Investigations on the effect of process parameters on the growth of vertically oriented graphene sheet in plasma-enhanced chemical vapour deposition system

A multistage numerical model comprising the plasma kinetics and surface deposition sub-models is developed to study the influence of process parameters, namely, total gas pressure and input plasma power on the plasma chemistry and growth characteristics of vertically oriented graphene sheets (VOGS) grown in the plasma-enhanced chemical vapour deposition system containing the Ar + H₂ + C₂H₂ reactive gas mixture. The spectral and spatial distributions of temperature and number densities, respectively, of plasma species, that is, charged and neutral species in the plasma reactor, are examined using inductively coupled plasma module of COMSOL Multiphysics 5.2 modelling suite. The numerical data from the computational plasma model are fed as the input parameters for the surface deposition model, and from the simulation results, it is found that there is a significant drop in the densities of various plasma species as one goes from the bulk plasma region to the substrate surface. The significant loss of the energetic electrons is observed in the plasma region at high pressure (for constant input power) and low input power (for constant gas pressure). At low pressure, the carbon species generate at higher rates on the catalyst nanoislands surface, thus enhancing the growth and surface density of VOGS. However, it is found that VOGS growth rate increases when input plasma power is raised from 100 to 300 W and decreases with further increase in the plasma power. A good comparison of the model outcomes with the available experimental results confirms the adequacy of the present model.     

Kinetics of chemical vapor deposition of SiC from methyltrichlorosilane and hydrogen

In this study, the dependence of the deposition rate on processing parameters, such as temperature, and partial pressure is studied by chemical vapor deposition from mixture of methyltrichlorosilane (CH₃SiCl₃, MTS) and hydrogen. The kinetics investigation is carried out in a tubular, hot-wall reactor coupled to a sensitive magnetic suspension microbalance. The results show that the active energy limited by surface reactions is 188 kJ/mol. In the case, the deposition rate is linear to the partial pressure of MTS and the square of partial pressure of hydrogen. SiCl₂ and CH₃ are proposed as the effective precursor for SiC. A reaction model was proposed concluding gas phase reactions and surface reactions. The theoretical relation between deposition rate and partial pressures of MTS and H₂ was in a good accordance with experimental results.     

The effects of process conditions on the plasma characteristic in radio-frequency capacitively coupled SiH4/NH3/N2 plasmas: Two-dimensional simulations

A two-dimensional (2D) fluid model is presented to study the behavior of silicon plasma mixed with SiH4 , N2 , and NH3 in a radio-frequency capacitively coupled plasma (CCP) reactor. The plasma-wall interaction (including the deposition) is modeled by using surface reaction coefficients. In the present paper we try to identify, by numerical simulations, the effect of variations of the process parameters on the plasma properties. It is found from our simulations that by increasing the gas pressure and the discharge gap, the electron density profile shape changes continuously from an edge-high to a center-high, thus the thin films become more uniform. Moreover, as the N2 /NH3 ratio increases from 6/13 to 10/9, the hydrogen content can be significantly decreased, without decreasing the electron density significantly.     

Explosion model applied to an intense pulsed plasma source for thinfilm deposition

A pulsed plasma source for deposition of thin polymer films was modeled numerically with the one-dimensional (1-D) time dependent fluid transport equations describing an explosion for an ideal gas. Initial number density, explosion temperature, and velocity were made consistent with values in an experimental reactor. These quantities as well as pressure and fluence were modeled for a distance of 2 m and for a time duration of 93 μs. The trajectory for maximum pressure calculated from the model was observed to be consistent with the experimentally measured trajectory of maximum emitted light from an acetylene plasma. Measured axial profiles of areal density for the deposited polymer films were compared with modeled fluence     

磁场-微波等离子体与大面积金刚石薄膜

在磁场辅助下电子回旋共振(ECR)效应在大的空间范围形成高密度的等离子体,为大面积金刚石薄膜的淀积提供有利条件,以CH₄-H₂为原料气体,在Si基片上,在比其他制备方法更低的压强(3Torr附近)下已制备出直径约为5cm的金刚石薄膜,从空间等离子体范围来看且有可能达更大的面积,在分析等离子体发射光谱的基础上,对0.5到50Torr压强的金刚石气相生长条件作了讨论。 关键词：     

管式等离子体化学气相沉积质量转换动力过程的研究

本文对管式装置中等离子体化学气相沉积过程提出了一种数学描述方式,具体讨论了沉积过程中活性粒子产生频率、沉积速率和沉积效率等与电子密度、气体流速、气体压强等的相互关系,并对部分结果进行了理论解释。 关键词：     

Atomic hydrogen concentration mapping in thermal plasma chemical vapour deposition

Two-dimensional maps of atomic hydrogen concentration in reactive gas layers were measured using two-photon laser-induced fluorescence. The measurements were made in conditions of diamond-film chemical vapour deposition using a thermal inductively coupled plasma. Their purpose was to investigate the influence of the atomic hydrogen concentration in the reactive gas layer on the diamond growth. Concentration maps were obtained under parametric variation of the plasma flow conditions. Axial profiles were extracted from the measured maps and compared to temperature profiles measured by Rayleigh scattering to determine the degree of chemical non-equilibrium in the reactive layer. The non-uniform quenching over the measured area was accounted for with an iterative calculation of the species concentrations. For small differences of the atomic hydrogen concentration in the reactive layer a large variation in quality of the grown diamond was observed. Received: 28 June 2000 / Revised version: 6 October 2000 / Published online: 21 February 2001     

Protective structures on the surface of zirconium components of light water reactor cores: Formation,testing, and prototype equipment

The results of tests of plasma treatment of zirconium and deposition of protective yttrium coatings used as the methods of protection of zirconium components of light water reactor cores against hydrogenation are detailed. The amount of hydrogen in the treated sample exposed to superheated steam for 2500 h at temperature T = 400°C and pressure p = 1 atm was five times lower than the corresponding value for the untreated one. The amount of hydrogen in the sample coated with yttrium remained almost unchanged in 4000 h of exposure. A plasma method for rapid testing for hydrogen resistance is proposed. The hydrogenation rate provided by this method is 700 times higher than that in tests with superheated steam. The results of preliminary experiments confirm the possibility of constructing a unit for batch processing of the surfaces of fuel rod claddings.     

Deposition of diamond structures from interacting gas jets

We have reported on the results of experiments on the gas-jet synthesis of diamond from methane and hydrogen flows for various mixing conditions. An original method of separate feed of gas jet has been proposed, which makes it possible to attain a high growth rate for the diamond phase. The synthesis of diamond structures in gas-jet deposition has been studied for separate feeds of two flows (hydrogen and the mixture of hydrogen with methane) in two versions, i.e., with a lateral feed of the methane-containing mixture and axisymmetric feed. Experiments were performed under the following conditions: the temperature of the surface (activating hydrogen) 2400 K, a substrate temperature of 900–1300 K, pressure in the deposition chamber 2 × 10² Pa, gas mixture fluxes (relative to hydrogen) 1500 ncm³/min, CH₄ concentration in H₂ of 0.1–0.7%, and the distance from the substrate to the reactor 10 mm. In the case of a separate feed of the methanecontaining gas and hydrogen, a deposition rate of 20 μm/h was attained. In the case of an axisymmetric separate feed of the gases, a single crystal with a mass of 0.6 mg was grown, which corresponded to the deposition rate of approximately 200 μm/h.     

Modeling of plasma-etch processes using well stirred reactorapproximations and including complex gas-phase and surfacereactions

A 0-D or well stirred reactor model determines spatially and time-averaged species composition in plasma-etch reactors, through solution of species, mass, and electron-energy balance equations. The use of well stirred reactor approximations reduces the computational expense of detailed kinetics calculations and allows investigation of the dependence of plasma chemistry on etch-process parameters. The reactor is characterized by a chamber volume, surface area, net mass flow or residence time, pressure, energy loss to surroundings, power deposition, and inlet-gas composition. The electron-energy equation includes a detailed power balance with losses to ions and electrons through the sheath, as well as inelastic and elastic collision losses. The model employs reaction-rate coefficients for electron-impact reactions, which require an assumption of the electron energy distribution function (EEDF). We compare model results using Maxwellian EEDF's, as well as reaction-rate coefficients determined as a function of average electron energy through solution of the Boltzmann equation, for chlorine chemistry. The Boltzmann rates are determined by time-lagging the equilibration of electrons with applied electric fields. The Maxwellian reaction rates give higher ionization fractions than the Boltzmann rates, affecting the predicted electronegativity and positive ion composition for chlorine plasmas. The model also shows a strong sensitivity of the plasma composition to the assumed surface-recombination probability of atomic chlorine     

射频容性耦合等离子体放电特性的光谱诊断

利用流体模型模拟和发射光谱实验诊断相结合的方法,研究了中等气压、中等功率下射频容性耦合等离子体的放电特性。理论上,采用基于流体模型的COMSOL软件仿真,建立一维等离子体放电模型,以Ar气为工作气体,研究了不同气压以及不同射频输入功率下等离子体电子温度和电子密度的分布规律。实验上,依据仿真模型设计制作了相同尺寸的密闭玻璃腔体和平板电极,采用13.56 MHz射频放电技术电离腔体内的工作气体Ar气,测量了不同气压、不同射频输入功率时放电等离子体的发射光谱。通过分析和选择适当的Ar Ⅰ和Ar Ⅱ的特征谱线,分别利用玻尔兹曼斜率法以及沙哈-玻尔兹曼方程计算了等离子体的电子温度与电子密度,并结合模拟仿真结果对光谱诊断结果进行了修正。结果表明：当气体压强为300~400 Pa、输入功率为600~800 W时,等离子体近似服从玻尔兹曼分布,此时利用光谱法得到的等离子体参数与仿真结果相符合。仿真模拟与光谱实验诊断相结合的方法可初步诊断出中等气压下等离子体的放电参数,增加了玻尔兹曼斜率法和沙哈-玻尔兹曼方程在等离子体放电中的使用范围,扩大了光谱法在低电子密度容性耦合等离子体参数诊断的应用场合,为中等气压容性耦合等离子体在工业与军事上的应用研究提供了重要物理状态的分析手段。     

Diamond deposition with plasma jet at reduced pressure

Carburizing and diamond deposition experiments were done on titanium, niobium, and molybdenum substrates with argon-methane-hydrogen gas mixture plasma jets at a pressure of 200 torr for various hydrogen concentrations. Diamond deposition was obtained at a volume of 7% hydrogen added to the plasma jet. The deposits were markedly different on the different metal substrates. Diamond deposits with habit planes were clearly observed on niobium and molybdenum, while the deposit on titanium consisted of ball-like particles. The emission spectra from the plasma jet were the same, for all the substrates, proving that the difference in the diamond deposit depends on the substrate characteristics. CH, C₂, hydrogen, and carbon atoms were identified in the plasma jet. The difference in the deposits is attributed to the reactivity of carbon species in the plasma with the metal surface as well as to the solubility of hydrogen in metals     

Flow Field and Temperature Field in GaN-MOCVD Reactor Based on Computational Fluid Dynamics Modeling

Metal organic chemical vapor deposition(MOCVD) growth systems are one of the main types of equipment used for growing single crystal materials, such as GaN. To obtain film epitaxial materials with uniform performance,the flow field and temperature field in a GaN-MOCVD reactor are investigated by modeling and simulating. To make the simulation results more consistent with the actual situation, the gases in the reactor are considered to be compressible, making it possible to investigate the distributions of gas density and pressure in the reactor.The computational fluid dynamics method is used to study the effects of inlet gas flow velocity, pressure in the reactor, rotational speed of graphite susceptor, and gases used in the growth, which has great guiding significance for the growth of GaN film materials.     

The high deposition of microcrystalline silicon thin film by very high frequency plasma enhanced chemical vapour deposition and the fabrication of solar cells

This paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with Hchemical vapour deposition, plasma deposition, solar cells, crystallinityProgram supported by the State Key Development Program for Basic Research of China (Grant No 2006CB202601), and Basic Research Project of Henan Province in China (Grant No 072300410140).7280N, 7830G, 8115HThis paper reports that the intrinsic microcrystalline silicon ($\mu $c-Si:H) films are prepared with plasma enhanced chemical vapour deposition from silane/hydrogen mixtures at 200\du\ with the aim to increase the deposition rate. An increase of the deposition rate to 0.88\,nm/s is obtained by using a plasma excitation frequency of 75\,MHz. This increase is obtained by the combination of a higher deposition pressure, an increased silane concentration, and higher discharge powers. In addition, the transient behaviour, which can decrease the film crystallinity, could be prevented by filling the background gas with H$_{2}$ prior to plasma ignition, and selecting proper discharging time after silane flow injection. Material prepared under these conditions at a deposition rate of 0.78\,nm/s maintains higher crystallinity and fine electronic properties. By H-plasma treatment before i-layer deposition, single junction $\mu $c-Si:H solar cells with 5.5{\%} efficiency are fabricated.     

Mass transport characteristics in a pulsed plasma enhanced chemicalvapor deposition reactor for thin polymer film deposition

A pulsed plasma enhanced chemical vapor deposition (PECVD) reactor is used for the preparation of thin polyacetylene films. A theoretical model based on the mass transport characteristics of the reactor is developed in order to correlate with experimentally obtained spatial deposition profiles for the acetylene plasma polymer film deposited within the cylindrical reactor. Utilizing a free radical mechanism with gas phase initiation of the polymerization reaction as the rate controlling step, a system parametric study is performed to predict the Peclet number range of operation for the pulsed PECVD reactor. This parametric study indicates radical decay by diffusion to the reactor walls to be the significant physical phenomenon in the system. It is concluded that a quasi-steady-state model is a good tool for predicting the important mass transfer phenomena occurring in the pulsed plasma reactor     

Two-dimensional atomic hydrogen concentration maps in hot-filament diamond-deposition environment

This paper reports the two-dimensional mapping of atomic hydrogen concentration with two-photon excited laser induced fluorescence in a multi-wire grid hot-filament chemical vapor deposition reactor. The measurements were made in a diamond film deposition environment under different filament temperatures and wire configurations. The measurement was calibrated with a titration reaction using NO₂ as a titrant. The kinetic gas temperature in the reactor was measured from the Doppler broadening of the Lyman-β transition excited in the fluorescence. The filament temperature was found to have a significant effect on atomic hydrogen production and transfer to the substrate. The axial concentration distributions were compared to a one-dimensional kinetic gas–surface chemistry model with good agreement. The model produced a reasonable estimate for the bulk diamond film growth rate. Received: 25 June 2001 / Revised version: 15 February 2002 / Published online: 2 May 2002     

Two-dimensional simulation of inductive plasma sources withself-consistent power deposition

A time averaged two-dimensional fluid model including an electromagnetic module with self-consistent power deposition was developed to simulate the transport of a low pressure radio frequency inductively coupled plasma source. Comparisons with experiment and previous simulation results show that the fluid model is feasible in a certain range of gas pressure. In addition, the effects of gas pressure and power input have been discussed     

Two-dimensional fluid model simulation of bell jar top inductivelycoupled plasma

In the present paper, argon (Ar) plasmas in a bell jar inductively coupled plasma (ICP) source are systematically studied over pressures from 5 to 20 mtorr and power inputs from 0.2 to 0.5 kW. In this study, both a two-dimensional (2-D) fluid model simulation and global model calculation are compared. The 2-D fluid model simulation with a self-consistent power deposition is developed to describe the Ar plasma behaviour as well as predict the plasma parameter distributions. Finally, a quantitative comparison between the global model and the fluid model is made to test their validity     

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在微波化学气相沉积装置上采用微波激发氢气甲烷体系等离子体,通过光学多道分析仪采集等离子的发射光谱.实验表明,甲烷在等离子体中的裂解产物主要以CH,CH-,C2基团的形式存在.这些基团的发射光谱强度主要受放电压强和放电功率的影响.随着微波功率的增加甲烷基团发射光谱强度呈增长的趋势;而随着放电压强的增加则是先增大,后减小.这些实验结果对于理解微波等离子体化学气相沉积(MPCVD)中各种反应过程,调整薄膜制备工艺提供了参考.     

Effects of deposition pressure and plasma power on the growth and properties of boron-doped microcrystalline silicon films

Using diborane as doping gas, p-doped μc-Si：H layers are deposited by using the plasma enhanced chemical vapour deposition （PECVD） technology. The effects of deposition pressure and plasma power on the growth and the properties of μc-Si：H layers are investigated. The results show that the deposition rate, the electrical and the structural properties are all strongly dependent on deposition pressure and plasma power. Boron-doped μc-Si：H films with a dark conductivity as high as 1.42 Ω^-1·cm^-1 and a crystallinity of above 50% are obtained. With this p-layer, μc-Si：H solar cells are fabricated. In addition, the mechanism for the effects of deposition pressure and plasma power on the growth and the properties of boron-doped μc-Si：H layers is discussed.