不同厚度四面体非晶碳薄膜的拉曼表征和内应力

为了探讨膜厚对四面体非晶碳薄膜拉曼结构表征和内应力的影响规律，进而确定应力与拉曼光谱之间的关系，采用过滤阴极真空电弧技术以相同的工艺条件在P（100）单晶抛光硅衬底上制备了从3nm～350nm不同厚度的四面体非晶碳薄膜。利用表面轮廓仪和原子力显微镜测试膜厚，表面轮廓仪确定曲率半径并计算薄膜应力，共聚焦拉曼光谱表征薄膜的结构细节。实验发现，随着膜厚的增加，四面体非晶碳薄膜的应力持续下降，当膜厚超过30nlll时，应力的下降趋势变得平缓，并保持在小于5GPa的较低水平。随着膜厚的增加，可见光拉曼光谱中衬底硅的一阶和二阶谱峰强度逐渐降低，在50nm～80nm膜厚范围，半高宽最窄，峰强最高，能够最有效地获得拉曼结构信息。随着膜厚的增加和应力的下降，非晶碳一阶谱峰的峰位表现为逐渐向低频偏移。     

Correlations between substrate bias, microstructure and surface morphology of tetrahedral amorphous carbon films

The microstructure and surface morphology of ta-C films deposited on p-type (1 0 0) single crystal silicon with the substrate negative bias varying from 0 to 2000 V by the filtered cathodic vacuum arc technology have been investigated by means of Raman spectroscopy and atomic force microscope. The optimal deposition process of sp³-rich ta-C films can be confirmed in light of the relations between the coupling coefficients or full-width at half-maximum and the substrate negative bias. The surfaces of these films are uniform and smooth and RMS surface roughness is less than 0.4 nm. At the lower energetic grades, the more the content of sp³ is in the film, the smoother the surface of the film is. The dependence of the surface morphology and the impinging energy of the species can be illustrated according to the subimplantation growth mechanism. Nevertheless at the high energetic grade, the impinging ions with appropriate energy sputter and smoothen the surface so that the roughness might be even lower than the one of the films with the richest sp³ component.     

A tribological study of tetrahedral amorphous carbon films prepared by filtered cathodic vacuum arc technique

In this study, a series of tetrahedral amorphous carbon films (ta-C) were deposited on silicon, W18Cr4 V high-speed and Cr18Ni9 stainless steel substrates respectively by using pulsed filtered cathodic vacuum arc system with a MEVVA source, and ta-C film’s tribological properties, including the structure, mechanical performance, adhesion, friction and wear character, were investigated. The results show: the hardness and elastic modulus of ta-C film on a high-speed substrate were reached to 76 and 453 Gpa, respectively; and the effects of substrate and film thickness on ta-C film’s friction coefficients have been studied as well; moreover, the corresponding adhesion damage mechanism and wear damage mechanism have been investigated, respectively.     

Stripping voltammetric behavior of nitrogen-doped tetrahedral amorphous carbon thin film electrodes in NaCl solutions

Conductive nitrogen-doped tetrahedral amorphous carbon (ta-C:N) thin films fabricated with a filtered cathodic vacuum arc technique were investigated for their ability to detect multiple trace heavy metals such as mercury, copper and lead by linear sweep anodic stripping voltammetry in sodium chloride aqueous solutions. The ta-C:N film electrodes exhibited a significant stripping response for determination of individual elements (Pb²⁺ and Hg²⁺) and multiple elements (Pb²⁺ + Hg²⁺ and Cu²⁺ + Hg²⁺), indicating that these electrodes have a great potential for simultaneously tracing multiple heavy metals in aqueous solutions.     

过滤阴极真空电弧法制备四面体非晶碳薄膜

利用离面双弯曲过滤阴极其空电弧沉积系统，在Ф200mm单晶硅片上制备四面体非晶碳薄膜。利用Dectek3型表面轮廓仪检验膜厚均匀性(小于5％)，并利用扫描电子显微镜(SEM)、原子力显微镜(AFM)、激光拉曼光谱(Raman)、X射线光电子谱(XPS)以及纳米压痕(Nano—Indenter)仪器测试薄膜的性能和结构。结果表明：试验制备的薄膜是四面体非晶碳薄膜，其中sp^3键含量高达80％以上，薄膜表面纯净，几乎没有大颗粒的污染，表面粗糙度(Rq)小于0．3nm(取样面积1μm^2)，薄膜硬度可达50GPa，杨氏弹性模量高于550GPa。     

纳米金增强掺磷四面体非晶碳膜的电化学活性

采用电沉积法在过滤阴极真空电弧技术合成的掺磷四面体非晶碳(ta-C∶P)薄膜表面沉积纳米金团簇,制备纳米金修饰的掺磷非晶碳(Au/ta-C∶P)薄膜电极。利用X射线光电子能谱、拉曼光谱、扫描电子显微镜和电化学伏安法表征ta-C∶P和Au/ta-C∶P的微观结构、表面形貌和电化学行为。结果表明,-80V的脉冲偏压更利于磷原子进入碳的网络,并明显增加薄膜的电导率和电化学活性。纳米金团簇可增加ta-C∶P电极的有效面积,提高对铁氰化钾氧化还原反应的活性和电极可逆性,增强对多巴胺的催化活性。研究结果揭示ta-C∶P和Au/ta-C∶P薄膜在电分析及生物传感器方面的潜在应用。     

Structural and surface energy analysis of nitrogenated ta-C films

Surface and bulk properties of the Filtered Cathodic Vacuum Arc prepared nitrogenated tetrahedral amorphous carbon (ta-C:N) films were characterized by X-ray Photoelectron Spectroscopy (XPS), Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS), Raman spectroscopy, Atomic Force microscopy and contact angle techniques. An increase in the Nitrogen (N) content of the films is accompanied by a reduction in the sp³ fraction, confirmed via the deconvolution of the C 1 s XPS spectra. Critical Raman parameters such as peak position and peak width of the G band, defect ratio, I_D/I_G and skewness of the G line were analyzed as a function of N content. ToF-SIMS showed the variance of chemical composition with the increase in the sputtering depth. While some amount of incorporated oxygen and hydrogen were observed for all films; for high N content ta-C:N films signature of CN bonds was evident. Surface energies (both polar and dispersive components) for these ta-C:N films were analyzed in a geometric mean approach. Contact angle measurements using both deionized water and ethylene glycol reveal that upon the insertion of nitrogen into ta-C films, the initial change in the contact angle is sharp, followed by a gradual decrease with subsequent increase in N content. The variation of contact angle with increasing N content corresponds to an increase of the total surface energy with an increase of the polar component and a decrease of the dispersive component.     

Effect of ambient gaseous environment on the properties of amorphous carbon thin films

Amorphous carbon films have been deposited by filtered cathodic jet carbon arc technique under different gaseous environments. Scanning electron microscope and atomic force microscope studies have been performed on the deposited films for the surface morphological studies. The morphology of the deposited film changes with the change in gas environment. X-ray photoelectron spectroscopic (XPS) and Raman studies have been carried out on the deposited samples for the evaluation of the chemical bonding of carbon atoms with the ambient gas atoms. The sp³ and sp² contents have been evaluated from the XPS studies and found to be dependent on the gaseous environment. The film deposited under hydrogen environment has the highest value of the sp³ content (54.6 at.%) whereas the film deposited under helium environment has the lowest value of sp³ content (37 at.%). For the evaluation of the electrical and mechanical properties of the deposited films, the electrical conductivity and nanoindentation measurements have been performed on the deposited films. It has been observed that the film deposited under helium environment has the highest electrical conductivity and the lowest hardness (∼15 GPa) value whereas film deposited under hydrogen environment has the highest hardness (∼21 GPa) and the lowest conductivity.     

Raman characterization of boron doped tetrahedral amorphous carbon films

Boron doped tetrahedral amorphous carbon films, having boron content from 0.59 to 6.04 at.%, have been prepared by a filtered cathodic vacuum arc system using boron mixed graphite targets. The influence of boron on the surface morphologies and microstructures of the films was studied by atomic force microscopy and Raman spectroscopy. The surface images showed that the irregular tops on the surface of the films tended to form larger clusters as boron content increased. The Raman spectra of the films were, respectively, deconvoluted using Gaussian and Breit-Wigner-Fano line shapes. The Raman parameters, including the intensity ratios, peak positions, peak widths and coupling coefficients, obtained from both line shapes were described and compared. It was found that both line shapes could produce consistent results except the peak widths of G bands. The major effect of boron introduction was to increase the clustering of the sp² phase in the films.     

Solvothermal approach for low temperature deposition of aluminium oxide thin films

At elevated pressure, stoichiometric and high quality Al₂O₃ thin films are fabricated at 65-105 °C. By using pre-organised single source precursor aluminium(III) diisopropylcarbamate, Al₂O₃ were deposited on the surface of a Si substrate in a single step in the liquid phase. Comprehensive removal of large carbamate ligands by proposed β-elimination during decomposition of precursor led to an effective delivery of enshrouded Al-O fragments. Scanning electron microscopy revealed dense and grainy surface morphology. The thicknesses of the films were measured to be 150-300 nm and independent to reaction temperatures or reaction times. Through the use of near edge X-ray absorption fine structure spectroscopy, Al absorption peaks suggest a short range crystalline formation in a film deposited at 105 °C.     

Electronic structure of amorphous InGaO3(ZnO)0.5 thin films

The electronic structure of amorphous semiconductor InGaO₃(ZnO)_0.5 thin films, which were deposited by radio-frequency magnetron sputtering process, was investigated using X-ray photoelectron spectroscopy and O K-edge X-ray absorption spectroscopy. The overall features of the valence and conduction bands were analyzed by comparing with the spectra of Ga₂O₃, In₂O₃, and ZnO films. The valence and conduction band edges are mainly composed of O 2p and In 5sp states, respectively. The bandgap of the films determined by spectroscopic ellipsometry was approximately 3.2 eV. Further, it is found that the introduction of oxygen gas during the sputter-deposition does not induce significant variations in the chemical states and band structure.     

Optical and ferromagnetic characteristics of Mn doped ZnO thin films grown by filtered cathodic vacuum arc technique

Mn doped ZnO (ZnO:Mn) thin films with ~ 10 at.% of Mn were grown on quartz substrates by filtered cathodic vacuum arc (FCVA) technique at low substrate temperature (≤ 200 °C). The influence of substrate temperature and oxygen flow rate on the optical, electrical and magnetic properties of the ZnO:Mn thin films was studied. Both room temperature ferromagnetism and ultraviolet photoluminescence were observed in all films. A maximum saturation moment of 2.9 × 10⁻²⁴ A m²/Mn can be achieved for the films grown in an optimum condition. This suggests that the fabrication of high-quality ZnO:Mn films by FCVA technique has the potential to realize efficient magneto-optic devices operating at ultraviolet regime.     

Effect of deposition temperature on chemical composition and electronic properties of amorphous carbon nitride (a-CNx) thin films grown by plasma assisted pulsed laser deposition

The effect of deposition temperature and nitrogen inclusion in amorphous carbon (a-C) films, deposited by plasma enhanced pulsed laser deposition, on chemical composition and electronic transport has been studied. a-CNx films were deposited on Si (100) by pulsed ArF laser ablation of a graphite target, under N₂ atmosphere. A radiofrequency (13.56 MHz RF) apparatus was used to generate plasma of excited nitrogen species, and its effect on nitrogen uptake and CNx film formation has been studied. Chemical and micro-structural changes associated to increased deposition temperature and nitrogen incorporation were examined by x-ray photoelectron spectroscopy; electrical properties were analyzed by the four-point-probe methods. Temperature-dependent conductivity measurements are tentatively interpreted and discussed in reference to chemical composition.     

Reflectance and photoluminescence spectra of as grown and hydrogen and nitrogen incorporated tetrahedral amorphous carbon films deposited using an S bend filtered cathodic vacuum arc process

The study of reflectance and photoluminescence (PL) spectra of as grown and also hydrogen and nitrogen incorporated tetrahedral amorphous carbon (ta-C) films, deposited using an S bend filtered cathodic vacuum arc process is reported here. First the effect of negative substrate bias on the properties of as grown ta-C films and next the effect of varying hydrogen and nitrogen partial pressure at a high substrate bias of − 300 V on the properties of hydrogen and nitrogen incorporated ta-C (ta-C:H and ta-C:N) films are reported for the first time. The values of the optical band gap (E_g) evaluated using the reflectance spectra were found to decrease with the increase of the substrate bias in the as grown ta-C films. Hydrogen incorporation up to 1.9 × 10^− 2 Pa partial pressure in as grown ta-C films increased the values of E_g and beyond which the values of E_g decreased while the nitrogen incorporation up to 3.0 × 10^− 1 Pa partial pressure has no effect on the E_g values. The PL spectra indicated a strong peak at ∼2.66 eV in as grown ta-C films deposited at − 20 V substrate bias. This main peak was found to shift to higher energy with the increase of the substrate bias up to − 200 V and thereafter the PL peak shifted towards the lower energy. Other peak at 3.135 eV starts appearing and this is found to start shifting to higher energy for films deposited at higher substrate bias. The intensity of the main PL peak was enhanced at low temperature and several other peaks started appearing in place of the broad peak at ∼3.16 eV. The peak width and area of both the main peak were found to decrease with the increase of substrate bias in as grown ta-C films and with the increase of the hydrogen and nitrogen partial pressure used in depositing ta-C:H and ta-C:N films. The current models on the source of luminescence in amorphous carbon have been discussed.     

Characterization of ultra-thin TiO2 films grown on Mo(112)

Ultra-thin TiO₂ films were grown on a Mo(112) substrate by stepwise vapor depositing of Ti onto the sample surface followed by oxidation at 850 K. X-ray photoelectron spectroscopy showed that the Ti 2p peak position shifts from lower to higher binding energy with an increase in the Ti coverage from sub- to multilayer. The Ti 2p peak of a TiO₂ film with more than a monolayer coverage can be resolved into two peaks, one at 458.1 eV corresponding to the first layer, where Ti atoms bind to the substrate Mo atoms through Ti-O-Mo linkages, and a second feature at 458.8 eV corresponding to multilayer TiO₂ where the Ti atoms are connected via Ti-O-Ti linkages. Based on these assignments, the single Ti 2p_3/2 peak at 455.75 eV observed for the Mo(112)-(8 × 2)-TiO_x monolayer film can be assigned to Ti³⁺, consistent with our previous results obtained with high-resolution electron energy loss spectroscopy.     

衬底偏压对四面体非晶碳膜结构和性能的影响

采用过滤阴极真空电弧技术并施加一定的衬底负偏压,在P(100)单晶硅片上制备出四面体非晶碳薄膜利用可见光Raman光谱研究薄膜的结构,通过BWF函数描述的单斜劳伦兹曲线拟合数据并获得表征曲线非对称性的耦合系数,从而反映了薄膜中sp3杂化的含量分别用原子力显微镜和纳米压入仪研究薄膜的表面形态和力学性能.结果表明:当衬底偏压为-80V时,薄膜中sp3杂化的含量最多,均方根表面粗糙度值最低(Rq=0.23nm),硬度、杨氏模量和临界刮擦载荷也最大,分别为51.49GPa、512.39GPa和11.72mN.随着衬底偏压的升高或降低,sp3键的含量减少,其它性能指标也分别降低.     

Orientation of B-C-N hybrid films deposited on Ni (111) and polycrystalline Ti substrates explored by X-ray absorption spectroscopy

Orientation of sp²-bonded boron carbonitride (BCN) hybrid films has been investigated. The films were synthesized on Ni (111) and polycrystalline Ti substrates by radio frequency plasma enhanced chemical vapor deposition using tris-dimethylamino borane as a single-source molecular precursor. The deposition was performed at the radiofrequency power 400-800 W at the working pressure 2.6 Pa. Formation of sp²-BCN hybrids in the samples was confirmed by X-ray diffraction (XRD). In the XRD profile, the peak at 26.3° revealed formation of crystalline phase in the samples in which the lattice planes are separated from each other by around 3.5 Å. The D band at ~ 1350 cm^− 1 and the G band at ~ 1570 cm^− 1 in Raman spectra also suggested presence of graphite-like sp²-B-C-N hybrid bonds. The films were composed of different B-N, B-C, and C-N bonds to form sp²-BCN atomic hybrids confirmed by X-ray photoelectron spectra. Orientation and local structures of the films were studied by near-edge X-ray absorption fine structure (NEXAFS) measurements. The dominant presence of π* and σ* resonance peaks of the sp² hybrid orbitals in B K-edge NEXAFS spectra revealed preferred formation of sp²-BCN atomic hybrids around B atoms like-BN₃ configuration in respect to the plane of Ni (111) substrate. Different orientations were suggested on the basis of polarization dependence of B K-edge and N K-edge of the NEXAFS spectra.     

Structural properties of low-temperature grown ZnO thin films determined by X-ray diffraction and X-ray absorption spectroscopy

The epitaxial growth of ZnO thin films on Al₂O₃ (0001) substrates have been achieved at a low-substrate temperature of 150 °C using a dc reactive sputtering technique. The structures and crystallographic orientations of ZnO films varying thicknesses on sapphire (0001) were investigated using X-ray diffraction (XRD). We used angle-dependent X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to examine the variation of local structure. The XRD data showed that the crystallinity of the film is improved as the film thickness increases and the strain is fully released as the film thickness reached about 800 Å. The Zn K-edge XANES spectra of the ZnO films have a strong angle-dependent spectral feature resulting from the preferred c-axis orientation. The wurtzite structure of the ZnO films was explicitly shown by the XRD and EXAFS analysis. The carrier concentration, Hall mobility and resistivity of the 800 Å-thick ZnO film were 1.84 × 10¹⁹ cm^− 3, 24.62 cm²V^− 1s^− 1, and 1.38 × 10^− 2 Ω cm, respectively.     

Nanosecond UV laser graphitization and delamination of thin tetrahedral amorphous carbon films with different sp/sp content

We have produced hydrogen-free tetrahedral amorphous carbon films with different densities and Young's modulus by coating silicon with a filtered vacuum arc under different angles. The films were modified with a pulsed laser (wavelength 355 nm) into sp² rich amorphous carbon and nano crystalline carbon films. The graphitization threshold of the films depends on the film thickness as well as on the carbon density. Simulations of the optical absorption of the different carbon films permitted to confirm the experimental results. On the other side, the delamination threshold of carbon films increases with the film thickness and was found to be controlled by thermal properties of the film. The thin film graphitization and delamination is investigated by optical microscopy, atomic force microscopy, scanning electron microscopy and Raman spectroscopy.     

磁过滤真空弧源沉积C/C多层复合膜的结构和力学性能研究

采用磁过滤直流阴极真空弧源沉积技术在不锈钢基体表面制备了C/C多层复合膜,通过X射线光电子能谱、Raman光谱对薄膜的结构进行表征;C/C多层膜大气下的摩擦损性能在销盘式摩擦磨损试验机上进行;用洛氏压痕法研究了薄膜与基体的结合强度.结果表明：C/C多层复合膜为类金刚石结构.它与SiC球大气下的摩擦系数为0.10左右,其摩损性能由于多层膜的引入而显著提高.Ti过渡层的引入显著提高了膜基结合力.