Monte Carlo Simulation of Electron Velocity Distribution and Gas Phase Process in Electron-Assisted Chemical Vapor Deposition

The gas phase process of diamond film deposition from CH4/H2 gas mixture by electron-assisted chemical vapor deposition is simulated by the Monte-Carlo method. The electron velocity distribution under different E/P (the ratio of the electric field to gas pressure) is obtained, and the velocity profile is asymmetric. The variation of the number density of CH3 and H with different CH4 concentrations and gas pressure is investigated, and the optimal experimental parameters are obtained: the gas pressure is in the range of 2.5 kPa ~ 15 kPa and the CH4 concentration is in the range of 0.5% ~ 1%. The energy carried by the fragment CH3 as the function of the experiment parameters is investigated to explain the diamond growth at low temperature. These results will be helpful to the selection of optimum experimental conditions for high quality diamond films deposition in EACVD and the modeling of plasma chemical vapor deposition.     

铀上激光辅助化学气相沉积镍薄膜研究

为防止金属铀的腐蚀,本文采用激光辅助化学气相沉积(LACVD)方法在铀上制备了镍薄膜。采用SEM、XRD分析了薄膜的形貌、物相以及界面特性,采用黏胶拉伸测试表征了膜-基结合性能,采用电化学极化法分析了薄膜的抗腐蚀性能。结果表明:压力和温度对化学气相沉积(CVD)方法制备镍薄膜的质量有较大的影响。随着基底温度和沉积气压的降低,薄膜变得致密、平整,质量提高。在优化的工艺条件165℃、3Pa下,CVD方法所得镍薄膜非常致密。采用LACVD方法时,激光能量为200mJ时所制得的薄膜致密,300mJ时膜变得粗糙。无激光辅助时,CVD方法所制得的薄膜较易剥落,激光辅助下所得薄膜的膜-基结合力较好。LACVD方法大幅提高了薄膜的抗腐蚀性能,抗腐蚀性能的提高主要源于激光辅助使薄膜致密化,提高了薄膜与基底的结合力。     

Optical Emission Spectroscopy Analysis of the Early Phase During Femtosecond Laser-Induced Air Breakdown

Single-pulse and double-pulse optical emission spectroscopy （OES） analyses were carried out in air by using ultrashort laser pulses at atmospheric pressure. The aim of this work is to use spectroscopic methods to analyze the early phase of laser-induced plasma after the femtosecond laser pulse. The temporal behavior of emission spectra of air plasma has been characterized. In comparison with the single-pulse scheme, the plasma emission obtained in the double-pulse scheme presents a more intense continuum along with several additional ionic lines. As only one line is available in the single-pulse scheme, the plasma temperature measurements were performed using only the relative line-to-continuum intensity ratio method, whereas the relative line-to-line intensity ratio method and the relative line-to-continuum intensity ratio method were used simultaneously to estimate the electron temperature in the double-pulse scheme. The results reveal that the temperature values obtained by the two methods in the double-pulse scheme agree. Moreover, this shows that the relative line-to-continuum intensity ratio method is suitable for early phase of laser-induced plasma diagnostics. The electron number density was estimated using the Stark broadening method. In the early phase of laser-induced plasma, the temporal evolution of the electron number density exhibits a power law decrease with delay time.     

化学气相沉积法制备ZrC涂层的热力学分析

ZrC涂层可能在新一代TRISO包覆颗粒上被用作阻挡裂变产物和承受主要载荷的关键层，是先进高温气冷堆燃料元件研究的一个重要方向。文章利用HSC-CHEMISTRY4.1软件分析化学气相沉积工艺参数对所制备的ZrC涂层的影响。分析结果表明，在载气中加入足够的氢气对制备单一ZrC涂层很有必要。ZrCl₄的转化率随着沉积温度的升高而增加，当温度过高时，其影响不明显；较佳的沉积温度范围为1400~1600℃。随着反应物浓度的增加，获得单一ZrC涂层对应的最低ZrCl₄与CH₄的摩尔分数比增加；反应物摩尔分数的最佳范围可选为：甲烷，1.0%～2.0%；ZrCl₄，为甲烷的1.5倍。     

Characteristics of C_2 Radical in CHF_3 and CF_4 Electron Cyclotron Resonance Plasmas Studied by Optical Emission Spectroscopy

The characteristics of CHF3 and CF4 electron cyclotron resonance (ECR) plasma have been studied by optical emission spectroscopy (OES) and Langmuir probe. It is found that C2 radical is one of main compositions in both of the two plasmas. We investigated the relative concentration of C2 radical as a function of F (H) radical and ion density. The formation mechanism of C2 radical is analyzed.     

Microwave Plasma Chemical Vapor Deposition of Diamond Films on Silicon From Ethanol and Hydrogen

Diamond films with very smooth surface and good optical quality have been deposited onto silicon substrate using microwave plasma chemical vapor deposition(MPCVD)from a gas mixture of ethanol and hydrogen at a low substrate temperature of 450℃.The effects of the substrate temperature on the diamond nucleation and the morphology of the diamond film have been investigated and observed with scanning electron microscopy(SEM).The microstructure and the phase of the film have been characterized using Raman spectroscopy and X-ray diffraction(XRD).The diamond nucleation density significantly decreases with the increasing of the substrate temperature.There are only sparse nuclei when the substrate temperature is higher than 800℃ although the ethanol concentration in hydrogen is very high.That the characteristic diamond peak in the Raman spectrum of a diamond film prepared at a low substrate temperature of 450℃ extends into broadban indicates that the film is of nanophase.No graphite peak appeared in the XRD pattern confirms that the film is mainly composed of SP^3 carbon.The diamond peak in the XRD pattern also broadens due to the nanocrystalline of the film.     

Effect of Gas Sources on the Deposition of Nano-Crystalline Diamond Films Prepared by Microwave Plasma Enhanced Chemical Vapor Deposition

Nano-crystalline diamond (NCD) films were deposited on silicon substrates by a microwave plasma enhanced chemical vapor deposition (MPCVD) reactor in C2H5OH/H2 and CH4/H2/O2 systems, respectively, with a constant ratio of carbon/hydrogen/oxygen. By means of atomic force microscopy (AFM) and X-ray diffraction (XRD), it was shown that the NCD films deposited in the C2H5OH/H2 system possesses more uniform surface than that deposited in the CH4/H2/O2 system. Results from micro-Raman spectroscopy revealed that the quality of the NCD films was different even though the plasmas in the two systems contain exactly the same proportion of elements. In order to explain this phenomenon, the bond energy of forming OH groups, energy distraction in plasma and the deposition process of NCD films were studied. The experimental results and discussion indicate that for a same ratio of carbon/hydrogen/oxygen, the C2H5OH/H2 plasma was beneficial to deposit high quality NCD films with smaller average grain size and lower surface roughness.     

Incorporation of Nitrogen into Amorphous Carbon Films Produced by Surface-Wave Plasma Chemical Vapor Deposition

In order to study the influence of nitrogen incorporated into amorphous carbon films, nitrogenated amorphous carbon films have been deposited by using surface wave plasma chemical vapor deposition under various ratios of N2/CH4 gas flow. Optical emission spectroscopy has been used to monitor plasma features near the deposition zone. After deposition, the samples are checked by Raman spectroscopy and x-ray photo spectroscopy (XPS). Optical emission intensities of CH and N atom in the plasma are found to be enhanced with the increase in the N2/CH4 gas flow ratio, and then reach their maximums when the N2/CH4 gas flow ratio is 5%. A contrary variation is found in Raman spectra of deposited films. The intensity ratio of the D band to the G band (ID/IG) and the peak positions of the G and D bands all reach their minimums when the N2/CH4 gas flow ratio is 5%. These show that the structure of amorphous carbon films has been significantly modified by introduction of nitrogen。     

Sheet Resistance and Gas-Sensing Properties of Tin Oxide ThinFilms by Plasma Enhanced Chemical Vapor Deposition＊

Tin oxide (SnO2) thin films are prepared at different temperatures by plasmaenhanced chemical vapor deposition (PECVD). The structural characterizations of the films are investigated by various analysis techniques. X-ray diffraction patterns (XRD) show that the phase of SnO2 films are different at different deposition temperatures. The sheet resistance of the films decreases with increase of deposition temperature. X-ray photoelectron spectroscopy (XPS) shows that the SnO2 thin film is non-stoichiometric. The sheet resistance increases with increase in oxygen flow. Sb-doped SnO2 thin films are more sensitive to alcohol than carbon monoxide, and its maximum sensitivity is about 220％.     

The Gas Nucleation Process Study of Anatase TiO2 in Atmospheric Non-Thermal Plasma EnhancedChemical Vapor Deposition简

Abstract The gas phase nucleation process of anatase TiO2 in atmospheric non-thermal plasma enhanced chemical vapor deposition is studied. The particles synthesized in the plasma gas phase at different power density were collected outside of the reactor. The structure of the collected particles has been investigated by field scanning electron microscope （FESEM）, X-ray diffraction （XRD）, high resolution transmission electron microscopy （HRTEM） and selected area electron diffraction （SAED）. The analysis shows that uniform crystalline nuclei with average size of several nanometers have been formed in the scale of micro second through this reactive atmo- spheric plasma gas process. The crystallinity of the nanoparticles increases with power density. The high density of crystalline nanonuclei in the plasma gas phase and the low gas temperature are beneficial to the fast deposition of the 3D porous anatase TiO2 film.     

Effect of Radio-Frequency and Low-Frequency Bias Voltage on the Formation of Amorphous Carbon Films Deposited by Plasma Enhanced Chemical Vapor Deposition

The effect of radio-frequency （RF） or low-frequency （LF） bias voltage on the for- mation of amorphous hydrogenated carbon （a-C：H） films was studied on silicon substrates with a low methane （CH4） concentration （2-10 vol.%） in CH4＋Ar mixtures. The bias substrate was applied either by RF （13.56 MHz） or by LF （150 kHz） power supply. The highest hardness values （~18-22 GPa） with lower hydrogen content in the fihns （~20 at.%） deposited at 10 vol.% CH4, was achieved by using the RF bias, However, the films deposited using the LF bias, under similar RF plasma generation power and CH4 concentration （50 W and 10 vol.%, respectively）, displayed lower hardness （~6-12 GPa） with high hydrogen content （~40 at.%）. The structures analyzed by Fourier Transform Infrared （FTIR） and Raman scattering measurements provide an indication of trans-polyacetylene structure formation. However, its excessive formation in the films deposited by the LF bias method is consistent with its higher bonded hydrogen concentration and low level of hardness, as compared to the film prepared by the RF bias method. It was found that the effect of RF bias on the film structure and properties is stronger than the effect of the low-frequency （LF） bias under identical radio-frequency （RF） powered electrode and identical PECVD （plasma enhanced chemical vapor deposition） system configuration.     

Plasma-Assisted Chemical Vapor Deposition of Titanium Oxide Films by Dielectric Barrier Discharge in TiCl_4/O_2/N_2 Gas Mixtures

Low-pressure dielectric barrier discharge（DBD） TiCl4/O2and N2 plasmas have been used to deposit titanium oxide films at different power supply driving frequencies. A homemade large area low pressure DBD reactor was applied, characterized by the simplicity of the experimental set-up and a low consumption of feed gas and electric power, as well as being easy to operate. Atomic force microscopy, scanning electron microscopy, energy dispersive spectroscopy,and contact angle measurements have been used to characterize the deposited films. Experimental results show all deposited films are uniform and hydrophilic with a contact angle of about 15 o.Compared to titanium oxide films deposited in TiCl4/O2gas mixtures, those in TiCl4/O2/N2gas mixtures are much more stable. The contact angle of titanium oxide films in TiCl4/O2/N2gas mixtures with the addition of 50% N2 and 20% TiCl4 is still smaller than 20 o, while that of undoped titanium oxide films is larger than 64 owhen they are measured after one week. The low-pressure TiCl4/O2plasmas consist of pulsed glow-like discharges with peak widths of several microseconds, which leads to the uniform deposition of titanium oxide films. Increasing a film thickness over several hundreds of nm leads to the film’s fragmentation due to the over-high film stress. Optical emission spectra（OES） of TiCl4/O2DBD plasmas at various power supply driving frequencies are presented.     

A Study on Optical Emission of CF4＋CH4 Plasma and Deposition Mechanisms of a-C ： F, H Films

Fluorinated amorphous carbon (a-C : F, H) films were deposited by inductively coupled plasma using CH4 and CF4 gases. Actinometrical optical emission spectroscopy (AOES) was used to determine the relative concentrations of various radicals, CF, CF2 CH, C2, H and F, in the plasma as a function of gas flow ratio R, R=[CH4]/([CH4] [CF4]). The structural evolution of the films were characterized by Fourier transform infrared transmission (FTIR) spectroscopy. The relationship between the film deposition and the precursor radicals in the plasma was discussed. It was shown that CH radical, as well as CF, CF2, C2 radicals are of the precursors, contributing to a-C : F, H film growth.     

ZrCl4蒸汽沉积法制备高温气冷堆包覆燃料颗粒ZrC涂层

采用ZrCl₄蒸汽、H₂和C₃H₆作为化学反应体系,以Ar为载气,在流化床沉积炉中制备高温气冷堆包覆燃料颗粒ZrC涂层。对所制备涂层进行了分析表征,结果显示：ZrC涂层剖面均匀光滑,无明显孔洞;与内致密热解炭层的界面清晰,厚度约为35μm;涂层主要成分为Zr和C,Zr/C摩尔比接近化学计量比1∶1,其主要相组成为面心立方的ZrC;晶粒生长无明显的择优取向。     

紫外激光荧光显微成像技术在光学薄膜损伤测试中的应用

光致荧光显微成像是观测电介质材料超微结构缺陷的有效手段。本工作研究利用KrF激光器照射光学器件表面激发的荧光成像探测光学元件薄膜激光损伤。建立了KrF激光的光致荧光成像系统,并用以进行了紫外光学镀膜损伤的现场测试。测试结果与采用Normaski显微镜的测试结果一致。     

Development of a Suppression Method for Deposition of Radioactive Cobalt after Chemical Decontamination: (I) Effect of the Ferrite Film Coating on Suppression of Cobalt Deposition

In the last decade, chemical decontamination at the beginning of periodical inspection has been applied to many Japanese BWR plants in order to reduce radiation exposure. However, following the chemical decontamination, a rapid dose rate increase can be seen in some plants after just a few operation cycles. Oxide film, which easily incorporates radioactivity, might be formed after the chemical decontamination. We developed a new way to reduce the recontamination after the chemical decontamination to maintain long-term continued decontamination effects without any chemical injections or chemical controls in reactor water during operation. In our approach, a fine ferrite film is formed by the Hitachi Ferrite Coat process after oxide films formed during the plant operation are removed by the chemical decontamination process.We select Fe(HCOO)₂ aqueous solution, H₂O₂, and N₂H₄ as the treatment chemicals for fine ferrite film formation for suitable BWR plant application. Our laboratory experiment results confirm a ⁶⁰Co deposition reduction effect of 1/5 compared with that of nontreatment for up to 3,100 hours. The fine ferritefilm that was formed on the specimen before the ⁶⁰Co deposition test remains as a film structure after the test. The corrosion amount of the specimen is suppressed to 1/4 through the effect of the fine ferrite film.