Deposition of Thin Titania Films by Dielectric Barrier Discharge at Atmospheric Pressure

A homogeneous atmospheric pressure dielectric barrier discharge is studied. It is in argon with small admixtures of titanium tetrachloride vapour and oxygen for the deposition of thin titania films on glass substrates. A special electrode configuration was applied in order to deposit the titania film uniformly. The sustaining voltage （6 kV to 12 kV）, current density （about 3 mA/cm^2） and total optical emission spectroscopy were monitored to characterize the discharge in the gap of 2 mm. Typical deposition rates ranged from approximately 30 nm/min to 120 nm/min. The film morphology was investigated by using scanning electron microscopy （SEM） and the composition was determined with an energy dispersive x-ray spectroscopy （EDS） analysis tool attached to the SEM. The crystal structure and phase composition of the films were studied by x-ray diffraction （XRD）. Several parameters such as the discharge power, the ratio of carrier gas to the precursor gas, the deposition time on the crystallization behavior, the deposition rate and the surface morphology of the titania film were extensively studied.     

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.     

Plasma Induced Grafting of PMMA onto Titanium Dioxide Powder

Grafting of polymer of methyl methacrylate （PMMA） onto titanium dioxide powder is investigated in this paper. The graft polymerization reaction is induced by dielectric-barrier- discharge produced N2 plasma treatment of titanium dioxide surfaces. IR, XPS and TGA results show that PMMA is grafted onto the surfaces of titanium dioxide powder. And crystal structure of the titanium dioxide powder observed with XRD spectra is unchanged after plasma graft polymerization.     

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.     

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.     

Growth of Fluorocarbon Films by Low-Pressure Dielectric Barrier Discharge

Plasma polymerized fluorocarbon （FC） films have been deposited on silicon substrates from dielectric barrier discharge （DBD） plasma of C4Fs at room temperature under a pressure of 25～125 Pa. The effects of the discharge pressure and frequency of power supply on the films have been systematically investigated. FC films with a less cross linked structure may be formed at a relatively high pressure. Increase in the frequency of power supply leads to a significant increase in the deposition rate. Static contact angle measurements show that deposited FC films have a stable, hydrophobic surface property. All deposited films show smooth surfaces with an atomic surface roughness. The relationship between plasma parameters and the properties of the deposited FC films are discussed.     

Growth of Free-Standing Diamond Films on Stainless Steel

Free-standing diamond films have been successfully deposited on stainless steel substrates using microwave plasma-assisted chemical vapor deposition. Although iron, which is the main element of stainless steel, is known to inhibit the nucleation of diamond and enhance the formation of graphite, we were able to grow relatively thick films （-1.2 mm）. The films were easily detachable from the substrates. The poor adhesion made it possible to obtain free-standing diamond films without chemical etching. Raman spectroscopy showed the 1332 cm^-1 characteristic Raman peak of diamond and the 1580 cm^-1, 1350 cm^-1 bands of graphite on the growth surface and backside of the films, respectively. By energy dispersive X-ray spectroscopy it was only possible to detect iron on the back of the films, but not on the surface. The role of iron in the film growth is discussed.     

Plasma Induced Grafting of PSt onto Titanium Dioxide Powder

An investigation of grafting of polymer of styrene （PSt） onto titanium dioxide powder is reported in this paper. The graft polymerization reaction was induced by N2 plasma treatment on the surface of titanium dioxide. Infrared （IR） spectra and X-ray photospectrum （XPS） results showed that PSt was grafted onto the titanium dioxide powder. An observation by X-ray diffraction （XRD） spectra indicated that the crystal structure of the titanium dioxide powder was unchanged after the plasma treatment.     

The Effects of Annealing and Discharging on the Characteristics of MgO Thin Films Prepared by Ion Beam-Assisted Deposition as a Protective Layer of AC-PDP

This study investigated the effects of annealing and discharging on the characteristics of MgO thin films prepared by ion beam-assisted deposition as a protective layer of AC-PDP. By an annealing process at a temperature of 450 ℃ for more than three hours, the crystallinity of the deposited MgO films was improved, but the surface of the （200）-oriented MgO thin films in the vicinity of the discharge electrodes, especially on the inner sides of the electrodes, was subjected to crack formation to the compressive stress of The failure mechanism of the MgO films plus the additional （200）-oriented MgO films was due compressive stress induced by the differences in the coefficient of thermal expansion between the electrode and the dielectric layer. In the discharging process, all MgO films were eroded unevenly, and the serious erosion occurred near the edges of the discharge electrodes. ATM（atomic force microscopy） images show that the eroded surface of the （200）-oriented MgO thin film is smoother than that of the （111）-oriented fihn. Also, the （200）-oriented MgO thin film shows an improved ability to resist ion erosion compared to the （111）-oriented film.     

自支撑薄膜剥离技术研究

自支撑薄膜的制备在核科学研究中至关重要。自支撑薄膜制备技术包括成膜技术和剥离技术。自支撑薄膜的成膜技术与普通有衬薄膜的相似,区别仅在于对薄膜剥离。本工作对自支撑薄膜的剥离技术进行了较为系统的研究,并在实践中比较分析各种脱膜方法及脱膜剂的优缺点。     

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity.     

Surface treatment of titanium dioxide nanopowder using rotary electrode dielectric barrier discharge reactor

Titanium dioxide (TiO2) nanopowder (P-25;Degussa AG) was treated using dielectric barrier discharge (DBD) in a rotary electrode DBD (RE-DBD) reactor.Its electrical and optical characteristics were investigated during RE-DBD generation.The treated TiO2 nanopowder properties and structures were analyzed using x-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR).After RE-DBD treatment,XRD measurements indicated that the anatase peak theta positions shifted from 25.3° to 25.1°,which can be attributed to the substitution of new functional groups in the TiO2 lattice.The FTIR results show that hydroxyl groups (OH) at 3400 cm-1 increased considerably.The mechanism used to modify the TiO2 nanopowder surface by air DBD treatment was confirmed from optical emission spectrum measurements.Reactive species,such as OH radical,ozone and atomic oxygen can play key roles in hydroxyl formation on the TiO2 nanopowder surface.     

Optical Characterization of Amorphous Hydrogenated Carbon(a-C:H)Thin Films Prepared by Single RF Plasma Method

Methane(CH4) plasma was used to produce amorphous hydrogenated carbon(aC:H) films by a single capacitively coupled radio frequency(RF) powered plasma system.The system consists of two parallel electrodes:the upper electrode is connected to 13.56 MHz RF power and the lower one is connected to the ground.Thin films were deposited on glass slides with different sizes and on silicon wafers.The influence of the plasma species on film characteristics was studied by changing the plasma parameters.The changes of plasma species during the deposition were investigated by optical emission spectroscopy(OES).The structural and optical properties were analyzed via Fourier transform infrared(FTIR) spectroscopy,X-ray diffraction(XRD) and UV-visible spectroscopy,and the thicknesses of the samples were measured by a profilometer.The sp~3/sp~2 ratio and the existing H atoms play a significant role in the determination of the chemical properties of thin films in the plasma.The film quality and deposition rate were both increased by raising the power and the flow rate.     

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。     

BIXS技术测量氚化钛膜氚活度实验方法研究

完成了BIXS能谱测量系统的组建及调试,对BIXS技术测量氚化钛膜氚活度的实验方法进行了研究。实验获得了空气和Ar气介质中的X射线能谱,与空气介质相比,除有两个相同峰位能量为4.5 keV和5.0 keV的谱峰和峰强度(或峰面积)分别减弱至约为0.4%、1%外,还增加了3.0 keV、9.0keV的两个谱峰;同时获得了不同氚活度氚化钛膜的X射线能谱,结果表明氚活度决定着X射线能谱的峰面积,具有良好的线性关系。     

基于单一气源的PECVD方法制备SiC薄膜及其微观结构研究

为制备出满足惯性约束聚变（ICF）实验要求的SiC薄膜,本文采用等离子体增强化学气相沉积（PECVD）法,以四甲基硅（TMS）作为唯一反应气源,在不同工作压强下制备SiC薄膜。利用扫描电子显微镜、表面轮廓仪、原子力显微镜、精密电子天平、X射线光电子能谱、傅里叶变换红外光谱对薄膜进行表征与分析。结果表明：SiC薄膜的成分与工作压强密切相关,随着工作压强的增加,薄膜中Si含量整体呈下降趋势;随着工作压强的增加,薄膜沉积速率先增大后减少,密度先减小后增大;与其他制备工艺相比,采用单一气源制备SiC薄膜,其表面粗糙度极低（1.25～1.85 nm）,薄膜粗糙度随工作压强的增加呈先增大后减小的趋势。     

Surface Modification of Polyethylene （PE） Films Using Dielectric Barrier Discharge Plasma at Atmospheric Pressure

Modification of the surface properties of polyethylene （PE） films is studied using air dielectric barrier discharge at atmospheric pressure. The treated samples are examined by Water contact angle measurements, Fourier transform infrared attenuated total reflection spectroscopy （FTIR-ATR）, X-ray photoelectron spectroscopy （XPS） and scanning electron microscopy （SEM）. With the increase in treating time, the water contact angle changes from 93.2° before treatment to a minimum of 53.3° after a treatment for 50 s. Both ATR and XPS results show some oxidized species are introduced into the sample surface by the plasma treatment and the tendency of the water contact angle with the treating time is the same as that of oxygen concentration on the treated sample surface. SEM result shows the surface roughness of PE samples increases with the treatment time increasing.     

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％.     

用于ICF的非晶SiC微球制备及微观结构研究

以四甲基硅烷、反式二丁烯和氢气为工作气源,采用化学气相沉积-高温热解法成功制备了壁厚约21μm的非晶SiC微球。利用能量色散X射线光谱仪、X射线光电子能谱仪、X射线衍射仪、Raman光谱仪、扫描电子显微镜、白光干涉仪和X射线照相机对SiC微球的化学成分、结晶状态、表面形貌与粗糙度以及密度与球形度等进行了测量和分析。结果表明:在无氧环境下,通过450~900℃的高温热解及致密化可将在聚α甲基苯乙烯芯轴上沉积的掺硅碳氢聚合物涂层转变成致密的SiC微球。SiC微球呈非晶态,其C/Si原子比约为1.3,主要含有C—Si键和C=C键,微观结构呈无规则状且颗粒分布均匀,密度、球形度和壁厚均匀性分别为2.62 g/cm~3、99.8%和96.8%。