掺氮四面体非晶碳的第一性原理研究

采用基于第一性原理的分子动力学方法对掺氮四面体非晶碳进行结构建模,并对其显微结构和电子结构进行了研究. 氮在非晶碳网络中的配位形态与密度没有明显关系,主要是以三配位形态存在,其次是两配位,四配位氮的比例很小. 掺氮后碳网络结构sp²含量大大增加,随着氮含量的增加,费米能级附近态密度增加. 氮掺入后并未使费米能级发生明显移动. 关键词： 掺氮四面体非晶碳 第一性原理 密度泛函理论 电子结构     

Dynamic roughening of tetrahedral amorphous carbon

The roughness of tetrahedral amorphous carbon (ta-C) films grown at room temperature is measured as a function of film thickness by atomic force microscopy, to extract roughness and growth exponents of alpha approximately 0.39 and beta approximately 0-0.1, respectively. This extremely small growth exponent shows that some form of surface diffusion and relaxation operates at a homologous temperature of 0.07, much lower than in any other material. This is accounted for by a Monte Carlo simulation, which assumes a smoothening during a thermal spike, following energetic ion deposition. The low roughness allows ta-C to be used as an ultrathin protective coating on magnetic disk storage systems with approximately 1 Tbit/in.(2) storage density.     

Platelet adhesion on phosphorus-incorporated tetrahedral amorphous carbon films

The haemocompatibility of phosphorus-incorporated tetrahedral amorphous carbon (ta-C:P) films, synthesized by filtered cathodic vacuum arc technique with PH₃ as the dopant source, was assessed by in vitro platelet adhesion tests. Results based on scanning electron microscopy and contact angle measurements reveal that phosphorus incorporation improves the wettability and blood compatibility of ta-C film. Our studies may provide a novel approach for the design and synthesis of doped ta-C films to repel platelet adhesion and reduce thrombosis risk.     

Synthesis and structure of nitrogenated tetrahedral amorphous carbon films prepared by nitrogen ion bombardment

The tetrahedral amorphous carbon (ta-C) films with more than 80% sp³ fraction firstly were deposited by filtered cathode vacuum arc (FCVA) technique. Then the energetic nitrogen (N) ion was used to bombard the ta-C films to fabricate nitrogenated tetrahedral amorphous carbon (ta-C:N) films. The composition and structure of the films were analyzed by visible Raman spectrum and X-ray photoelectron spectroscopy (XPS). The result shows that the bombardment of energetic nitrogen ions can induce the formation of CN bonds, the conversion of C-C bonds to CC bonds, and the increase of size of sp² cluster. The CN bonds are made of CN bonds and C-N bonds. The content of CN bonds increases with the increment of N ion bombardment energy, but the content of C-N bonds is inversely proportional to the increment of nitrogen ion energy. In addition, C≡N bonds are not existed in the films. By the investigation of AFM (atom force microscopy), the RMS (root mean square) of surface roughness of the ta-C film is about 0.21 nm. When the bombarding energy of N ion is 1000 eV, the RMS of surface roughness of the ta-C:N film decreases from 0.21 to 0.18 nm. But along with the increment of the N ion energy ranging from 1400 to 2200 eV again, the RMS of surface roughness of the ta-C:N film increases from 0.19 to 0.33 nm.     

Auger-spectroscopy studies of the electronic structure of amorphous carbon films

Information on the density of valence states (DOVS) of aC films has been determined by Auger spectroscopy. The films were prepared by magnetron sputtering of graphite and plasma decomposition of hydrocarbon gas. The relative contents of graphite-like and diamond-like components in aC have been determined by comparison of the area under the π-band of aC with that of graphite. The effect of annealing on the aC structure has benn studied.     

氮离子轰击能量对ta-C:N薄膜结构的影响

利用磁过滤真空阴极电弧技术制备了sp³键含量不小于80%的四面体非晶碳薄膜(ta-C), 然后通过氮离子束改性技术制备了氮掺杂的四面体非晶碳(ta-C:N)薄膜. 利用Raman光谱和X射线光电子能谱对薄膜结构的分析,研究了氮离子轰击能量对ta-C:N薄膜结构的影响. 氮离子对ta-C薄膜的轰击,形成了氮掺杂的ta-C:N薄膜. 氮离子轰击诱导了薄膜中sp³键向sp²键转化, 以及CN键的形成.在ta-C:N薄膜中,氮掺杂的深度和浓度随着氮离子能量的增大而增大. ta-C:N薄膜中sp²键的含量和sp²键团簇的尺寸随着氮离子轰击能量的增大而增加; 在ta-C:N薄膜中, CN键主要由C-N键和C＝N键构成, C-N 键的含量随着氮离子轰击能量的增大而减小,但是C＝N 键含量随着氮离子轰击能量的增大而增大.在ta-C:N薄膜中不含有C≡N键结构.     

Structural and optical properties of nitrogen-containing tetrahedral amorphous carbon films

Tetrahedral amorphous carbon films (ta-C) and nitrogen-containing ta-C films have been prepared using a magnetic-filtered plasma-deposition method in pure Ar, and Ar with N₂ ambient, respectively. The structural and optical properties of these films have been studied using UV-visible optical absorption spectroscopy, Raman spectroscopy, and measurements of electrical conductivity in the temperature range from 300 to 500 K. The value of the optical band gap for the ta-C films deposited at suitable conditions were found to be larger than 3 eV. For nitrogen-containing ta-C films deposited at low partial pressure of nitrogen, the incorporation of a small amount of nitrogen will result in a slight drop in activation energy of conductivity and a decrease in band gap, which indicates that there are evidently both doping effect of nitrogen and graphitization of bonding. The study of surface morphology has been performed using atomic force microscopy (AFM), and results show that the surface roughness increases with the amount of nitrogen incorporated in ta-C films. The correlation between surface roughness and configuration of N atoms in ta-C network is also discussed.     

硼掺杂对四面体非晶碳膜电导性能的影响

以单质硼和高纯石墨的混合粉末压制成型的靶材作为靶源,采用过滤阴极真空电弧技术制备不同硼含量的掺硼四面体非晶碳膜.分别采用四探针法、阻抗分析仪和电化学界面对薄膜的变温电导率、I-V特性和C-V特性进行了测试和研究.实验结果表明,当B含量由0增加至6.04 at%时,薄膜的室温电导率先逐渐增大而后逐渐减小,相应薄膜的电导激活能先逐渐减小而后逐渐增大,并在2.13 at%时分别出现最大和最小值1.42×10^-7S/cm和0.1eV.此外,掺硼四面体非晶碳/n型硅异质结的I-V曲线表现出典型的整流特性,表明p-n结二极管已经形成,且结两端的掺杂能级在空间上连续统一. 关键词： 四面体非晶碳 电导率 I-V曲线')" href="#">I-V曲线 C-V曲线')" href="#">C-V曲线     

Tight-binding molecular dynamics study of the hydrogen-induced structural modifications in tetrahedral amorphous carbon

A tight-binding molecular dynamics study of the structural evolution in tetrahedral amorphous carbon networks under dynamic hydrogen saturation is presented. The incorporation of hydrogen results in higher degrees of network disorder in second-neighbour distances, and initiates orbital re-hybridization that relaxes network stress. Using the simulated structures, numerical tests are performed to verify the effectiveness of a new structural order parameter for tetrahedrally-bonded solids. It is found that the island of accessible information, within the order parameter field shows a linear dependence between the fluctuations in first- and second-nearest-neighbour distances at a preferred orientation of 36°. A comparison with similar studies on hydrogenated amorphous silicon suggests that the local network structure of tetrahedrally-bonded amorphous solids obey the same ordering rule irrespective of differences in chemical species.     

Microstructure and tribological performance of self-lubricating diamond/tetrahedral amorphous carbon composite film

In order to smooth the rough surface and further improve the wear-resistance of coarse chemical vapor deposition diamond films, diamond/tetrahedral amorphous carbon composite films were synthesized by a two-step preparation technique including hot-filament chemical vapor deposition for polycrystalline diamond (PCD) and subsequent filtered cathodic vacuum arc growth for tetrahedral amorphous carbon (ta-C). The microstructure and tribological performance of the composite films were investigated by means of various characterization techniques. The results indicated that the composite films consisted of a thick well-grained diamond base layer with a thickness up to 150 μm and a thin covering ta-C layer with a thickness of about 0.3 μm, and sp³-C fraction up to 73.93%. Deposition of a smooth ta-C film on coarse polycrystalline diamond films was proved to be an effective tool to lower the surface roughness of the polycrystalline diamond film. The wear-resistance of the diamond film was also enhanced by the self-lubricating effect of the covering ta-C film due to graphitic phase transformation. Under dry pin-on-disk wear test against Si₃N₄ ball, the friction coefficients of the composite films were much lower than that of the single PCD film. An extremely low friction coefficient (∼0.05) was achieved for the PCD/ta-C composite film. Moreover, the addition of Ti interlayer between the ta-C and the PCD layers can further reduce the surface roughness of the composite film. The main wear mechanism of the composite films was abrasive wear.