高阻隔碳氢膜的制备及性能研究

利用射频等离子体化学气象沉积法（r.f.PECVD），在12μm厚的聚对苯二甲酸乙二醇酯 (PET)上制备了碳氢膜. 用原子力显微镜（AFM），x射线光电子能谱（XPS），激光拉曼光谱，傅里叶红外光谱等仪器，对碳氢膜的表面形貌和内部结构特性进行了较详细研究. 镀碳氢膜PET的阻隔性能在标准透水蒸气测试仪上进行检测. 实验结果证明：沉积工艺参数对碳氢膜的生长速率及结构性能有重要影响；在PET上沉积的是纳米碳氢膜，该膜主要由sp2和sp3杂化的碳氢化合物组成；当PET上碳氢膜厚度为900nm时，阻水蒸气性能可提高7倍. 关键词： 碳氢膜 射频等离子体化学气象沉积法 聚对苯二甲酸乙二醇酯 阻隔性能     

碳纳米片-碳纳米管复合材料的一步合成及其场 发射性质研究

利用等离子体化学气相沉积技术, 在引入Ti过渡层后的Co膜表面一步制备出碳纳米片-碳纳米管复合材料, 研究了Co膜厚度对复合材料形貌及场发射性质的影响. 当Co薄膜厚度为11 nm时, 得到了垂直基片定向生长的碳纳米管和碳纳米片复合物, 此时, 碳纳米片分布在碳纳米管的管壁上和管的顶端, 样品的场发射性能最佳.     

Surface characteristics of Ni catalystic films on growth behavior of multi-walled carbon nanotubes

The effect of the surface characteristics of Ni catalyst films on the growth behavior of multi-walled carbon nanotubes (MWCNTs) were investigated using Ni catalyst films prepared by different physical vapor deposition methods, electron-beam evaporation and sputtering. The growth behavior of MWCNTs was dependent upon the surface roughness of the Ni films. After a pretreatment process with NH₃, the root mean squares of surface roughness of e-beam evaporated and sputtered Ni catalyst films increased to 16.6 and 3.2 nm, respectively. Curled-MWCNTs and carbon-encapsulated Ni nanoparticles were formed on the Ni film deposited by e-beam evaporation while vertically aligned-MWCNTs were grown on the sputter-deposited film. In addition, the surface roughness of the Ni films affected the field emission properties of the MWCNTs. This was considered to originate from the specific growth behavior of the MWCNTs which was primarily caused by the initial surface roughness of the Ni films.     

Ti/Ti-类金刚石多层膜的制备与表征

采用电子回旋共振-化学气相沉积结合中频磁控溅射的真空镀膜技术, 以99.99%Ti为靶材, 乙炔为碳源制备了Ti/Ti-类金刚石(DLC)多层膜. 利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱仪 对Ti/Ti-DLC多层膜进行了相结构、组织、成分及形态分析. 采用显微硬度仪、摩擦磨损仪、表面粗糙度仪对Ti/Ti-DLC多层膜进行了力学性能考察. 结果表明: Ti/Ti-DLC多层膜中主要含有TiC晶相; Ti层和Ti-DLC层中未出现柱状晶体生长模式, 分层中均以岛状模式生长; 当调制周期Λ≤ 50 nm时, 分层结构变模糊; 调制周期Λ对Ti/Ti-DLC多层膜的复合硬度、摩擦系数、表面形貌、表面粗糙度都有影响, 当调制周期Λ较小时表现出纳米增硬效应, 表面出现大颗粒, 表面粗糙度和摩擦系数均变大.     

金刚石薄膜的红外椭圆偏振光谱研究

采用红外椭圆偏振光谱对微波等离子体化学气相沉积法（MPCVD）和热丝化学气相沉积法（H-FCVD）制备的金刚石薄膜在红外波长范围（2.5—12.5μm）的光学参数进行了测量.建立了不同的光学模型，且在模型中采用Bruggeman有效介质近似方法综合考虑了薄膜表面和界面的椭偏效应.结果表明，MPCVD金刚石膜的椭偏数据在模型引入了厚度为77.5nm的硅表面氧化层、HFCVD金刚石膜引入879nm粗糙层之后能得到很好的拟合.最后对两种模型下金刚石薄膜的折射率和消光系数进行了计算，表明MPCVD金刚石薄膜的红外 关键词： 金刚石薄膜 红外椭圆偏振光谱 光学参数 有效介质近似     

Effect of H2 and O2 plasma etching treatment on the surface of diamond-like carbon thin film

In this study, we investigated the surface properties of diamond-like carbon (DLC) films for biomedical applications through plasma etching treatment using oxygen (O₂) and hydrogen (H₂) gas. The synthesis and post-plasma etching treatment of DLC films were carried out by 13.56 MHz RF plasma enhanced chemical vapor deposition (PECVD) system. In order to characterize the surface of DLC films, they were etched to a thickness of approximately 100 nm and were compared with an as-deposited DLC film. We obtained the optimum condition through power variation, at which the etching rate by H₂ and O₂ was 30 and 80 nm/min, respectively. The structural and chemical properties of these thin films after the plasma etching treatment were evaluated by Raman and Fourier transform infrared (FT-IR) spectroscopy. In the case of as-deposited and H₂ plasma etching-treated DLC film, the contact angle was 86.4° and 83.7°, respectively, whereas it was reduced to 35.5° in the etching-treated DLC film in O₂ plasma. The surface roughness of plasma etching-treated DLC with H₂ or O₂ was maintained smooth at 0.1 nm. These results indicated that the surface of the etching-treated DLC film in O₂ plasma was hydrophilic as well as smooth.     

Investigation of the protective properties of a subnanometer diamond-like carbon film

The influence of diamond-like carbon coatings on the corrosion resistance of zirconium is investigated. Zirconium films with a thickness of 20 nm and different thicknesses of carbon protective films are examined. The chemical state of atoms on the surface is characterized using the measured photoelectron, electron energy loss, and Auger electron spectra. The results obtained demonstrate that the diamond-like carbon coating with a thickness of approximately 1 nm almost completely protects the metal film against oxidation. These protective properties of the diamond-like carbon coatings are explained by their high chemical inertness and uniformity over the thickness.     

MOCVD生长Si衬底上HT-AlN缓冲层低生长压力对GaN薄膜的影响

采用金属有机化学气相沉积（MOCVD）技术在Si（111）衬底上外延GaN薄膜,对高温AlN（HT-AlN）缓冲层在小范围内低生长压力（6.7~16.6 kPa）条件下对GaN薄膜特性的影响进行了研究。研究结果表明GaN外延层的表面形貌、结构和光学性质对HT-AlN缓冲层的生长压力有很强的的依赖关系。增加HT-AlN缓冲层的生长压力,GaN薄膜的光学和形貌特性均有明显改善,当HT-AlN缓冲层的生长压力为13.3 kPa时,得到无裂纹的GaN薄膜,其（002）和（102）面的X射线衍射峰值半高宽分别为735 arcsec和778 arcsec,由拉曼光谱计算得到的张应力为0.437 GPa,原子力显微镜（AFM）观测到表面粗糙度为1.57 nm。     

Control of structure and electric properties of amorphous organic semiconductive thin films prepared by excimer laser ablation

Excimer laser ablation (ELA) of 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) with ArF (193 nm), KrF (248 nm), XeCl (308 nm), and XeF (351 nm) beams under optimized conditions enables us to obtain organic semiconductor thin films with various structures such as amorphous carbon, polyperinaphthalene (PPN), and PTCDA itself. Electric conductivity and carrier species of the films depend strongly on the ablation wavelength, fluence, substrate temperature, and ambient vapor species. It is found that electric conductivities of the films are controllable, ranging from 10^-6 to 10¹ S cm^-1 with the selection of appropriate ablation conditions. An organic pn junction is successfully constructed by the change of ablation conditions during ELA. Furthermore, ELA of PTCDA at 248 nm in iodine vapor leads to formation of tetraiodoallene in the film.     

氮离子注入对类球状微米金刚石聚晶膜的影响

利用微波等离子体化学气相沉积法,在覆盖金属钛层的陶瓷衬底上制备出类球状微米金刚石聚晶膜,后对膜的表面进行氮离子的注入.通过扫描电子显微镜、拉曼光谱、X射线衍射谱及二级结构场发射测试,对膜进行了注入前后的分析.氮离子注入后场致电子发射的效果变强,这可能是氮离子的注入增加了类球状微米金刚石聚晶膜表面的缺陷度,从而增加了价带和导带间的缺陷能级,使电子更容易跃迁到高能级上,提高了场致电子的发射效果.     

Enhanced water vapor barrier properties for biopolymer films by polyelectrolyte multilayer and atomic layer deposited Al2O3 double-coating

Commercial polylactide (PLA) films are coated with a thin (20 nm) non-toxic polyelectrolyte multilayer (PEM) film made from sodium alginate and chitosan and additionally with a 25-nm thick atomic layer deposited (ALD) Al₂O₃ layer. The double-coating of PEM + Al₂O₃ is found to significantly enhance the water vapor barrier properties of the PLA film. The improvement is essentially larger compared with the case the PLA film being just coated with an ALD-grown Al₂O₃ layer. The enhanced water vapor barrier characteristics of the PEM + Al₂O₃ double-coated PLA films are attributed to the increased hydrophobicity of the surface of these films.     

The effects of thermal annealing on the structure and the electrical transport properties of ultrathin gadolinia-doped ceria films grown by pulsed laser deposition

Ultrathin crystalline films of 10 mol% gadolinia-doped ceria (CGO10) are grown on MgO (100) substrates by pulsed laser deposition at a moderate temperature of 400°C. As-deposited CGO10 layers of approximately 4 nm, 14 nm, and 22 nm thickness consist of fine grains with dimensions ≤∼11 nm. The films show high density within the thickness probed in the X-ray reflectivity experiments. Thermally activated grain growth, density decrease, and film surface roughening, which may result in the formation of incoherent CGO10 islands by dewetting below a critical film thickness, are observed upon heat treatment at 400°C and 800°C. The effect of the grain coarsening on the electrical characteristics of the layers is investigated and discussed in the context of a variation of the number density of grain boundaries. The results are evaluated with regard to the use of ultrathin CGO10 films as seeding templates for the moderate temperature growth of thick solid electrolyte films with improved oxygen transport properties.     

Microstructure, chemical bonds, and friction properties of nanocrystalline diamond films deposited in two different plasma media

Nanocrystalline diamond films with the properties dependent on the composition of the gaseous medium have been prepared using the microwave plasma enhanced chemical vapor deposition (MPECVD) method. A nanocrystalline film formed in the Ar/CH₄ plasma is characterized by a high crystallinity factor, a small grain size, a large fraction of sp ²-amorphous carbon, and, consequently, by an increase in the hardness and elastic modulus. The low value of the friction coefficient of this film is associated with the small grain size and large fraction of the sp ²-amorphous carbon boundary phase that ensures an easy sliding. The contact angle of the film is small (hydrophilic properties) in the case when the plasma consists of an Ar/CH₄ mixture. It has been shown that the wetting properties of the films are provided by a thin layer of carboxyl and hydroxyl functional groups passivating the dangling bonds at the surface that are responsible for the boundary lubrication mechanism. It has also been found that the friction coefficient of these films is inversely proportional to the contact pressure dependent on the diameter of the sliding counterbody ball.     

Structural and magnetic properties of Co-C composite films and Co/C multilayer films

CoC composite films and Co/C multilayer films have been prepared by a method incorporating ion beam sputtering and plasma chemical vapor deposition. It has been found that the structure and magnetic properties of both the Co-C composite and the Co/C multilayer films depend strongly on the substrate temperature during deposition. The Co-C composite film deposited at room temperature is amorphous, with relatively low saturation magnetization and coercivity. On the other hand, the film deposited at 250 °C is composed of fine Co crystallites separated by amorphous C or Co-C phase. As a result, both the saturation magnetization and coercivity are increased compared with the film deposited at room temperature. When deposited at room temperature, the Co/C multilayer film exhibits good periodicity, with a period of 70 nm (Co: 40 nm, C: 30 nm) and sharp and flat Co-C interfaces. High magnetization (602 emu/cm³) and low coercivity (1.6 Oe) are obtained for such a film. However, increasing the substrate temperature to 250 °C was found to be detrimental to the magnetic properties due to the formation of cobalt carbide at the Co-C interface. Received: 11 July 2000 / Accepted: 13 July 2000 / Published online: 30 November 2000     

Effects of the ion-beam voltage on the properties of the diamond-like carbon thin film prepared by ion-beam sputtering deposition

Diamond-like carbon(DLC) thin film is one of the most widely used optical thin films.The fraction of chemical bondings has a great influence on the properties of the DLC film.In this work,DLC thin films are prepared by ion-beam sputtering deposition in Ar and CH4 mixtures with graphite as the target.The influences of the ion-beam voltage on the surface morphology,chemical structure,mechanical and infrared optical properties of the DLC films are investigated by atomic force microscopy(AFM),Raman spectroscopy,nanoindentation,and Fourier transform infrared(FTIR) spectroscopy,respectively.The results show that the surface of the film is uniform and smooth.The film contains sp2 and sp3hybridized carbon bondings.The film prepared by lower ion beam voltage has a higher sp3 bonding content.It is found that the hardness of DLC films increases with reducing ion-beam voltage,which can be attributed to an increase in the fraction of sp3 carbon bondings in the DLC film.The optical constants can be obtained by the whole infrared optical spectrum fitting with the transmittance spectrum.The refractive index increases with the decrease of the ion-beam voltage,while the extinction coefficient decreases.     

The study of magnetic properties and microstructures of nano-size FePt islands on amorphous carbon film

This work focuses on the formation mechanisms of nano-island FePt film on commercial copper grids covered with an amorphous carbon film. FePt films of different thickness (1-7.5 nm) were deposited on amorphous carbon film and then post-annealed at 700 °C for 30 min. The configuration of the film was changed during the annealing process due to the surface energy difference between the amorphous carbon films and FePt alloy. We have prepared nanometer-size island-shaped FePt films on the amorphous carbon films and investigated their magnetic properties and microstructures. A discontinuous nano-size island magnetic film can reduce the exchange coupling of the media and increase the recording density.     

Nanoparticles for dewetting suppression of thin polymer films used in chemical sensors

Addition of fullerenes (C₆₀ or buckyballs) to a linear polymer has been found to eliminate dewetting when a thin (∼50 nm) film is exposed to solvent vapor. Based on neutron reflectivity measurements, it is found that the fullerenes form a coherent layer approximately 2 nm thick at the substrate – polymer film interface during the spin-coating process. The thickness and relative fullerene concentration (∼29 vol%) is not altered during solvent vapor annealing and it is thought this layer forms a solid-like buffer shielding the adverse van der Waals forces promoted by the underlying substrate. Several polymer films produced by spin- or spray-coating were tested on both silicon wafers and live surface acoustic wave sensors demonstrating fullerenes stabilize many different polymer types, prepared by different procedures and on various surfaces. Further, the fullerenes drastically improve sensor performance since dewetted films produce a sensor that is effectively inoperable.     

Peculiarities of the reflection spectra of PECVD nanocrystalline porous silicon films

Photoluminescent nanocrystalline porous silicon films have been formed on silicon substrates by plasma-enhanced chemical vapor deposition. In the visible spectral range, a nontrivial character of the reflection spectra (dependent on the film thickness) has been found. The sizes of crystallites and the root-mean-square roughness of the deposited film surface have been determined by X-ray diffraction and atomic force microscopy. It is shown that the significant decrease in the reflectance in the spectral range from 200 to 900 nm and the red shift of the characteristic peaks in the reflection spectra are related to the sizes of nanocrystallites in the films formed.     

AgGaSe2 thin films grown by chemical close-spaced vapor transport for photovoltaic applications: structural, compositional and optical properties

Thin films of chalcopyrite AgGaSe(2) have been successfully grown on glass and glass/molybdenum substrates using the technique of chemical close-spaced vapor transport. The high crystallinity of the samples is confirmed by grazing-incidence x-ray diffraction, scanning and transmission electron microscopy, and optical transmission/reflection spectroscopy. Here, two of the three expected direct optical bandgaps are found at 1.77(2) and 1.88(6) eV at 300 K. The lowest bandgap energy at 4 K is estimated to be 1.82(3) eV. Photoluminescence spectroscopy has further revealed the nature of the point defects within the AgGaSe(2), showing evidence for the existence of very shallow acceptor levels of 5(1) and 10(1) meV, and thus suggesting the AgGaSe(2) phase itself to exhibit a p-type conductivity. At the same time, electrical characterization by Hall, Seebeck and four-point-probe measurements indicate properties of a compensated semiconductor. The electrical properties of the investigated thin films are mainly influenced by the presence of Ag(2)Se and Ga(2)O(3) nanometer-scaled surface layers, as well as by Ag(2)Se inclusions in the bulk and Ag clusters at the layers' rear side.     

CH基团与金刚石(111)面的碰撞反应及其对碳膜生长的影响

等离子体增强化学气相沉积技术中的碳膜选择性自组装机理是高性能碳膜制备过程中的挑战性基础课题.采用经典分子动力学方法,模拟了不同能量(1.625-65 eV)的CH基团在清洁金刚石和吸氢金刚石(111)面上的轰击行为,获得了吸附、反弹、反应等各类事件的发生概率,并据此探讨了含氢碳膜制备过程中CH基团的贡献.结果表明,随着入射能量的增加,CH基团对薄膜生长的贡献由单纯的吸附、反弹机理向反应、吸附混合机理转变,其中最主要的反应过程是释放一个或两个氢原子的反应,而释放氢分子的反应则很少发生.这些反应不仅使薄膜生长过程更均匀、薄膜表面更平整,还降低了薄膜的氢含量.生长机理的转变导致低能量条件下所成薄膜中的多数碳原子都包含一个氢原子作为配位原子,而高能量条件下的薄膜中的碳原子则很少有氢原子作为配位原子.另外,通过分析sp~3-C和sp~2-C数目的变化,研究了CH基团对金刚石基底的破坏作用.