a-C∶H(N)薄膜结构的X射线光电子能谱分析

采用直流-射频等离子增强化学汽相沉积技术制备a-C∶H(N)薄膜，用X射线光电子能谱研究了混合气体中N₂含量对薄膜成分与结构的影响.a-C∶H(N)薄膜中含氮量可达9.09%.对a-C∶H(N)薄膜的C1s和N1s结合能谱的分析表明a-C∶H(N)薄膜的结构是由C₃N₄相镶嵌在sp²键结合的CN_x基体中组成.其中C₃N₄相中N和C原子比接近4∶3，不随薄     

Functionalization of hydrogen-free diamond-like carbon films using open-air dielectric barrier discharge atmospheric plasma treatments

A dielectric barrier discharge (DBD) technique has been employed to produce uniform atmospheric plasmas of He and N₂ gas mixtures in open air in order to functionalize the surface of filtered-arc deposited hydrogen-free diamond-like carbon (DLC) films. XPS measurements were carried out on both untreated and He/N₂ DBD plasma-treated DLC surfaces. Chemical states of the C 1s and N 1s peaks were collected and used to characterize the surface bonds. Contact angle measurements were also used to record the short- and long-term variations in wettability of treated and untreated DLC. In addition, cell viability tests were performed to determine the influence of various He/N₂ atmospheric plasma treatments on the attachment of osteoblast MC3T3 cells. Current evidence shows the feasibility of atmospheric plasmas in producing long-lasting variations in the surface bonding and surface energy of hydrogen-free DLC and consequently the potential for this technique in the functionalization of DLC-coated devices.     

Structure and hardness of a-C:H films prepared by middle frequency plasma chemical vapor deposition

a-C:H films were prepared by middle frequency plasma chemical vapor deposition (MF-PCVD) on silicon substrates from two hydrocarbon source gases, CH₄ and a mixture of C₂H₂ + H₂, at varying bias voltage amplitudes. Raman spectroscopy shows that the structure of the a-C:H films deposited from these two precursors is different. For the films deposited from CH₄, the G peak position around 1520 cm⁻¹ and the small intensity ratio of D peak to G peak (I(D)/I(G)) indicate that the C-C sp³ fraction in this film is about 20 at.%. These films are diamond-like a-C:H films. For the films deposited from C₂H₂ + H₂, the Raman results indicate that their structure is close to graphite-like amorphous carbon. The hardness and elastic modulus of the films deposited from CH₄ increase with increasing bias voltage, while a decrease of hardness and elastic modulus of the films deposited from a mixture of C₂H₂ + H₂ with increasing bias voltage is observed.     

Chemical and morphological difference between TiN/DLC and a-C:H/DLC grown by pulsed vacuum arc techniques

In order to improve the adherence of DLC films, interlayers of amorphous hydrogenated carbon (a-C:H) and titanium nitride (TiN) were deposited by means of the pulsed vacuum arc technique. Bilayers were obtained by using a carbon target of 99.98% of purity in mixtures of (Ar + CH₄) and (Ar + H₂) for producing a-C and DLC, respectively and a target of titanium of 99.999% in a mixture of (Ar + N₂) for growing TiN. After the deposition, chemical and morphological differences between TiN/DLC and a-C:H/DLC bilayers grown on silicon and stainless steel 304 were studied using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and scanning probe microscopy (SPM) techniques. XPS analysis showed a difference in sp³/(sp²+sp³) bonds ratio for each bilayer, being 0.67 for TiN/DLC and 0.45 for a-C:H/DLC bilayers. sp³ and sp² bonds were also observed by the FTIR technique. SPM images, in atomic force microscopy (AFM) and lateral force microscopy (LFM) modes were carried out for illustrating the comparison between TiN/DLC and a-C/DLC morphologic characteristics. Roughness and grain size were studied as a function of the H₂ concentration for both bilayers.     

Chemical modification of the electrical properties of hydrogenated amorphous carbon films

Semiconducting films of hydrogenated amorphous carbon (a-C:H), prepared via the dc glow discharge decomposition of C₂H₂, have been successfully doped via incorporation of B and P during growth. The doping efficiency achieved was comparable to that achieved in a-Si:H produced in a like manner. For a-C:H films deposited at T_d=250C,

(RT) increased from 10^-12 to 10^-7 ohm^-1 cm^-1 when either 1% PH₃ or 10% B₂H₆ were added to the C₂H₂. A shift of the Fermi level E_F of about 0.7 eV is inferred from changes in the “activation” energy of conduction.     

The analysis of structural and electronic environments of silicon network in HWCVD deposited a-SiC:H films

Hydrogenated amorphous silicon carbon alloys (a-SiC:H) films were deposited by hot wire chemical vapour deposition (HWCVD) using SiH₄ and C₂H₂ as precursor gases. a-SiC:H films were characterized by Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Solid-state plasmon of Si network shifts from 19.2 to 20.5 eV by varying C₂H₂ flow rate from 2 to 10 sccm. Incorporation of carbon content changes the valence band structure and s orbital is more dominant than sp and p orbital with carbon incorporation.     

Structure and elastic recovery of Cr-C:H films deposited by a reactive magnetron sputtering technique

Cr-containing hydrogenated amorphous carbon (Cr-C:H) films were deposited on silicon substrates using a DC reactive magnetron sputtering with Cr target in an Ar and C₂H₂ gas mixture. The composition, bond structure, mechanical hardness and elastic recovery of the films were characterized using energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and nano-indentation. The film tribological behavior was also studied by a ball-on-disc tribo-tester. The results showed that the films deposited at low C₂H₂ flow rate (<10 sccm) presented a feature of composite Cr-C:H structure, which consisted of hard brittle chromium carbide phases and amorphous hydrocarbon phase, and thus led to the observed low elastic recovery and poor wear resistance of the films. However, the film deposited at high C₂H₂ flow rate (40 sccm) was found to present a typical feature of polymer-like a-C:H structure containing a large amount of sp³ C-H bonds. As a result, the film revealed a high elastic recovery, and thus exhibited an excellent wear resistance.     

In-depth modifications of implanted amorphous carbon films

Amorphous carbon films (a-C:H) and nitrogen incorporated carbon films [a-C:H(N)] deposited by a self-bias glow discharge have been implanted with 70 keV nitrogen ions at fluences of 0.6, 1 and 2×10¹⁷ N/cm². The in-depth modifications caused by ion implantation were determined by means of nuclear techniques, such as Rutherford Backscattering Spectrometry (RBS), Nuclear Reaction Analysis (NRA) and Elastic Recoil Detection Analysis (ERDA), as well as by Auger Electron Spectroscopy (AES) and Raman scattering. ERDA profiles show that nitrogen implantation causes hydrogen depletion, the amount of which depends on the film composition and on the ion fluence. In a-C:H(N) films nitrogen loss was also measured. The induced structural modifications in both a-C:H and a-C:H(N) films were followed by both AES, using factor analysis, and microprobe Raman spectroscopy. They turn out to be related to the energy deposited by the incident ions. Our results indicate that the ion-beam bombardment causes in both a-C:H and a-C:H(N) films an increase of either the degree of disorder or the ratio between sp²/sp³ bonds across the hydrogen-depleted layer, which depends on the ion fluence.     

Electrochemical corrosion behaviors of a-C:H and a-C:NX:H films

The a-C:H and a-C:N_X:H films were deposited onto silicon wafers using radio frequency (rf) plasma enhanced chemical vapor deposition (PECVD) and pulsed-dc glow discharge plasma CVD, respectively. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize chemical nature and bond types of the films. The results demonstrated that the a-C:H film prepared by rf-CVD (rf C:H) has lower I_D/I_G ratio, indicating smaller sp² cluster size in an amorphous carbon matrix. The nitrogen concentrations of 2.9 at.% and 7.9 at.% correspond to carbon nitride films prepared with rf and pulse power, respectively.Electrochemical corrosion performances of the carbon films were investigated by potentiodynamic polarization test. The electrolyte used in this work was a 0.89% NaCl solution. The corrosion test showed that the rf C:H film exhibited excellent anti-corrosion performance with a corrosion rate of 2 nA cm⁻², while the carbon nitride films prepared by rf technique and pulse technique showed a corrosion rate of 6 nA cm⁻² and 235 nA cm⁻², respectively. It is reasonable to conclude that the smaller sp² cluster size of rf C:H film restrained the electron transfer velocity and then avoids detriment from the exchange of electrons.     

Structural and optical properties of Fe-doped hydrogenated amorphous carbon films prepared from trans-2-butene by plasma enhanced metal organic chemical vapor deposition

Fe-doped hydrogenated amorphous carbon (a-C:H:Fe) films were deposited from a gas mixture of trans-2-butene/ferrocene/H₂ by plasma enhanced metal organic chemical vapor deposition. X-ray photoelectron spectroscopy, Fourier transform infrared spectra and Raman spectra were used to characterize the composition and the bonding structure of the a-C:H:Fe and a-C:H films. Optical properties were investigated by the UV–visible spectroscopy and the photoluminescence (PL) spectra. The Fe-doped films contain more aromatic structures and C=C bonds than the undoped films. The sp ² carbon content and sp ² clustering of the films increase, and aromatic-like rings’ structures become richer after Fe-doping. The Tauc optical gap of the a-C:H:Fe films become narrower by 0.3 eV relative to the value of the a-C:H films. The PL peak shifts from 2.35 eV of the a-C:H films to 1.95 eV of the a-C:H:Fe films, and the PL intensity of the a-C:H:Fe films is greatly enhanced. A deep level emission peak around 2.04 eV of the a-C:H:Fe films is observed.     

Composite SiO2/TiO2 and amine polymer/TiO2 nanoparticles produced using plasma-enhanced chemical vapor deposition

Plasma-enhanced chemical vapor deposition was used to conformally coat commercial TiO₂ nanoparticles to create nanocomposite materials. Hexamethyldisiloxane (HMDSO)/O₂ plasmas were used to deposit SiO₂ or SiO_xC_yH_z films, depending on the oxidant concentration; and hexylamine (HexAm) plasmas were used to deposit amorphous amine-containing polymeric films on the TiO₂ nanoparticles. The composite materials were analyzed using Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). These analyses reveal film composition on the nanoparticles was virtually identical to that deposited on flat substrates and that the films deposit a conformal coating on the nanoparticles. The performance of the nanocomposite materials was evaluated using UV-vis spectroscopy to determine the dispersion characteristics of both SiO_x and HexAm coated TiO₂ materials. Notably, the coated materials stay suspended longer in distilled water than the uncoated materials for all deposited films.     

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.     

含氮氟化类金刚石(FN-DLC)薄膜的研究：(Ⅳ)氮掺杂对薄膜结构的影响

不同条件下，在单晶硅基片上沉积了含氮氟化类金刚石(FN-DLC)薄膜.原子力显微(AFM)形貌显示，掺N后，薄膜变得致密均匀.傅里叶变换吸收红外光谱(FTIR)表明，随着r(r=N₂/［N₂+CF₄+CH₄］)的增大薄膜中C—H键的逐渐减少，C〖FY=,1〗N和C≡N键含量逐渐增加.X射线光电子能谱(XPS)的C1s和N1s峰拟合结果发现，N掺入导致在薄膜中出现β-C₃N₄和a-CN_x(x=1,2,3)成分.Roman散射谱的G峰向高频方向位移和峰值展宽等证明：随着r的增大，薄膜内sp²键态含量增加. 关键词： 氟化类金刚石膜 键结构 氮掺杂     

Raman spectroscopy of a-C:H:N films deposited using ECR-CVD with mixed gas

Ultraviolet (UV) and visible Raman spectroscopy were used to study a-C:H:N films deposited using ECR-CVD with a mixed gas of CH₄ and N₂. Small percentage of nitrogen from 0 to 15% is selected. Raman spectra show that CN bonds can be directly observed at 2220 cm⁻¹ from the spectra of visible and UV Raman. UV Raman enhances the sp¹ CN peak than visible Raman. In addition, the UV Raman spectra can reveal the presence of the sp³ sites. For a direct correlation of the Raman parameter with the N content, we introduced the G peak dispersion by combining the visible and UV Raman. The G peak dispersion is directly relative to the disorder of the sp² sites. It shows the a-C:H:N films with higher N content will induce more ordered sp² sites. In addition, upper shift of T position at 244 nm excitation with the high N content shows the increment of sp² fraction of films. That means the films with high N content will become soft and contain less internal stress. Hardness test of films also confirmed that more N content is with less hardness.     

Ellipsometry,FTIR, Raman and X-Ray Spectroscopy Analysis of PECVD a-Si1-xCx:H Film

Hydrogenated amorphous silicon carbide (a-Si_1-xC_x:H) films were deposited by RF plasma enhanced chemical vapor deposition (PECVD) and subsequently annealed in N₂ atmosphere at different temperatures. Systematic investigations of the deposition temperature and annealing effect on the film's properties, including film thicknesses, optical bandgap, refractive indexes, absorption coefficient (α), chemical bond configurations, stoichiometry and crystalline structures, were performed using ellipsometry, FTIR absorbance spectroscopy, Raman spectroscopy, XPS, and XRD. All of the results indicate that the structural and optical properties of the a-Si_1-xC_x:H film can be effectively engineered by proper annealing conditions. Moreover, molecular vibrational level equation was introduced to explain the peak shift detected by FTIR and Raman spectroscopy.     

Nanomechanical characterization of amorphous hydrogenated carbon thin films

Amorphous hydrogenated carbon (a-C:H) thin films deposited on a silicon substrate under various mixtures of methane-hydrogen gas by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD) was investigated. Microstructure, surface morphology and mechanical characterizations of the a-C:H films were analyzed using Raman spectroscopy, atomic force microscopy (AFM) and nanoindentation technique, respectively. The results indicated there was an increase of the hydrogen content, the ratio of the D-peak to the G-peak (I_D/I_G) increased but the surface roughness of the films was reduced. Both hardness and Young's modulus increased as the hydrogen content was increased. In addition, the contact stress-strain analysis is reported. The results confirmed that the mechanical properties of the amorphous hydrogenated carbon thin films improved using a higher H₂ content in the source gas.     

Simultaneous interaction of methyl radicals and atomic hydrogen with amorphous hydrogenated carbon films, as investigated with optical in situ diagnostics

Methyl radicals (CH₃) and atomic hydrogen (H) are dominant radicals in low-temperature plasmas from methane. The surface reactions of these radicals are believed to be key steps leading to deposition of amorphous hydrogenated carbon (a-C:H) films or polycrystalline diamond in these discharges. The underlying growth mechanism is studied, by exposing an a-C:H film to quantified radical beams of H and CH₃. The deposition or etching rate is monitored via ellipsometry and the variation of the stoichiometry is monitored via isotope labeling and infrared spectroscopy. It was shown recently that, at 320 K, methyl radicals have a sticking coefficient of 10^-4 on a-C:H films, which rises to 10^-2 if an additional flux of atomic hydrogen is present. This represents a synergistic growth mechanism between H and CH₃. From the interpretation of the infrared data, a reaction scheme for this type of film growth is developed: atomic hydrogen creates dangling bonds by abstraction of bonded hydrogen within a surface layer corresponding to the range of H in a-C:H films. These dangling bonds serve at the physical surface as adsorption sites for incoming methyl radicals and beneath the surface as radicalic centers for polymerization reactions leading to carbon–carbon bonds and to the formation of a dense a-C:H film. Received: 18 July 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Modification of polyethylene powder with an organic precursor in a spiral conveyor by hollow cathode glow discharge

Hexamethyldisiloxane (HMDSO) films were deposited on polyethylene (PE, (C₂H₄)_n) powder by hollow cathode glow discharge. The reactive species in different HMDSO/Ar plasmas were studied by optical emission spectroscopy (OES). Increasing the HMDSO fraction in the gas mixture additional compounds like CH_x, OH, SiC and SiO can be identified. After deposition the formed silicon and carbon containing groups (C–O, C=O, SiC and SiO) on the PE powder surface have been analyzed by X-ray photoemission spectroscopy (XPS). Changes in wettability depending on the HMDSO fraction were investigated by contact angle measurements (CAM). The free surface energy of the PE powder decreases with increasing HMDSO fraction in the process gas and encapsulation of the powder particles occurs. An aging effect of the plasma treated PE surface was observed depending on the process gas composition. The higher the HMDSO fraction the less is the aging effect of the plasma treated PE surface.     

Comparison of the X-ray photoelectron and electron-energy-loss spectra of the nitrogen-doped hydrogenated amorphous carbon bond

The composition of nitrogen-doped hydrogenated amorphous carbon (a-C : H : N) films grown in a magnetically confined rf plasma-enhanced chemical vapour deposition system has been determined by X-ray photoelectron spectroscopy (XPS) and compared with that determined using a combination of elastic recoil detection analysis, Rutherford back-scattering and nuclear reaction analysis. The importance of nitrogen doping or 'incorporation' in hydrogenated amorphous carbon (a-C : H) films is discussed in relation to the significant variation in the sp 2 -to-sp 3 ratio that takes place. At 7 at.% N in the a-C : H matrix, a critical change in the microstructure is observed, which governs the resulting mechanical, optical and electronic properties. Finally, the correlation between the sp 2 and sp 3 fractions determined by a non-destructive method of obtaining the bond fractions (XPS) and by electron-energy-loss spectroscopy is discussed, with a view to evaluating accurately the sp 2 fraction in a-C : H : N films.     

Structural and optical properties of the SiCN thin films prepared by reactive magnetron sputtering

Silicon carbonitride (SiCN) thin films were deposited on n-type Si (1 0 0) and glass substrates by reactive magnetron sputtering of a polycrystalline silicon target in a mixture of argon (Ar), nitrogen (N₂) and acetylene (C₂H₂). The properties of the films were characterized by scanning electron microscope with an energy dispersive spectrometer, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectrometry and ultraviolet-visible spectrophotometer. The results show that the C₂H₂ flow rate plays an important role in the composition, structural and optical properties of the films. The films have an even surface and an amorphous structure. With the increase of C₂H₂ flow rate, the C content gradually increases while Si and N contents have a tendency to decrease in the SiCN films, and the optical band gap of the films monotonically decreases. The main bonds are Si-O, N-H_n, C-C, C-N, Si-N, Si-C and Si-H in the SiCN films while the chemical bonding network of Si-O, C-C, C-O, C-N, N-Si and CN is formed in the surface of the SiCN films.