液相电沉积类金刚石薄膜的组成及结构分析

利用液相电沉积的方法，从乙腈中在硅片上沉积非晶碳薄膜，首次发现了电流密度随反应时间呈波动变化的规律。红外光谱和拉曼光谱分析表明所得薄膜是一种典型的含氢类金刚石薄膜(a-C：H薄膜)，并用高斯分解的方法对非晶碳薄膜的拉曼光谱和X射线光电子能谱进行定量分析，从而确定这种a-C：H薄膜中sp^3的相对含量为30％～35％。     

Aroused problems in the deposition of diamond-like carbon films by using the liquid phase electrodeposition technique

Hydrogenated diamond-like carbon (DLC) films were prepared by using liquid phase electrodeposition technique. The effects of the applied potential and the carbon sources on the deposition process and film structures were studied. It has been found that the organic liquids with high dielectric constants, small viscosities and the methyl group bonding to the polar group are appropriate carbon sources. The increasing of potential improves the formation of sp³ carbon during the deposition process. In a high electric field, organic molecules are polarized and reacted on the surface of the electrode, turning out DLC and other products. It is believed that the reaction follows a polarization-reaction mechanism.     

Deposition of diamond-like carbon films by using liquid phase electrodeposition technique and its electron emission properties

We have deposited diamond-like carbon (DLC) films by electrodeposition technique in methanol liquid. XPS showed the films mainly contain carbon. IR spectrum indicated that as-deposited films are hydrogenated carbon films, with the hydrogen mainly bonded to sp³ carbon. Raman measurement suggested that the films consisted of sp³ and sp² carbon. The field emission (FE) property of DLC coated on Si has been measured. The field emission of DLC films started at an applied voltage of 160 V, compared with silicon tip arrays at 600 V, and an emission current of DLC films up to 55 A at 360 V was achieved.     

类金刚石薄膜的紫外辐照研究

对射频等离子体方法制备的类金刚石（以下简称DLC）薄膜样品进行了紫外辐照，采用电阻率，Raman光谱及红外光谱研究了紫外光（以下简称UV）辐照对DLC薄膜结构与特征的影响，Raman光谱表明：紫外光对DLC薄膜中SP^3C-H键的破坏作用非常明显，红外（IR）光谱结果进一步验证了这一结果，经UV辐照后，DLC薄膜的电阻率呈变小趋势，这说明薄膜被强烈氧化，最后呈现石墨化趋势。     

液相法新工艺制备类金刚石膜的结构及其电学性能分析

采用液相法，在以硅片为阳极的工艺条件下沉积了一层DLC薄膜。通过Raman和FFIR光谱的分析，证实了该薄膜为含氢类金刚石薄膜（a-C：H）。并且对薄膜的交流阻抗谱（EIS）进行了测试和分析，确定该膜有非常高的阻抗值和良好的耐蚀性。     

Low temperature internal friction of diamond-like carbon films

We have studied the internal friction of amorphous diamond-like carbon films prepared by pulsed-laser deposition from 0.4 to 300 K. The low temperature internal friction below 10 K is dominated by the atomic tunneling states for amorphous solids, which is a measure of structure disorder. We have tried to vary the content of sp³ carbon atoms versus sp² ones by changing laser fleunce, by doping with N and Ar, and by annealing at 500 °C for 20 min. Our results show that the internal friction varies about one order of magnitude from 2×10⁻⁵ to 2×10⁻⁴, and its value is higher with higher sp³ content when the film quality is generally considered superior. However, it is known that as-deposited diamond-like carbon films with high sp³ content are heavily stressed. Annealing and doping are used to release the stress. We conclude that in addition to tetrahedral bonding, low stress is also important in reducing structure disorder associated with the low energy tunneling states in amorphous solids.     

Implantation effect of diamond-like carbon films by 110 keV nitrogen ions

Diamond-like carbon films, grown on microscope slides by a dual-ion beam sputtering system, were implanted by 110 keV N⁺ under the doses of 1 × 10¹⁵, 1 × 10¹⁶ and 1 × 10¹⁷ions cm⁻² respectively. The implantation induced changes in electrical resistivity of the films and in infrared (IR) transmittance of the specimens were investigated as a function of implantation dose. The structural changes of the films were also studied using IR spectroscopy and Raman spectroscopy. It was observed that, with the increase of implantation dose, the diamond-like carbon films display two different stages in electrical and optical behaviours. The first is the increase of both the film resistivity and the IR transmittance of specimen at the dose of 1 × 10¹⁵ ions cm⁻² which, we consider, is attributed to the implantation-induced increase sp³ C---H bonds. However, when the doses are higher than 1 × 10¹⁵ ions cm⁻², the film resistivity and the IR transmittance of specimen decrea significantly and the decrease rates at dose range of 1×10¹⁶ to 1×10¹⁷ ions cm⁻² are smaller than those between 1×10¹⁵ and 1 × 10¹⁶ ions cm⁻². We conclude that the significant reductions of the two parameters at high doses are caused by the decreases of bond-angle disorder and of sp³ C---H bonds, the increases of sp² C---C bonds dominated the crystallite size and/or number and also the sp² C---H bonds. The smaller decrease rates at a dose range of 1 × 10¹⁶ to 1 × 10¹⁷ ions cm⁻² may be caused by further recombination of some retained hydrogen atoms to carbon atoms.     

The effect of surfactant on the structure and properties of ZnO films prepared by electrodeposition

The effect of surfactant on the formation, structure and properties of ZnO films synthesized by electrodeposition was studied in this work. It was carried out in an aqueous Zn(NO₃)₂ solution containing surfactant op-10 using cathodic galvanostatic method. The results showed that the additive surfactant effectively inhibited hydrogen evolution reaction on cathode surface, maintained stability of the solution pH and improved deposition rate of the films to two times. Grown ZnO films with uniform grain and smooth surface were observed by using atomic force microscopy. Optical characterizations indicated that average optical transmittance of such films was more than 80% in the visible wavelength range, and its optical band gap was near 3.21 eV.     

反应磁控溅射法沉积的氟化类金刚石薄膜的结构分析

以高纯石墨作靶、Ar／CHF3作源气体采用射频反应磁控溅射法室温下制备了氟化类金刚石薄膜(F-DLC)。发现随着射频功率的增加,F-DLC薄膜拉曼光谱的D峰与G峰强度之比ID／IG加大,薄膜中芳香环式结构比例上升。红外吸收光谱则显示射频功率增加导致薄膜中的氟含量上升．氟原子与碳原子以及芳香环的耦合加强。控制射频功率可以有效调制薄膜中的氟含量以及芳香环结构的比例,F—DLC可能成为热稳定性较好的碳氟薄膜。     

Comparing internal stress in diamond-like carbon films with different structure

Diamond-like carbon (DLC) films with different structures were deposited on Si (100) and stainless steel substrates in a hybrid deposition system with Ar and CH₄ as the feedstocks. The effects of the bias voltage, Ti-interlayer, Ti functional gradient layer and Ti-doping on the internal stress in DLC films were investigated. The results show that the internal stress in DLC films arises from both the intrinsic stress generated during the film growth and the thermal stress generated due to the mismatching of the thermal expansion coefficient between the DLC films and the substrate materials. The intrinsic stress can be released through doping titanium element at the expense of reducing the sp³/sp² ratio. The thermal stress in DLC films can be decreased through introducing Ti-interlayer or Ti functional gradient layer. Noticeably, DLC films with very low internal stress deposited on stainless steel can be obtained through the combination of Ti-doping and Ti functional gradient layer.     

辅助气体组成对类金刚石薄膜结构和性能的影响

分别以氩气-甲烷、氩气-乙炔为辅助气体,高纯石墨为靶材,利用中频脉冲非平衡磁控溅射技术制备了类金刚石薄膜.采用Raman光谱、X射线光电子能谱、纳米压痕测试仪、原子力显微镜对所制备类金刚石薄膜的键结构、机械性能、表面形貌进行了分析.Raman光谱和X射线光电子能谱测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜中sp3杂化键的含量比以氩气-乙炔为辅助气体制备的类金刚石薄膜的高.纳米压痕测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜的纳米硬度比以氩气-乙炔为辅助气体的高.原子力显微镜测试结果表明,以氩气-甲烷为辅助气体制备的类金刚石薄膜的RMS表面粗糙度比以氩气-乙炔为辅助气体的低.以上结果说明辅助气体组成对类金刚石薄膜的键结构、机械性能、表面形貌有较大的影响.     

Metal-doped diamond-like carbon films synthesized by filter-arc deposition

Diamond-like carbon (DLC) thin films are extensively utilized in the semiconductor, electric and cutting machine industries owing to their high hardness, high elastic modulus, low friction coefficients and high chemical stability. DLC films are prepared by ion beam-assisted deposition (BAD), sputter deposition, plasma-enhanced chemical vapor deposition (PECVD), cathodic arc evaporation (CAE), and filter arc deposition (FAD). The major drawbacks of these methods are the degraded hardness associated with the low sp³/sp² bonding ratio, the rough surface and poor adhesion caused by the presence of particles. In this study, a self-developed filter arc deposition (FAD) system was employed to prepare metal-containing DLC films with a low particle density. The relationships between the DLC film properties, such as film structure, surface morphology and mechanical behavior, with variation of substrate bias and target current, are examined. Experimental results demonstrate that FAD-DLC films have a lower ratio, suggesting that FAD-DLC films have a greater sp³ bonding than the CAE-DLC films. FAD-DLC films also exhibit a low friction coefficient of 0.14 and half of the number of surface particles as in the CAE-DLC films. Introducing a CrN interfacial layer between the substrate and the DLC films enables the magnetic field strength of the filter to be controlled to improve the adhesion and effectively eliminate the contaminating particles. Accordingly, the FAD system improves the tribological properties of the DLC films.     

Characterization of ion-beam-deposited diamond-like carbon films

Diamond-like carbon (DLC) films are excellent prospects for a wide range of high-technology applications but their precise structure and properties are not well understood. The purpose of the present work was to use several complementary techniques to characterize the nature, structure and microstructure of DLC films. Thin DLC films were deposited on various substrates in the presence of a Si interlayer (500 Å thick) using CH₄ ion-beam deposition at an acceleration energy of 750 eV and a current density of about 2.5 mA cm⁻². The Si interlayer was deposited by either e-beam evaporation or Si evaporation enhanced by Ar⁺ beam bombardment (1 keV). The produced DLC films were featureless, very smooth and of high hardness (2900–3300 kg mm⁻²). Auger electron spectroscopy and electron diffraction showed that the films were mainly amorphous. Their microstracture was characterized by a three-dimensional network structure with a medium-range order of about 25 nm. Fourier transform infrared and Raman spectroscopies showed that the films were mainly composed of sp³ and sp² carbon-bonded hydrogen. The sp³/sp² ratio varied from 3.2 to 4.1 and was found to depend on the nature of the Si bond layer. The results showed that the nucleation of the diamondlike structure was promoted on the Si interlayer that was deposited under Ar⁺ beam bombardment. This effect can be explained by the higher surface roughness produced in this interlayer as suggested by the reflectivity measurements. Spectroscopic ellipsometry revealed that the films had an optical band gap between 1.56–1.64 eV. The present results are consistent with previous proposals suggesting that the DLC structure is composed of small graphitelike clusters (involving fused six-fold rings) that are interconnected by sp³-bonded carbon.     

退火温度对Ge-SiO2薄膜结构的影响

用射频磁控溅射制备了Ge-SiO2薄膜，在N2的保护下对薄膜进行了不同温度的退火处理。使用傅里叶变换红外光谱分析（FTIR）技术，X射线衍射谱（XRD），X射线光电子能谱（XPS）分析样品的微结构，研究样品在退火中发生的结构，组分的变化，结果表明退火温度对薄膜的结构，尤其是薄膜中的GeO含量和GeO晶粒的大小的影响是显著的，并对其做了详尽的分析讨论。     

类金刚石碳膜的热稳定性

总结了各种ＤＬＣ膜的热稳定性及分析手段,概述了加热退火情况下ＤＬＣ膜结构,内应力的变化,评述了国内的最新研究进展,并提出了有等进一步研究的问题。     

等离子体化学气相沉积类金刚石碳膜的特性及应用

类金刚石（DLC）膜是含有sp^3杂化态的亚稳态非晶碳膜，是具有极高的硬度、化学稳定性和光学透明性的半导体材料。这篇综述介绍了用等离子体化学气相沉积DLC膜的沉积方法、所制备薄膜的特性及应用，最后展望了DLC膜的发展趋势。     

Effect of annealing on diamond-like carbon characteristics by electron spin resonance spectral analysis

We have examined the effect of annealing on physicochemical properties of the diamond-like carbon (DLC) films to produce higher quality films by the electron spin resonance spectral analyses of the immobilized dangling-bond sites (DBS), since amount of DBS reflects the characteristics of DLC films. On heat treatment of DLC deposited from ethylene monomer under anaerobic condition, the DBS decay was clearly shown, as the temperature raised. The decay described by second-order kinetics indicated that the recombination reaction of DBS progressed on heat treatment, suggesting that annealing treatment would accelerate the carbon-carbon covalent bonding network to produce harder films. In fact, the resulted DLC film derived from ethylene monomer showed non-existence of any type of oxygen atom based on X-ray photoelectron spectrum measurement, and water contact angle measurement showed higher hydrophobic surface of the DLC films.     

激光辐照对类金刚石薄膜改性及损伤研究

介绍了激光损伤的检测及损伤阈值的测量方法.讨论激光辐照对类金刚石结构和性质的影响规律.并论述不同工作参数的激光对类金刚石薄膜的激光破坏行为及其损伤阈值.在此基础上分析类金刚石薄膜激光损伤的机理.还从物理特性及制备技术方面着手,比较分析金刚石及类金刚石薄膜各自的优缺点和实际应用状况,并提出类金刚石薄膜的应用前景和有待进一步研究的问题.     

Surface plasmon effect in nanocrystalline copper/DLC composite films by electrodeposition technique

Composite films of nanocrystalline copper embedded in DLC matrix prepared by electrodeposition technique were studied for their optical properties. Particle size and metal volume fractions were tailored by varying the amount of copper containing salt in the electrolyte. Blue-shift of the surface plasmon resonance peak in the absorbance spectra of the films was observed with the reduction in size and volume fraction of metal particles. Mie theory was found to describe the experimental spectra quite well.     

Effects of annealing temperature on the structure and photoluminescence properties of ZnO films

Zinc oxide (ZnO) films with c-orientation were deposited on Si (1 1 1) substrates at room temperature (RT) by RF-magnetron sputtering. Violet (394 and 412 nm) and green (560 and 588 nm) photoluminescence (PL) were observed from the as-deposited and annealed samples. The PL intensity was increasing with increasing annealing temperature (T_a). The 412 nm violet peak shifted from 412 to 407 nm and the 394 nm violet peak shifted from 394 to 399 nm on increasing the temperature from 500 to 900 °C, whereas no shift in PL green peaks was observed over the whole range of temperature examined. The 412 nm violet luminescence is ascribed to radiative defects related to the interface traps existing at grain boundaries. With the increase of T_a, the stress in the films changed from compressive to tensile, which is believed to have resulted in the observed 412 nm violet emission peak shifts from 412-407 nm. The 394 nm violet luminescence observed is attributed to free excitonic emission, and the increase of the crystal size may result in the 394 nm violet emission peak shifts from 394 to 399 nm. The other two PL bands located at 560 and 588 nm are attributed to oxygen deficiency.