微波等离子体化学气相沉积——一种制备金刚石膜的理想方法

综述了微波等离子体化学气相沉积(MPCVD)法制备金刚石膜技术,表明MPCVD是高速、大面积、高质量制备金刚石膜的首选方法。介绍了几种常用的MPCVD装置类型,从MPCVD装置的结构特点可以看到,用该类型装置在生长CVD金刚石膜时显示出独特的优越性和灵活性。用MPCVD法制备出的金刚石膜其性能接近甚至超过天然金刚石,并在多个领域得到广泛应用。     

圆柱谐振腔式微波等离子体金刚石膜CVD沉积室的FDTD模拟与优化

微波等离子体化学气相沉积(MPCVD)技术被认为是制备高质量金刚石膜的一种最重要的技术手段。对微波等离子体金刚石膜沉积装置进行模拟与优化,可大大减少设计和改进MPCVD装置时所需要的时间与成本。本文在结合使用谐振腔质量因子和沉积台上方等离子体的密度与分布两个优化判据的基础上,采用Matlab语言和时域有限差分方法,模拟了圆柱谐振腔式微波等离子体金刚石膜沉积装置,并对其主要尺寸进行了优化。     

一种用于金刚石膜沉积装置的重入式微波谐振腔

微波等离子体化学气相沉积法(MPCVD)是制备高品质金刚石膜的重要方法,而MPCVD技术的关键是其设备核心部件谐振腔的设计。本文基于目前广泛应用的圆柱式和椭球式两种MPCVD谐振腔中微波传输的特点和其各自的优点,提出了一种重入式微波谐振腔的设计构想,并利用数值模拟的方法对这一构想进行了验证。模拟的结果表明,微波在重入式微波谐振腔内外壁之间的路径传输后,可在金刚石膜沉积台处形成一最强且相对均匀的电场。在相同的输入功率下,其形成的最大电场强度高于圆柱式和椭球式两种谐振腔时的情况。由于重入式的微波谐振腔具有结构简单、频率易于调节的优点,因而这一构想可为设计制造新型的MPCVD金刚石膜沉积设备提供参考依据。     

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。     

微波等离子体化学气相沉积金刚石膜装置的研究进展

综述了各种微波等离子体化学气相沉积（MPCVD）金刚石膜装置的结构及工作原理,并对它们各自的优缺点做了比较分析;基于MPCVD金刚石膜装置的发展现状,构想设计了一种新型高效的大功率大面积快速沉积CVD金刚石膜装置,并对其可行性做了初步分析研究。     

金刚石膜在多孔硅发光中的应用

采用微波等离子体化学气相沉积（MPCVD）法成功地在多孔硅上沉积出均匀、致密的金刚石膜。光致发光测量表明,金刚石膜可以有效稳定多孔硅的发光波长和发光强度,具有明显的钝化效应。金刚石膜的这个特点再加上高硬度特性使金刚石膜成为多孔硅的一种潜在的钝化膜。     

MPCVD金刚石膜装置的研究进展

微波等离子体(MPCVD)法因其独特的优势,成为高速、大面积、高质量制备金刚石膜的首选方法,MPCVD金刚石膜装置的研究受到科研人员和工业界的广泛关注。文章对金刚石膜的性质和各种制备方法进行了简要概述,论述了CVD金刚石膜的生长机理,着重阐述了各种MPCVD装置的结构特点及工作原理,并对各种装置的优、缺点进行了分析。研究结果表明:研制具有高品质因数谐振腔能激发均匀微波等离子体的MPCVD装置,是进一步开发金刚石膜工业化应用所需解决的主要问题。     

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。     

MPCVD同质外延单晶金刚石研究进展

微波等离子体化学气相沉积法(Microwave plasma chemical vapor deposition, MPCVD)外延单晶金刚石被认为是制备大尺寸、高质量的单晶金刚石极具前景的技术手段之一。本文首先对MPCVD同质外延单晶金刚石生长机理及最新进展做了简要介绍,然后着重阐述了MPCVD法制备大尺寸、高质量单晶金刚石在籽晶筛选与预处理、基台结构设计及生长工艺探索等方面的工作,并对MPCVD高品质单晶金刚石在力学、热学、光学及电子学等领域的应用进行了介绍,对未来单晶金刚石的应用前景进行了展望。     

微波等离子体化学气相沉积系统谐振腔研究

微波等离子体化学气相沉积(MPCVD)法是目前最有发展前景的高质量金刚石薄膜沉积方法之一,但由于谐振腔中微波与等离子体之间强烈的相互作用,人们很难根据经验对谐振腔进行改进,本文利用HFSS软件对不锈钢式MPCVD的谐振腔进行了模拟,通过分析谐振腔内电场以及等离子体的分布,对谐振腔的主要参数进行了优化处理,并根据模拟结果设计出谐振腔系统,在一定条件下,沉积出了优质的金刚石膜,沉积速率可达到0.33 μm/h.     

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.     

甲烷浓度对金刚石薄膜质量的影响

纳米金刚石薄膜具有优异的性能,已在多个领域获得广泛应用.但微波等离子体化学气相沉积制备的金刚石薄膜质量却严重受沉积工艺的影响,为了深入了解沉积工艺对制备的金刚石薄膜质量的影响,本文详细研究了甲烷浓度对微波等离子体化学气相沉积( MPCVD)金刚石薄膜质量的影响,利用扫描电镜、X射线衍射、拉曼光谱以及原子力显微镜对其进行...     

分体圆柱谐振腔法用于金刚石膜微波介电性能测试的研究

针对金刚石膜微波介电损耗低、厚度薄带来的微波介电性能测试难点, 研制了一台分体圆柱谐振腔式微波介电性能测试装置。利用不同直径的蓝宝石单晶样品, 用上述装置对低损耗薄膜类样品微波介电性能的测试能力及样品直径对测试结果的影响进行了实验研究。在此基础上, 使用分体圆柱谐振腔式微波介电性能测试装置对微波等离子体化学气相沉积法和直流电弧等离子体喷射法制备的高品质金刚石膜在Ka波段的微波介电性能进行了测试比较。测试结果表明, 由Raman光谱、紫外-可见光谱等分析证明品质较优的微波等离子体化学气相沉积法制备的金刚石膜具有更高的微波介电性能, 其相对介电常数和微波介电损耗值均低于直流电弧等离子体喷射法制备的金刚石膜。     

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%。     

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.     

大面积高光学质量金钢石自支撑膜的制备

介绍了一种新型的磁控/流体动力学控制的大口径长通道直流电弧等离子体炬，并据此设计建造了100千瓦级高功率DC Arc Plasma Jet CVD金刚石膜沉积系统，讨论了该系统采用的半封闭式气体循环系统的工作原理，以及在气体循环条件下制备大面积高光学质量金刚石自支撑膜的研究结果。     

氢等离子作用下Fe、Co对金刚石膜刻蚀的研究

金刚石具有很高的硬度,加工困难,为寻找一种刻蚀效率较高的材料,利用微波等离子体化学气相沉积（MPCVD）技术,在氢等离子体作用下,研究了Fe、Co对CVD金刚石膜表面的刻蚀效率。用SEM观察刻蚀效果,用Raman光谱对其表面结构进行表征。结果表明：在氢等离子体的作用下,Fe、Co对金刚石表面都有明显的腐蚀作用,其中Fe的刻蚀速率较高,并且可以通过对溶碳材料的厚度控制,来实现对刻蚀速率与刻蚀量的有效控制。对刻蚀后的样品用混合酸及丙酮处理后,得到了可与原始金刚石相媲美的质量。     

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.