金刚石簿膜淀积过程中微波等离子体特性

一、引言 在金刚石薄膜的制备过程中,人们往往监测成膜过程中的宏观参量,使其工艺的重复性,优选性受到了很大限制。而随着对膜质量和结构的要求越来越高,人们开始开展对低压下合成金刚石机理的研究,但至今未见系统地研究宏观参量与等离子体参量方面的工作报道。     

金刚石膜合成条件下的鞘层与等离子体参数分布

本文报导了在用热阴极直流放电等离子体化学气相沉积（通常也称ＥＡＣＶＤ．即电子辅助化学气相沉积）方法合成金刚石的条件下的等离子体密度、电子温度、等离子体空间电位分布及基片附近等离子体鞘结构，并讨论其对成膜的影响．     

FTIR监测金刚石薄膜生长的研究

用电子回旋共振等离子体（ECR）系统, 在气压、衬底温度以及微波功率等外界条件不变的情况下,仅改变甲烷浓度制备金刚石薄膜,利用傅里叶红外吸收光谱仪（FTIR）对甲烷浓度为6％的ECR系 统进行实时监测,分析研究了不同沉积时间条件下,甲烷和氢气产生的等离子体对薄膜早期成核、生长过程以及衬底的影响,并结合Raman光谱X射线衍射（XRD）和扫描电镜（SEM）对金刚石薄膜进行 了分析。     

MPCVD金刚石的Raman光谱分析

用微波等离子体化学气相淀积法（MPCVD）在Si基片上生长了金刚石薄膜，通过对其进行Raman光谱分析，一次表征了金刚石的结构，纯度及应力状况等材料性能，同时并研究了生长过程中微波功率与金刚石性质的关系。研究表明，微波等离子体化学气相溶积法生长的金刚石薄膜，除了金刚石成分的生长外，还会有部分非金刚石成分的生长，金刚石的纯度与微波功率的关系不明显，另外此种方法生长的金刚石薄膜主要表现为张应力。     

OES study of the gas phase during diamond films deposition in high power DC arc plasma jet CVD system

This paper used optical emission spectroscopy (OES) to study the gas phase in high power DC arc plasma jet chemical vapour deposition (CVD) during diamond films growth processes. The results show that all the deposition parameters (methane concentration, substrate temperature, gas flow rate and ratio of H₂/Ar) could strongly influence the gas phase. C₂ is found to be the most sensitive radical to deposition parameters among the radicals in gas phase. Spatially resolved OES implies that a relative high concentration of atomic H exists near the substrate surface, which is beneficial for diamond film growth. The relatively high concentrations of C₂ and CH are correlated with high deposition rate of diamond. In our high deposition rate system, C₂ is presumed to be the main growth radical, and CH is also believed to contribute the diamond deposition.     

Heat resistance of the interface in the silicon-on-diamond structure at a temperature of 80 K

Heat propagation at liquid nitrogen temperature in a heterostructure consisting of a polycrystalline diamond film deposited from hydrocarbon plasma on an oriented silicon substrate is studied. A technique for measuring the cooling kinetics of a thin-film indium thermometer deposited on a diamond film after heating by nanosecond pulses of a nitrogen laser is used. The experimental data are compared with the results calculated within the theory of heat conduction for multilayer systems. The analysis performedmade it possible to simultaneously determine the thermal conductivity of the diamond film and the interfacial heat resistance of diamond/Si and In/diamond interfaces at liquid nitrogen temperature.     

Investigation of growth, coverage and effectiveness of plasma assisted nano-films of fluorocarbon

Plasma-assisted functional films have significant potential in various engineering applications. They can be tailored to impart desired properties by bonding specific molecular groups to the substrate surface. The aim of this investigation was to develop a fundamental understanding of the atomic level growth, coverage and functional effectiveness of plasma nano-films on flat surfaces and to explore their application-potential for complex and uneven shaped nano-materials. In this paper, results on plasma-assisted nano-scale fluorocarbon films, which are known for imparting inertness or hydrophobicity to the surface, will be discussed. The film deposition was studied as a function of time on flat single crystal surfaces of silicon, sapphire and graphite, using microwave plasma. X-ray photoelectron spectroscopy (XPS) was used for detailed study of composition and chemistry of the substrate and coating atoms, at all stages of deposition. Atomic force microscopy (AFM) was performed in parallel to study the coverage and growth morphology of these films at each stage. Combined XPS and AFM results indicated complete coverage of all the substrates at the nanometer scale. It was also shown that these films grew in a layer-by-layer fashion. The nano-films were also applied to complex and uneven shaped nano-structured and porous materials, such as microcellular porous foam and nano fibers. It was seen that these nano-films can be a viable approach for effective surface modification of complex or uneven shaped nano-materials.     

Experimental Study of Planar Langmuir Probe Characteristics in Electron Current-Carrying Magnetized Plasma

Experimental study of planar Langmuir probe characteristics in a magnetized plasma with an electron current along the direction of the magnetic field shows that the usual procedure for determination of the electron temperature and plasma density, which is applicable in a current-free magnetized plasma, gives erroneous results for these plasma parameters. When this procedure is applied on the characteristics measured at two opposite orientations of the probe collecting surface with respect to the direction of the electron drift, different values of the electron temperature are obtained. These virtual electron temperatures and corresponding plasma densities calculated from the measured ion saturation currents are higher and/or smaller than the exact local electron temperature and plasma density. Calculation of particular averages of these quantities is proposed as a possible way to obtain correct results for the local electron temperature and plasma density. These averages are used in the approximate evaluation of the electron drift velocity from the electron saturation currents measured at the two orientations of the probe collecting surface.     

A relation between a metallic film covering on diamond formed during growth and nanosized inclusions in HPHT as-grown diamond single crystals

One of the most important characteristics and basic phenomena during diamond growth from liquid metal catalyst solutions saturated with carbon at high temperature–high pressure (HPHT) is that there exists a thin metallic film covering on the growing diamond, through which carbon-atom clusters are delivered to the surface of the growing diamond by diffusion. A study of microstructures of such a metallic film and a relation between the thin metallic film and the inclusions trapped in HPHT as-grown diamond single crystals may be helpful to obtain high-purity diamond single crystals. It was found that both the metallic film and the HPHT as-grown diamond single crystals contain some nanostructured regions. Examination by transmission electron microscopy suggests that the microstructure of the thin metallic film is in accordance with nanosized particles contained in HPHT as-grown diamond single crystals. The nanosized particles with several to several tens of nanometers in dimension distribute homogeneously in the metallic film and in the diamond matrix. Generally, the size of the particles in the thin metallic film is relatively larger than that within the diamond matrix. Selected area electron diffraction patterns suggest that the nanosized particles in the metallic film and nanometer inclusions within the diamond are mainly composed of f.c.c. (FeNi)₂₃C₆, hexagonal graphite and cubic γ-(FeNi). The formation of the nanosized inclusions within the diamond single crystals is thought not only to relate to the growth process and rapid quenching from high temperature after diamond synthesis, but also to be associated with large amounts of defects in the diamond, because the free energy in these defect areas is very high. The critical size of carbide, γ-(FeNi)and graphite particles within the diamond matrix should decrease and not increase according to thermodynamic theory during quenching from HPHT to room temperature and ambient pressure. Received: 13 September 2001 / Accepted: 12 June 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-0531/295-5081; E-mail: yinlw@sdu.edu.cn     

Effect of the substrate temperature and deposition rate on the initial growth of thin lithium niobate-tantalate films deposited from a thermal plasma

Thin lithium niobate-tantalate (LiNb_0.5Ta_0.5O₃) films are studied at the initial stage of deposition from a thermal plasma. The effect of two deposition parameters (the substrate temperature and the deposition rate) on the film morphology, the film crystallinity, and the density of nuclei growing on a (0001) sapphire substrate are investigated. It is shown that the crystalline structure and roughness of a film are determined, for the most part, in the initial growth stage and therefore depend directly on both parameters. At the optimum temperatures and growth rates for obtaining good characteristics of (0006) texture, crystallinity, and surface roughness of the films, the film nuclei on the substrate have a high density and good epitaxial orientation to it. If the growth conditions are not optimum, the islands are either amorphous or have a low density on the substrate surface. The nucleation activation energy is observed to decrease as the deposition rate increases, which supports the assumption that the species that are active in film deposition are “hot” clusters forming in an oxygen-argon plasma in the immediate vicinity of the substrate.     

侧吹气体对光纤激光修锐青铜金刚石砂轮等离子体特性影响

为了研究辅助侧吹氩气对光纤激光修锐青铜结合剂金刚石砂轮等离子体的影响,利用高速摄像机拍摄不同侧吹工艺参数下等离子体空间膨胀形态,结果表明：氩气降低了等离子体的膨胀高度,随着压力增加,等离子体的膨胀距离减小,等离子抑制作用增强。 利用光谱仪研究了等离子体发射光谱在砂轮径向上的最大值随氩气压力的变化情况,并根据Boltzmann斜线法和Stark展宽法,计算不同氩气压力下等离子体在砂轮径向上电子温度和电子数密度的最大值,结果表明：气体压力增大,等离子体光谱线强度先增大后减小,等离子体光谱线强度在0.2 MPa时达到峰值,较大的氩气压力明显降低等离子体电子温度和电子数密度,从而减小对砂轮表面形貌的影响。 利用超景深三维扫描仪观测添加侧吹气体前后砂轮表面形貌,结果表明：0.5 MPa侧吹氩气后,砂轮表面形貌质量明显优于未添加侧吹气体时。     

Substrate heating effects on the propagation dynamics of laser produced plume during pulsed laser deposition of oxides

We report on the expansion dynamics of laser-produced plasma plumes of complex oxides in an oxygen atmosphere. In particular, we have studied the combined effects of background gas pressure and substrate heating on the plume propagation in typical pressure and temperature regimes of oxides thin film deposition by pulsed laser deposition. Our results evidence a reduced resistance of the background gas to the plume propagation as the substrate temperature increases. The experimental data are analyzed in the frame of a model describing the plume propagation into the background gas. Our experimental findings clearly indicate that the deposition temperature might influence film growth, not only through its direct thermal effect on the surface kinetics of adatoms, but also by affecting the energetic properties of the precursors in the gas phase.     

模板对异构体选择性生长的动力学控制作用与化学气相沉积金刚石的生长机理

阐述了模板的动力学控制作用对大尺度有序结构特别是亚稳相的生长，对自由能相差很小的异构体的选择生长所具有的重要作用.汲取现有金刚石生长理论的合理思想，以模板概念为基础给出了对化学气相沉积(CVD)过程的动力学热力学综合描述：1)碳原子在碳氢化合物中的化学势高于固相碳，气相碳氢化合物的碳原子有可能落到化学势较低的固态碳的各种异构体.2)气相碳通过表面反应实现向固相碳的转化.3)表面的模板作用是控制气相碳原子转换方式的主要动力学因素，不同的表面(石墨各种取向的表面及金刚石不同取向的表面)选择了落入其上的碳原子的结构方式及能量状态.4)因此,衬底的不同区域可发生几种不同的独立的表面反应过程,这些反应对应于不同表面的生长.5）而这些表面反应的方向性及速度受表面临域热力学因素的影响，反应的方向性决定了某种晶面是生长或刻蚀，在特定的温度、压强及各种气体分压下可以实现金刚石的生长和石墨的刻蚀.6)衬底局域晶格结构及键价结构和衬底表面气相的温度、压强及各种气体分压等热力学条件共同决定了成核的临界条件.7）与外界有能量和物质交换的等离子体系统，以及气相中发生的一系列化学反应，仅起到了维持某种固相表面生长所需要的非平衡热力学条件和化学条件的作用.金刚石和石墨表面具有的模板动力学控制作用，在特定热力学条件下主导自身外延层的生长方式；异质衬底的某些局域微观结构可以作为新相生长成核的局域模板；不同材料、不同的处理方法、及不同的化学环境下的衬底具有不同的局域微观结构，从而决定了多晶薄膜的取向优势. 关键词： 模板 异构体 选择性生长 金刚石薄膜     

Investigation of optical emission spectroscopy in diamond chemical vapor deposition by Monte Carlo simulation

The optical emission spectra(atomic hydrogen(Hα,Hβ,Hγ),atomic carbon C(2p3s→2p2:λ=165.7 nm) and radical CH(A2△→X2П:λ=420-440 nm))in the gas phase process of the diamond film growth from a gas mixture of CH4 and H2 by the technology of electron-assisted chemical vapor deposition (EACVD)have been investigated by using Monte Carlo simulation.The results show that the growth rate may be enhanced by the substrate bias due to the increase of atomic hydrogen concentration and the mean temperature of electrons.And a method of determining the mean temperature of electrons in the plasma in-situ iS given.The strong dependence on substrate temperature of the quality of diamond film mainly attributes to the change of gas phase process near the substrate surface.     

化学气相淀积中甲烷含量变化的等离子体参数诊断

一、引言 金刚石薄膜以其优异的特性越来越受到人们的重视。人们已用各种方法制备出金刚石薄膜、并详细研究了膜质量、膜的形貌与各种宏观参量的关系。在这里,含碳物源相对于氢气的浓度比对金刚石膜的结构和形貌的影响是相当严重的。从许多报道中可知,当     

FEM simulations and experimental studies of the temperature field in a large diamond crystal growth cell

We investigate the temperature field variation in the growth region of a diamond crystal in a sealed cell during the whole process of crystal growth by using the temperature gradient method (TGM) at high pressure and high temperature (HPHT). We employ both the finite element method (FEM) and in situ experiments. Simulation results show that the temperature in the center area of the growth cell continues to decrease during the process of large diamond crystal growth. These results are in good agreement with our experimental data, which demonstrates that the finite element model can successfully predict the temperature field variations in the growth cell. The FEM simulation will be useful to grow larger high-quality diamond crystal by using the TGM. Furthermore, this method will be helpful in designing better cells and improving the growth process of gem-quality diamond crystal.     

Photothermal and micro-thermal characterization of metal coated diamond crystallites

Photoacoustic effect and scanning near field microscopy have been applied to characterise the thermal properties of diamond crystallites which were coated by a Cu film, a Cr-film and a Cr-Cu film. The Cu-coated diamond exhibits a considerable thermal barrier at the Cu-diamond interface which had disappeared for the crystallites with a thin bond Cr-layer between diamond and Cu. The local inspection of the thermal conductivity with a thermal nano-probe operated in the 3ω-mode reveals slight local variations of the thermal conductivity of the Cr-coated crystallite.     

灯丝温度对原位吸收光谱和金刚石薄膜生长的影响

 报道了原位红外吸收光谱在气相合成金刚石薄膜生长过程中的应用，研究了灯丝温度对原位红外吸收光谱和金刚石薄膜生长的影响。较高的灯丝温度使甲烷分解更充分，从而产生更多诸如C₂H₂等可能对金刚石薄膜生长有利的基团，导致金刚石薄膜质量和生长速率的提高。     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

电子增强化学气相沉积法制备金刚石膜

 采用EACVD方法在Si衬底上制备出生长速率高的优质金刚石膜，其生长速率最大可达7 μm/h，成膜范围Φ40 mm，并对优质金刚石膜的生长特性进行了研究。