A magnetron sputtering technique to prepare a-C:H films: Effect of substrate bias

Amorphous hydrogenated carbon (a-C:H) films were deposited by magnetron sputtering with a mixture gas of Ar and CH₄. The a-C:H films deposited by this method have relatively low internal stress (<1 GPa) compared to some films deposited by conventional deposition process. The effects of substrate bias voltage on microstructure, surface morphology and mechanical properties of the films were investigated by various techniques. It has been found that the polymer-like structure is dominated at low bias voltage (−100 V), while the diamond-like structure with the highest hardness and internal stress is the main feature of the a-C:H films deposited under high bias voltage (−300 V). With increasing the bias voltage further, the feature of diamond-like structure decreases associating with the increase of graphitization. The frictional test shows that the friction coefficient and wear rate of the a-C:H films are depended strongly on structure and mechanical properties, which were ultimately influenced by the deposition method and bias voltage.     

Negative magnetoresistance in Cr-containing diamond-like carbon-based heterostructures

We have characterized the local structure around the Cr atom, as a function of Cr content, in films of chromium-doped hydrogenated amorphous diamond-like carbon (Cr-DLC) synthesized by plasma-enhanced chemical vapor deposition (PECVD). The composition appears to be related to the structure and forward bias magnetoresistance in heterojunction devices. Chromium in diamond-like carbon (DLC) has a chemical state much like chromium carbide and, at low Cr content, the Cr is dissolved in an amorphous DLC matrix forming an atomic-scale composite. At higher Cr content, Cr is present as nano-composite and chromium carbide precipitates preferentially form at the surface of the film. In these films of higher chromium concentration, a large coefficient of negative magnetoresistance is observed in heterojunction devices with n-type silicon.     

Amorphous hydrogenated carbon synthesized by pulsed laser deposition from cyclohexane

It is demonstrated that a liquid hydrocarbon precursor, cyclohexane, is appropriate for laser-induced carbon deposition. Amorphous hydrogenated carbon films (a-C:H) were deposited by KrF excimer laser irradiation of single-crystal silicon surface immersed under cyclohexane. The technique is simple and easy to operate. IR absorption spectra of the deposited films confirmed the presence of carbon in the diamond phase. Raman and XPS studies showed diamond-like character of the deposited films. Moreover, these two studies provided strong evidence that laser fluence played an important role in the formation of DLC bondings and the quality of the deposited films. Received: 15 September 1998 / Accepted: 5 January 1999 / Published online: 5 May 1999     

Electrochemical synthesis and STM-STS studies of thin diamond-like films on the surface of oxidized aluminum

Thin carbon films on the surface of aluminum containing native oxide were prepared at room temperature by electrochemical deposition from a solution of lithium acetylenide in dimethylsulfoxide. The structure of the coatings obtained was studied by scanning tunnel microscopy and spectroscopy. The mechanical characteristics of carbon coatings were found to depend strongly on the main parameters determining deposition conditions. The presence of a considerable amount of sp ³ carbon (diamond-like phases) in the films was substantiated.     

Effects of flow ratios on surface morphology and structure of hydrogenated amorphous carbon films prepared by microwave plasma chemical vapor deposition

A series of hydrogenated amorphous carbon (a-C:H) films were deposited on silicon substrates by microwave plasma chemical vapor deposition technique with a mixture of hydrogen and acetylene. The effects of flow ratio of hydrogen to acetylene on surface morphology and structure of a-C:H films were investigated using surface-enhanced Raman spectroscopy and scanning probe microscope (SPM) in the tapping AFM mode. Raman data imply a transition from graphite-like phase to diamond-like bonding configurations when the flow ratio increases. AFM measurements show that the increase in hydrogen content, to some extent, can smoothen the surface morphology and decrease the RMS roughness. Excessive hydrogen is found to cause the formation of polymeric hydrocarbon clusters in the films and reduce deposition rate.     

电解有机溶液法在Si表面制备类金刚石薄膜及退火对其结构的影响

在对不同有机溶剂分子结构分析的基础上,选取甲醇、DMF(N,N-二甲基甲酰胺)和乙腈溶液为碳源,以脉冲直流电源电解有机溶液的方法在Si片上制得了含氢类金刚石薄膜(DLC薄膜),并研究了退火对薄膜结构的影响.通过X射线光电子能谱(XPS),喇曼(Raman)和红外(IR)光谱对薄膜的结构进行了分析表征.XPS表明薄膜的主要成分为C,喇曼光谱显示所得薄膜为典型DLC薄膜.喇曼和红外光谱还表明,膜中含有大量H并且主要键合于sp³碳处.随着退火的进行薄膜中的H被去除.随温度升高薄膜电阻率的下 关键词： 类金刚石薄膜 退火     

射频功率对类金刚石薄膜结构和性能的影响

利用直流-射频-等离子体增强化学气相沉积技术在单晶硅表面制备了类金刚石薄膜，采用原子力显微镜、Raman光谱、x射线光电子能谱、红外光谱和纳米压痕仪考察了射频功率对类金刚石薄膜表面形貌、微观结构、硬度和弹性模量的影响.结果表明，制备的薄膜具有典型的含H类金刚石结构特征，薄膜致密均匀，表面粗糙度很小.随着射频功率的升高，薄膜中成键H的含量逐渐降低，而薄膜的sp3³含量、硬度以及弹性模量先升高， 后降低，并在射频功率为100W时达到最大. 关键词： 等离子增强化学气相沉积 类金刚石薄膜 射频功率 结构和性     

Structural, mechanical and hydrophobic properties of fluorine-doped diamond-like carbon films synthesized by plasma immersion ion implantation and deposition (PIII–D)

Fluorine-doped diamond-like carbon (a-C:F) films with different fluorine content were fabricated on Si wafer by plasma immersion ion implantation and deposition (PIII–D). Film composition and structure were characterized by X-ray photoelectron spectroscopy (XPS) and Raman scattering spectroscopy. Surface morphology and roughness were analyzed by atomic force microscopy (AFM). Hardness and scratch resistance were measured by nano-indentation and nano-scratch, respectively. Water contact angles were measured by sessile drop method. With the increase of the CF₄ flux, fluorine content was gradually increased to the film. Raman spectra indicates that these films have a diamond-like structure. The addition of fluorine to diamond-like carbon films had a critical influence on the film properties. The film surface becomes more smoother due to the etching behavior of F⁺. Hardness was significantly reduced, while the scratch resistance results show that these films have a fairly good adhesion to the substrate. Evident improvements of the hydrophobicity have been made to these films, with contact angles of double-stilled water approaching that of polytetrafluoroethylene (PTFE). Our study suggests that broad application regions of the fluorine-doped amorphous carbon films with diamond-like structure, synthesized by PIII–D, can be extended by combining the non-wetting properties and mechanical properties which are far superior to those of PTFE.     

Influence of crystalline diamond nanoparticles on diamond-like carbon friction behavior

Crystalline diamond (CD) particles have been incorporated in diamond-like carbon (DLC) film structure in order to improve DLC electrochemical corrosion resistance. This paper shows the investigation of CD-DLC friction behavior according to the CD average sizes and concentration. The films were growth over 304 stainless steel using plasma enhanced chemical vapor deposition. The response surface methodology was used to develop a mathematical modeling of friction for these films, using the experimental results, in order to identify parameters that control friction and construct tribological maps according to the CD average sizes. The presence of bigger CD particles (250 and 500 nm) increased the film roughness. Films with CD particles of 4 nm presented the most homogeneous friction map, with minor variation in friction coefficient with the increase/decrease of load and sliding speed even when the CD concentration increase. This result suggests that in CD-DLC films containing CD particles of 4 nm average size, the nanoparticles are better incorporated in DLC structure due to its average size (4 nm) that is near than DLC grain size and could occupy the nanospaces between DLC grains.     

脉冲激光沉积无氢钨掺杂类金刚石膜的摩擦与机械性能

采用脉冲激光沉积技术制备出无氢钨掺杂非晶态类金刚石膜.膜中的钨含量与靶材中的钨含量保持稳定的线性关系,显示了脉冲激光沉积在难熔金属掺杂技术方面的亮点.由于碳-钨结构的形成和表面粗糙度影响,膜层的干摩擦系数随着钨含量的增加显现出先减后增的趋势,钨含量为9.67 at.%时达到最低值0.091.钨含量的增大降低了类金刚石膜纳米硬度和杨氏模量,但最佳的膜层耐磨性参数并非表现在硬度最大(52.2 GPa)的纯类金刚石膜中,而是出现在低掺杂含量(6.28 at.%)的类金刚石膜中.研究为脉冲激光沉积技术制备低摩擦、高硬度无氢钨掺杂类金刚石膜的应用提供了技术实践.     

电化学方法制备ZnO纳米颗粒掺杂类金刚石薄膜及其场发射性能研究

采用液相电化学沉积技术制备了ZnO纳米颗粒掺杂的类金刚石(DLC)薄膜, 研究了ZnO纳米颗粒掺杂对DLC薄膜场发射性能的影响. 利用X射线光电子能谱、透射电子显微镜、Raman光谱以及原子力显微镜分别对薄膜的化学组成、 微观结构和表面形貌进行了表征. 结果表明: 薄膜中的ZnO纳米颗粒具有纤锌矿结构, 其含量随着电解液中Zn源的增加而增加. ZnO纳米颗粒掺杂增强了DLC薄膜的石墨化和表面粗糙度. 场发射测试表明, ZnO纳米颗粒掺杂能提高DLC薄膜的场发射性能, 其中Zn与Zn+C的原子比为10.3%的样品在外加电场强度为20.7 V/μm时电流密度达到了1 mA/cm². 薄膜场发射性能的提高归因于ZnO掺杂引起的表面粗糙度和DLC薄膜石墨化程度的增加.     

原子层沉积方法制备核-壳型纳米材料研究

采用原子层沉积方法在碳黑纳米颗粒表面分别沉积Al₂O₃, ZnO, TiO₂和Pt, 成功制备出核-壳型纳米材料. 通过高分辨率透射电子显微镜、X射线光电子能谱仪、 能谱仪对材料的表面形貌、晶体结构、薄膜成分进行了表征和分析. 结果表明, 原子层沉积方法是制备核壳型纳米材料的理想方法. 此外, 还分析了采用原子层沉积方法沉积不同材料, 所生长的薄膜材料有单晶、多晶、非晶等多种存在形式的形成原因. 关键词： 原子层沉积 核-壳型纳米材料 碳黑纳米颗粒     

Encapsulation and controlled release from core–shell nanoparticles fabricated by plasma polymerization

Core–shell nanostructures have been synthesized by plasma deposition in radio-frequency plasma reactor. Silica and KCl nanoparticles were encapsulated by deposition of isopropanol-based films of amorphous hydrogenated carbon. Through control of the deposition time, under constant deposition rate of 1 nm/min, particles are encapsulated in a layer of plasma polymer with thickness between 15 and 100 nm. Films are robust, chemically inert, thermally stable up to 250°C. The permeability of the shells is determined by depositing films of various thickness onto KCl nanoparticles and monitoring the dissolution of the core in aqueous solution. The dissolution profile is characterized by an initial rapid release, followed by a slow release that lasts up to 30 days for the thickest films. The profile is analyzed by Fickian diffusion through a spherical matrix. We find that this model captures very accurately the entire release profile except for the first 12 hours during which, the dissolution rate is higher than that predicted by the model. The overall diffusion coefficient for the dissolution of KCl is 3 × 10⁻²¹ m²/s.     

Atomic oxygen resistant behaviors of Mo/diamond-like carbon nanocomposite lubricating films

Mo doped diamond-like carbon (Mo/DLC) films were deposited on Si substrates via unbalanced magnetron sputtering of molybdenum combined with plasma chemical vapor deposition of CH₄/Ar. The microstructure of the films, characterized by transmission electron microscopy and selected area electron diffraction, was considered as a nanocomposite with nano-sized MoC particles uniformly embedded in the amorphous carbon matrix. The structure, morphology, surface composition and tribological properties of the Mo/DLC films before and after the atomic oxygen (AO) irradiation were investigated and a comparison made with the DLC films. The Mo/DLC films exhibited more excellent degradation resistant behaviors in AO environment than the DLC films, and the MoC nanoparticles were proved to play a critical role of preventing the incursion of AO and maintaining the intrinsic structure and excellent tribological properties of DLC films.     

衬底温度对类金刚石薄膜力学性能的影响

 采用脉冲激光沉积方法在不同衬底温度下制备了最高硬度与弹性模量分别达45 GPa和290 GPa,且表面十分光滑的类金刚石薄膜。在相对湿度为80%的条件下,薄膜最低的摩擦系数与磨损率分别为0.045与5.74×10^-10 mm³·N^-1·m^-1。实验结果表明,硬度与弹性模量随衬底温度升高而降低,摩擦系数与磨损率随衬底温度升高而增大。拉曼光谱表明:在室温下制备的薄膜为典型类金刚石结构,sp³含量高达76.8%,而随温度升高,薄膜结构逐渐经无定形碳结构向纳米晶石墨结构方向发展,sp³含量也随之降低,力学性能变差。     

Deposition of fullerene films from the ablation plasma generated by high-power ion beams on graphite targets

A possibility of deposing carbon films with a high content of C₆₀ and C₇₀ fullerenes from an ablation plasma generated as a result of irradiation of graphite targets by pulsed high-power ion beams is shown. The relative contents of the crystalline diamond-like carbon phase, crystalline fullerene phase, and amorphous carbon phase have been determined by X-ray diffraction analysis for different deposition conditions. The nanohardness and Young’s modulus of the deposited films and their adhesion to the single-crystal silicon substrate have been measured.     

Influence of deposition conditions on the antireflection properties of diamond-like carbon films for Si-based solar cells

The influence of deposition conditions on the antireflection properties of diamond-like carbon films for Si-based solar cells is studied theoretically. The values of the short-circuit current density for Si solar cells covered by diamond-like carbon films deposited at different concentrations of nitrogen in the gas mixture are calculated and compared with the associated values for uncovered solar cells. It is shown that the short-circuit current density increases with nitrogen concentration in the gas mixture because of a lower light absorption by the growing film. Optimum thicknesses of the diamond-like carbon films are calculated that provides a maximal increase in the output short-circuit current density of Si-based solar cells under both AM1.5 and AM0 conditions. Published in Russian in Zhurnal Tekhnicheskoĭ Fiziki, 2006, Vol. 76, No. 5, pp. 122–126. The article was translated by the authors.     

The importance of non-local shadowing for the topography evolution of a-C:H films grown by toluene based plasma enhanced chemical vapor deposition

The topography evolution of hydrogenated diamond-like carbon coatings deposited through toluene based capacitively coupled plasma enhanced chemical vapor deposition has been studied experimentally and with continuum growth models. The experimentally observed mound formation and surprisingly large growth exponents (β≈ 0.9±0.1) cannot be reproduced by familiar local stochastic differential equations that are successfully used for other thin film deposition techniques. Here we introduce a novel numerical approach to simulate a continuum growth model that takes into account non-local shadowing effects. We show that the major characteristics of the experimentally observed topography evolution can be accurately represented by this model.     

Ripple surface generated on hydrogenated amorphous carbon nitride films

It is reported for the first time that the periodical ripple surface feature at micrometer-scale was observed on hydrogenated amorphous carbon nitride films deposited by pulse plasma chemical vapor deposition (CVD) technique. Nitrogen incorporation to hydrogenated amorphous carbon films and the different growing environments of pulse dc plasma discharge perhaps played crucial role in the surface morphology transformation of hydrogenated amorphous carbon nitride films.     

Preparation and characterization of amorphous hydrogenated carbon films containing Au nanoparticles from heat-treatment of polymer precursors

Amorphous hydrogenated carbon (aC:H) films containing Au nanoparticles have been successfully prepared by heat-treatment of the precursors including poly(phenylcarbyne) polymer and HAuCl₄ at 600 °C in Ar atmosphere. The microstructure and morphology of the obtained films were investigated by means of Raman, XPS, XRD, TEM, and AFM. The sheet resistivity of the films was measured by a four-point probe method. Moreover, a ball-on-disc test was employed to obtain information about the frictional properties and sliding wear resistance of the films. The results show that heat-treatment of the precursors at 600 °C causes the change of the polymer into amorphous hydrogenated carbon phase, and the reduction of AuCl₄^- anions into zero-valence Au. All of the AuaC:H films exhibit smooth morphologies, with the RMS roughness smaller than 0.80 nm. Au nanoparticles are well dispersed in the amorphous carbon matrix, with size ranging from several to tens of nanometers, and the particle size increases with increasing gold content. The incorporation of Au in the carbon matrix can drastically decrease the resistivity and the resistivity of composite films gradually decreases with increasing Au concentration. AuaC:H films with the Au concentration of 2% and 4% show much better friction-reduction and wear-resistance than aC:H film. PACS 81.15.Np; 81.07.-b; 81.40.Pq