamond thin-film electrodes grown by microwave plasma CVD

In this paper, we report the investigation of the electrochemical properties of nano-structured diamond thin-film electrodes on porous silicon (PSi) synthesized by microwave plasma chemical vapor deposition (MPCVD). For the application, boron-doped and undoped diamond thin film has been performed and fabricated into an electrode device, and its microstructure, electrical and chemical properties have been studied. In order to enlarge the surface area of diamond electrodes, a negative bias was applied to the MPCVD process to deposit diamond thin film in a nano-structured form, so that its surface remained rough and nano-fine structured. Diamond thin films were analyzed by Raman spectroscopy and SEM. The morphology of boron-doped diamond thin films on PSi reveals nano-rods in the shape of diamond crystallites. Their electrochemical properties were evaluated by performing cyclic voltammetry (CV) measurement in inorganic K₄[Fe(CN)₆] in a K₂HPO₄ buffer solution. Boron-doped diamond thin film on PSi has demonstrated good electrochemical properties, with a larger redoxidation current of CV, due to its rough surface, which provides a more active electrochemical interface.     

Crystalline carbon nitride films prepared by microwave plasma chemical vapour deposition

Crystalline carbon nitride films have been synthesized on Si (100) substrates by a microwave plasma chemical vapour deposition technique, using mixture of N₂, CH₄ and H₂ as precursor. Scanning electron microscopy shows that the films consisted of hexagonal bars, tetragonal bars, rhombohedral bars, in which the bigger bar is about 20 μm long and 6 μm wide. The X-ray photoelectron spectroscopy suggests that nitrogen and carbon in the films are bonded through hybridized sp² and sp³ configurations. The x-ray diffraction pattern indicates that the films are composed of α-, β-, pseudocubic and cubic C₃N₄ phase and an unidentified phase. Raman spectra also support the existence of α- and β-C₃N₄ phases. Vickers microhardness of about 41.9 GPa measured for the films.     

Comparative study of the electrical properties of diamond films grown by microwave plasma assisted and hot-filament chemical vapor deposition

Schottky diodes were built on different polycrystalline diamond films grown by Microwave Plasma and Hot Filament Chemical Vapor Deposition and their electrical properties were studied. The barrier height increased with the diamond film quality and the corresponding ideality factor decreased. Even though the lower-quality HFCVD film displayed poor rectifying properties, it was found to be much less sensitive to variations in the operating conditions (air vs. vacuum). The activation energies of the films depend on morphological parameters, as preferable grain size or orientation. The bulk conduction also depends on the quality of the deposited films, changing from ohmic to trap-free or shallow trap SCLC and SCLC with an exponential distribution of traps. The hypothesis of using the electrical measurements as an indicator for film quality has been discussed.