The properties of N-doped diamond-like carbon films prepared by helicon wave plasma chemical vapor deposition

In this paper, N-doped diamond-like carbon(DLC) films were deposited on silicon substrates by using helicon wave plasma chemical vapor deposition(HWP-CVD) with the Ar/CH_4/N_2 mixed gas. The surface morphology, structural and mechanical properties of the N-doped DLC films were investigated in detail by scanning electron microscopy(SEM), x-ray photoelectron spectroscopy(XPS), Raman spectra, and atomic force microscopy(AFM). It can be observed from SEM images that surface morphology of the films become compact and uniform due to the incorporation of N. The maximum of the deposition rate of the films is 143 nm min~(-1), which is related to the high plasma density. The results of XPS show that the N incorporates in the films and the C-C sp~3 bond content increases firstly up to the maximum(20%) at 10 sccm of N_2 flow rate, and then decreases with further increase in the N_2 flow rate. The maximum Young's modulus of the films is obtained by the doping of N and reaches 80 GPa at 10 sccm of N_2 flow rate, which is measured by AFM in the scanning probe microscope mode. Meanwhile, friction characteristic of the N-doped DLC films reaches a minimum value of 0.010.     

The effect of nitrogen concentration on the properties of N-DLC prepared by helicon wave plasma chemical vapor deposition

Nitrogen-doped diamond-like carbon (N-DLC) films were synthesized by helicon wave plasma chemical vapor deposition (HWP-CVD). The mechanism of the plasma influence on the N-DLC structure and properties was revealed by the diagnosis of plasma. The effects of nitrogen doping on the mechanical and hydrophobicity properties of DLC films were studied. The change in the ratio of precursor gas flow reduces the concentration of film-forming groups, resulting in a decrease of growth rate with increasing nitrogen flow rate. The morphology and structure of N-DLC films were characterized by scanning probe microscopy, Raman spectroscopy, and X-ray photoemission spectroscopy. The mechanical properties and wettability of N-DLC were analyzed by an ultra-micro hardness tester and JC2000DM system. The results show that the content ratio of N+ and ${{\rm{N}}}_{2}^{+}$ is positively correlated with the mechanical properties and wettability of N-DLC films. The enhancement hardness and elastic modulus of N-DLC are attributed to the increase in sp3 carbon–nitrogen bond content in the film, reaching 26.5 GPa and 160 GPa respectively. Water contact measurement shows that the increase in the nitrogen-bond structure in N-DLC gives the film excellent hydrophobic properties, and the optimal water contact angle reaches 111.2°. It is shown that HWP technology has unique advantages in the modulation of functional nanomaterials.     

Development of a helicon-wave excited plasma facility with high magnetic field for plasma-wall interactions studies

The high magnetic field helicon experiment system is a helicon wave plasma(HWP)source device in a high axial magnetic field(B_0)developed for plasma–wall interactions studies for fusion reactors.This HWP was realized at low pressure(5?×?10~(-3)?-?10 Pa)and a RF(radio frequency,13.56 MHz)power(maximum power of 2 k W)using an internal right helical antenna(5 cm in diameter by 18 cm long)with a maximum B_0of 6300 G.Ar HWP with electron density~10~(18)–10~(20)m~(-3)and electron temperature~4–7 e V was produced at high B_0 of 5100 G,with an RF power of 1500 W.Maximum Ar~+ion flux of 7.8?×?10~(23)m~(-2)s~(-1)with a bright blue core plasma was obtained at a high B_0 of 2700 G and an RF power of 1500 W without bias.Plasma energy and mass spectrometer studies indicate that Ar~+ion-beams of 40.1 eV are formed,which are supersonic(~3.1c_s).The effect of Ar HWP discharge cleaning on the wall conditioning are investigated by using the mass spectrometry.And the consequent plasma parameters will result in favorable wall conditioning with a removal rate of 1.1?×?10~(24)N_2/m~2 h.     

类金刚石碳剥离膜的制备及其性能研究

采用磁过滤阴极真空弧(FCVA)技术制备了质量厚度为5~7μg/cm2的类金刚石碳(DLC)剥离膜。用XP2U型精密电子天平测试分析了100mm范围内的DLC剥离膜均匀性,结果显示其最大不均匀性小于10%。通过扫描电子显微镜(SEM)、原子力显微镜(AFM)、万能摩擦磨损试验机和X光电子谱(XPS)测试分析了DLC剥离膜的表面形貌、耐磨损特性和结构,结果显示采用双90°FCVA技术沉积的DLC剥离膜表面光滑致密、耐磨,几乎没有大颗粒的污染,表征金刚石特性的sp3键含量超过70%。在北京HI-13串列加速器上使用107 Ag-、70 Ge-、48 Ti-、28Si-、197 Au-和127I-六种典型质量的离子束对质量厚度为5~7μg/cm2的DLC剥离膜和碳剥离膜寿命进行测试比较,结果显示DLC剥离膜寿命比碳剥离膜的高2.6~10倍。     

On the use of MWCVD diamond as thermoluminescent gamma dosimeter

The thermoluminescence (TL) characterization of microwave plasma assisted chemical vapor deposition diamond (MWCVD) films of 6 and 12 μm thickness grown on (1 0 0) silicon substrates was performed. The films exhibited a single well-resolved TL peak around 580 K at doses lower than 40 Gy. As the irradiation dose increased the TL peak broaden and shifted towards the low temperature side of the glow curve. The diamond samples exposed to 0.67 Gy/min ⁶⁰Co gamma radiation displayed a linear dose behavior up to 100 Gy being non-linear for higher doses. The 12 μm film showed lower TL efficiency as compared to the 6 μm specimen. The discrepancy was attributed to the non-uniform distribution of nucleated sp³ diamond and sp² bonded carbon on the substrate as revealed by SEM micrograph and Raman spectroscopy of the samples. The integrated TL glow curve of the samples exhibited low room temperature thermal fading and 3% reproducibility. The results show that MWCVD diamond films possess promising properties for radiation dosimetry applications.     

Study of 160 MeV Ni ion irradiation effects on electrodeposited polypyrrole films

Conducting polymer polypyrrole thin films doped with LiCF₃SO₃, [CH₃(CH₂)₃]₄NBF₄ and [CH₃(CH₂)₃]₄NPF₆ have been electrodeposited potentiodynamically on ITO coated glass substrate. The polymer films are irradiated with 160 MeV Ni¹²⁺ ions at three different fluences of 5 × 10¹⁰, 5 × 10¹¹ and 3 × 10¹² ions cm⁻². An increase in dc conductivity of polypyrrole films from 100 S/cm to 170 S/cm after irradiation with highest fluence is observed in four-probe measurement. X-ray diffractogram shows increase in the crystallinity of the polypyrrole films upon SHI irradiation, which goes on increasing with the increase in fluence. Absorption intensity increase in the higher wavelength region is observed in the UV–Vis spectra. The SEM studies show that the cauliflower like flaky microstructure of the surface of polypyrrole films turns globular upon SHI irradiation at fluence 5 × 10¹¹ ions cm⁻² and becomes smooth and dense at the highest fluence used. The cyclic voltammetry studies exhibit that the redox properties of the polypyrrole films do not change much on SHI irradiation.     

Measurement of the Fermi potential of diamond-like carbon and other materials

The Fermi potential V_f of diamond-like carbon (DLC) coatings produced with laser-controlled vacuum arc deposition and that of diamond, Al, Si, Be, Cu, Fe and Ni was measured using two different methods, (i) transmission of slow neutrons through foils in a time-of-flight experiment and (ii) cold neutron reflectometry (CNR). For diamond-like carbon in transmission we obtain V_f = (249 ± 14) neV. This is approximately the same as for beryllium and consistent with the theoretical expectations for the measured diamond (sp³) content of 45%. For an sp³-content of 67%, we find V_f = (271 ± 13) neV from reflectometry, again in agreement with theory. These findings open new perspectives in using DLC as storage volume and neutron guide coatings for ultracold neutron sources.     

Synthesis of Ag-decorated vertical graphene nanosheets and their electrocatalytic efficiencies

Herein we report the successful preparation of silver (Ag)-decorated vertically oriented graphene sheets (Ag/VGs) via helicon wave plasma chemical vapor deposition (HWP-CVD) and radiofrequency plasma magnetron sputtering (RF-PMS). VGs were synthesized in a mixture of argon and methane (Ar/CH4) by HWP-CVD and then the Ag nanoparticles on the prepared VGs were modified using the RF-PMS system for different sputtering times and RF power levels. The morphology and structure of the Ag nanoparticles were characterized by scanning electron microscopy and the results revealed that Ag nanoparticles were evenly dispersed on the mesoporous wall of the VGs. X-ray diffraction results showed that the diameter of the Ag particles increased with the increase in Ag loading, and the average size was between 10.49 nm and 25.9 nm, consistent with the transmission electron microscopy results. Ag/VGs were investigated as effective electrocatalysts for use in an alkaline aqueous system. Due to the uniquely ordered and interconnected wall structure of VGs, the area of active sites increased with the Ag loading, giving the Ag/VGs a good performance in the oxygen evolution reaction. The double-layer capacitance (Cdl) of the Ag/VGs under different Ag loadings were studied, and the results showed that the highest Ag content gave the best Cdl (1.04 mF cm−2). Our results show that Ag/VGs are likely to be credible electrocatalytic materials.     

ICPECVD类金刚石膜沉积过程的发射光谱诊断研究

利用发射光谱(Optical emission spectroscopy,OES)对感应耦合等离子体增强化学气相沉积(Inductivelycoupled plasma enhance chemical vapor d印osition,ICPECVD)类金刚石(Diamondlike carbon,DLC)膜过程中的各种基团进行分析,并对不同条件下薄膜沉积速率以及薄膜显微硬度进行测试.分析结果发现,感应耦合等离子体源激发甲烷等离子体中存在比较突出的碳氢离子成分,从而促进形成高硬度的DLC膜.而且射频功率、沉积气压等沉积参数的变化对DLC薄膜沉积过程的中性基团、离子基团以及原子氢等成分都有着明显影响,从而最终影响薄膜沉积过程及薄膜性质.     

Numerical simulation of plasma-assisted combustion of methane-air mixtures in combustion chamber

A two-dimensional mathematical model was developed to investigate the effects of dielectric barrier discharge (DBD) plasma on CH₄-air mixtures combustion at atmospheric pressure. Considering the physical and chemical processes of plasma-assisted combustion (PAC), plasma discharge, heat transfer and turbulent were simultaneously coupled into simulation of PAC. This coupling model consists of DBD kinetic model and methane combustion model. By comparing simulations and the original reference’s results, a high-accuracy of this model was validated. In addition, the effects of PAC actuation parameters on combustion characteristics were studied. Numerical simulations show that with an inlet airflow velocity of 10 ms ^-1, a CH₄-air mixtures’ equivalence ratio of 0.5, an applied voltage of 10 kV, a frequency of 1200 kHz, compared to conventional combustion (CC), the highest flame temperature rises by 32 K; outlet temperature distribution coefficient drops by 2.3%; the maximum net reaction rate of CH₄ and H₂O increase by 11.22% and 12.80% respectively; the maximum CO emission index decreases by 14.61%; the mixing region turbulence mixing time reduces by 89 ms.     

Comparison of heating mechanisms of argon helicon plasma in different wave modes with and without blue core

In this work,we investigated the discharge characteristics and heating mechanisms of argon helicon plasma in different wave coupled modes with and without blue core.Spatially resolved spectroscopy and emission intensity of argon atom and ion lines were measured via local optical emission spectroscopy,and electron density was measured experimentally by an RFcompensated Langmuir probe.The relation between the emission intensity and the electron density was obtained and the wavenumbers of helicon a...     

含氚废气中杂质气体去除材料研制

为去除含氚惰性废气中的CH₄、水气、O₂等杂质气体,采用溶胶凝胶法制备了65%Ni-10%Cu-25%SiO₂材料作为杂质气体消除材料,对材料进行XRD、SEM及程序升温还原表征,结果显示,少量Cu的加入增加了Ni的分散度,有助于稳定Ni的形态,避免Ni过早发生氧化。材料可以使Ar中的少量CH₄、O₂和水气得到有效的去除,在空速1000 h^-1时Ar中φ=1%CH₄和φ=1%CO₂重整时CH₄去除率达到81.5%以上,对于Ar中φ=1%O₂的去除率达到91.8%以上,对于Ar中φ=1%水气的去除率达到91.7%以上。实验还发现低浓度的CH₄可以与水气及O₂发生反应而去除,空速10000 h^-1催化φ=1%水气和φ=1%CH₄反应,CH₄的去除率均高于80.7%;空速10000 h^-1催化φ=0.67%CH₄和φ=0.33%O₂的反应,CH₄的去除率均高于84.2%。     

Synthesis of vertical graphene nanowalls by cracking n-dodecane using RF inductively-coupled plasma-enhanced chemical vapor deposition

A facile and controllable one-step method to treat liquid hydrocarbons and synthesize vertical graphene nanowalls has been developed by using the technique of inductively-coupled plasma-enhanced chemical vapor deposition for plasma cracking of n-dodecane.Herein,the morphology and microstructure of solid carbon material and graphene nanowalls are characterized in terms of different operating conditions,i.e.input power,H2/Ar ratio,injection rate and reaction temperature.The results reveal that the optimal operating conditions were 500 W,5:10,30μl min^-1 and 800℃ for the input power,H2/Ar ratio,injection rate and reaction temperature,respectively.In addition,the degree of graphitization and the gaseous product are analyzed by Raman spectroscopy and gas chromatography detection.It can be calculated from the Raman spectrum that the relative intensity of ID/IG is approximately 1.55,and I2D/IG is approximately 0.48,indicating that the graphene prepared from n-dodecane has a rich defect structure and a high degree of graphitization.By calculating the mass loading and detecting the outlet gas,we find that the cracking rate of n-dodecane is only 6%-7%and that the gaseous products below C2 mainly include CH4,C2H2,C2H4,C2H6 and H2.Among them,the proportion of hydrogen in the outlet gas of n-dodecane cracking ranges from 1.3%-15.1%under different hydrogen flows.Based on our research,we propose a brand new perspective for both liquid hydrocarbon treatment and other value-added product syntheses.     

高质量类金刚石薄膜的制备与性能分析

采用直流/射频耦合磁控溅射法在Si(100)衬底上成功制备出类金刚石(DLC)薄膜。利用Raman光谱仪、X射线光电子能谱仪表征不同射频功率下所制备薄膜的化学结构,讨论射频功率对薄膜化学结构的影响。采用X射线小角反射法表征薄膜的质量密度,利用曲率弯曲法表征薄膜的残余内应力,采用扫描电镜和原子力显微镜表征所制备薄膜的表面形貌与粗糙度。研究表明:薄膜中sp3键的含量随着射频功率的增加而呈现出先增大后减小的趋势,且在射频功率为40 W时达到最大值45.6%。随着射频功率的增加,薄膜的表面粗糙度呈现出先减小后增大的趋势,当射频功率为40 W时薄膜的表面粗糙度最小,为1.6 nm。直流/射频耦合磁控溅射法在不同射频功率下制备出的薄膜,其内应力均低于1.0 GPa,薄膜质量密度的变化范围为2.26~2.44 g/cm~3,有望成功制备出内应力低、密度高的高质量DLC薄膜。     

氢气流量对类金刚石薄膜结构与性能的影响

采用直流/射频耦合反应磁控溅射法在Si（100）衬底上成功制备出类金刚石（DLC）薄膜。利用表面轮廓仪、Raman光谱仪、X射线光电子能谱仪表征所制备薄膜在不同氢气流量下的沉积速率和化学结构,讨论了氢气流量对薄膜沉积速率和化学结构的影响;利用纳米压痕技术及曲率弯曲法表征薄膜的力学性能;利用扫描电镜和原子力显微镜表征薄膜的表面形貌与粗糙度。研究表明：随着氢气流量的增加,所制备薄膜的沉积速率逐渐减小,而薄膜中sp³键的含量逐渐增大。当氢气流量为25 mL/min时,薄膜中sp³键的含量为36.3%,薄膜的硬度和体弹性模量分别达到最大值17.5 GPa和137 GPa。同时,所制备薄膜的内应力均低于0.5 GPa,有望成功制备出低内应力的高质量DLC厚膜。随着氢气流量的增加,DLC薄膜的表面变得更致密光滑,且表面均方根粗糙度由5.40 nm降为1.46 nm。     

Plasma density measurement and downstream etching of silicon and silicon oxide in Ar/NF3 mixture remote plasma source

In this study, plasma density measurements were performed near the plume region of the remote plasma source (RPS) in Ar/ NF₃ gas mixtures using a microwave cutoff probe. The measured plasma density is in the range of 10 ¹⁰ –10 ¹¹ cm ⁻³ in the discharge conditions with RPS powers of 2–4 kW and gas pressures of 0.87–4 Torr. The plasma density decreased with increasing gas pressures and RPS powers under various Ar/ NF₃ mixing ratios. This decrease in the plasma density measured at the fixed measurement position (plume region) can be understood by the reduction of the electron energy relaxation length with increases in the gas pressures and mixing ratio of NF₃/(Ar / NF₃). We also performed downstream etching of silicon and silicon oxide films in this system. The etch rate of the silicon films significantly increases while the silicon oxide is slightly etched with the gas pressures and powers. It was also found that the etch rate strongly depends on the wafer position on the processing chamber electrode, and that the etch selectivity reached 96–131 in the discharge conditions of RF powers (3730–4180 W) and gas pressures (3.6–4 Torr).     

Effects of 160 MeV Ni ion irradiation on polypyrrole conducting polymer electrode materials for all polymer redox supercapacitor

Electronically conducting polymers are suitable electrode materials for high performance supercapacitors, for their high specific capacitance and high dc conductivity in the charged state. Supercapacitors and batteries are energy storage and conversion systems which satisfies the requirements of high specific power and energy in a complementary way. Ion beam {energy > 1 MeV} irradiation on the polymer is a novel technique to enhance or alter the properties like conductivity, density, chain length and solubility.

Conducting polymer polypyrrole thin films doped with LiClO₄ are synthesized electrochemically on ITO coated glass substrate and are irradiated with 160 MeV Ni¹²⁺ ions at different fluence 5 × 10¹⁰, 5 × 10¹¹ and 3 × 10¹² ions cm⁻². Dc conductivity measurement of the irradiated films showed 50–60% increase in conductivity which is may be due to increase of carrier concentration in the polymer film as observed in UV–Vis spectroscopy and other effects like cross-linking of polymer chain, bond breaking and creation of defects sites. X-ray diffractogram study shows that the degree of crystallinity of polypyrrole increases in SHI irradiation and is proportionate to ion fluence. The capacitance of the irradiated films is lowered but the capacitance of the supercapacitors with irradiated films showed enhanced stability compared to the devices with unirradiated films while characterized for cycle life up to 10,000 cycles.     

Pumping experiment of water on B and LaB6 films with an electron beam evaporator

The pumping characteristic of water vapor on boron and lanthanum hexaboride films formed with an electron beam evaporator have been investigated in high vacuum between 10⁻⁴ and 10⁻³ Pa. The measured initial maximum pumping speeds of water for the fresh B or LaB₆ films with a deposition amount from 2.3 × 10²¹ to 6.7× 10²¹ molecules/m² separately formed on a substrate are 3.2–4.9 m³/sm², and the saturation values of adsorbed water on these films are 2.1 ×10²⁰−1.3 × 10²¹ H₂O molecules/m².     

Electrical and optical properties of Co ion implanted a-Si1 − xCx:H alloys

Low resistivity a-Si_1 − xC_x:H alloy films have been formed by high dose Co⁺ ion implantation. The influence of the carbon content of the films on the resistivity has been studied and the lowest values, of the order of 10 Ω/Sq, have been observed for the carbon free films. Even lower resistivities, a further reduction of up to 50%, have resulted from annealing at temperatures up to 500°C. Changes in the optical and structural properties of the implanted a-Si_1 − xC_x:H films have been studied by means of IR and Raman spectroscopy. Results show that the implantation produces considerable structural and chemical modifications. The formation of, and the transition to, a possible CoSi₂ phase has been observed by examining the IR and Raman spectra as a function of implant dose.     

类金刚石薄膜的同步辐射光电子能谱研究

利用同步辐射光电子能谱全电子产额模式(TEY)对石墨、金刚石薄膜和类金刚石薄膜(DLC)的ClsX射线吸收谱进行了研究。在高真空里表面净化处理后,在类金刚石薄膜的Cls吸收谱中分别观察到对应于金刚石sp^3杂化结构成分和石墨sp^2杂化结构成分的特征峰,说明了类金刚石薄膜是由碳sp^2、sp^3两种杂化结构无序混合形成的非晶碳结构;然后,测量了一系列类金刚石薄膜样品的ClsX射线光电子能谱(XPS),得到了每组样品的sp^2、sp^3成分比。