Electrical conditioning of diamond-like carbon films for the formation of coated field emission cathodes

Diamond-like carbon (DLC) films deposited on different substrates by plasma enhanced chemical vapour deposition were investigated. Bonding states and film quality were characterized by FT-IR spectroscopy. The influence of the power of plasma and the deposition time on the sp²/sp³ ratio as well as the concentration of CH_n bonds was studied. The influence of sp²/sp³ ratio on the formation process of conducting channels in diamond-like carbon films as a result of electrical breakdown was determined. Reproducible increase of diamond-like carbon film conductivity, with initial sp²/sp³ ratio larger than 0.16, was observed after electrical breakdown.     

Characterization of BCN films synthesized by radiofrequency plasma enhanced chemical vapor deposition

Boron carbonitride (BCN) films have been synthesized on Si(1 0 0) substrate by radio frequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane (TDMAB) as a precursor. The deposition was performed at the different RF powers of 400-800 W, at the working pressure of 2×10⁻¹ Torr. The formation of the sp²-bonded BCN phase was confirmed by Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy measurements showed that B atoms were bonded to C and N atoms to form the BCN atomic hybrid configurations with the chemical compositions of B₅₂C₁₂N₃₆ (sample 1; prepared at the RF power of 400 W), B₅₂C₁₀N₃₈ (sample 2; at 500 W) and B₄₆C₁₈N₃₆ (sample 3; at 800 W), respectively. Near-edge X-ray absorption fine structure (NEXAFS) measurements indicated that B atoms were bonded not only to N atoms but also to C atoms to form various configurations of sp²-BCN atomic hybrids. The polarization dependence of NEXAFS suggested that the predominant hybrid configuration of sp²-BCN films oriented in the direction perpendicular to the Si substrate.     

Cathodic and anodic pre-treated boron doped diamond with different sp content: Morphological,structural, and impedance spectroscopy characterizations

In this work, the influence of cathodic (Red) and anodic (Ox) pre-treatment on boron doped diamond (BDD) films grown with different sp²/sp³ ratios was systematically studied. The sp²/sp³ ratios were controlled by the addition of CH₄ of 1,3,5 and 7 sccm in the gas inlet during the growth process. The electrodes were treated in 0.5 mol L⁻¹ H₂SO₄ at −3 and 3 V vs Ag/AgCl, respectively, for 30 min. The electrochemical response of BDD films was investigated using electrochemical impedance spectroscopy (EIS) and Mott–Schottky Plot (MSP) measurements. Four film sample sets were produced in a hot filament chemical vapor deposition reactor. During the growth process, an additional H₂ line passing through a bubbler containing the B₂O₃ dissolved in methanol was used to carry the boron. The scanning electron microscopy morphology showed well faced films with a small decrease in their grain size as the CH₄ concentration increased. The Raman spectra depicted a pronounced sp² band, mainly for films with 5 and 7 sccm of CH₄. MSP showed a decrease in the acceptor concentration as the CH₄ increased indicating the CH₄ influence on the doping process for Red–BDD and Ox–BDD samples. Nonetheless, an apparent increase in the acceptor concentrations for both Ox–BDD samples was observed compared to that for Red–BDD samples, mainly attributed to the surface conductive layer (SCL) formation after this strong oxidation process. The EIS Nyquist plots for Red–BDD showed a capacitance increase for the films with higher sp² content (5 and 7 sccm). On the other hand, the Nyquist plots for Ox–BDD can be described as semicircles near the origin, at high frequencies, where their charge transfer resistance strongly varied with the sp² increase in such films.     

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.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

Plasma parameters in a dual-camera low-power inductive RF discharge with an external magnetic field

The results from studying a dual-camera inductive radio-frequency (RF) discharge that was placed in an external magnetic field are presented. The operating conditions were as follows: an argon pressure of 5 × 10^–5–6 × 10^–2 Torr, an external magnetic field strength of 0–60 G, and an RF generator power supply of 25–300 W. During the experiment the resonant RF power consumption and the correspondence between the local power-consumption maxima and spatial maxima of the plasma concentration as a function of the external magnetic field were observed. The comparison of the experimental results with the results of the mathematical simulation indicates that the resonant character of the discharge is associated with the excitation of helicons and Trivelpiece–Gould waves.     

Role of carbon in the formation of hard Ge1−xCx thin films by reactive magnetron sputtering

We have deposited germanium carbide (Ge_1−xC_x) films on Si(1 0 0) substrate via radio-frequency (RF) reactive magnetron sputtering in a CH₄/Ar mixture discharge, and explored the effects of carbon content (x) on the chemical bonding and hardness for the obtained films. We find that x significantly influences the chemical bonding, which leads to a pronounced change in the hardness of the film. To reveal the relationship between the chemical bonding and hardness, first-principles calculations have been carried out. It is shown that as x increases from 0 to 0.33, the fraction of sp³ C-Ge bonds in the film increases at the expense of Ge-Ge bonds, which promotes formation of a strong covalently bonded network, and thus enhances the hardness of the film. However, as x further increases from 0.33 to 0.59, the fraction of sp³ C-Ge bonds in the film gradually reduces, while that of sp³ C-H and graphite-like sp² C-C bonds increases, which damages the compact network structure, resulting in a sharp decrease in the hardness. This investigation suggests that the medium x (0.17<x<0.40) is most favorable to the preparation of hard Ge_1−xC_x films due to the formation of dominant sp³ C-Ge bonds.     

Supersonic CO2 laser excited by RF discharge in closed cycle

A supersonic gas flow having a Mach number of 2 has been realized in a closed-cycle radio-frequency (RF)-discharge-excited supersonic CO₂ laser system. Stable RF discharge at a high CO₂ gas concentration has become possible using supersonic gas flow and RF discharge generated between dielectric electrodes. As a result, high RF input power density has been obtained. In addition, a high small-signal gain has been obtained in the supersonic section through decreases in gas pressure and gas temperature due to supersonic gas flow.This revised version was published online in August 2005 with a corrected cover date.     

Controllable wettability of poly(ethylene terephthlate) film modified by oxygen combined inductively and capacitively coupled radio-frequency plasma

Poly(ethylene terephthalate) (PET) film was modified by using oxygen combined inductively coupled radio-frequency plasma (ICP) and capacitively coupled radio-frequency plasma (CCP) at the radio-frequency (RF) power of 200 W and 100 W, respectively, for a treatment time up to 300 s. The RF plasma modification under the combined ICP and CCP mode with the controllable oxygen plasma density and oxygen ion-flux energy significantly improved the wettability of PET film, due to the creation of the polar functional groups containing oxygen, such as C-O and O-CO, and the increase of the surface roughness. At a low surface roughness, the polar functional groups on the PET film affected both the advancing contact angles and receding contact angles. When the surface roughness increased over a threshold, the advancing contact angles mainly depended on the polar functional groups, and the receding contact angles were particularly dependent on the surface roughness. Therefore, the controllable advancing contact angles and receding contact angles on the plasma-modified PET film were independently determined by plasma functionalization and plasma etching under the combined ICP and CCP mode.     

Electrical and structural properties of In-doped ZnO films deposited by RF superimposed DC magnetron sputtering system

Zinc-indium-oxide (ZIO) films were deposited on non-alkali glass substrates by RF superimposed DC magnetron sputtering with a ZIO (9.54 wt% In₂O₃ content) high-density, sintered target at room temperature. The electrical, structural and optical properties of the ZIO films deposited with different sputtering parameters were examined. The total power for RF superimposed DC magnetron sputtering was 80 W. The RF power ratio in the total sputtering power was changed from 0 to 100% in steps of 25%. The ZIO films deposited with a 100% RF discharge showed the lowest resistivity, 1.28×10⁻³ Ω cm, due to the higher carrier concentration. The ZIO film deposited at 50% RF power showed a relatively larger grain size and smaller FWHM. XPS suggested an increase in the level of In³⁺ substitution for Zn²⁺ in the ZnO lattice with increasing RF/(DC+RF) due to the low damage process. The average transmittance of all ZIO films in the visible light region was >80%. The increasing RF power portion of the total sputtering power led to a broadening of the optical band gap, which was attributed to the increase in carrier density according to Burstein-Moss shift theory.     

Annealing effects on the microstructure of amorphous carbon nitride films

Amorphous carbon nitride films, prepared using a dc facing-target reactive sputtering system, were annealed at temperatures up to 650 °C for 1 h in vacuum. The effects of heat treatment on the films, i.e. changes in the composition and structure, were investigated. It was found that annealing at temperatures ranging from 300 to 650 °C, results in the N content decreasing from ∼33 at.% in the as-deposited films to ∼5 at.%. The loss of N, especially those bonded to sp³C, causes the rearrangement of the film's microstructure, and the dual effects of the thermal annealing are quite noticeable: (1) annealing destroys most graphite-like structures, and more non-aromatic sp²C components and C≡N terminal structures are formed at higher annealing temperatures, contributing to a looser film's structure. (2) Annealing makes the remaining aromatic sp²C structure become more order. The results also reveal that N atoms bonded to sp³C are easily removed with the increasing temperature compared to those bonded to sp²C, which indicates that Nsp²C bonds had a higher thermal stability than Nsp³C.     

Microstructure, porosity and roughness of RF sputtered oxide thin films: Characterization and modelization

Spinel CoMnFeO₄ thin films are stable materials useful to study the influence of radio-frequency (RF) sputtering experimental conditions on the microstructure of oxide films. It has been demonstrated by various techniques such as electronic and atomic force microscopy (AFM), gas adsorption techniques and ellipsometry, that films prepared with 0.5 Pa sputtering argon pressure and 5 cm target-substrate distance are very dense. On the other hand, the samples obtained under higher pressure and/or longer distances are microporous with a mean pore size generally lower than 2 nm. The specific surface areas of such films reach about 75 m²/g.According to the simple model proposed, the films are made of three layers. From the bottom to the top of the film, the first one at the interface with the substrate is 100% dense. The second layer is made of cylindrical rods set up according to a compact plane. Its porosity is due to the lattice interstices. Hemispheric domes covering each rod make up the third layer, which displays a degree of roughness related to the shape and the hexagonal arrangement of the domes. The surface enhancement factor (SEF), the porosity and roughness, calculated from the model, are in corroboration with the experimental values. The porosity factor is however slightly underestimated by the model for very porous samples.     

Residual stress in diamond-like carbon films: Role of growth conditions and ion irradiation

The dependence of the internal residual stress in thin diamond-like carbon films grown by the plasma-enhanced chemical vapor deposition technique on the most important growth parameters, namely, the radio-frequency (RF) power and direct-current (DC) bias voltage, was studied. It was shown that the compressive stress reaches its highest value of 2.7 GPa at the low RF power and DC bias values. Both increase and decrease of these parameters result in stress decrease. The stress increases with increase in the growth temperature from 250 to 350°C. Thermal annealing of up to 350°C does not affect the stress value. Subsequent irradiation of the films by In⁺ and P⁺ ions with the energy of 350 and 120 keV, respectively, results in the decrease in the compressive stress followed by its inversion to the tensile one. The stress linearly depends on the effective dose of up to 0.5 DPA with the slope of (8.7 ± 1.3) Gpa/DPA.     

Investigation of evolution hydrocarbon species on a Si surface during methane plasma with and without substrate bias, using infrared spectroscopy in multiple internal reflection geometry

We investigated evolution of hydrocarbon species on a Si surface during methane plasma both with and without substrate bias, using infrared spectroscopy in multiple internal reflection geometry (MIR-IRAS). We found that the relative density of the sp³-CH or sp³-CH₂ species to the sp³-CH₃ species was low in the low exposure regions, but that the relative density of the sp³-CH or sp³-CH₂ species increased as the exposure was higher. Substrate temperatures rose as the plasma exposure was higher. The changes of ratios would be ascribed to the substrate heating effect by plasma exposure, which would enhance the etching and/or hydrogen abstraction effects. We also found the change of CH_1-2/CH₃ ratios was enhanced when the high substrate bias was applied. The enhancement of the ratio was due to ion effects.     

Electrochemical properties of undoped CVD diamond films

The electrochemical properties of undoped diamond polycrystalline films grown on tungsten wire substrates using methanol as a precursor are described. The diamond film quality was changed by introducing sp²-bonded non-diamond carbon impurity through adjustment of the methanol-to-hydrogen (C/H) source gas ratio used for diamond growth.The electrodes were characterized by Raman spectroscopy, scanning electronic microscopy (SEM) and cyclic voltammetry (CV).Diamond coated tungsten wires were then used as a working electrode to ascertain their electrochemical behavior in electrolytic medium. Electrochemical windows of these films were found to be suitable in the potential range of [−2.5 V, +2.2 V] vs. Ag/AgCl in acid medium (0.1 M KCl).The electrochemical behavior was evaluated also using the Fe(CN)₆^3−/4−redox couple.The results demonstrate that the grain boundaries and sp²-hybridized carbon impurity can have a significant influence on electrochemical window of undoped diamond electrodes. It was observed that with increasing sp² carbon impurity concentration the electrochemical window decreases.     

The sp2 and sp3 fractions of unknown carbon materials: electron energy-loss near-edge structure analysis of C-K spectra acquired under the magic-angle condition by the electron nanobeam technique

A method is described for the quantification of the sp², sp³ and intermediate hybridizations in several carbon (C) material samples. Electron energy-loss near-edge spectra were acquired using fast electrons (120 keV) in an electron microscope in nanobeam configuration under the so-called ”magic-angle” condition, and were analysed to extract the sp² and sp³ fractions, and identify the possible mixed sp^2+ε hybridizations. The method consists in projecting the unknown spectra on a basis made up of pure sp² and sp³ spectra, obtained under the same experimental conditions from graphite and diamond crystals, respectively. The residual spectra contain information about the intermediate hybridizations sp^2+ε occurring in the samples. The method was successfully tested on “ab initio” numerically generated spectra relative to amorphous C materials. Finally, it was applied to actual C amorphous and pyrolytic samples, and results were compared to those obtained by the most commonly used, conventional ”three-Gaussian” method. The combined application of electron diffraction and spectroscopy, in the nanobeam configuration, yielded useful information about the atomic and electronic structure from very small volumes of the unknown C material.     

类金刚石膜不同能量下的离子注入

本文对等离子体气相沉积法制备的类金刚石膜(a-C:H)进行了离子注入研究。注入剂量固定为5×10⁵Ar/cm²,注入能量分别为50,100,140和180keV。离子注入前后分别作了红外吸收谱,Raman谱,光学能隙,氢含量和电阻率的测量。结果表明,注入离子破坏了膜中的C—H键,sp²和sp³态都减少,而(sp²/sp³)比值增大;光学能隙E_opt,电阻 关键词：     

不同射频输入功率下制备的氟化类金刚石碳膜疏水性研究

以高纯石墨作靶、氩气（Ar）和三氟甲烷（CHF₃）为源气体,用反应磁控溅射法在不同射频功率下制备了氟化类金刚石碳（F-DLC）膜,并对其疏水性进行研究.双蒸水液滴与膜表面接触角的测试结果表明,所制备薄膜表面的最大水接触角可达115°左右.通过原子力显微镜获得的薄膜表面AFM图谱、拉曼光谱以及傅里叶变换红外光谱探讨了影响薄膜的疏水性的因素.结果表明,薄膜的疏水性与薄膜的表面粗糙度和表面键结构直接相关,表面粗糙度越大,疏水性越好,但与薄膜中的F含量和sp³/sp²的比值并未呈单调增加或减小的对应关系.射频输入功率影响着薄膜的沉积速率,与薄膜表面粗糙度、薄膜中芳香环单核的比例以及薄膜表面的键结构（F的接入方式）直接相关. 关键词： 疏水性 反应磁控溅射 氟化类金刚石膜 射频功率     

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     

The characterization of fluorocarbon films on NiTi alloy by magnetron sputtering

Fluorocarbon films were deposited on nickel-titanium (NiTi) alloy substrate by radio-frequency (RF, 13.56 MHz) magnetron sputtering using a polytetrafluoroethylene (PTFE) target. The deposition parameters of fluorocarbon films including the RF power, the working gas pressure and Ar flow rate were systematically studied. The structure of the deposited films was studied by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The surface morphology of the deposited films was measured by atomic force microscopy (AFM). The mechanical properties of the deposited films were characterized by a nanoindenter. C-Fx and C-C units were found in the deposited fluorocarbon films, which corresponded to the results of XPS. The surface roughness of the fluorocarbon film was 7.418 nm (Ra).