Pulsed-Spray Radiofrequency Plasma Enhanced Chemical Vapor Deposition of CuInS2 Thin Films

Thin films of CuInS₂ were grown on various substrates at a temperature of 523 K from two metal-organic precursors using radiofrequency plasma enhanced chemical vapor deposition (PECVD). Two precursor molecules, with different solubility properties, were dissolved in appropriate solvents and sprayed into the plasma region in the PECVD chamber. The resulting films were examined for atomic composition, growth rate, crystalline orientation, and uniformity. Films made from each precursor differed in thickness, atomic composition, and crystallinity. The uniformity of the film was fairly good from near the edge to the center of the substrate, and evidence for a chalcopyrite-like structure was found in several samples deposited from one of the precursor molecules.     

Structure,Composition, Mechanical,and Tribological Properties of BCN Films Deposited by Plasma Enhanced Chemical Vapor Deposition

In this work thin BCN films were deposited by plasma enhanced chemical vapor deposition (PECVD) using chloridic precursors. Through adjusting the BCl₃ content in the inlet gas mixture the chemical composition of the deposited films was changed from carbon rich to boron rich. Based on optical emission spectroscopy (OES) measurements, a correlation between film composition and precursor species concentration in the plasma was established. The films were amorphous as detected by grazing incidence X-ray diffraction (GIXRD). The hardness and the elastic modulus have maximal values of 25.5±1.2 and 191±6 GPa, respectively, for the films with a boron concentration of 45.2 at.%. GIXRD data suggest that a depletion in boron content may initiate the formation of graphitic domains in the amorphous matrix. The observed degradation of the mechanical properties is associated with the graphitization. The tribological behavior was studied with a tribometer operated in pin-on-plate configuration at the temperatures 25 and 400°C. The wear mechanisms were discussed with respect to the formation of a boric acid surface layer which was detected by reflection electron energy loss spectroscopy (REELS) analysis.     

沉积温度对等离子增强化学气相沉积法制备的SiNx:H薄膜特性的影响

利用Centrotherm公司生产的管式等离子增强化学气相沉积(PECVD)设备在p型抛光硅片表面沉积SiN_x:H薄膜, 研究沉积温度对SiN_x:H薄膜的组成及光学特性、结构及表面钝化特性的影响. 然后采用工业化的单晶硅太阳电池制作设备和工艺制作太阳电池, 研究不同温度制备的薄膜对电池电性能的影响. 测试结果表明: SiN_x:H薄膜的折射率随着沉积温度的升高而变大, 分布在1.926-2.231之间, 这表明Si/N摩尔比随着沉积温度的增加而增加; 当沉积温度增加时, 薄膜中Si－H键和N－H键浓度呈现减小趋势, 而Si－N键浓度逐渐升高, 薄膜致密度增加; 随着沉积温度的升高, SiN_x:H薄膜中的氢析出导致了钝化硅片的有效少子寿命先升高后降低, 并且有效少子寿命出现明显的时间衰减特性. 当沉积温度为450 °C时, 薄膜具有最优的减反射和表面钝化效果. 采用不同温度PECVD制备的5组电池的电性能测试结果也验证了这一结果.     

脉冲激光沉积法制备SnSe薄膜电极及其电化学性质

采用脉冲激光溅射Sn和Se粉末的混合靶制备SnSe薄膜, XRD结果显示室温下得到的是Sn和Se的混合薄膜, 当基片温度为200 ℃时, 薄膜主要由晶态的SnSe组成. 该薄膜的首次放电容量为498 mAh•g-1, 30次循环之后的放电容量为260 mAh•g-1. 充放电测试、循环伏安曲线和ex-situ XRD结果显示, SnSe能够和Li发生可逆的电化学反应, 充电过程中能够重新生成SnSe, 表现出不同于其它氧族元素锡化物的电化学性质.     

Microstructure and Chemical Bonding in Silicon Carbonitride Films Synthesized by Plasma Enhanced Chemical Vapor Deposition

Silicon carbonitride films were synthesized by plasma enhanced chemical vapor deposition using silyl derivatives of asymmetric dimethylhydrazine, (CH₃)₂HSiNHN(CH₃)₂ and (CH₃)₂Si[NHN(CH₃)₂]₂, as molecular precursors. The film material consists of an amorphous matrix with nanocrystalline inclusions. Indexing of synchrotron radiation Xray diffraction patterns suggests that the structure of the nanocrystals is tetragonal with lattice parameters a = 9.6 and c = 6.4. Xray photoelectron spectra indicate that Si—N and C—N sp ³ hybrid bonds are predominant. The absence of G or Dmodes in Raman spectra, which are otherwise typical of structures possessing sp ² bonding, provides further support for the tetragonal structure of the nanocrystals.     

脉冲激光沉积LiFePO4阴极薄膜材料及其电化学性能

采用脉冲激光沉积结合高温退火的方法在不锈钢基片上制备了LiFePO₄薄膜电极. XRD谱图显示, 经650 ℃退火制得的是具有橄榄石结构的LiFePO₄薄膜. 充放电测试表明, LiFePO₄薄膜具有3.45/3.40 V的充放电平台, 与LiFePO₄粉体材料相当. 首次放电容量约为27 mAh•g^－1, 充放电循环100次后容量衰减51%.     

The Role of Oxygen Dissociation in Plasma Enhanced Chemical Vapor Deposition of Zinc Oxide from Oxygen and Diethyl Zinc

The influence of electron impact dissociation of oxygen on neutral chemistry was studied for plasma-enhanced chemical vapor deposition (PECVD) of zinc oxide using oxygen and diethyl zinc. Electron conditions in the reactor were estimated based on simulations of well-known Ar-O₂ plasmas, while the majority of the thermal chemistry was abstracted from the combustion literature. A rudimentary model of film growth was developed using the rate of oxygen dissociation as the lone adjustable parameter.n Model results were compared directly with experimental measurements of deposition rates and neutral species densities for a wide range of conditions. Good quantitative agreement between experiments and model were observed as a function of composition and rf power. The system is highly sensitive to the electron impact dissociation of oxygen, which creates the radical pool that drives the majority of the chemistry. The approach detailed here provides a framework for the development of models of oxide PECVD derived from other metalorganic precursors.     

Plasma Enhanced Chemical Vapor Deposition of Fluorinated Amorphous Carbon Thin Films from Tetrafluoroethylene and Tetraisocyanatesilane

Fluorinated amorphous carbon films were prepared from tetrafluoroethylene (TFE; C₂F₄) and tetraisocyanatesilane (TICS; Si(NCO)₄) using an RF plasma enhanced chemical vapor deposition method for the purpose of application to inter layer low permittivity films used in large scale integrated circuits. Structure of the deposited films was investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Adhesion characteristics were examined by a tape-peel method. Permittivity of the films was investigated from capacitance measurement on metal-insulator-semiconductor structure. The structural analysis revealed that the deposited films contained imide-like group in spite of the fact that TICS molecules contained isocyanate group . The films deposited under the flow ratio TICS/(TFE + TICS) = 70% showed permittivity of 2.3, good adhesion on silicon substrates, and higher thermal stability than the films deposited without TICS.     

Plasma Enhanced Chemical Vapor Deposition of Poly(Cyclohexyl Methacrylate) as a Sacrificial Thin Film

Plasma Chemistry and Plasma Processing - In this study, thin films of poly(cyclohexyl methacrylate) (PCHMA) were deposited on silicon wafer using PECVD technique, in which the plasma power is...     

Use of Neural Network to Control a Refractive Index of SiN Film Deposited by Plasma Enhanced Chemical Vapor Deposition

Refractive index of silicon nitride film deposited in a plasma enhanced chemical deposition system is modeled by using neural network. The deposition process was characterized with a full factorial experiment. Additional 12 experiments were conducted to test model appropriateness. Predicted model behaviors were in good agreement with actual measurements. Deposition mechanisms were qualitatively examined especially with respect to the pressure. Possible interactions between the pressure and other factors (SiH₄, NH₃, radio frequency (RF) power, and substrate temperature) were examined on the basis of SiH/NH bond ratio. The refractive index increased with increasing either SiH₄ flow rate or RF power. In contrast, the refractive index decreased with increasing NH₃ flow rate. Little interactions between the pressure and RF power were observed. Pressure effect on the refractive index was quite different depending on the level of SiH₄ flow rate or substrate temperature. In general, increasing the pressure increased the refractive index. Meanwhile, the refractive index was insensitive to parameter variations at relatively high pressures. The most complex interaction occurred as the pressure interacted with the temperature. Useful clues to control the refractive index were revealed from the predictive model.     

Electroluminescence and Photoluminescence of Conjugated Polymer Films Prepared by Plasma Enhanced Chemical Vapor Deposition of Naphthalene

Polymer light-emitting devices were fabricated utilizing plasma polymerized thin films as emissive layers. These conjugated polymer films were prepared by RF plasma enhanced chemical vapor deposition using naphthalene as monomer. The effect of different applied powers on the chemical structure and optical properties of the conjugated polymers was investigated. Fourier transform infrared (FTIR) and Raman spectroscopies confirmed that a conjugated polymer film with a 3-D cross-linked network was developed. By increasing the power, products tended to form as highly cross-linked polymer films. The fabricated devices showed broadband Electroluminescence (EL) emission peaks with center at 535–550 nm. Photoluminescence (PL) spectra of plasma polymers showed different excimeric emissions, resulted from crosslinked architecture. As the plasma power increased, the optical properties showed two different domains; up to 200 W, EL, PL and UV–Vis spectra red-shifted and broadened significantly. At higher powers, a reverse behavior was observed. Also, the relation between the film structure and plasma species was investigated using optical emission spectroscopy.     

The Application of Nano-SiOx Coatings as Migration Resistance Layer by Plasma Enhanced Chemical Vapor Deposition

Accumulative intake of plasticizers that are generally used to produce flexibility of webs in plastics has been proven to cause reproductive system problems and women??s infertility, and long-term consumption may even cause cancer. Hence a nano-scale layer, named as functional barrier layer, was deposited on the plastic surface to prevent plasticizer diethylhexyl phthalate (DEHP) migration from food-contact materials to foods. The feasibility of a functional barrier layer, i.e. SiO_x coating through plasma enhanced chemical vapor deposition process was then described in this paper. In this research we used Fourier transform infrared spectroscope to analyze the chemical composition of the coatings, scanning electron microscope to explore the topography of the coating surfaces, surface profilemeter to measure coating thickness in plastics, and high-performance liquid chromatography to evaluate the barrier properties of coatings. The results have clearly shown that the coatings can perfectly block the migration of the DEHP from plastics to their containers. It is to be noted that process parameters had a critical influence on the block properties of coatings. When the deposition conditions of SiO_x coatings were optimized, i.e. the discharge power of 50?W, 4:1 of O₂: HMDSO ratio and the thickness of 100?nm, the 71.2?% DEHP was effectively blocked in the plastic film.     

微波等离子体化学气相沉积法低温制备直纳米碳管膜

Among the three main methods for the synthesis of carbon nanotubes (CNTs)， chemical vapor deposition (CVD) has received a great deal of attention since CNTs can be synthesized at significantly low temperature. Plasma chemical vapor deposition methods can synthesize CNTs at lower temperature than thermal CVD. But in the usual catalytic growth of CNTs by CVD， CNTs are often tangled together and have some defects. These will limit the property research and potential applications. How to synthesize the straight CNTs at low temperature becomes a challenging issue. In this letter， straight carbon nanotube (CNT) films were achieved by microwave plasma chemical vapor deposition (MWPCVD) catalyzed by round Fe-Co-Ni alloy particles on Ni substrate at 610℃. It was found that， in our experimental condition， the uniform growth rate along the circumference of round alloy particles plays a very important role in the growth of straight CNT films. And because the substrate is conducting， the straight CNT films grown at low temperature may have the benefit for property research and offer the possibility to use them in the future applications.     

微波等离子体辅助化学气相沉积法低温合成定向碳纳米管阵列

自碳纳米管被发现以来[1] ,这种准一维纳米新材料由于其优异的力学、电学、储氢等理化性质而显示出非常重要的理论研究与实际应用价值[2 ,3] .碳纳米管阵列更可作为场致发射器件 ,有望应用于冷阴极平板显示器或纳米电子学等前沿领域[4 ] ,成为碳纳米管研究中的热点 .在已有报道的多种制备碳纳米管阵列的方法中 ,以孔性硅或孔性 Al2 O3作为模板剂 ,通过化学气相沉积制备的方法较为普遍[5～ 7] ,但此类方法往往需要在较高温度 (高于 70 0℃[6 ,7] )下进行 ,对于碳纳米管阵列最诱人的应用前景之一平板显示器而言 ,要求在显示玻璃表面直接生长…     

CVD法制备单壁碳纳米管的纯化与表征

针对CVD法合成的单壁碳纳米管的特点提出了较为有效的纯化方法，并对纯化后碳管的存在形式进行了表征.结果表明,CVD法制备的单壁碳纳米管中所含的载体和催化剂绝大部分可以通过盐酸除去.在表面活性剂溶液中超声分散碳纳米管,可以使管与无定形碳及石墨状碎片进行有效的剥离.空气加热氧化法和稀硝酸回流法可有效地去除碳杂质,稀硝酸回流可以在纯化的同时对管的末端及侧壁进行功能化.     

An Investigation of the Plasma Composition in Plasma-enhanced Hot Filament Catalytic Chemical Vapor Deposition of Carbon Nanotubes

A mixture of acetylene, hydrogen and ammonia (C₂H₂/H₂/NH₃) is used to produce carbon nanotubes (CNTs) by a plasma-enhanced catalytic chemical vapor deposition process either without (PE CCVD) or with hot filaments-assistance (PE HF CCVD). A mathematical model based on Chemkin^™ computer package is used for analyzing specific conditions of nanotube synthesis. Simulations are compared with optical emission spectroscopy (OES) measurements. Morphological and structural investigations on the grown carbon nanostructures are also performed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was shown that the significant change in the density and the morphology of the CNTs grown in the presence of NH₃ could be mainly explained by the gas phase formation of CN and HCN. Both species display a high etching activity, whereas the species C, CH, CH₂, CH₂(S), C₂ and C₂H are expected to be the most probable carbon nanotube precursors.     

Atomic Hydrogen Induced Chemical Vapor Deposition of Silicon Oxycarbide Thin Films Derived from Diethoxymethylsilane Precursor

Amorphous silicon oxycarbide (a-SiOC:H) films produced by remote plasma RPCVD from diethoxymethylsilane (DEMS) were characterized in terms of their basic properties related to the coatings deposited using conventional plasma enhanced PECVD method. The effect of substrate temperature (T_S) on the growth rate, chemical composition, structure, and properties of resulting a-SiOC:H films is reported. Film growth is an adsorption-controlled process, wherein two mechanisms can be distinguished with a transition at about T_S=70°C. Depending on the temperature, films of different nature can be obtained, from polymer-like to highly crosslinked material with C-Si-O network. The chemical structure of a-SiOC:H films was characterized by FTIR, ¹³C and ²⁹Si solid-state NMR, and X-ray photoelectron spectroscopes. The a-SiOC:H films were also characterized in terms of their density, refractive index, surface morphology, conformality of coverage, hardness, adhesion to a substrate, and friction coefficient. The films were found to be morphologically homogeneous materials exhibiting good conformality of coverage and small surface roughness. Their refractive index exhibits anomalous effect revealing a minimum value at T_S=125°C. Due to their exceptional physical properties a-SiOC:H films produced by RPCVD from DEMS precursor seems to be useful as potential dielectric materials or coatings for various encapsulation applications.     

化学气相淀积法合成氮化铝薄膜及其工艺设计

对ＡｌＢｒ３－ＮＨ３－Ｎ２体系化学气相淀积法合成Ａ１Ｎ膜进行了热力学分析和工艺设计，研究了在不同淀积温度和体系总压时，体系中主要气态物种的平衡分压和Ａ１Ｎ膜的理论淀积速率与源温和载气流量的关系，并与微波等离子体化学气相淀积Ａ１Ｎ膜的实验结果进行了比较。     

Molecular Beam Mass Spectrometry System for Characterization of Thermal Plasma Chemical Vapor Deposition

A molecular beam mass spectrometry system for in situ measurement of the concentration of gas phase species including radicals impinging on a substrate during thermal plasma chemical vapor deposition (TPCVD) has been designed and constructed. Dynamically controlled substrate temperature was achieved using a variable thermal contact resistance method via a backside flow of an argon/helium mixture. A high quality molecular beam with beamtobackground signal greater than 20 was obtained under film growth conditions by sampling through a small nozzle (75 m) in the center of the substrate. Mass discrimination effects were accounted for in order to quantify the species measurements. We demonstrate that this system has a minimum detection limit of under 100 ppb. Quantitative measurements of hydrocarbon species (H, H₂, C, CH₃, CH₄, C₂H₂, C₂H₄) using Ar/H₂/CH₄ mixtures and silicon species (Si, SiH, SiH₂, SiCl, SiCl₂, Cl, HCl) using Ar/H₂/SiCl₄ mixtures were obtained under thermal plasma chemical vapor deposition conditions.     

Cross‐Linking and Degradation Properties of Plasma Enhanced Chemical Vapor Deposited Poly(2‐hydroxyethyl methacrylate)

Plasma Enhanced Chemical Vapor Deposition (PECVD) of poly‐2‐hydroxyethyl methacrylate (pHEMA) biocompatible, biodegradable polymer films were produced alone and cross‐linked with ethylene glycol diacrylate (EGDA). Degree of cross‐linking was controlled via manipulation of the EGDA flow rate, which influenced the amount of swelling and the extent of degradation of the films in an aqueous solution over time. Noncross‐linked pHEMA films swelled 10% more than cross‐linked films after 24 h of incubation in an aqueous environment. Increasing degree of film cross‐linking decreased degradation over time. Thus, PECVD pHEMA films with variable cross‐linking properties enable tuning of gel formation and degradation properties, making these films useful in a variety of biologically significant applications.