微波ECR等离子体辅助物理汽相沉积技术

微波电子回旋共振（ＥＣＲ）能够在低气压下产生高密度、高电离度的等离子休．这种等离子体是离子镀最合适的等离子体源，可广泛地应用于等离子体沉积薄膜和表面处理的新工艺，生产高质量的各种金属薄膜、氮化物膜，碳化物膜、氧化物膜、硅化物膜及其他化合物膜．本文着重介绍微波ＥＣＫ等离子体辅助物理汽相沉积（ＥＣＲＰＰＶＤ）技术．     

微波等离子体化学气相沉积金刚石薄膜形貌分析

 本文给出了微波等离子体化学气相沉积多晶金刚石薄膜及外延单晶金刚石薄膜的各种形貌，并对这些形貌的形成作了理论分析。     

微波等离子体化学气相沉积金刚石膜

微波等离子体化学气相沉积是制备金刚石膜的一个重要方法，能制备出表面光滑平整的大面积均匀金刚石膜，文章概述了ＭＰＣＶＤ制备金刚石膜的情况，介绍了ＭＰＣＶＤ制备金刚石膜装置的典型类型及其特点，在国内研制成功天线耦合石英钟罩式ＭＰＣＶＤ制备金刚石膜装置，并在硅片上沉积出大面积均匀的优质金刚石膜。     

低温等离子体沉积类金刚石薄膜

一、引 言 类金刚石薄膜有很多优越的性质,除了化学惰性外,它还具有很好的电学、光学和机械性能,如电阻率高,可见,紫外和红外光的透射性好以及附着力强等。至今已有各种各样的制备类金刚石的方法。如热解、离子束、溅射和等离子体化学气相沉积(PCVD)等。 本文采用的方法是在热丝CVD中加入直流放电。由于把直流放电和热解化学的方法结合起来,增强了CH_4的分解,同时为了了解成膜的微观过程,采用等离子体参数的诊断方法,实地监测膜的生成过程,对实现具有一定性质的类金刚石膜的重复生长是有利的。     

辉光等离子体辅助化学气相沉积低温合成金刚石薄膜的研究

采用辉光放电等离子体增强化学气相沉积 (GP CVD)技术在低温条件下合成了高品质的亚微米金刚石薄膜 ,并通过对合成过程的实时发射光谱诊断确定了 [CH4 H2 ]系统参与金刚石合成反应的主要荷能粒子。对合成过程的研究表明 :采用这种技术能使电子增强热丝化学气相沉积 (EACVD)合成高品质金刚石薄膜的温度从 85 0℃降至 (340± 5 )℃ ;薄膜低温合成中的主要荷能粒子为CH3 、CH ,CH+ 、H 等 ,其中过饱和原子氢保证了高品质金刚石薄膜的合成 ;根据光诊断和探针测量的结果推断近表面辉光放电可在基片表面形成电偶极层 ,该偶极层是进行超常态反应的必要环境 ,并在低温合成中起重要作用     

脉冲高能量密度等离子体法类金刚石膜的制备及分析

利用脉冲高能量密度等离子体法在光学玻璃衬底上、在室温下成功的制备了光滑、致密、均匀的纳米类金刚石膜.工艺研究表明：放电电压和放电距离以及工作气体种类对纳米类金刚石膜的沉积起着关键作用.利用拉曼光谱、扫描电镜以及电子能量损失谱分析薄膜的形态结构表明：薄膜具有典型的类金刚石特征；纳米类金刚石膜的晶粒尺寸小于20nm甚至为非晶态；类金刚石膜中含有一定量的氮原子，随着沉积能量的升高，氮的含量增大.纳米类金刚石膜的薄膜电阻超过109Ω/cm2.对放电溅射过程进行了理论分析，结果与工艺研究的结论吻合.     

Diamond-like carbon films deposited by a hybrid ECRCVD system

A novel hybrid technique for diamond-like carbon (DLC) film deposition has been developed. This technique combines the electron cyclotron resonance chemical vapor deposition (ECRCVD) of C₂H₂ and metallic magnetron sputtering. Here we described how DLC film is used for a variety of applications such as stamper, PCB micro-tools, and threading form-tools by taking advantage of hybrid ECRCVD system. The structure of the DLC films is delineated by a function of bias voltages by Raman spectroscopy. This function includes parameters such as dependence of G peak positions and the intensity ratio (I_D/I_G). Atomic force microscope (AFM) examines the root-mean-square (R.M.S.) roughness and the surface morphology. Excellent adhesion and lower friction coefficients of a DLC film were also assessed.     

MPCVD方法制备军用光学元件纳米金刚石膜

介绍了用MPCVD方法制备纳米金刚石膜的工艺。用MPCVD方法实验研究了在光学玻璃上镀纳米金刚石膜:膜层厚度为0 4551μm,粒度小于200nm,表面粗糙度小于29 5nm,最大透过率为80%;平均显微硬度为34 9GPa,平均体弹性模量为238 9GPa,均接近天然金刚石的力学性能。与衬底材料表面应力-2 78GPa相比,具有较好的抗压和耐磨效果。     

Substrate bias effects during diamond like carbon film deposition by microwave ECR plasma CVD

Diamond like carbon (DLC) coatings were deposited on silicon(1 1 1) substrates by microwave electron cyclotron resonance (ECR) plasma CVD process using a plasma of Ar and CH₄ gases under the influence of DC self bias generated on the substrates by application of RF (13.56 MHz) power. DLC coatings were deposited under the varying influence of DC bias (−60 V to −150 V) on the Si substrates. Deposited films were analyzed by different techniques like: X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), atomic force microscopy (AFM), Hardness and elastic modulus determination technique, Raman spectroscopy, scanning electron microscopy (SEM) and contact angle measurement. The results indicate that the film grown at −100 V bias has optimised properties like high sp³/sp² ratio of carbon bonding, high refractive index (2.26–2.17) over wide spectral range 400–1200 nm, low roughness of 0.8 nm, high contact angle (80°) compared to the films deposited at other bias voltages (−60 V and −150 V). The results are consistent with each other and find august explanation under the subplantation model for DLC growth.     

铜上采用过渡层沉积类金刚石薄膜的研究

将等离子增强非平衡磁控溅射物理气相沉积(PEUMS-PVD)和电子回旋共振-微波等离子体增强化学气相沉积(MW-ECRPECVD)技术相结合，通过制备不同的过渡层，在铜基上成功地制备了类金刚石膜.拉曼光谱分析表明，所制备的碳膜具有典型的类金刚石结构特征.检测结果表明，随着沉积偏压的增大，D峰和G峰均向高波数漂移，I_D/I_G值增大，表面粗糙度减小，而平均硬度和弹性模量呈先增大后减小的趋势. 关键词： 铜基体 类金刚石膜 过渡层 拉曼光谱     

Intertwisted fibrillar diamond-like carbon films prepared by electron cyclotron resonance microwave plasma enhanced chemical vapour deposition

In this paper, the structures, optical and mechanical properties of diamond-like carbon films are studied, which are prepared by a self-fabricated electron cyclotron resonance microwave plasma chemical vapour deposition method at room temperature in the ambient gases of mixed acetylene and nitrogen. The morphology and microstructure of the processed film are characterized by the atomic force microscope image, Raman spectra and middle Fourier transform infrared transmittance spectra, which reveal that there is an intertwisted fibrillar diamond-like structure in the film and the film is mainly composed of sp^3 CH, sp^3 C—C, sp^2 C═C, C═N and C_{60}. The film micro-hardness and bulk modulus are measured by a nano-indenter and the refractive constant and deposition rate are also calculated.     

Studies of diamond-like carbon （DLC） films deposited on stainless steel substrate with Si/SiC intermediate layers

In this work, diamond-like carbon （DLC） films were deposited on stainless steel substrates with Si/SiC intermediate layers by combining plasma enhanced sputtering physical vapour deposition （PEUMS-PVD） and microwave electron cyclotron resonance plasma enhanced chemical vapour deposition （MW-ECRPECVD） techniques. The influence of substrate negative self-bias voltage and Si target power on the structure and nano-mechanical behaviour of the DLC films were investigated by Raman spectroscopy, nano-indentation, and the film structural morphology by atomic force microscopy （AFM）. With the increase of deposition bias voltage, the G band shifted to higher wave-number and the integrated intensity ratio ID/IG increased. We considered these as evidences for the development of graphitization in the films. As the substrate negative self-bias voltage increased, particle bombardment function was enhanced and the sp^3-bond carbon density reducing, resulted in the peak values of hardness （H） and elastic modulus （E）. Silicon addition promoted the formation of sp^3 bonding and reduced the hardness. The incorporated Si atoms substituted sp^2- bond carbon atoms in ring structures, which promoted the formation of sp^3-bond. The structural transition from C-C to C-Si bonds resulted in relaxation of the residual stress which led to the decrease of internal stress and hardness. The results of AFM indicated that the films was dense and homogeneous, the roughness of the films was decreased due to the increase of substrate negative self-bias voltage and the Si target power.     

The influence of substrate emissivity on plasma enhanced CVD of diamond-like carbon films

In a planar capacitively coupled RF reactor we deposited diamond-like carbon (DLC) films from the mixture of methane and argon. The self biased electrode was in a poor thermal contact with walls of the reactor, neither water cooled nor electrical heated by a special external circuit. The heating of the electrode was caused mainly by the ion bombardment. We measured the temperatures of a self biased electrode and silicon substrates placed on it with Raytek Thermalert pyrometer in the temperature range 0–500°C. The temperatures were continuously increasing even during the longest deposition time of 120 min and differed for the electrode and the silicons of different specific resistances correlated to their emissivities. Ellipsometric and reflectance measurements of films deposited on two different silicon substrates of different emissivities were carried out. We discussed appropriate models for a film optical characterisation and found that apart a transient layer the studied films were homogeneous. Their deposition rate depended significantly on the silicon emissivities because of the different temperatures. The influence of the silicon substrate emissivity on the mechanical properties of DLC films was studied by means of Vickers microhardness tester. Dedicated to Prof. Jan Janča on the occasion of his 60th birthday. The present work was supported by the Grant Agency of the Czech Republic, contract 106/96/K245.     

Diamond-like phase formation in an amorphous carbon films prepared by periodic pulsed laser deposition and laser irradiation method

Diamond-like carbon (DLC) films were fabricated by pulsed laser ablation of a liquid target. During deposition process the growing films were exited by a laser beam irradiation. The films were deposited onto the fused silica using 248 nm KrF eximer laser at room temperature and 10⁻³ mbar pressure. Film irradiation was carried out by the same KrF laser operating periodically between the deposition and excitation regimes. Deposited DLC films were characterized by Raman scattering spectroscopy. The results obtained suggested that laser irradiation intensity has noticeable influence on the structure and hybridization of carbon atoms deposited. For materials deposited at moderate irradiation intensities a very high and sharp peak appeared at 1332 cm⁻¹, characteristic of diamond crystals. At higher irradiation intensities the graphitization of the amorphous films was observed. Thus, at optimal energy density the individual sp³-hybridized carbon phase was deposited inside the amorphous carbon structure. Surface morphology for DLC has been analyzed using atomic force microscopy (AFM) indicating that more regular diamond cluster formation at optimal additional laser illumination conditions (∼20 mJ per impulse) is possible.     

反应磁控溅射法制备的氟化类金刚石薄膜的XPS结构研究

采用射频反应磁控溅射法用高纯石墨作靶、三氟甲烷(CHF₃)和氩气(Ar)作源气体制 备了氟化类金刚石（FDLC）薄膜，通过XPS光谱结合拉曼光谱、红外透射光谱和紫外 可见光光谱研究了源气体流量比等工艺条件对薄膜中键结构、sp2/sp3杂化比以及光学带隙等性能的影响.结果表明在低功率(60W)、高气压(2.0Pa)和适当的流量比(Ar/CHF₃=2∶ 1)下利用射频反应磁控溅射法可制备出氟含量高且具有较宽光学带隙和超低介电常数的FDLC薄膜. 关键词： 反应磁控溅射 氟化类金刚石薄膜 红外透射光谱 XPS光谱