Time history of diesel particle deposition in cylindrical dielectric barrier discharge reactors

Non-thermal plasma (NTP) treatment reactors have recently been developed for elimination of diesel particulate matter for reducing both the mass and number concentration of particles. The role of the plasma itself is obscured by the phenomenon of particle deposition on the reactor surface. Therefore, in this study, the Lagrangian particle transport model is used to simulate the dispersion and deposition of nano-particles in the range of 5 to 500 nm in a NTP reactor in the absence of an electric field. A conventional cylindrical dielectric barrier discharge reactor is selected for the analysis. Brownian diffusion, gravity and Saffman lift forces were included in the simulations, and the deposition efficiencies of different sized diesel particles were studied. The results show that for the studied particle diameters, the effect of Saffman lift is negligible and gravity only affects the motion of particles with a diameter of 500 nm or larger. Time histories of particle transport and deposition were evaluated for one-time injection and a continuous (multiple-time) injection. The results show that the number of deposited particles for one-time injection is identical to the number of deposited particles for multiple-time injections when adjusted with the shift in time. Furthermore, the maximum number of escaped particles occurs at 0.045 s after the injection for all particle diameters. The presented results show that some particle reduction previously ascribed to plasma treatment has ignored contributions from the surface deposition.     

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     

First nucleation steps during deposition of SiO2 thin films by plasma enhanced chemical vapour deposition

The initial nucleation stages during deposition of SiO₂ by remote plasma enhanced chemical vapour deposition (PECVD) have been monitored by XPS inelastic peak shape analysis. Experiments have been carried out on two substrates, a flat ZrO₂ thin film and a silicon wafer with a native silicon oxide layer on its surface. For the two substrates it is found that PECVD SiO₂ grows in the form of islands. When the SiO₂ particles reach heights close to 10 nm they coalesce and cover completely the substrate surface. The particle formation mechanism has been confirmed by TEM observation of the particles grown on silicon substrates. The kinetic Monte Carlo simulation of the nucleation and growth of the SiO₂ particles has shown that formation of islands is favoured under PECVD conditions because the plasma species may reach the substrate surface according to off-perpendicular directions. The average energy of these species is the main parameter used to describe their angular distribution function, while the reactivity of the surface is another key parameter used in the simulations.     

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.     

Two-dimensional model of a large area, inductively coupled,rectangular plasma source for chemical vapor deposition

A novel design for an inductively coupled, rectangular plasma source is described. The design encompasses several key issues of large area thin film growth by chemical vapor deposition: structural integrity, electrostatic screening, substrate temperature control and maximal growth surface. A test reactor has been utilized to grow diamond films over ~1800 cm² at 13 MHz and ~1 torr pressure with 45 kW coupled power. The design is readily scalable to larger areas. To analyze the axial plasma uniformity, a two-dimensional (2-D) simulation model is presented. The electromagnetic coupling, nonequilibrium plasma chemistry and multispecies diffusion are self-consistently treated. In this 2-D approach, the slotted Faraday screen behaves as a diamagnetic medium in transmitting the magnetic field. Results are compared with experimental data for the hydrogen plasma extent, electron and gas temperatures. Neutral gas thermal conduction and hydrogen recombination dominate the energy deposition to the wall and in turn govern the plasma length. A tradeoff between quality and growth area is predicted for the reactor as the pressure is decreased     

PECVD制备AZO（ZnO:Al）透明导电薄膜

采用PECVD（等离子体增强化学气相沉积）工艺在普通玻璃和Si基上制备出了方块电阻低至89 Ω,可见光透过率高达79%,对基体附着力强的多晶态的AZO（ZnO:Al）薄膜.采用PECVD法制备AZO薄膜是一种有益的尝试,AZO透明导电薄膜不仅具有与ITO（透明导电薄膜,如In₂O₃:Sn）可比拟的光电特性,而且价格低廉、无毒,在氢等离子体环境中更稳定,所获结果对实际工艺条件的选择具有一定借鉴作用和参考价值. 关键词： AZO（ZnO:Al） 等离子体增强化学气相沉积 透明导电薄膜     

Influence of inert gas pressure on deposition rate during pulsed laser deposition

The deposition rates of permalloy and Ag are monitored during pulsed laser deposition in different inert gas atmospheres. Under ultrahigh vacuum conditions, resputtering from the film surface occurs due to the presence of energetic particles in the plasma plume. With increasing gas pressure, a reduction of the particle energy is accompanied with a decrease of resputtering and a rise in the deposition rate for materials with high sputtering yield. In contrast, at higher gas pressures, scattering of ablated material out of the deposition path between target and substrate is observed, leading to a decrease in the deposition rate. While in the case of Xe and Ar these processes strongly overlap, they are best separated in He. A He pressure of about 0.4 mbar should be used to reduce the kinetic energy of the deposited particles, to reach the maximum deposition rate and to avoid implantation of the particles. This is helpful for the preparation of stoichiometric metallic alloy films and multilayers with sharp interfaces. Received: 27 March 2002 / Accepted: 3 April 2002 / Published online: 5 July 2002     

Detection of free radicals produced by a pulsed electrohydraulic discharge using electron spin resonance

The detection of free radicals such as hydroxyl radical and hydrogen radical for plasma in solution induced by a pulsed electrohydraulic discharge are successfully performed using electron spin resonance measurement. The plasma reactor is a barrier-type and consists of a stainless needle high-voltage (+35 to 65 kV) electrode partially immersed in the solution and a Pyrex glass solution container around which an aluminum film grounded electrode is wrapped. Streamers are induced in the solution. After adding iron (II) sulfate or radical trapping agent before the plasma application, the spectrum for radicals is clearly detected. A reactive dye solution is dramatically decolorized.     

A point source analytical model of inverse pulsed laser deposition

A simple analytical model for inverse pulsed laser deposition is proposed. In the model the motion of the evaporated material is assumed to emerge as from a point source located above the surface of evaporation at some distance. The obtained thickness profiles of inverse deposited films agree well with those calculated by the test particle Monte Carlo method. The proposed approach has been applied for analysis of experimental data on inverse pulsed laser deposition of graphite in nitrogen atmosphere with nanosecond pulses of laser fluences between 1 and 7 J/cm². The model describes well the thickness profiles and pressure dependence of film growth rate for inverse deposition.     

Patterned deposition by plasma enhanced spatial atomic layer deposition

An atmospheric pressure plasma enhanced atomic layer deposition reactor has been developed, to deposit Al₂O₃ films from trimethyl aluminum and an He/O₂ plasma. This technique can be used for 2D patterned deposition in a single in‐line process by making use of switched localized plasma sources. It was observed that the sharpness of the patterns is primarily influenced by the concentration of reactive plasma species and by the dimensions of the plasma source. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Description of a hybrid PECVD-PVD process: Application to Zn-Si-O and Ti-Si-O composites thin films

A radio frequency hybrid process where sputtering and plasma enhanced chemical vapour deposition (PECVD) occur simultaneously is studied to describe the specificity it gains when the two techniques are merged. A model is developed to describe how the deposition rate evolves when the flow rate of the PECVD precursor increases. First, it is shown that it is constant below a critical value of the precursor flow rate because of the wind effect due to sputtering that strongly limits the transport of the precursor. Then it increases almost linearly with the precursor flow rate when PECVD and sputtering simultaneously occur. Finally, above a certain threshold in the precursor flow rate, the surface of the target is poisoned by the precursor and composite thin films can no longer grow. The previous model is deduced from results obtained in deposition of Zn-Si-O and Ti-Si-O thin films. These composites are synthesised respectively by sputtering of zinc and titanium targets in a vapour of oxygen and hexamethyldisiloxane (HMDSO-Si₂C₆H₁₈O). Limitations of the model used are also discussed.     

Deposition of thick and adherent Teflon-like coating on industrial scale stainless steel shell using pulsed dc and RF PECVD

A unique combination of pulsed dc and radio frequency (RF) discharge deposition was used to deposit thick (∼5 μm) and adherent (2-4 MPa) Teflon-like coatings on a stainless steel (SS) shell of 2 m diameter size, through plasma enhanced chemical vapor deposition (PECVD). The details of deposition on such a big industrial scale component are reported for the first time. In this method, highly adherent thin interface layers were grown on SS shell that was electrically grounded, using pulsed dc discharge, followed by RF discharge deposition to build up the required coating thickness. The fluorocarbon precursor molecules, required for the deposition of Teflon-like coating, are generated indigenously by pyrolyzing the Teflon powder. The deposited coating was studied for its chemical bond state, surface roughness (Ra), morphology, thickness, and adhesive strength. These studies were carried out by using XPS, AFM, SEM, etc. The adhesive strength of the coating was measured by pin-pull test as per ASTM D4541 standard test. The coatings deposited with pulsed dc discharge were observed to have higher adhesive strength when compared with those deposited with RF discharge.     

时间、能量分辨的光电离质谱技术研究气相自由基反应

闪光光解流动管反应器与同步辐射光电离质谱技术两者相结合组成实验平台用于探测气相自由基反应动力学。外触发的脉冲激光光解流动管反应器内的先驱物来产生待反应的自由基;自由基与反应气体发生反应后,由流动管侧壁小孔取样、取样后的混合气体被同步辐射光电离;飞行时间质谱探测光电离产生的离子。同时脉冲信号触发脉冲发生器使其产生一连串的脉冲,间隔40~50μs,此脉冲外触发质谱的采集,连续采集覆盖单次光解反应过程。质谱的时间分辨率为40μs,满足微秒时间内探测反应动力学过程。通过同步辐射光电离反射飞行质谱能直接探测自由基反应产物,并利用光电离效率曲线获得其电离能并区分不同的异构体。实验利用光解产生Cl自由基并与1-丁烯和异丁烯反应,测得反应的加成和消除产物,并获得其加成产物的电离能。     

Laser processing for deposition of high Tc superconducting films

Model considerations are applied to investigate the process of pulsed laser deposition of high T_c superconducting films. At low power densities, heat conduction and evaporation above a thermal threshold energy dominate. Increase of the laser flux results in the generation of a dense plasma with a mass ablation flow away from the target. According to different wave lengths the relation of the energy density to the pulse duration is estimated. Very short light pulses above a threshold energy density favour the ablation of a stoichiometric mass flow from a multicomponent target and suppress evaporation according to different vapor pressures.     

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.     

Inverse pulsed laser deposition

Since the advent of pulsed laser deposition (PLD), several different target-substrate arrangements have been proposed. Besides the most common on-axis PLD, several off-axis geometries were studied, mainly to protect the substrate from the agglomerated species (clusters, droplets, particulates) of the plasma plume, which are detrimental to the homogeneity of films. Recently we introduced a novel geometry, termed inverse pulsed laser deposition (IPLD), in which the substrate is placed parallel to and slightly above the target plane. In this paper we summarize our results on this new geometry, and show how it can extend the perspectives of pulsed laser deposition, e.g., by improving the surface morphology of the films. Effects of ambient pressure are presented and exemplified on metallic and compound IPLD films, including Ti, CN _x , and Ti-oxides. AFM topographic images are used to prove that under optimized conditions IPLD is capable of growing compact and smooth films that are superior to PLD ones. A special—but easy-to-implement—IPLD arrangement is also introduced that considerably improves the homogeneity of IPLD films. In this geometry, the properties (e.g., deposition rate and roughness) of the films grown in the 1–25 Pa pressure domain are examined.     

Modeling of hazardous air pollutant removal in the pulsed corona discharge

This study investigated the effects of two parts of the performance equation of the pulsed corona reactor, which is one of the non-thermal plasma processing tools of atmospheric pressure for eliminating pollutant streams. First, the effect of axial dispersion in the diffusion term and then the effect of different orders of the reaction in the decomposition rate term were considered. The mathematical model was primarily developed to predict the effluent concentration of the pulsed corona reactor using mass balance, and considering axial dispersion, linear velocity and decomposition rate of pollutant. The steady state form of this equation was subsequently solved assuming different reaction orders. For the derivation of the performance equation of the reactor, it was assumed that the decomposition rate of the pollutant was directly proportional to discharge power and the concentration of the pollutant. The results were validated and compared with another predicted model using their experimental data. The model developed in this study was also validated with two other experimental data in the literature for N₂O.     

Diamond-like-carbon films produced by magnetically guided pulsed laser deposition

We have compared the quality of carbon films deposited with magnetically guided pulsed laser deposition (MGPLD) and conventional pulsed laser deposition (PLD). In MGPLD, a curved magnetic field is used to guide the plasma but not the neutral species to the substrate to deposit the films while, in conventional PLD, the film is deposited with a mixture of ions, neutral species and clusters. A KrF laser pulse (248 nm) was focused to intensities of 10 GW/cm² on a carbon source target and a magnetic field strength of 0.3 T was used to steer the plasma around a curved arc to the deposition substrate. Electron energy loss spectroscopy was used in order to measure the fraction of sp³ bonding in the films produced. It is shown that the sp³ fraction, and hence the diamond-like character of the films, increased when deposited only with the pure ion component by MGPLD compared with films produced by the conventional PLD technique. The dependence of film quality on the laser intensity is also discussed. Received: 7 December 2000 / Accepted: 20 August 2001 / Published online: 2 October 2001     

A study of the Soret effect in laser-induced chemical vapor deposition

This paper presents an investigation of the modeling of the process of pyrolytic laser-induced chemical vapor deposition (LCVD) applied to study the Soret effect. LCVD is a thermally activated process characterized by strongly coupled mass and energy transport phenomena, together with chemical reactions, which are difficult to investigate experimentally. A physical and numerical model based on a commercial computational fluid dynamics package is developed and used to simulate a reactor operating at conditions of room temperature and pressure. The proposed numerical methodology will allow us to assess and analyze the effect of various factors controlling the process, and in particular the Soret effect. This numerical model is validated by comparison with the measured growth rate of the fiber. While several studies have proposed simulations of the LCVD process, this is among the first attempts at including the Soret effect in the numerical modeling at the micro-scale level. It is expected that the fundamental insights thus obtained will guide experimental investigations which can be applied to establish reactor design and process control guidelines.     

Low temperature plasma assisted atomic layer deposition in nitrogen carrier gas studied by optical emission spectroscopy

A low temperature plasma assisted atomic layer deposition process from tetrakis (dimethylamino)-titanium (TDMAT) and oxygen plasma was investigated using optical emission spectroscopy in a commercial TFS-500 atomic layer deposition reactor in industrial-like conditions with different plasma powers to optimize the plasma-assisted deposition process and to develop a tool for process control. The major emitting species recognized were the nitrogen first followed by the second positive system, carbon monoxide, nitrogen monoxide (γ)-system, atomic carbon and atomic nitrogen. The process measurements were compared to background measurements to see the process induced differences. CH _x appearance in the plasma lowered the intensities of CO, NO and N₂ 1st⁺ system peaks. Also, the nitrogen atom content varied in the process measurements. By monitoring the affected species and vibrational temperature, the effect of TDMAT oxidation on the surface could be seen through the resulting changes in the plasma emission.