Oxidation of vanadium nitride and titanium nitride coatings

The oxidation of vanadium nitride (VN) and titanium nitride (TiN) coatings in ultra-high vacuum has been investigated in situ by X-ray photoelectron spectroscopy. On the VN coatings mixed oxide layers containing V³⁺ and V⁴⁺ species form at elevated temperatures (?600°C) and at high oxygen exposures, which cover completely the VN surface. Under similar oxidation conditions the TiN surface oxidises partially to a mixture of TiO₂ and Ti oxynitride (TiO_xN_y) phases. This oxidation behaviour has been correlated to the tribological properties of the VN and TiN coatings investigated recently.     

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.     

Substrate temperature influence on the trombogenicity in amorphous carbon nitride thin coatings

Carbon nitride thin films were obtained through plasma assisted physical vapor deposition technique by pulsed arc, varying the substrate temperature and investigating the influence of this parameter on the films hemocompatibility. For obtaining approaches of blood compatibility, environmental scanning electron microscopy (ESEM) was used in order to study the platelets adherence and their morphology. Moreover, the elemental chemical composition was determined by using energy dispersive spectroscopy (EDS), finding C, N and O. The coatings hemocompatibility was evaluated by in vitro thrombogenicity test, whose results were correlated with the microstructure and roughness of the films obtained.During the films growth process, the substrate temperature was varied, obtaining coatings under different temperatures, room temperature (T_room), 100 °C, 150 °C and 200 °C. Parameters as interelectrodic distance, voltage, work pressure and number of discharges, were remained constant. By EDS, carbon and nitrogen were found in the films.Visible Raman spectroscopy was used, and it revealed an amorphous lattice, with graphitic process as the substrate temperature was increased. However, at a critical temperature of 150 °C, this tendency was broken, and the film became more amorphous. This film showed the lowest roughness, 2 ± 1 nm. This last characteristic favored the films hemocompatibility. Also, it was demonstrated that the blood compatibility of carbon nitride films obtained were affected by the I_D/I_G or sp³/sp² ratio and not by the absolute sp³ or sp² concentration.     

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.     

The effect of alloying on the structure and peculiarities of tribological behavior of vacuum-deposited diamond-like coatings

In this work, we report the results of a study of the atomic and crystalline structures, phase and chemical compositions and tribological properties of DLC coatings deposited by plasma-assisted (PA) CVD (a-C:H:Si and a-C:H:Si:Mo) and magnetron reactive sputtering (a-C:H:Cr). The a-C:H:Si:Mo coatings revealed the formation of ultra-dispersed inclusions of either molybdenum carbides or silicides, whereas no such inclusions were found in the a-C:H:Si compound. The a-C:H:Cr coatings that were deposited in an acetylene–nitrogen gas mixture exhibited a nanocomposite structure composed of chromium, its carbide and nitride phases. The tribological tests showed that the DLC coatings with silicon and silicon–molybdenum have a high friction coefficient and a low working performance, while the chromium-containing coatings have high levels of their mechanical and tribological characteristics, making them promising materials for operation under high contact pressures.     

Synthesis of carbon nitride films by direct current plasma assisted pulsed laser deposition

Carbon nitride films were deposited by pulsed laser ablation of a graphite target under a nitrogen atmosphere at room temperature. A direct current discharge apparatus was used to supply active nitrogen species during the deposition of carbon nitride films. The composition and bonding structure of carbon nitride films were determined by Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy. The incorporation of nitrogen atoms in the films is greatly improved by the using of a dc glow discharge. The ratio N/C can reach 0.34 at the discharge voltage of 400 V. Six peaks centered at 1025 cm^-1, 1226 cm^-1, 1381 cm^-1, 1534 cm^-1, 1629 cm^-1, and 2200 cm^-1 can be clearly distinguished from the FTIR spectra of the deposited films, which indicates the existence of C–N, C=N, and C≡N bonds. The fraction of sp² C, C≡N bonds, and C=N bonds in the deposited films increases with increasing discharge voltage. Deconvolution results of C 1s and N 1s spectra also indicate that nitrogen atoms in the films are chemically bonded to sp¹ C, sp² C, and sp³ C atoms. Most of the nitrogen atoms are bonded to sp² C atoms. Increasing the discharge voltage leads to a decrease of the fraction of nitrogen atoms bonded to sp² C and the fraction of amorphous carbon; however, it leads to an increase of the fraction of nitrogen atoms bonded to sp³ C and the fraction of sp² C and sp³ C atoms bonded to nitrogen atoms. Received: 7 June 2000 / Accepted: 19 February 2001 / Published online: 27 June 2001     

Electrical and electronic properties of nitrogen doped amorphous carbon (a-CNx) thin films

Nitrogen-doped amorphous carbon thin films (a-CN_x) were prepared on silicon substrate by pulsed laser deposition process using methane (CH₄) and nitrogen (N₂) as source gas. The electrical properties of a-CN_x films changes with nitrogen concentration in the film structure. The intensity ratio of the D and G peak (I_D/I_G) increases with higher nitrogen concentration, which means that sp²-clusters were formed in these films and is responsible for the enhancement of conductivity of the a-CN_x films. We observed that the amorphous carbon (a-C) films becoming more graphitic in nature yielding higher conductivity/lower resistivity with increase of nitrogen concentration. Electron field emission result shows that the emission current density enhances with nitrogen doping that indicates the useful in electron field emission devices application.     

Correlation of sp and sp fraction of carbon with electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon films

In the present work the correlation of electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon (Ar-DLC) thin films with sp³ and sp² fractions of carbon have been explored. These Ar-DLC thin films have been deposited, under varying C₂H₂ gas pressures from 25 to 75 mTorr, by radio frequency-plasma enhanced chemical vapor deposition technique. X-ray photoelectron spectroscopy studies are performed to estimate the sp³ and sp² fractions of carbon by deconvoluting C 1s core level spectra. Various electrical, optical and nano-mechanical parameters such as conductivity, I-V characteristics, optical band gap, stress, hardness, elastic modulus, plastic resistance parameter, elastic recovery and plastic deformation energy have been estimated and then correlated with calculated sp³ and sp² fractions of carbon and sp³/sp² ratios. Observed tremendous electrical, optical and nano-mechanical properties in Ar-DLC films deposited under high base pressure conditions made it a cost effective material for not only hard and protective coating applications but also for electronic and optoelectronic applications.     

辉光放电等离子体辅助XeCl准分子激光溅射沉积碳氮薄膜

利用直流辉光放电等离子体辅助的脉冲激光沉积技术在Si衬底上生长了碳氮薄膜.通过扫描电子显微镜、X射线衍射、X射线光电子能谱、俄歇电子能谱等多种手段,对薄膜的形貌、成分、晶体结构、价键状态等特性进行了分析和确定.结果表明,沉积薄膜为含有非晶SiN和晶态氮化碳颗粒结构,晶态成分呈多晶态,主要为α-C₃N₄相、β-C₃N₄相,晶粒大小为40—60nm.碳氮之间主要以C-N非极性共价键形式相结合. 关键词： 脉冲激光沉积 直流辉光放电 碳氮薄膜     

Effect of ECR-assisted microwave plasma nitriding treatment on the microstructure characteristics of FCVA deposited ultra-thin ta-C films for high-density magnetic storage applications

There are higher technical requirements for protecting layer of magnetic heads and disks used in future high-density storage fields. In this paper, ultra-thin (2 nm thickness) tetrahedral amorphous carbon (ta-C) films were firstly prepared by filtered cathodic vacuum arc (FCVA) method, then a series of nitriding treatments were performed with nitrogen plasma generated using electron cyclotron resonance (ECR) microwave source. Here it highlighted the influence of nitrogen flow and applied substrate bias voltage on the structural characteristics of ta-C films during the plasma nitriding process. The chemical compositions, element depth distribution profiles, physical structures and bonding configurations of plasma-nitrided ta-C films were investigated by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and UV-vis Raman spectroscopy. The experimental results show that the carbon nitride compounds (CN_x) are formed in nitrogenated ta-C films in which the N content and its depth distribution depends on bias voltage to large extent rather than N₂ flow. The N content of nitrogenated ta-C films can reach 16 at.% for a substrate bias of −300 V and a N₂ flow of 90 sccm. With increasing nitrogen content, there is less G peak dispersion and more ordering of structure. Furthermore, appropriate nitriding treatment (substrate bias: −100 V, N₂ flow: 150 sccm) can greatly increase the fraction of sp³ and sp³C-N bonds, but the values begin to fall when the N content is above 9.8 at.%. All these indicate that suitable ECR-assisted microwave plasma nitriding is a potential modification method to obtain ultra-thin ta-C films with higher sp³ and sp³C-N fractions for high-density magnetic storage applications.     

Comparison and semiconductor properties of nitrogen doped carbon thin films grown by different techniques

Amorphous carbon nitride (a-CN_x) thin films have been synthesised by three different deposition techniques in an Ar/N₂ gas mixture and have been deposited by varying the percentage of nitrogen gas in the mixture (i.e. the N₂/Ar + N₂ ratio) from 0 to 10%. The variation of the electrical conductivity and the gap values of the deposited films versus the N₂/Ar + N₂ ratio were investigated in relation with their local microstructure. Film composition was analysed using Raman spectroscopy and optical transmission experiments. The observed variation of electrical conductivity and optical properties are attributed to the changes in the atomic bonding structures, which were induced by N incorporation, increasing both the sp² carbon content and their relative disorder. The low N content samples seem to be an interesting material to produce films with interesting properties for optoelectronic applications considering the facility to control the gas composition as a key parameter.     

Low voltage electrodeposition of CNx films and study of the effect of the deposition voltage on bonding configurations

Carbon nitride (CN_x) films were deposited from acetonitrile at low voltage (150-450 V) through electrodeposition. The films were characterized by atomic force microscopy (AFM), Raman spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. AFM investigations revealed that the grain size was ∼200 nm and roughness was ∼10 nm. The films were found to be continuous and close packed. IR spectra revealed existence of strong sp³, sp² type bonding and weak sp type carbon nitrogen bonds and these bonds were found to increase with voltage. The fraction of sp³-bonded species in the sample increased in low voltage range and after reaching maximum at 350 V, decreased for higher voltages. However, the concentration of sp² CN ring structures in the film increased with increasing voltage. Also, the peak width decreased at low voltages reaching a minimum and increased thereafter. It was observed that the voltage dependent increase in the concentration of polymeric type sp² CN (chain) structures was much more pronounced than that of graphitic type sp² CN (ring) structures. Raman spectra showed the presence of both the D and G bands. The shift in the G band indicated the presence of nitrogen in the film. The I_D/I_G ratio was found to increase with the incorporation of nitrogen. Auger electron spectroscopy (AES) showed a clear increase in the nitrogen content with increase in the voltage. The formation of the film could be explained on the basis of dissociation of electrolyte under applied voltage.     

Preparation and characterization of boron-incorporated amorphous carbon films from a natural source of camphoric carbon as a precursor material

The boron-incorporated amorphous carbon (a-C:B) film has been prepared by pulsed laser deposition (PLD) in high vacuum at room temperature using natural source of camphoric carbon (CC) as a precursor material. The effects of various B weight percentages in the target (Bwt.%) on the properties of a-C:B films have been investigated using standard measurement techniques and discussed. The optical band gap (E_g) is almost unchanged up to 10 Bwt.%, decreased a little, and with decrease of electrical resistivity (ρ) with higher Bwt.%, we considered that the variation of E_g and electrical properties can be related to interstitial doping of B in carbon films through modifications of C-B bonding configurations by rearranging B atoms and the B incorporation induced by doping, which are responsible for the decrease in ρ. The decrease of ρ is considered not due to the graphitization caused by the increase of sp²-bonded carbon. This is further confirmed by the variation of surface morphology (AFM), Raman and FT-IR as the structural and bonding properties of these films was unchanged with B incorporation up to 16 Bwt.%.     

The impact of ultra thin silicon nitride buffer layer on GaN growth on Si (1 1 1) by RF-MBE

Ultra thin films of pure silicon nitride were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma with a high content of nitrogen atoms. The effect of annealing of silicon nitride surface was investigated with core-level photoelectron spectroscopy. The Si 2p photoelectron spectra reveals a characteristic series of components for the Si species, not only in stoichiometric Si₃N₄ (Si⁴⁺) but also in the intermediate nitridation states with one (Si¹⁺) or three (Si³⁺) nitrogen nearest neighbors. The Si 2p core-level shifts for the Si¹⁺, Si³⁺, and Si⁴⁺ components are determined to be 0.64, 2.20, and 3.05 eV, respectively. In annealed sample it has been observed that the Si⁴⁺ component in the Si 2p spectra is significantly improved, which clearly indicates the crystalline nature of silicon nitride. The high resolution X-ray diffraction (HRXRD), scanning electron microscopy (SEM) and photoluminescence (PL) studies showed a significant improvement of the crystalline qualities and enhancement of the optical properties of GaN grown on the stoichiometric Si₃N₄ by molecular beam epitaxy (MBE).     

含氮氟化类金刚石(FN-DLC)薄膜的研究：(Ⅰ) sp结构与化学键分析

以CF₄，CH₄和N₂为源气体，利用射频等离子体增强化学气相沉积法，在不同功率下制备了含氮氟化类金刚石膜.用俄歇电子能谱、拉曼光谱、X射线光电子能谱和傅里叶变换红外光谱对薄膜的电子结构和化学键进行了表征，并结合高斯分峰拟合方法分析了薄膜中sp²，sp³结构比率.结果表明，制备的薄膜属于类金刚石结构，不同沉积功率下，薄膜内的sp²/sp³值在2.0—9.0之间，随着沉积功率的增加薄膜内sp²的相对含量增加.膜内主要有C—F_x(x=1，2)，C—C，C=C和C≡N等化学键.沉积功率增加，C—C基团增加，膜内F的浓度降低，C—F基团减少，薄膜的关联加强，稳定性提高. 关键词： 含氮氟化类金刚石膜 sp结构 化学键结构 射频功率     

Microstructure and tribological behavior of pulsed laser deposited a-CNx films

The a-CN_x films were deposited onto high-speed steel substrate by pulsed laser deposition at different nitrogen pressures. The tribological properties of the films in humid air and in vacuum were investigated using a ball-on-disk tribometer under various loads. The composition, microstructure and morphology of the films, wear tracks and paired balls were characterized by energy dispersive X-ray analysis (EDXA), X-ray photoelectron spectrum (XPS), Raman spectroscopy and scanning electron microscopy (SEM). With increasing the deposition pressure, the fraction of sp³ C bond reduces, the fraction of trapped nitrogen increases and the friction coefficient of the films declines both in humid air and vacuum. The friction coefficient of a-CN_x film decreases with increasing normal load. The tribological performances of the films in humid air are better than those of in vacuum. A transferred graphite-like tribo-layer is observed from a-CN_x film to the paired ball for both environments.     

Properties of amorphous carbon nitride prepared by RF reactive sputtering

The local microstructure and optical and electrical properties were investigated of amorphous carbon nitride (a-CN) films deposited by reactive radio-frequency (RF) sputtering. Two series prepared in nitrogen or in a nitrogen and argon mixture were studied. The optical properties were investigated by transmittance/reflectance and photothermal deflection spectroscopies. Combined infrared measurements and Raman scattering spectroscopies were used to investigate the microstructure of a-CN films in terms of nitrogen incorporation within the films and C sp ² content. These experiments were completed by dark electrical conductivity measurements performed in coplanar configuration in the temperature range 50–450?K. The films exhibit semiconductor behaviour and the temperature dependence suggests two types of conduction. An increase in nitrogen incorporation induces an increase with clustering of sp ² phase replacing C=C olefinic groups with aromatic groups.     

A new carbon allotrope with C28 cage: T-C64

A new tetragonal carbon allotrope (named T-C₆₄) is predicted by swarm structural searches combined with first principles calculation. It contains 64 carbon atoms in a Tetragonal unit cell with I4₁/amd symmetry and exhibits distinct topologies including C28 cages. This new carbon phase has an sp²-sp³ network with calculated hardness of 68.2 GPa. In order to examine the stability of T-C₆₄ under ambient pressure, we calculated the properties of elastic constant and phonon spectrum. In addition, by calculating the electronic properties of the crystal, it is concluded that T-C₆₄ is an indirect band gap semiconductor with a band gap of 2.23 eV.     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

Light emission from a-Si:C:O:H films fabricated by C2F6 and O2/C2F6 plasma treating silicone oil liquid

Amorphous Si:C:O:H films were fabricated at low temperature by C₂F₆ and O₂/C₂F₆ plasma treating silicone oil liquid. The a-Si:C:O:H films fabricated by C₂F₆ plasma treatment exhibited white photoluminescence at room temperature, while that by O₂/C₂F₆ plasma treatment exhibited blue photoluminescence. Fourier transformed infrared spectroscopy and Raman spectroscopy studies showed that the sp³ and sp² hybridized carbons, SiC bond, SiO bond and carbon-related defects in a-Si:C:O:H films correlated with photoluminescence. It is suggested that the blue emission at 469 nm was related to the sp³ and sp² hybridized carbons, SiC bond, carbon dangling bonds as well as SiO short chains and small clusters, while the light emitting at 554 nm was related to the carbon-related defects.