Fe纳米颗粒嵌埋对类金刚石薄膜结构及电学性能的影响

 采用脉冲激光气相沉积方法制备了不同Fe嵌埋浓度的Fe: DLC多层纳米复合薄膜。用X射线光电子能谱仪(XPS)对薄膜的组成成分进行分析。利用透射电子显微镜（TEM）、拉曼光谱、电流-电压曲线研究Fe纳米颗粒嵌埋对薄膜的微观结构及电学性能的影响。XPS和TEM表明,Fe纳米颗粒周期性地均匀地嵌埋在碳薄膜中。拉曼光谱表明薄膜中的C为典型的类金刚石结构,Fe纳米颗粒促进芳香环式结构的形成,薄膜结构的有序度提高。电流 电压曲线表明,Fe纳米颗粒的嵌埋导致薄膜的室温电导率增加。     

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     

Characterization of doped diamond-like carbon films deposited by hot wire plasma sputtering of graphite

Diamond-like carbon (DLC) films doped with nitrogen and oxygen were deposited on silicon(100) and polytetrafluoroethylene (PTFE) substrates by hot wire plasma sputtering of graphite. The morphology and chemical composition of deposited films has been characterized by scanning electron microscopy, XPS, Auger, FTIR spectroscopy and micro-Raman scattering. Plasmon loss structure accompanying the XPS C 1s peak and electron energy loss spectroscopy (EELS) in reflection mode was used to study the fraction of sp³ bonded C atoms and the density of valence electrons. Raman spectra show two basic C–C bands around 1575 cm^-1 (G line) and 1360 cm^-1 (D line) . Auger depth profiling spectroscopy was used to measure the spatial distributions of C, N and O atoms in the surface layer of DLC films. The fraction of sp³ bonded atoms of about 40% was detected in DLC films by XPS plasmon loss and EELS techniques. Nitrile and iso-nitrile groups observed in FTIR spectra demonstrated the existence of sp bonded carbon in doped DLC films. The typical for DLC films specific density 1.7–1.8 g/cm³ was obtained from EELS and XPS data. PACS 52.77.Dq; 81.65.-b; 82.80.Pv     

Electrodeposition of diamond-like amorphous carbon films on aluminum from acetonitrile

Diamond-like carbon (DLC) films were electrodeposited on aluminum from acetonitrile with a pulse-modulated power at room temperature. The films were grey with 1 7m in thickness. The resistivity of the films was of the order of 10⁷ Q cm The films were characterized by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XPS shows that the main composition of the films is carbon. Raman spectra indicate that typical DLC films were formed when high potential (>800 V) was applied.     

Electrical conductivity of nitride carbon films with different nitrogen content

The electrical conductivity of nitride carbon (DLC: N) films has been studied. It is found that the electrical conductivity of the deposited films increases slowly with increasing nitrogen content, however, it decreases after the nitrogen content in the film reaches a certain value of 12.8 at%. Thermal treatment results show that the electrical conductivity of the lowly nitrogen doped DLC film increases rapidly, while that of the heavily doped film decreases after annealing at 300 °C for 30 min. Raman and XPS spectra results show that when the nitrogen content in the films reaches a certain value, there appears nonconductive phases. Therefore the electrical conductivity of the heavily doped films decreases. FTIR spectra analysis results show that the nitrogen atom as an impurity center undergoes an ‘activation’ process during the thermal treatment, which leads to the increase of the electrical conductivity. Therefore, the nitrogen in these two kinds of films has different effects on the electrical conductivity.     

Mechanical properties and platelet adhesion behavior of diamond-like carbon films synthesized by pulsed vacuum arc plasma deposition

Diamond-like carbon (DLC) is an attractive biomedical material due to its high inertness and excellent mechanical properties. In this study, DLC films were fabricated on Ti6Al4V and Si(1 0 0) substrates at room temperature by pulsed vacuum arc plasma deposition. By changing the argon flow from 0 to 13 sccm during deposition, the effects of argon flow on the characteristics of the DLC films were systematically examined to correlate to the blood compatibility. The microstructure and mechanical properties of the films were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) surface analysis, a nano-indenter and pin-on-disk tribometer. The blood compatibility of the films was evaluated using in vitro platelet adhesion investigation, and the quantity and morphology of the adherent platelets was investigated employing optical microscopy and scanning electron microscopy.The Raman spectroscopy results showed a decreasing sp³ fraction (an increasing trend in I_D/I_G ratio) with increasing argon flow from 0 to 13 sccm. The sp³:sp² ratio of the films was evaluated from the deconvoluted XPS spectra. We found that the sp³ fraction decreased as the argon flow was increased from 0 to 13 sccm, which is consistent with the results of the Raman spectra. The mechanical properties results confirmed the decreasing sp³ content with increasing argon flow. The Raman D-band to G-band intensity ratio increased and the platelet adhesion behavior became better with higher flow. This implies that the blood compatibility of the DLC films is influenced by the sp³:sp² ratio. DLC films deposited on titanium alloys have high wear resistance, low friction and good adhesion.     

Structural modifications of diamond like carbon films induced by MeV nitrogen ion irradiation

Diamond-like carbon (DLC) films were deposited on Si(1 0 0) substrates using plasma deposition technique. The deposited films were irradiated using 2 MeV N⁺ ions at fluences of 1×10¹⁴, 1×10¹⁵ and 5×10¹⁵ ions/cm². Samples have been characterized by using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). Analysis of Raman spectra shows a gradual shift of both D and G band peaks towards higher frequencies along with an increase of the intensity ratio, I(D)/I(G), with increasing ion fluence in irradiation. These results are consistent with an increase of sp² bonding. XPS results also show a monotonic increase of sp²/sp³ hybridization ratio with increasing ion fluence. Plan view TEM images show the formation of clusters in the irradiated DLC films. HRTEM micrographs from the samples irradiated at a fluence of 5×10¹⁵ ions/cm² show the lattice image with an average interplanar spacing of 0.34 nm, revealing that the clusters are graphite clusters. The crystallographic planes in these clusters are somewhat distorted compared to the perfect graphite structure.     

Correlation between substrate bias, growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon films

We investigate the growth process and structural properties of phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films which are deposited at different substrate biases by filtered cathodic vacuum arc technique with PH₃ as the dopant source. The films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, Raman spectroscopy, residual stress measurement, UV/VIS/NIR absorption spectroscopy and temperature-dependent conductivity measurement. The atomic fraction of phosphorus in the films as a function of substrate bias is obtained by XPS analysis. The optimum bias for phosphorus incorporation is about −80 V. Raman spectra show that the amorphous structures of all samples with atomic-scaled smooth surface are not remarkably changed when PH₃ is implanted, but some small graphitic crystallites are formed. Moreover, phosphorus impurities and higher-energetic impinging ions are favorable for the clustering of sp² sites dispersed in sp³ skeleton and increase the level of structural ordering for ta-C:P films, which further releases the compressive stress and enhances the conductivity of the films. Our analysis establishes an interrelationship between microstructure, stress state, electrical properties, and substrate bias, which helps to understand the deposition mechanism of ta-C:P films.     

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     

Synthesis of DLC films by PLD from liquid target and dependence of film properties on the synthesis conditions

DLC (Diamond-like carbon films) were prepared by pulsed laser ablation of a liquid target at substrate temperatures from 18 to 600°C using 248 nm KrF excimer laser. The sp³ hybridization state carbon formation was additionally promoted by gaseous H₂O₂ flow through the reaction chamber and substrate excitation by the same laser beam. Deposited DLC films were characterised by Raman scattering spectroscopy and atomic force microscopy (AFM). Comparative AFM and Raman study shows that the increase in the content of sp³ type bonding in DLC is in correlation with the increase of the surface roughness of the samples prepared.     

Influence of sulfidation treatment on the structure and tribological properties of nitrogen-doped diamond-like carbon films

The nitrogen-doped diamond-like carbon (DLC) films were deposited on high speed steel (HSS) substrates in the direct current unbalanced magnetron sputtering system. Sulphurized layer was formed on the surface of DLC films by means of liquid sulfidation in the intermixture of urea and thiourea solution in order to improve the tribological properties of DLC films. The influence of sulfidation treatment on the structure and tribological properties of DLC films was investigated in this work. The structure and wear surface morphology of DLC films were analyzed by Raman spectroscopy, XPS and SEM, respectively. It reveals that the treated films are smooth and uniform; and sulfur atoms are bonded chemically. The treated films have broader distribution of Raman spectra in the range of 1000-1800 cm⁻¹ and higher I_D/I_G ratio than the untreated films as a result of the appearance of the crystalline graphite structure after the sulfidation treatment. It is showed that the sp² relative content increase in the treated films from the XPS measurement. The Raman results are consistent with the XPS results. The tribological properties of DLC films were investigated using a ball-on-disk rotating friction and wear tester under dry friction conditions. It is found that the sulfidation concentration plays an important part in the tribological properties of the treated DLC films. The results showed the treated films with low sulfidation concentration have a lower friction coefficient (0.1) than the treated films with high sulfidation concentration (0.26) and the untreated films (0.27) under the same friction testing conditions, which can be attributed to both the presence of sulfur-containing materials and the forming of the mechanical alloyed layer on the wear surface. Adding the dry nitrogen to the sliding surface in the testing system helps the friction coefficient of the treated films with low sulfidation concentration to decrease to 0.04 further in this work. On the basis of the experimental results, it is indicated that the liquid sulfidation technique, which is low-cost, non-polluting and convenience, would be an appropriate method for the surface treatment of DLC films.     

Improving the conductivity of diamond-like carbon films with zinc doping and its material properties

Zinc doped diamond-like carbon (DLC) nanocomposite thin films are fabricated by KrF pulsed laser deposition. Carbon targets containing 3.0, 5.0 and 10.0 atomic percentages of zinc are used as the source for the laser system. Investigation of electrical properties by the four-point probe shows that doping zinc into DLC can lower the electrical sheet resistivity. Microstructural analysis by Raman spectroscopy and XPS show a lower sp³ content but a higher SiC content with an increasing amount of zinc incorporation. The increase of SiC leads to an increase in adhesion strength. Surface roughness of the films also increases while the coefficients of friction for the films do not change.     

等离子体增强化学气相沉积法制备含氢类金刚石膜的紫外Raman光谱和X射线光电子能谱研究

利用脉冲辉光放电的方法,在硅片上采用不同的沉积工艺制备了含氢类金刚石膜层,并采用Raman光谱和X射线光电子能谱(XPS)对膜层进行表征.用Raman光谱仪在波长为325 nm的紫外光源的激励下观察膜层的键结构.紫外Raman光谱对含氢类金刚石膜是非常有用的,它能有效避免可见光Raman光谱测量时的荧光干扰,清晰地得到膜层的D峰和G峰.同时利用XPS分析得到膜层的sp3键含量,并与Raman光谱所得数据进行比较.通过Raman光谱和XPS分析可以发现,在紫外光源的激励下,膜层的G峰峰位向高频移方向移动,G峰峰位、I(D)/I(G),G峰半高宽和sp3键含量之间存在一定的关系.     

Low voltage electrodeposition of diamond like carbon (DLC)

Attempt has been made to deposit diamond like carbon (DLC) films from ethanol through electrodeposition at low voltages (80-300 V) at 1 mm interelectrode separation. The films were characterized by atomic force microscopy (AFM), Scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and Auger electron Spectroscopy (AES). AFM investigations revealed the grain sizes are of tens of nanometers. The films were found to be continuous, smooth and close packed. Presence of peaks at 2958, 2929 and 2869 cm⁻¹ in FTIR spectrum indicates the bonding states to be of predominantly sp³ type (C-H). Raman spectroscopy analysis revealed two broad bands at ∼1350 and ∼1570 cm⁻¹. The downshift of the G-band of graphite is indicative of presence of DLC. Analysis of the Raman spectra for the samples revealed an improvement in the film quality with increase in the voltage. Micro Raman investigations indicate the formation of diamond phase at the deposition potential of 80 V. The sp² contents the films calculated from Auger electron spectra were calculated and were found to be 31, 19 and 7.8% for the samples prepared at 80, 150 and 300 V, respectively. A tentative mechanism for the formation of DLC has been proposed. These results indicate the possibility of deposition of DLC at low voltage.     

Formation of CNx thin films by reactive pulsed laser deposition assisted by electron cyclotron resonance microwave discharge

Amorphous carbon nitride thin films were synthesized by pulsed laser deposition combined with electron cyclotron resonance (ECR) microwave discharge in nitrogen gas. The ECR discharge supplies active nitrogen species in the deposition environment and to the growing film surface, enhancing the film growth in complex processes accompanied by chemical reaction. The synthesized films were characterized by Rutherford backscattering spectroscopy (RBS), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and Raman spectroscopy. The films were determined to consist purely of carbon and nitrogen with a nitrogen concentration of 42%, and have a thickness of 550 nm over which carbon and nitrogen are well distributed. Structural characterizations based on XPS, FTIR and Raman analysis showed that these films appear to contain several bonding configurations between carbon and nitrogen with a small amount of C≡N bonds compared with other bonding states. Received: 31 August 2000 / Accepted: 12 December 2000 / Published online: 23 May 2001     

Effect of phosphorus content on structural properties of phosphorus incorporated tetrahedral amorphous carbon films

With phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films prepared using filtered cathodic vacuum arc technique with PH₃ as the dopant source, we investigate the effect of phosphorus content on the structural properties of the films by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XPS analysis indicates that a function is established between the atomic fraction of phosphorus in the samples and the flow rate of PH₃ during deposition, and that phosphorus implantation increases the graphite-like trihedral sp² bonds deduced from fitted C 1s and P 2p core level spectra. Raman spectra of a broad range show that there are two notable features for all ta-C:P films: the first-order band centered at about 1560 cm^-1 and the second-order band between 2400 and 3400 cm^-1. The broad first-order band demonstrates that the amorphous structure of all samples does not remarkably change when a lower flow rate of PH₃ is implanted, while a higher concentration of phosphorus impurity enhances the clustering of sp² sites dispersed in sp³ skeleton and the evolution of structural ordering. Furthermore, the second-order Raman spectra confirm the formation of small graphitic crystallites in size due to a finite-crystal-size effect. PACS 81.05.Uw; 81.15.Ef; 63.50.+x     

Nitrogen 1s electron binding energy assignment in carbon nitride thin films with different structures

Carbon nitride thin films deposited by dc unbalanced magnetron sputtering have been analyzed by high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS data show that N 1s binding states depend on substrate temperature (T_s). By comparison with the Raman spectra, N 1s binding states are assigned in which nitrogen atoms are mainly bound to sp² and sp³ carbon atoms at T_s = 100°C, whereas at T_s = 500°C nitrogen atoms are mainly bonded to sp², sp³ and sp¹ carbon atoms.     

Low energy repetitive miniature plasma focus device as high deposition rate facility for synthesis of DLC thin films

Diamond-like carbon (DLC) films were deposited on Si (1 0 0) substrate using a low energy (219 J) repetitive (1 Hz) miniature plasma focus device. DLC thin film samples were deposited using 10, 20, 50, 100 and 200 focus shots with hydrogen as filling gas at 0.25 mbar. The deposited samples were analyzed by XRD, Raman Spectroscopy, SEM and XPS. XRD results exhibited the diffraction peaks related to SiO₂, carbon and SiC. Raman studies verified the formation amorphous carbon with D and G peaks. Corresponding variation in the line width (FWHM) of the D and G positions along with change in intensity ratio (I_D/I_G) in DLC films was investigated as a function of number of deposition shots. XPS confirmed the formation sp² (graphite like) and sp³ (diamond like) carbon. The cross-sectional SEM images establish the 220 W repetitive miniature plasma focus device as the high deposition rate facility for DLC with average deposition rate of about 250 nm/min.     

Polymeric like carbon films prepared from liquid gas and the effect of nitrogen

Polymeric like carbon (PLC) films are grown by a capacitance coupled RF-PECVD on the grounded electrode at room temperature from liquid gas (40% propane and 60% butane) in two regimes with nitrogen and without nitrogen gas. Films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Fourier transform infrared (FTIR) absorption and Raman spectroscopy. The result of FTIR analyses indicates that more than 90% of hydrogen atoms are bonded to carbon with sp³ hybridization. The abundance of CH₃ is more than that of CH₂ and this one is more than that of CH for carbon with sp³ hybridization in these films. The C 1s line of the XPS spectra is deconvoluted to several peaks that are attributed to the CH₃, CH₂ and CH terminations. The result of this deconvolution is consistent with FTIR results. AFM images show that the mean nanoparticle size is reduced from about 100 nm for films without nitrogen to less than 80 nm for films with nitrogen. This is in agreement with our Raman results. By addition of nitrogen to the feed gas, no variation in the C-H stretching vibration mode is observed. The effect of N-H bonds is observable in both FTIR and XPS spectra and a very small trace of N-C bonds is present only in deconvolution of N 1s line of XPS spectra. These results indicate that by addition of nitrogen to feed gas, internal structure of a-C:H nanoparticles is not changed but particle size is decreased. We suggest that the internal stress reduction due to nitrogen addition in the feed gas for PLC films can be related to decreasing of the a-C:H particle size.     

Diamond-like carbon layer formation on graphite by excimer laser irradiation

2 fluence results in the formation of a thin hydrogen-free diamond-like carbon (DLC) film on the surface. The density of the laser-formed DLC layer is approximately 2.8 g/cm³, as calculated from area-selective Raman spectroscopy and atomic force microscopic (AFM) measurements. The proportion of the sp³ hybrid states of carbon is estimated to be approximately 50%. Annealing in air at 650 °C for 30 min recovers the graphite structure. Received: 26 March 1998/Accepted: 27 March 1998