Measurement of electron densities by a microwave cavity method in 13.56-MHz RF plasmas of Ar,CF4, C2F6, and CHF3

Electron densit ies have been determined /or RF plasmas that were generated within a microwave resonant cavity by measuring the difference of the resonance frequencies with and without plasma. Since that method only yields a value of the electron density weighted ouer the microwave electric field distribution, to obtain real values an assumption on the spatial distribution of the electron density had to he made. Spatial profiles were taken of the emission of a 4s–5p Ar line at 419.8 not (with a small Ar admixture). The electron densities have been determined as a function of pressure and RF power in Ar, CF₄, C₂ F₆ and CHF, plasmas. The results indicate that the electron density for the last three gases decreases as a function of pressure above 50 m Torr. Typical values for the electron density for the investigated parameter range are 1–6 · 10³ cm^–3. Furthermore, the electron density is the lowest in gases with a high attachment cross .section.     

Structural investigations of electrical conducting plasma polymerized films from 2-iodothiophene

Summary Thin plasma polymerized films were produced in a microwave (2.45 GHz) plasma discharge using 2-iodothiophene as the initial monomer. The structure of these electrically conducting films (10^–6–10^–1 S/cm), the chemical state of the doping element iodine and the elemental homogeneity at the surface and in the films have been investigated by XPS, FTIR and AES. An interesting relationship was found that indicates some similarity to conventional polythiophene, prepared by electrodeposition. Besides covalently bound iodine, considerable amounts of I ₃ ^– and I ₅ ^– were detected and also a small number of O-I bonds were identified.     

Atomic spectroscopy with surface wave plasmas

The use of microwave induced plasmas, particularly of surface wave plasmas, as detectors in atomic emission spectrometry for elemental analysis is reviewed. Surface wave plasmas have been produced at low HF power and used as gas chromatographic detectors. The analytical performances for the detection of non-metals with a Fourier transform spectrometer and a two-channel filter unit are reported. The excitation behavior of non-metals in helium-based mixed gas-plasmas has also be studied. In particular, the effect of power and of nitrogen concentration on the bromine emission has been systematically investigated. A nine-fold improvement of the detection limits for bromine can be obtained in a high power (900 W) helium-nitrogen (0.1–0.2%) plasma.     

Optical emission spectroscopy of electron-cyclotron-resonance-heated helium mirror plasmas

In this experiment emission spectroscopy in the 3000–5000 Å range has been utilized to determine the electron temperature (15–60 eV) and ion density (2–5 x 10¹¹ cm^–3) of helium plasmas produced by the Michigan mirror machine⁽¹⁾ (MIMI). The plasma is generated and heated by whistler-mode electron-cyclotron resonance (ECR) waves at 7.43 GHz with 400–900 W power in 80-ms-long pulses. Gas fueling is provided at the midplane region by a leak valve with a range in pressure of 3 x 10 to 2 x 10⁴ Torr. Emission line intensities are interpreted using a model of the important collisional and radiative processes occurring in the plasma. The model examines secondary processes such as radiation trapping, excitation transfer between levels of the carne principle quantum number, and excitation front metastable states for plasmas in the parameter range of MIMI (n _c = 1–6 x 10¹¹ cm^–3). Front the analysis of line intensity ratios for neutral helium, the electron temperature is measured and its dependence upon the gas pressure and microwave power is determined. These temperatures agree with those obtained by Langmuir probe measurements. Art analysis of the line intensity ratio between singly ionized helium and neutral helium yields a measurement of the ion density which is in good agreement with electron density measurements made by a microwave interferometer.     

A kinetic study of methane conversion by a dinitrogen microwave plasma

Conversion of CH₄ with a N₂ microwave plasma (2.45 GHz) is studied. The experiments cover the absorbed microwave power range 300–700 W with 17–62% of methane in the gas mixture, with pressures of 10–40 mbar and flow rates of 140–650 ml· min^–1. The yields of C₂ hydrocarbons and dihydrogen are analyzed by gas chromatography. The distance of methane addition downstream of the plasma plays an important role on the composition and the concentration of the products obtained. This distance mainly determines the energy concentrated in the active species of the plasma when they react with methane. Different behaviors for acetylene formation, on the one hand, and for ethane and ethene formation, on the other hand, have been observed, and this finding allows us to propose a kinetic mechanism for the decay of methane and for the formation of C₂ hydrocarbons.     

Methane conversion by an air microwave plasma

Activation of methane is carried out by means of an air microwave plasma (2.45 GHz). The experiments cover the absorbed microwave power range 350–650 W (20–50 W cm³ with 17–62%, of methane in the gas mixture, with pressures of 10–66 mbar and flow rates of 140700 ml min¹. Methane, dioxygen, and dinitrogen consumptions as well as C₂ hydrocarbons, carbon monoxide, and dihydrogen yields are analyzed hr gas chromatography. The distance of methane addition from the end of the discharge plays an important role in the composition and the concentration of the products obtained. This distance mainly determines the energy concentrated in the active species of the plasma when they react with methane. A kinetic mechanism jar the activation and decay of inethane and for the formation of C₂ hydrocarbons and carbon monoxide is discussed based on the experimental results and kinetic data in the literature.     

Microwave Diagnostics in Diffusive and Constricted Medium-Pressure Discharges

The high-frequency (HF) electron current induced in a dc discharge plasma bysuperimposing a HF electric field presents a useful tool for the diagnosticsof the time-dependent electron behavior of the plasma. This response to theHF field has been recently studied in diffusive discharge plasmas at lowergas pressures and discharge currents. These studies are extended tomedium-pressure plasmas operating in the diffusive as well as in theconstricted mode. In particular, the impact of the electron–electroninteraction on the phase delay between the HF field and electron current inconstricted column plasmas has been experimentally and theoreticallyanalyzed. Furthermore, the problem has been studied if, under the conditionsof pronounced electron–electron interaction, the determination of theelectron density will further on be possible by using the phase delay. Themeasurements of the delay have been performed by means of the microwaveresonator method in a medium-pressure krypton glow discharge operating inthe diffusive as well as the strongly constricted mode. In addition, thedelay has been theoretically determined by treating the appropriatetime-dependent electron kinetic equation at high frequencies of thesuperimposed microwave field.     

Tunable Diode Laser Diagnostic Studies of H2-Ar-O2 Microwave Plasmas Containing Methane or Methanol

Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and ten stable molecules in H₂-Ar-O₂ microwave plasmas containing up to 7.2% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbons varied between 30 and 90% and the methyl radical concentration was found to be in the range 10 ¹⁰ –10 ¹² molecules cm ^–3 . The methyl radical concentration and the concentrations of the stable C-2 hydrocarbons C ₂ H ₂ , C ₂ H ₄ , and C ₂ H ₆ , produced in the plasma decayed exponentially when increasing amounts of O ₂ were added at fixed methane or methanol partial pressures. In addition to detecting the hydrocarbon species, the major products CO, CO ₂ , and H ₂ O were also monitored. For the first time, formaldehyde, formic acid, and methane were detected in methanol microwave plasmas, formaldehyde was detected in methane microwave plasmas. Chemical modeling with 57 reactions was used to successfully predict the concentrations in methane plasmas in the absence of oxygen and the trends for the major chemical product species as oxygen was added.     

Nitriding of titanium with plasma jet under reduced pressure

The nitriding of titanium with argon-nitrogen (3%) and argon-nitrogen (3%)-hydrogen (2%) plasma jets at pressures of 190 torr was studied. The reaction kinetics obeyed mainly a parabolic law. The parabolic kinetic constants were 10^–10–10^–8 g² cm^–4 s^–1, which were 2–3 orders of magnitude larger than those in R.F. discharges. From emission spectroscopy, nitrogen atoms in the excited states were observed. The nitrogen atoms can promote the nitriding reaction. The effect of the addition of hydrogen to nitrogen is also briefly discussed.     

In-Flight Spheroidization of Alumina Powders in Ar–H<Subscript>2</Subscript> and Ar–N<Subscript>2</Subscript> Induction Plasmas

In-flight spheroidization of alumina powders in Ar–H₂ (H₂–7.6%, vol/vol) and Ar–N₂ (N₂–13.0%, vol/vol) RF induction plasmas was investigated numerically and experimentally. The mathematical model for the plasma flows incorporates the k– turbulence model, and that for particles is the Particle-Source-in-Cell (PSI-Cell) model. Experimental results demonstrate that spheroidized alumina particles are produced in both Ar–H₂ and Ar–N₂ RF plasmas, with different particle size distributions and crystal phases. Agreement between the predicted and measured particle size distributions is satisfactory under high particle feed rate conditions, while the results obtained for the Ar–H₂ plasma are better than those for the Ar–N₂ plasma. The discrepancy occurring in low feed rate conditions suggests that particle evaporation is an important factor affecting the plasma–particle heat transfer.     

Attachment and ionization in a self-consistent treatment of the electron kinetics of a collision-dominated rf plasma

This paper deals with the self-consistent determination of the rf field amplitude for sustaining the steady-state collision-dominated weakley ionized plasmas in the bulk of the rf discharge and of the time-resolved behavior of the isotropic part of the distribution function as well as of relevant macroscopic quantities in plasmas whose particle loss is dominantly determined by electron attachment. The strict timeresolved treatment is based on the nonstationary Boltzmann equation of the electrons and its numerical solution including, apart from electron number conservative collision processes, the electron attachment and ionization. The investigations are related to an rf plasma in a model gas and in SF₆ and are performed for reduced rf field frequencies around 10 MHz Torr^–1 which are of particular interest from the point of application of rf discharges for plasma processing. The numerical results show that a large field amplitude of around 160 V cm^–1 Torr^–1 is necessary to maintain the discharge and that the isotropic distribution, the relevant collision frequencies for attachment and ionization, and the electron density undergo a large modulation during a period of the rf field.     

Effect of RF and microwave oxygen plasma on the performance of Pd gate MOS sensor for hydrogen

The combined effect of microwave and RF oxygen plasma treatment of SiO₂ surface on the hydrogen sensitivity of Pd gate MOS sensor has been studied. Nine different samples of thermally grown SiO₂ surface have been taken and treated with oxygen plasma of different microwave power (100 W, 150 W and 200 W respectively) while keeping RF power fixed (20 W) for different durations (5 min, 10 min and 15 min). Pd gate MOS sensors with these plasma treated SiO₂ surface as dielectric have been fabricated and tested for different concentrations (500–3500 ppm) of hydrogen at room temperature. It is observed that the sensitivity of the sensor increases for higher duration of plasma exposure and also with microwave power but decreases when the sensor is treated with 200 W microwave power for 10 min and 15 min durations. The sensor treated with oxygen plasma of 200 W microwave power for 5 min duration exhibited the highest hydrogen sensitivity (74.4%). Fixed oxide charge density has also been evaluated as a function of exposure time for varying microwave power. Surface morphology of plasma treated SiO₂ surfaces was studied by AFM to have the estimation of porosity. The high sensitivity can be attributed to the fact that oxygen plasma treatment provides the availability of higher number of adsorption sites and modification in the surface state density i.e. surface state density increases for plasma treated sensors.     

The role of dissociative attachment from Rydberg states in enhancing H concentration in moderate- and low-pressure H2 plasma sources

A numerical code, recently developed for describing the kinetics of H₂ microwave discharges obtained in diamond deposition plasma reactors, was used to estimate the importance of dissociative attachment from H₂ Rydberg states in enhancing the production of H⁻ in this kind of discharge. It was also used to investigate H⁻ production in multicusp low-pressure magnetic plasmas. Results show that the dissociative attachment from Rydberg states can be as important as the mechanism involving vibrationally excited molecules in both types of plasmas.     

The influence of flow rate and pressure on the excitation conditions in low-pressure microwave induced plasmas

Using a double probe technique, electron temperatures and electron concentrations together with spectral line intensities have been measured in low-pressure microwave induced plasmas at various pressures and flow rates of monoatomic and polyatomic support gases. For two distinct pressures viz. 0.2 and 1.0 torr (0.267–1.333 mbar) the flow rate has been independently varied.

Measurements of spectral-line intensities in the absence and presence of the probes demonstrate that the probes exert little or no influence upon the plasma conditions. The results show that when low-pressure microwave induced plasmas in flow systems are applied for quantitative analytical purposes exact specification of both flow rate and pressure of the carrier gas is required.     

Comparison of the effect of excimer laser irradiation and RF plasma treatment on polystyrene surface

Polystyrene (PS) samples were treated with excimer laser, argon and oxygen plasmas. The surface of PS was irradiated using ArF excimer pulsed laser (λ=193 nm). Radio frequency glow discharge (RF) was used to generate the argon and oxygen plasmas. The samples were processed at different number of pulses and treatment times. The changes were characterized by atomic force microscopy (AFM), attenuated total reflectance Fourier transform infrared (ATR-FTIR), scanning electron microscopy (SEM) and contact angle measurements. The data from ATR-FTIR spectra showed the induction process of oxygen-based functional group in both PS samples treated with RF plasma and laser. AFM and SEM observations demonstrated that a specific nanostructure was created on the laser-treated PS surface. Contact angle measurement indicated higher wettability of the treated PS with both argon and oxygen plasmas and lesser wettability of laser-treated samples. The data from in vitro assays showed the significant cell attachment and growth onto plasma-treated surfaces in comparison with laser treated samples.     

Hybrid electron cyclotron resonance-radio-frequency plasma etching of III–V semiconductors in Cl2-based discharges. Part II: InP and related compounds

Electron Cyclotron Resonance (ECR) discharges of CCl₂F₂ or PCl₃ have been used to etch InP, InAs, InSb, InGaAs and AlInAs. The etch rates of these materials increase linearly with additional RF power level applied to the cathode and are in the range 50–180 Å · min^–1 for 50 W (DC bias 308 V), 10 mTorr, 38 CCl₂F₂/2 O₂ plasmas. The etch rates fall rapidly with increasing pressure or increasing O₂-to-CCl₂F₂ ratio. Polymeric surface residues up to 40 Å thick are found on all of these semiconductors when using Freon-based gas mixtures. Etching at practical rates is possible with only 100 V self-bias when using PCl₃ discharges, and the addition of microwave excitation under these conditions enhances the etch rates by factors of 2–9. At higher self-biases (300 V) etch rates of 3500–8000 Å · min^–1 are possible with PCl₃ although the surface morphologies are significantly rougher and the etching less anisotropic than with CCl₂F₂-based mixtures.     

Rapid analysis of fluoxetine and its metabolite in plasma by LC-MS with column-switching approach

A rapid and sensitive method was developed for the simultaneous determination of fluoxetine and its primary metabolite, norfluoxetine, in plasma. It was based on a column-switching approach with a precolumn packed with large size particles coupled with a liquid chromatography–electrospray ionisation–mass spectrometry (LC-ESI-MS). After a simple centrifugation, plasma samples were directly injected onto the precolumn. The endogenous material was excluded thanks to a high flow rate while analytes were retained by hydrophobic interactions. Afterwards, the target compounds were eluted in back flush mode to an octadecyl analytical column and detected by ESI-MS. The overall analysis time per sample, from plasma sample preparation to data acquisition, was achieved in less than 4 min. Method performances were evaluated. The method showed good linearity in the range of 25–1000 ng mL^–1 with a determination coefficient higher than 0.99. Limits of quantification were estimated at 25 ng mL^–1 for fluoxetine and norfluoxetine. Moreover, method precision was better than 6% in the studied concentration range. These results demonstrated that the method could be used to quantify target compounds. Finally, the developed assay proved to be suitable for the simultaneous analysis of fluoxetine and its metabolite in real plasma samples.     

Static pressure and heat flux measurements of a thermal argon plasma flow in a water-cooled tube

The momentum and energy transfer phenomena with large temperature difference were investigated experimentally and theoretically, using an argon atmospheric thermal plasma. The plasma was generated by an arc discharge, 4–6 kW, and flowed into a water-cooled copper tube for static pressure measurements and into a copper block with the same size hole (8 mm i.d.) for measuring heat fluxes using a transient method. The argon flow rate was 2.77–8.31×10^–4 kg/s. The static pressure of the plasma flow shows a different variation from that of an ordinary flow and does not decrease monotonically. The axial distributions of the numerical calculations are in fair agreement with those of the experiments, and it is concluded that the contributions of recombination and of physical properties play important roles in the behavior of the confined thermal plasma flow.     

Multilayer graphene/amorphous carbon hybrid films prepared by microwave surface‐wave plasma CVD: synthesis and characterization

Hybrid films of multilayer graphene (MG) containing amorphous carbon (a‐C) were synthesized on Al substrates by microwave surface‐wave plasma chemical vapor deposition. Raman scattering and surface transmission electron microscopy showed that the carbon films contained a large quantity of MG when a radio frequency (RF) substrate bias was not applied. Amorphization of graphene in the carbon film was promoted by applying an RF bias, which generated Ar⁺ in the plasma. The bandgaps of the films were found to increase as the Raman intensity ratios between the 2D‐band (at 2700 cm^?1) and D‐band (at 1350 cm^?1) decreased, indicating the formation of a‐C. The MG/a‐C all‐sp² phase of carbon hybrid films exhibited an increase in current density under 5 mW/cm² of AM1.5G solar simulated irradiation as the RF bias increased because of Ar⁺‐induced amorphization of the graphene. Copyright © 2016 John Wiley & Sons, Ltd.     

Some observations on the development of a gas chromatographic microwave plasma ionization detector

A novel gas chromatographic microwave plasma ionization detector (MPID) has been developed. The detector is based on the ionization of analyte caused by microwave plasma or the ionization quenching of microwave plasma by the analyte. The detector is simple in construction and can be operated without dangerous gas. It responds with high sensitivity to various kinds of chemical species that can be treated by GC. The sensitivities to 39 chemical species were shown to be in the range of 10⁻¹¹ − 10⁻⁷ g/sec.