衬底表面预处理对金刚石薄膜形核及长大的影响

用燃烧火焰法在 TC4 Ti 合金和单晶 Si(001)面上沉积了金刚石薄膜。对合成的膜进行了扫描电镜、激光喇曼光谱分析。结果表明,金刚石薄膜的结构和形貌强烈取决于沉积温度、O_2/C_2H_2流量比等工艺参数。研究了衬底表面预处理对金刚石薄膜形核及长大的影响,并对表面预处理影响形核的原因进行了初步探讨。     

微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石

研究了衬底温度、核化密度、衬底表而预处理等工艺参数对微波等离子体化学气相沉积法在硅片上同时生长碳化硅和金刚石的影响.采用扫描电镜、X-射线衍射、喇曼光谱和红外光谱对样品进行了表征.结果表明:从高核化密度生长的金刚石膜中探测不到碳化硅;不论对硅衬底进行抛光预处理还是未抛光预处理,从低核化密度牛长的金刚石厚膜中总能探测到碳化硅.碳化硅生长在硅衬底上未被金刚石覆盖的地方,或者是在金刚石晶核之间的空洞处.碳化硅形成和金刚石生长是同时发生的两个竞争过程.此研究结果为制备金刚石和碳化砟复合材料提供了一种新的方法.     

火焰法沉积金刚石薄膜过程中碳在基底中的行为

采用火焰法在Ｍｏ基底上沉积金刚石薄膜，研究了在沉积过程中Ｃ在Ｍｏ基底中的行为，结果表明，在Ｍｏ基层上沉积金刚石时，碳原子与Ｍｏ反应形成Ｍｏ２Ｃ，随时间延长，Ｍｏ２Ｃ层加厚，Ｃ原子扩散进入基底的速率下降，之后Ｃ原子在Ｍｏ２Ｃ层表面达到过饱和开始金刚石形核。     

Selective Oxidation of Graphite on Diamond Films Induced by UV Exposure

A selective oxidation technique for diamond films based on the extended exposure to UV light in air at room temperature was developed and studied by Raman Spectroscopy and Scanning Electron Microscopy. The diamond films were synthesized by the combustion flame technique in open atmosphere by using an oxy-acetylene gas mixture as the carbon source. A 125 W UV lamp was used to irradiate the films in the wavelength range of 180–250 nm, from 2 to 10 days. The Raman spectrum from the as-deposited diamond films shows the typical band at 1333 cm^–1, characteristic of the sp ³diamond structure, with a certain nondiamond or graphite content. After UV irradiation, graphite was selectively oxidized and partially removed without oxidation of diamond, indicating that the strong reaction of ozone (O₃) and atomic oxygen (O·) produced by the UV irradiation oxidized the graphite, even at room temperature, without the need of an additional heating source. The oxidation of graphite was best observed after 2 days of UV treatment. A sensible improvement in the diamond film quality was obtained after 2 days of irradiation, as revealed by the sharpening of the corresponding Raman band.     

Synthesis of Diamond Thin Films on TC4 by Using a Scanning Linear Flame

A scanning linear flame is used to deposit diamond films over a large area, and with high quality and good continuity by employing appropriate cooling means for the substrate. It is found that the structure and morphology of the deposited films mainly depend on the substrate temperature, the ratio of 0₂ to C₂H₂ flow rate and the relative position of the substrate with respect to the flame. These factors affecting the structure and morphology of diamond films are interrelated. Moreover, the influences of surface pretreatments on nucleation and growth of diamond films are also studied. The experimental results show that the nucleation density of diamond films is enhanced by scratching the surface of the substrate with diamond grit and initially coating a mechanical pump oil layer. For the substrate surface etched with metallographic etching acid, the nucleation and growth of diamond films are very uniform. In addition, the adhesion between the film and substrate is enhanced. Nucleation is favored on the prominent features of the substrate, i.e. scratch and crystal boundary.     

直流热阴极CVD金刚石薄膜生长特性研究

为了获得高质量的金刚石薄膜,采用直流热阴极化学气相沉积系统分别在不同基片温度和不同碳源气体含量条件下生长金刚石薄膜,利用Raman光谱、SEM和XRD检测方法研究了基片温度和碳源气体含量对金刚石薄膜生长特性的影响.结果表明,金刚石薄膜与基片Mo之间有Mo2C的过渡层存在;1000℃的温度能够促进金刚石晶体的生长,抑制其他碳杂质的形成,CH4体积分数为2%适于快速生长高纯度的金刚石薄膜.     

氧气-乙炔火焰法在Al2O3陶瓷上沉积金刚石薄膜

用氧气－乙炔火焰法在氧化铝陶瓷片上沉积出了金刚石薄膜，并观察了薄膜的形貌结构及其在基片上的分布规律。对基片进行了适当的预处理，可以提高金刚石薄膜在基片上的成核密度。认为氧化铝陶瓷片与沉积金刚石薄膜之间易形成过渡层，初步探讨了在氧化铝陶瓷片上沉积金刚石薄膜的机理。     

Adhesion Enhancement of Diamond Films on Various Substrates by Carbide Interlayer

Diamond films were prepared on various substrates by a combustion flame technique using an oxyacetylene torch. During the deposition, a carbide interlayer was formed between the surface of the substrate and deposited diamond. The hard interlayers were seen on the molybdenum, tungsten as well as silicon substrates. The adhesion of diamond on the molybdenum substrate was improved with increase in the hardness of the carbide layer. This result strongly supports the premise that the carbide interlayer and/or carbon diffused layer enhances the adhesion of diamond to substrates.     

Mo2C过渡层对金刚石-碳膜场发射均匀性的影响

在经过不同特殊预处理的金属钼衬底上沉积了金刚石 -碳膜 ,分别用X射线衍射谱 (XRD)、拉曼光谱 (Raman)和扫描电子显微镜 (SEM)对样品进行了分析和测试 ,并研究了样品器件的场发射特性。结果发现在金属钼衬底和金刚石 -碳膜之间形成的Mo2 C过渡层与金刚石 -碳膜场发射均匀性有着密切的联系     

Investigation of the nucleation mechanism in bias-enhanced diamond deposition on silicon and molybdenum

Polycrystalline diamond films were deposited on Si and Mo substrates in a microwave plasma-enhanced chemical vapour deposition reactor employing bias-enhanced nucleation. The deposition process was subdivided into two consecutive steps: the pretreatment (bias-enhanced nucleation) and the diamond growth step. To investigate the nucleation process we kept the deposition parameters during the diamond growth step constant and only changed the parameters during the pretreatment. The methods employed to analyze the deposited films after the pretreatment step were electron energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy.

The nucleation density (N_D) on Si following the complete deposition cycle (pretreatment and diamond growth step) increases considerably from 5 × 10⁸ cm⁻² to 5 × 10¹⁰ cm⁻² with an increase in the substrate temperature during the pretreatment (T_p) in the temperature range from 680 to 750 °C. For T_p ≥ 770 °C continuous films are formed. The structure of the pretreatment deposit undergoes likewise considerable changes: if T_p exceeds 770 °C the appearance of an intense diamond plasmon at 34 eV is observed, indicative of an increase in the concentration of diamond crystallites embedded in an otherwise amorphous carbon matrix. Our experiments suggest that diamond crystallites formed during the pretreatment serve as nucleation centres for the subsequent diamond growth.

The same deposition parameters which result in the formation of a continuous diamond film on Si, yield only low nucleation densities on Mo. An increase in N_D from 6 × 10⁶ cm⁻² to 2 × 10⁸ cm⁻² can be achieved by raising the methane concentration [CH₄] in the gas phase during the pretreatment from 5 to 50% (T_p = 820 °C). The carbon concentration at the surface for the pretreatment deposit, determined by XPS analysis, increases likewise with [CH₄]. According to the EELS analysis the structure of the pretreatment deposit is comparable with disordered graphite or a-C and no diamond plasmon is observed. The high [CH₄] is required to form the Mo-carbide interface and balance the diffusion of carbon into the metal before the a-C layer can be formed.

The formation of nucleation centres during the bias-enhanced nucleation seems under these deposition conditions to proceed via different pathways on Si and Mo. While the nucleation on Si appears to be linked to the formation of diamond nanocrystals during the pretreatment, this is not the case for Mo.     

Growth and characterization of diamond films deposited at high-pressure using a low-power microwave plasma reactor

Diamond films were deposited on molybdenum substrates from mixtures of methane diluted in hydrogen using a high-pressure microwave plasma reactor. In this reactor, a compressed waveguide structure was used to increase the electric field strength, and accordingly the reactor was able to operate stably with low gas flow rate and microwave power. The films deposited on 12 mm diameter substrates were characterized by film morphology, Raman spectra, growth rate and crystalline quality. The morphology of diamond films deposited in this reactor depends mainly on the substrate temperature. When the deposition pressure was 48 kPa and microwave power was only 800 W, high quality diamond films could be uniformly deposited with a growth rate around 20 μm/h.     

Simultaneous fabrication of nanocrystalline and {100} textured large-grained diamond films

In this work, we report the simultaneous synthesis of both nanocrystalline and {100} textured large-grained diamond films in one deposition run performed in a 5-kW microwave plasma chemical vapor deposition (MPCVD) reactor. This was achieved by employing the coupled effect of nitrogen addition in the gas phase and substrate temperature on the growth of diamond films. In one deposition run, different substrate surface temperatures were obtained by a novel substrate arrangement, nanocrystalline diamond of high growth rate around 3 μm/h was formed at low temperature, while {100} textured large-grained diamond of much higher growth rate about 11 μm/h was grown at high temperature. This new method opens way for mechanical and tribological applications of both nano-diamond and {100} textured diamond in industrial level. This result indicates that distinct growth modes or growth mechanisms were involved at different substrate temperatures with a certain amount of nitrogen addition. The coupled effect of nitrogen addition and temperature on the growth of CVD diamond films and the involved growth mechanism is briefly discussed from the point of view of gas phase chemistry and surface reactions.     

Structural morphology of amorphous conducting carbon film

Amorphous conducting carbon films deposited over quartz substrates were analysed using X-ray diffraction and AFM technique. X-ray diffraction data reveal disorder and roughness in the plane of graphene sheet as compared to that of graphite. This roughness increases with decrease in preparation temperature. The AFM data shows surface roughness of carbon films depending on preparation temperatures. The surface roughness increases with decrease in preparation temperature. Also some nucleating islands were seen on the samples prepared at 900°C, which are not present on the films prepared at 700°C. Detailed analysis of these islands reveals distorted graphitic lattice arrangement. So we believe these islands to be nucleating graphitic. Power spectrum density (PSD) analysis of the carbon surface indicates a transition from the nonlinear growth mode to linear surface-diffusion dominated growth mode resulting in a relatively smoother surface as one moves from low preparation temperature to high preparation temperature. The amorphous carbon films deposited over a rough quartz substrate reveal nucleating diamond like structures. The density of these nucleating diamond like structures was found to be independent of substrate temperature (700–900° C).     

Nanocrystalline diamond growth on different substrates

Nanocomposite films consisting of diamond nanoparticles of 3-5 nm diameter embedded in an amorphous carbon matrix have been deposited by means of microwave plasma chemical vapour deposition (MWCVD) from CH₄/N₂ gas mixtures. Si wafers, Si coated with TiN, polycrystalline diamond (PCD) and cubic boron nitride films, and Ti-6Al-4V alloy have been used as substrates. Some of the substrates have been pretreated ultrasonically with diamond powder in order to enhance the nucleation density n_nuc. It turned out that n_nuc depends critically on the chemical nature of the substrate, its smoothness and the pretreatment applied. No differences to the nucleation behaviour of CVD PCD films were observed. On the other hand, the growth process seems to be not affected by the substrate material. The crystallinity (studied by X-ray diffraction) and the bonding environment (investigated by Raman spectroscopy) show no significant differences for the various substrates. The mechanical and tribological properties, finally, reflect again the influence of the substrate material: on TiN, a lower hardness was measured as compared to Si, PCD and c-BN, whereas the adhesion of c-BN/nanocrystalline diamond (NCD) system was determined by that of the c-BN film on the underlying Si substrate.     

Growth of nanocrystalline diamond films in CCl4/H2 ambient

We investigated the growth characteristics of the nanocrystalline diamond films using CCl₄/H₂ as gas sources in a hot-filament chemical vapor deposition (CVD) reactor. Successful growth of nanocrystalline diamond at typical growth condition of 1.5-2.5% CCl₄ and 550-730 °C substrate temperature has been demonstrated. Glancing angle X-ray diffraction (XRD) clearly indicated the formation of diamond in the films. Typical root-mean-square surface roughness of 10-15 nm and an optimal root-mean-square surface roughness of 6 nm have been achieved. Transmission electron microscopy (TEM) analyses indicated that nanocrystalline diamond film with an average grain size in the range of 10-20 nm was deposited from 2.5% CCl₄/H₂ at 610 °C. Effects of different source gas composition and substrate temperature on the grain nucleation and grain growth processes, whereby the grain size of the nanocrystalline film could be controlled, were discussed.     

Epitaxy of cubic boron nitride on (001)-oriented diamond

Cubic boron nitride (c-BN), although offering a number of highly attractive properties comparable to diamond, like hardness, chemical inertness and a large electronic bandgap, up to now has not found the attention it deserves. This mostly has to do with preparational problems, with easy chemical routes not available and, instead, the necessity to apply ion-bombardment-assisted methods. Hence, most of the c-BN samples prepared as thin films have been nanocrystalline, making the prospect of using this material for high-temperature electronic applications an illusion. Although heteroepitaxial nucleation of c-BN on diamond substrates has been demonstrated using the high-pressure-high-temperature technique, none of the low-pressure methods ever succeeded in the epitaxial growth of c-BN on any substrate. Here, we demonstrate that heteroepitaxial c-BN films can be prepared at 900 degrees C on highly (001)-oriented diamond films, formed by chemical vapour deposition, using ion-beam-assisted deposition as a low-pressure technique. The orientation relationship was found to be c-BN(001)[100]||diamond(001)[100]. High-resolution transmission electron microscopy additionally proved that epitaxy can be achieved without an intermediate hexagonal BN layer that is commonly observed on various substrates.     

Epitaxial growth of AlN on single crystal Mo substrates

We have grown AlN films on single-crystalline Mo(110), (100), and (111) substrates using a low temperature pulsed laser deposition (PLD) growth technique and investigated their structural properties. Although c-axis oriented AlN films grow on Mo(100), the films contain 30° rotated domains due to the difference in the rotational symmetry between AlN(0001) and Mo(100). AlN films with only poor crystalline quality grow on Mo(111) substrates, probably due to the poor surface morphology and high reactivity of the substrates. On the other hand, single crystal AlN films grow epitaxially on Mo(110) substrates with an in-plane relationship of AlN[11-20] // Mo[001]. Reflection high-energy electron diffraction or electron backscattered diffraction analysis has revealed that neither in-plane 30° rotated domains nor cubic phase domains exist in the AlN films. X-ray reflectivity measurements have revealed that the heterointerface between AlN and Mo prepared by PLD at 450 °C is quite abrupt. These results indicate that PLD epitaxial growth of AlN on single crystal Mo substrates is quite promising for the fabrication of future high frequency filter devices.     

镍衬底上定向金刚石膜的成核与生长

提出了一种包括晶粒接种、高温退火、成核、生长四过程的薄膜沉积新方法 ,用射频等离子体增强热丝化学气相沉积系统 ,在Ni衬底上制备了定向金刚石膜。通过对成核和生长两过程工艺条件的研究 ,掌握了提高成核密度和金刚石定向生长规律。实验还表明 ,膜与Ni衬底之间未见Ni C H界面层的形成     

一种提高金刚石薄膜形核密度的新方法

报导了一种提高火焰法合成高质量金刚石薄膜形核密度的新方法-化学腐蚀法;研究了在化学腐蚀试样表面上金刚石的形核与生长行为、晶粒度与形核密度之间的关系。试验表明:经腐蚀后的样品,金刚石形核均匀致密,2min内便能形成连续的膜。金刚石形核密度随晶粒度的增加而增大。初步分析了化学腐蚀法提高形核密度的原因,认为晶界对金刚石的形核起重要作用。     

SiC在异质衬底生长金刚石膜的作用分析

利用扫描电子显微镜 (SEM)、Raman光谱分析了Si衬底上金刚石膜核化和生长的过程 ,并着重分析了核化过程产生的SiC的性能。利用划痕法测量了在WC衬底上沉积SiC和未沉积SiC时生长金刚石膜的粘附力 ,同时还分析了WC衬底上有和没有SiC沉积层时表面附近金刚石膜的内应力。结果表明 ,SiC层大大地增强了含碳粒子的聚集和金刚石膜与衬底之间的粘附性 ,降低了金刚石膜与衬底之间的内应力