热丝法化学气相沉积金刚石系统温度分布与薄膜生长关系研究

对热丝化学气相沉积金刚石薄膜系统内的三种传热方式（传导、对流和辐射）进行了比较分析,数值计算了气相空间温度分布和衬底表面二维温度分布。采用热丝化学气相沉积工艺制备了金刚石薄膜,扫描电镜结果显示金刚石薄膜在不同生长区域呈现出与温度分布相关的微观结构与形貌。     

大面积长生金刚石相关物理参量的空间分布

研究了在热丝化学气相生长金刚石的过程中,衬底温度、衬底表面附近的气体温度以及气流的质量流密度分布对金刚石膜的形核和生长的影响。模拟计算结果表明,这三个参量是空间位置的参数,在某些区域,这三个参量均匀分布。当热丝阵列面与衬底间距离超过７ｍｍ之后,这三个参量在衬底上有一个较大的均匀区域,在该区域的两侧,各参量值显著变化。在衬底中心的均匀区域,金刚石膜晶形清楚而致密;偏离该区域,这三个参量数值明显下降,形核密度和生长速度较低,三个参量均匀的区域可作为金刚石大面积均匀的形核和生长的位置。     

Wide area polycrystalline diamond coating and stress control by sp hot filament CVD reactor

This paper discusses large area uniform diamond coatings deposited in the sp³ Inc. Model 600 hot filament diamond deposition system (made by sp³ Inc., California, USA). This model combines proven hot filament thermal reactor technology with advanced controls to produce high quality polycrystalline diamond films over a maximum square area of 380 mm × 380 mm on a wide variety of substrate materials such as carbide-based cutting tools, wear surfaces, Si wafers, etc. The reactor is characterized using instrumented 300 mm Si wafers and modified, accordingly, to optimize performance on 300 mm diameter wafers or multiple 100 mm diameter wafers. Roles of temperature and other process parameters in stress formation and development in the diamond thin films, grown in a wide area hot filament deposition system, are discussed along with some of the ways of controlling these stresses on a production basis.     

热丝法化学气相沉积大面积金刚石膜中辐射场和温度场的尺寸效应

对热丝法化学气相沉积金刚石膜中的辐射场和温度场进行了计算，结果表明，在样品平面沿Ｘ，Ｙ方向均辐照度（温度）区的线性尺寸比高温梯度区的尺寸快速增大，沿Ｚ方向均匀辐照度（温度）区的深度随样品到加热丝距离的增加而增大，辐照度（温度）的大小可通过改变加热丝间距得到控制。     

热丝CVD方法中气体状态参数的二维模拟计算

使用在连续介质中建立的二维流场数学模型，模拟计算了在用HFCVD方法生长金刚石薄膜过程中影响气体温度分布的多个沉积工艺参数，研究了气体的速度和体密度的空间分布．结果表明，在优化工艺参数条件下，高温热丝的热阻塞作用导致气体状态参数的不均匀空间分布；在热丝附近气体的速度大而靠近反应腔体侧壁处小；热丝附近处气体体密度减小而靠近冷反应腔体侧壁处增加，采用绝热或高等温边界的反应腔管道壁可以消除气体的热绕流现象，有利于大面积金刚石薄膜的快速均匀生长．     

Simulations of the Dependence of Gas Physical Parameters on Deposition Variables during HFCVD Diamond Films

During the growth of the hot filament chemical vapor deposition （HFCVD） diamond films, numerical simulations in a 2-D mathematical model were employed to investigate the influence of various deposition parameters on the gas physical parameters, including the temperature, velocity and volume density of gas. It was found that, even in the case of optimized deposition parameters, the space distributions of gas parameters were heterogeneous due primarily to the thermal blockage come from the hot filaments and cryogenic pump effect arisen from the cold reactor wall. The distribution of volume density agreed well with the thermal round-flow phenomenon, one of the key obstacles to obtaining high growth rate in HFCVD process. In virtue of isothermal boundary with high temperature or adiabatic boundary condition of reactor wall, however, the thermal roundflow was profoundly reduced and as a consequence, the uniformity of gas physical parameters was considerably improved, as identified by the experimental films growth.     

HFCVD金刚石膜过程的气氛模拟与分析

对热丝法化学气相沉积金刚石膜过程的气氛进行了模拟与分析。使用GRI－Mech3.0甲烷燃烧过程C／H／O／N四元体系热化学反应机理和动力学数据，模拟并分析了HFCVD金刚石膜的C／H气相化学反应，通过对反应流的简单模拟得到了衬底位置气相组成，结果与前人实验数据吻合，探讨了灯丝温度、碳源浓度和碳源种类等因素变化对衬底位置气相组成的影响。结果表明甲基是金刚石膜生长最主要的前驱基团，其作用远高于乙炔，而超平衡态原子氢的存在对金刚石膜的质量至关重要。     

Two-step growth of HFCVD diamond films over large areas

This paper reports the results of a two-step hot filament chemical vapor deposition method to improve the quality of diamond films. Diamond films were deposited on a Si(100) substrate having an area of 45 cm² and a thickness of 60 μm, employing a HFCVD system. The first step is the growth of CVD diamond in the HFCVD reactor. In the second step, the samples were treated in a saturated solution of H₂SO₄:CrO₃ and rinsed in a (1:1) solution of H₂O₂:NH₄OH. After this procedure, a second diamond layer was deposited. The diamond films were analyzed by Raman scattering spectroscopy (RSS), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The films showed a high degree of purity with a thickness of 60 μm, presenting uniform characteristics over a large area.     

热丝化学气相沉积纳米金刚石修复损伤PCD刀具的研究

利用热丝化学气相沉积装置, 以聚晶金刚石片为衬底, 在氢气/丙酮/氩气反应体系中研究了衬底温度对纳米金刚石生长的影响。采用扫描电子显微镜对生长结果进行了表征, 结果表明在衬底温度950℃的情况下, 金刚石薄膜表面结构呈\     

High-quality single-walled carbon nanotubes synthesis by hot filament CVD on Ru nanoparticle catalyst

We investigated the single-walled carbon nanotubes (SWCNTs) growth on Ru nanoparticle catalyst via hot filament assisted chemical vapor deposition (HFCVD) with two independent W filaments for the carbon precursor (methane) and the hydrogen dissociation respectively. The Ru nanoparticles were obtained following a two-step strategy. At first the growth substrate is functionalized by silanisation, then a self assembly of a ruthenium porphyrin complex monolayer on pyridine-functionalized metal oxide substrates. We have studied the impact of the filaments power and we optimized the SWCNTs growth temperature. The as grown SWCNTs were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and Raman spectroscopy. It was found that the quality, density and the diameter of SWCNTs depends on the filament and growth temperature. Results of this study can be used to improve the understanding of the growth of SWCNTs by HFCVD.     

Surface transformations of carbon (graphene, graphite, diamond, carbide), deposited on polycrystalline nickel by hot filaments chemical vapour deposition

The deposition of carbon has been studied at high temperature on polycrystalline nickel by hot filaments activated chemical vapor deposition (HFCVD). The sequences of carbon deposition are studied by surface analyses: Auger electron spectroscopy (AES), electron loss spectroscopy (ELS), X-ray photoelectron spectroscopy (XPS) in a chamber directly connected to the growth chamber. A general scale law of the (C/Ni) intensity lines is obtained with a reduced time. Both, shape analysis of the AES C KVV line and the C1s relative intensity suggest a three-step process: first formation of graphene and a highly graphitic layer, then multiphase formation with graphitic, carbidic and diamond-like carbon and finally at a critical temperature that strongly depends on the pretreatment of the polycrystalline nickel surface, a rapid transition to diamond island formation. Whatever the substrate diamond is always the final product and some graphene layers the initial product. Moreover it is possible to stabilize a few graphene layers at the initial sequences of carbon deposition. The duration of this stabilization step is strongly depending however on the pre-treatment of the Ni surface.     

热灯丝CVD金刚石膜的微结构和形貌对其电子性质的影响

利用热灯丝CVD法在硅衬底上合成出了金刚石膜。金刚石膜的质量和电子性质由扫描电子显微镜、拉曼谱、阴极发光及霍尔系数测量来表征。实验结果表明,沉积条件对金刚石膜电子性质和质量有重要影响。载流子迁移率随甲烷浓度增加而减少,但场发射随其增加而增强。压阻效应随微缺陷增多而降低。异质外延金刚石膜压阻因子在室温下100微形变时为1200,但含有大量缺陷的多晶金刚石膜压阻因子低于200,这是由于薄膜中缺陷态密度增加,并依赖于膜结构的变化。     

Nucleation and Oriented Textured Growth of Diamond Films on Si(100) via Electron Emission in Ho.t Filament Chemical Vapor Deposition

1. IntroductionIn recent years, there has been increasing illterest in the heteroepitaxial growth of diamond films'by chemicisl vapor deposition(CVD) owing to theirpromising applications for the electronic devices. Epitaxial diamond films have been successfully grown onc-BN and monocrystal diamond substrated~4]. However, it is a more imperative task to deposit heteroepitarial diamond films on St which was anticipated tobe as a low cost substrate to achieve synthesis of singlecrystalline diam…     

热丝CVD系统内衬底温度分布的数值研究

热丝法化学气相沉积金刚石薄膜系统内 ,衬底温度和碳源气体浓度是金刚石薄膜生长最为重要的参数。本文根据传热学基本原理 ,数值模拟了衬底表面辐照度、温度分布 ,讨论了衬底热传导等因素对衬底温度分布的影响 ,探讨了如何改善衬底温度均匀性。结果表明 ,考虑衬底横向热传导后 ,衬底表面温度分布均匀性明显优于基于辐射热平衡得到的温度分布 ,在一定程度上有利于生长大面积薄膜。     

热丝化学气相沉积制备BDD薄膜电极的电催化特性

研究了热丝化学气相沉积法(HFCVD)制备得到掺硼金刚石膜电极电催化氧化典型有机物苯酚的特性.Raman光谱测试显示制备BDD电极具有较好的金刚石相,循环伏安测试表明该电极具有较高的析氧过电位(+2.3V vsSCE).在电催化氧化苯酚过程中,化学需氧量(COD)能够有效去除,降解过程中有较高的电流效率,在COD较高的情况下,瞬时电流效率(ICE)可达100%,随着COD的降低ICE逐渐减少.催化实验结果表明,BDD电极是一种优良的电催化降解有机物新型电极.     

Fluidized bed micro-machining and HFCVD of diamond films onto Co-cemented tungsten carbide (WC-Co) hardmetal slabs

The effect of fluidized bed (FB) treatment upon hot filament chemical vapor deposition (HFCVD) of polycrystalline diamond films onto WC-Co hardmetal substrates was investigated. Several scenarios to make the substrates ready for HFCVD were, comparatively, evaluated and the resulting diamond films were examined in terms of their morphology and adhesion. The diamond grain density was measured by scanning electron microscopy. The adhesion of continuous diamond film to substrate was evaluated by the reciprocal of the slope of crack radius-indentation load functions. Surface binder dissolution followed by FB treatment (PF pretreatment) allowed very high diamond nucleation density and smaller grain size. The adhesion of films grown on PF pretreated substrates was found to be very close to that of films deposited on hardmetal slabs pretreated by Murakami's reagent followed by Co etching with Caro's acid and seeded with diamond suspension in an ultrasonic vessel (MPS pretreatment). However, diamond coatings on MPS pretreated samples exhibited a rougher surface morphology as a result of both lower diamond nucleation density and larger substrate surface roughening by Murakami's etching. Based upon experimental findings, our newly developed PF pretreatment was found to be a very promising technique in substrates conditioning as well as in promoting adherent, uniform and smooth diamond coatings onto hardmetal tools and wear parts.     

分离送入甲烷和氢气的热丝法沉积金刚石膜

采用热丝法沉积金刚石膜，分离送入氢气和甲烷，使作为发热体的钨丝电阻值比经典的热丝法降低２０％，用此法制得的金刚石晶形较好，实验表明：反应气体的流量对膜的致密生长区影响很大。     

Laterally organized carbon nanotube arrays based on hot-filament chemical vapor deposition

Lateral porous anodic alumina (PAA) templates were used to organize carbon nanotubes (CNTs) grown by a hot-filament assisted chemical vapor deposition (HFCVD) process. For the CNT growth, we used a modified “home-made” HFCVD system with two independently powered filaments which are fitted respectively on the methane (CH₄) gas line, which serves as a carbon precursor and on the hydrogen (H₂) gas line, which acts as an etching agent for the parasitic amorphous carbon. Various activation powers of the hot filaments were used to directly or indirectly decompose the gas mixtures at relatively low substrate temperatures. A parametric study of the HFCVD process has been carried out for optimizing the confined CNTs growth inside the lateral PAA templates.     

<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     

Tuning the conditions for the deposition of nanocrystalline diamond by hot filament chemical vapour deposition

Although large focus has been placed into the deposition of nanocrystalline and ultra-nanocrystalline diamond films, most of this research uses microwave plasma assisted CVD systems. However, the growth conditions used in microwave systems cannot be directly used in hot-filament CVD systems. This paper, aims to enlarge the knowledge of the diamond film depositing process. H2/CH4/Ar gas mixtures have been used to deposit micro, nano and ultra-nanocrystalline diamond films by hot-filament CVD systems. Additionally, the distance between the filaments array and the substrate was varied, in order to observe its effect and consequently the effect of a lower substrate temperature in the nucleation density and deposition. All the samples were characterized for microstructure and quality, using scanning electron microscopy and Raman spectroscopy.