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.

Preliminary Investigation on a Sheet Plasma Produced by a Single Hot-Filament Cathode Discharge

A sheet plasma is generated by a mesh anode and a single hot-filament cathode with a DC power supply, and its characteristics are experimentally investigated. The sheet plasma is observed to locate around the anode. Both electron density and electron temperature derived from the average energy of the energetic electrons in nitrogen are estimated to be 10s cm^-3 and 20- 40 eV, respectively, using the optical emission spectroscopy （OES） method based on a kinetic model of low-pressure nitrogen discharge. The electron density, electron temperature and their spatial distributions are found to be affected by the supplying voltage on the anode（70 V to 300 V）, filament temperature （600℃ to 780℃） and gas pressure （2 Pa to 20 Pa）. By adjusting these parameters the discharge status can be easily controlled.

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.

Response of the low-pressure hot-filament discharge plasma to a positively biased auxiliary disk electrode

In a steady-state plasma,the loss rate of plasma particles to the chamber wall and surfaces in contact with plasma is balanced by the ionization rate of background neutrals in the hot-filament discharges.The balance between the loss rate and ionization rate of plasma particles(electrons and ions)maintains quasi-neutrality of the bulk plasma.In the presence of an external perturbation,it tries to retain its quasi-neutrality condition.In this work,we studied how the properties of bulk plasma are affected by an external DC potential perturbation.An auxiliary biased metal disk electrode was used to introduce a potential perturbation to the plasma medium.A single Langmuir probe and an emissive probe,placed in the line of the discharge axis,were used for the characterization of the bulk plasma.It is observed that only positive bias to the auxiliary metal disk increases the plasma potential,electron temperature,and plasma density but these plasma parameters remain unaltered when the disk is biased with a negative potential with respect to plasma potential.The observed plasma parameters for two different-sized,positively as well as negatively biased,metal disks are compared and found inconsistent with the existing theoretical model at large positive bias voltages.The role of the primary energetic electrons population in determining the plasma parameters is discussed.The experimentally observed results are qualitatively explained on the basis of electrostatic confinement arising due to the loss of electrons to a biased metal disk electrode.

Friction and Cutting Properties of Hot-Filament Chemical Vapor Deposition Micro-and Fine-grained Diamond Coated Silicon Nitride Inserts

The micro-crystalline diamond (MCD) and fine-grained diamond (FGD) films are deposited on commercial silicon nitride inserts by the hot-filament chemical vapor deposition (HFCVD) method. The friction andcutting properties of as-deposited MCD and FGD films coated silicon nitride (Si3N4) inserts are comparatively investigated in this study. The scanning electron microscopy (SEM) and Raman spectroscopy are adopted to studythe characterization of the deposited diamond films. The friction tests are conducted on a ball-on-plate typereciprocating friction tester in ambient air using Co-cemented tungsten carbide (WC-Co), Si3N4 and ball-bearing steel (BBS) balls as the mating materials of the diamond films. For sliding against WC-Co, Si3N4 and BBS,the FGD film presents lower friction coeffcients than the MCD film. However, after sliding against Si3N4, the FGD film is subject to more severe wear than the MCD film. The cutting performance of as-deposited MCD and FGD coated Si3N4 inserts is examined in dry turning glass fiber reinforced plastics (GFRP) composite materials,comparing with the uncoated Si3N4 insert. The results indicate that the lifetime of Si3N4 inserts can be prolonged by depositing the MCD or FGD film on them and the FGD coated insert shows longer cutting lifetime than the MCD coated one.

Si3N4工程陶瓷基底金刚石涂层生长规律及性能

为了避免氮化硅材料因产生裂纹或延伸破裂等造成的失效,利用热丝化学气相沉积法(Hot filament chemical vapor deposition,HFCVD)在氮化硅基底上沉积具有高硬度的金刚石涂层,采用单因素影响试验,分别探究碳源浓度、腔室压力、基底温度对金刚石成膜过程的影响机制,探究微米和纳米金刚石涂层的最优生长工艺参数。利用拉曼光谱仪(Raman)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)和原子力显微镜(AFM)对不同参数制备出的金刚石的形核、表面形貌、薄膜质量、表面粗糙度等进行表征,利用洛氏硬度计分析膜基结合力。结果表明,腔室压力越大,活性物质到达基底的动能越小,不利于金刚石的成核和生长。生长速率和表面粗糙度主要受甲烷浓度的影响:甲烷浓度从1%到7%,生长速率从0.84μm/h上升到1.32μm/h;表面粗糙度Ra从53.4 nm降低到23.5 nm;甲烷浓度过高导致涂层脱落严重,膜基结合力变差;晶面形貌和金刚石含量受到基底温度的影响较为明显,随着温度升高,金刚石质量提高。综合基底温度、腔室压力对金刚石涂层的影响,确定最佳生长温度为900℃,气压为1 kPa。调节甲烷浓度1%为微米金刚石;甲烷浓度5%为纳米金刚石。研究方法可以优化在陶瓷基底上制备具有优异性能的金刚石薄膜的制备参数。

热丝化学气相沉积法制备单晶金刚石的试验研究

热丝化学气相沉积法沉积区域可达12英寸(30.48 cm),其具备大批量生产单晶金刚石的潜力。采用尺寸为3 mm×3 mm×1 mm,(100)取向的单晶金刚石为基体,利用热丝化学气相沉积法以甲烷和氢气为前驱体,同时通入少量氮气进行同质外延生长。结果表明,在热丝温度为2200℃、碳源浓度为4%、腔体气压为4 kPa的条件下,单晶金刚石以3.41μm/h的速度生长,表面无多晶、破口、孔洞等缺陷;外延层X射线衍射光谱在(400)面处峰值的半高宽为0.11°,低于基体的半高宽0.16°,证明外延层具有较高的晶体质量;氮气的引入可以提升单晶金刚石的生长速度,同时降低外延层的晶体质量,较高的氮气浓度还会使得单晶金刚石的生长模式转为岛状生长。

热阴极离子规阴极灯丝断裂机理研究

介绍热阴极离子规的工作原理及组成结构,从热阴极灯丝变细、材料缺陷和工艺缺陷3方面分析离子规阴极灯丝断裂机理,根据断裂机理提出使用过程中的一些建议,以便延长使用寿命。

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。

HFCVD衬底三维温度场有限元法模拟

热丝化学气相沉积(Hot filament chemical vapor deposition,HFCVD)方法制备金刚石薄膜设备简单,成本低廉,适合大面积金刚石膜的产业化生产,其中衬底温度是沉积高质量CVD金刚石膜的重要参数之一。基于此,首先分析大面积HFCVD系统的热交换过程,建立大面积HFCVD系统衬底温度场的三维有限元模型。与传统纯热辐射模型相比,本模型更加接近实际系统,并较好符合试验测定的结果。根据三维有限元模型开展对大面积HFCVD系统衬底温度场的有限元仿真研究,得到HFCVD系统衬底温度场的三维分布规律,并讨论热丝直径、热丝温度、热丝根数、热丝-衬底距离和水冷散热系数等对衬底温度大小及均匀性的影响。仿真结果表明,在适宜金刚石膜生长的参数范围内,热丝参数和衬底接触热阻对衬底温度大小有显著影响,由于衬底内部的三维热传导使得衬底温度场更加均匀,各参数对衬底温度场的均匀性影响不大。研究结果为高质量制备金刚石膜提供理论基础。

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。

高性能复杂形状金刚石薄膜涂层刀具的制备和切削性能研究

通过偏压辅助增强热丝化学气相沉积法,采用螺旋形热丝排布方式以及优化的预处理方法和沉积工艺,在硬质合金印刷电路板铣刀的表面沉积了均匀的金刚石薄膜,采用扫描电镜和拉曼光谱研究了金刚石薄膜的表面特征。随后,通过铣削试验研究了金刚石涂层刀具的附着强度和切削性能。试验结果表明,复杂形状金刚石薄膜涂层铣刀既具有附着力强、耐磨性好的特点,同时又具备优异的切削性能,并且其制备无需后续抛光处理就能得到平整光滑的表面,这对于推动金刚石薄膜在复杂形状刀具上的产业化应用具有重要意义。

连续多试样纳米金刚石膜沉积设备及工艺

首先对热丝化学气相沉积(Chem ica l vapor depos ition,CVD)系统进行改造,设计了在真空室外对室内试样进行操纵的机械手系统和储料台,实现了一次热丝碳化后完成多个不同工艺条件下试样的连续沉积。有限元仿真研究结果表明,多衬底温度场比较均匀,适合于金刚石膜的生长。最后,采用改进沉积系统,在A r-CH4-H2气氛中,在多晶钼衬底上成功制备了纳米金刚石薄膜。R am an,XRD和AFM等结果表明,制备的金刚石纯度较高,晶粒大小在30 nm左右,表面光滑。

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。

负衬底偏压热灯丝CVD金刚石膜成核的研究

本文利用扫描电子显微镜和原子力显微镜研究了Ｓｉ（１００）衬底上热灯丝金刚石膜成核过程。在－２４０Ｖ和２５０ｍＡ下，在镜面抛光的Ｓｉ（１００）衬底上金刚石最大成核密度超过了１０１０ｃｍ－２。研究表明，负衬底偏压增强成核主要是发射电子和离子轰击的结果。

纳米金刚石薄膜的微结构和残余应力

采用双偏压热丝化学气相沉积法在不同栅极和衬底偏流下制备出纳米金刚石薄膜.采用Raman谱、SEM、AFM、纳米压痕法和XRD分析纳米金刚石膜的微结构、弹性模量和残余应力.分析结果表明,金刚石晶粒尺寸随着栅极和衬底偏流的增加而减小,而衬底偏流的加入会引起非金刚石成分的显著增加.金刚石晶界的畸变使得弹性模量随着栅极和衬底偏流的增加而减小,薄膜热应力也随之减小.晶界非金刚石成分引起金刚石本征应力呈压应力性质,晶界密度的增加使得本征应力随着栅极偏流的增加而增加,但衬底偏流引起薄膜抵抗变形能力剧烈下降,导致金刚石本征压应力的减小.

热丝CVD在涂巴基管硅基片上沉积大面积金刚石膜

本文采用多排热丝化学气相沉积法在涂巴基管的硅基底上沉积金刚石膜，研究了金刚石膜的生长面积和质量均匀性。实验结果表明，随着热丝数量增加，金刚石膜的面积增加；随着丝底距增加和真空度提高，金刚石膜的质量均匀性提高。利用多排热丝和间歇转动工作台，在涂巴基管的单晶硅基底上沉积出了３０×６０ｍｍ、质量均匀的金刚石薄膜。扫描电镜和拉曼光谱检测确认了这一结果。

热丝碳化促进CVD金刚石成核增强的物理机制

采用扫描电镜、Ｘ射线衍射及喇曼光谱等手段研究了ＨＦＣＶＤ过程中热丝碳化对金刚石成核特性的影响。热丝经充分碳化后能发射出更多热电子，进而从反应气体中激发出更多原子Ｈ和ＣＨ３＋，使金刚石晶核的孕育期大为缩短，３ｍｉｎ内即可在未经表面预处理的Ｓｉ衬底上获得１０１０ｃｍ－２以上的高晶核密度。

梯度基体温度法和反应溅射TiC过渡层对钛合金基体沉积金刚石薄膜的影响

以H2和CH4作为反应气体,采用热丝化学气相沉积法(HFCVD)在钛合金(Ti6Al4V)平板基体上制备金刚石薄膜,利用扫描电镜(SEM)、X射线衍射仪(XRD)、激光拉曼光谱(Raman)和洛氏硬度仪分析薄膜的表面形貌、结构、成分和附着性能,研究了高温形核-低温生长的梯度降温法对原始钛合金和反应磁控溅射TiC过渡层的钛合金表面沉积金刚石薄膜的影响。结果表明:原始基体区和TiC过渡层区沉积的金刚石薄膜平均尺寸分别为0.77μm和0.75μm,薄膜内应力分别为-5.85GPa和-4.14GPa,TiC层的引入可以有效提高金刚石的形核密度和晶粒尺寸的均匀性,并减少薄膜残余应力;高温形核-低温生长的梯度降温法可以有效提高金刚石的形核密度和质量,并提高原始基体上沉积金刚石薄膜的附着性能。

纳米压痕法研究金刚石薄膜的力学性能

用热丝化学气相沉积法在硅基体上制备了大面积硼掺杂金刚石薄膜,硼的浓度大约为2×10^(20)/cm3。利用纳米压痕仪及其附件研究了薄膜和纳米划擦有关的力学性能。结果表明:薄膜具有较高的硬度,平均硬度约为30GPa,弹性模量约为419GPa;薄膜与基体的结合强度较高,薄膜发生剥落的第一次破坏力大约是4N。比较而言,薄膜中心区域的硬度高于边缘,结合强度则相反。