Plasma Gas Phase Research Articles

The effect of gas phase plasma treatment on the anthocyanin and phenolic acid content of sour cherry Marasca (Prunus cerasus var. Marasca) juice

The purpose of this research was to evaluate the effect of cold atmospheric pressure gas phase plasma treatment on anthocyanins and phenolic acids in sour cherry Marasca juice. Plasma treatment was optimized using a response surface methodology regarding the treatment time, sample volume and applied gas flow and compared to thermal pasteurization and untreated juice. Short treatment (3 min) of larger volume of the juice (3 mL) resulted in the highest concentration of both anthocyanins and phenolic acids. Compared to pasteurized and untreated juice, plasma treated sour cherry Marasca juice at optimized conditions had higher amount of phenolic compounds. Observed increase in phenolic compounds content in sour cherry Marasca juices could be a result of undefined small-sized aggregates or particles, which would be dissociated by the plasma treatment.

Microwave Plasma Synthesis of Materials—From Physics and Chemistry to Nanoparticles: A Materials Scientist’s Viewpoint

In this review, microwave plasma gas-phase synthesis of inorganic materials and material groups is discussed from the application-oriented perspective of a materials scientist: why and how microwave plasmas are applied for the synthesis of materials? First, key players in this research field will be identified, and a brief overview on publication history on this topic is given. The fundamental basics, necessary to understand the processes ongoing in particle synthesis—one of the main applications of microwave plasma processes—and the influence of the relevant experimental parameters on the resulting particles and their properties will be addressed. The benefit of using microwave plasma instead of conventional gas phase processes with respect to chemical reactivity and crystallite nucleation will be reviewed. The criteria, how to choose an appropriate precursor to synthesize a specific material with an intended application is discussed. A tabular overview on all type of materials synthesized in microwave plasmas and other plasma methods will be given, including relevant citations. Finally, property examples of three groups of nanomaterials synthesized with microwave plasma methods, bare Fe2O3 nanoparticles, different core/shell ceramic/organic shell nanoparticles, and Sn-based nanocomposites, will be described exemplarily, comprising perspectives of applications.

The effect of substrate temperature and growth rate on the doping efficiency of single crystal boron doped diamond

The substrate growth temperature dependence of the plasma gas-phase to solid-phase doping efficiency in single crystal, boron doped diamond (BDD) deposition is investigated. Single crystal diamond (SCD) is grown by microwave plasma assisted chemical vapor deposition (MPACVD) on high pressure, high temperature (HPHT) type Ib substrates. Samples are grown at substrate temperatures of 850–950°C for each of five doping concentration levels, to determine the effect of the growth temperature on the doping efficiency and defect morphology. The substrate temperature during growth is shown to have a significant effect on the grown sample defect morphology, and a temperature dependence of the doping efficiency is also shown. The effect of the growth rate on the doping efficiency is discussed, and the ratio of the boron concentration in the gas phase to the flux of carbon incorporated into the solid diamond phase is shown to be a more predictive measure of the resulting boron concentration than the gas phase boron to carbon ratio that is more commonly reported.

Synthesis of mono-dispersed nanofluids using solution plasma.

Small-sized and well-dispersed gold nanoparticles (NPs) for nanofluidics have been synthesized by electrical discharge in liquid environment using termed solution plasma processing (SPP). Electrons and the hydrogen radicals are reducing the gold ions to the neutral form in plasma gas phase and liquid phase, respectively. The gold NPs have the smallest diameter of 4.9 nm when the solution temperature was kept at 20 °C. Nucleation and growth theory describe the evolution of the NP diameter right after the reduction reaction in function of the system temperature, NP surface energy, dispersion energy barrier, and nucleation rate. Negative charges on the NPs surface during and after SPP generate repulsive forces among the NPs avoiding their agglomeration in solution. Increasing the average energy in the SPP determines a decrease of the zeta potential and an increase of the NPs diameter. An important enhancement of the thermal conductivity of 9.4% was measured for the synthesized nanofluids containing NPs with the smallest size.

Plasma polymerization chemistry of unsaturated hydrocarbons: neutral species identification by mass spectrometry

Radio frequency discharges ignited in low-pressure and pure hydrocarbon gases were investigated by mass spectrometry. The plasma process was applied to four unsaturated monomers: styrene C8H8, benzene C6H6, ethylene C2H4 and acetylene C2H2. The remote mass spectrometer location restricted species identification to neutral closed-shell molecules in their respective plasmas. Among the peaks in the mass spectra, those directly due to neutrals produced in the plasma were determined following a successful two-step methodology. Firstly, the use of low electron impact energy limited the fragmentation and strongly simplified the cracking patterns. Secondly, attribution of peaks directly due to neutrals was confirmed or ruled out by systematically measuring their appearance potential. In the case of styrene, not less than 48 new molecules were detected.The discussion of the observed stable by-products in each discharge suggested several radicals responsible for their production. Comparing the set of species among the four plasmas showed that the repeated addition of intermediates with one or two carbon atoms and with low H content dominated the chemistry. Under our conditions of intermediate to high W/FM (power over mass flow ratio), the gas-phase plasma polymerization then preferentially occurred through significant fragmentation and recombination. Finally, the measured appearance potentials during plasma provided estimation for the threshold ionization energy of several highly unsaturated hydrocarbons, useful for modeling.

Controlled doping of silicon nanocrystals investigated by solution-processed field effect transistors.

The doping of semiconductor nanocrystals (NCs), which is vital for the optimization of NC-based devices, remains a significant challenge. While gas-phase plasma approaches have been successful in incorporating dopant atoms into NCs, little is known about their electronic activation. Here, we investigate the electronic properties of doped silicon NC thin films cast from solution by field effect transistor analysis. We find that, analogous to bulk silicon, boron and phosphorus electronically dope Si NC thin films; however, the dopant activation efficiency is only ∼10(-2)-10(-4). We also show that surface doping of Si NCs is an effective way to alter the carrier concentrations in Si NC films.

Enhancing the ammonia to hydrogen (ATH) energy efficiency of alternating current arc discharge

In order to enhance the ammonia to hydrogen (ATH) energy efficiency, systematic study was carried out with atmospheric pressure alternating current arc discharge reactor (using a pair of stainless steel (SS) tube electrodes). Results showed that, using small-diameter SS tube electrodes with small discharge gaps forced more ammonia molecules to go through the effective plasma volume and obtained high electrodes temperature. Adopting low discharge frequency increased the discharge time, the effective plasma volume and the electrode temperature. These changes can enhance both the gas-phase plasma decomposition and the electrode-surface catalytic decomposition of ammonia. Insulating the reactor significantly increased the electrode temperature in small-diameter reactor, so as to enhance the electrode-surface catalytic decomposition of ammonia. In large-diameter reactors, however, the electrodes temperature increased less rapidly and more ammonia bypass of the effective plasma volume occurred. A 12.5 mol/kW h ATH energy efficiency was reached when ammonia was completely converted under the conditions of electrode diameter 3 mm, electrode gap 4 mm, discharge frequency 5 kHz, reactor diameter 8 mm, NH3 flow rate 150 ml/min and input power 48 W. The ATH energy efficiency was further enhanced under similar conditions when incomplete ammonia conversion was allowed.

Numerical simulation of electric double layer in contact with dielectric barrier discharge: Effects of ion transport parameters in liquid

The spatiotemporal distribution of charged particles has been investigated through numerical simulation of charged particle behavior in gas and liquid phases in the dielectric barrier discharge of Ar gas in contact with a liquid. In the case of a liquid with a low ion concentration such as de-ionized water, the amount of liquid-phase ions generated by electron or ion irradiation from gas-phase plasma is higher by approximately one order of magnitude than that in the pure electric double layer formed only with the potential difference between the top and bottom of the liquid. When the molecular weight of the ions is larger, the residence time of the ions at the liquid surface becomes longer. If the molecular weight of positive and negative ions is different, heavier ions become dominant at the liquid surface. These characteristics are pronounced by employing a higher frequency voltage, which implies the possibility of preferential reactions at the plasma-liquid interface.

Boron- and phosphorus-doped silicon germanium alloy nanocrystals—Nonthermal plasma synthesis and gas-phase thin film deposition

Alloyed silicon-germanium (SiGe) nanostructures are the topic of renewed research due to applications in modern optoelectronics and high-temperature thermoelectric materials. However, common techniques for producing nanostructured SiGe focus on bulk processing; therefore little is known of the physical properties of SiGe nanocrystals (NCs) synthesized from molecular precursors. In this letter, we synthesize and deposit thin films of doped SiGe NCs using a single, flow-through nonthermal plasma reactor and inertial impaction. Using x-ray and vibrational analysis, we show that the SiGe NC structure appears truly alloyed for Si1−xGex for 0.16 < x < 0.24, and quantify the atomic dopant incorporation within the SiGe NC films.

The Gas Nucleation Process Study of Anatase TiO2 in Atmospheric Non-Thermal Plasma Enhanced Chemical Vapor Deposition

The gas phase nucleation process of anatase TiO2 in atmospheric non-thermal plasma enhanced chemical vapor deposition is studied. The particles synthesized in the plasma gas phase at different power density were collected outside of the reactor. The structure of the collected particles has been investigated by field scanning electron microscope (FESEM), X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). The analysis shows that uniform crystalline nuclei with average size of several nanometers have been formed in the scale of micro second through this reactive atmospheric plasma gas process. The crystallinity of the nanoparticles increases with power density. The high density of crystalline nanonuclei in the plasma gas phase and the low gas temperature are beneficial to the fast deposition of the 3D porous anatase TiO2 film.

Carbon Nanotube-Polypyrrole Composite Electrode Materials Produced In Situ by Electron Bombardment in Radio-Frequency Plasma Afterglows

Free electrons, produced in radio-frequency (13.56 MHz) glow discharges of O2, N2, and Ar, are recruited to multi-walled carbon nanotubes (MWNTs) by a positive electric field. Electron bombardment degradation is restricted to the tips of the MWNTs. SEM images show that a surface deposited layer develops during degradation. Gas phase plasma reactions form polycyclic aromatic hydrocarbons and plasma polymers, which are re-deposited on the MWNTs as thin films. The plasma polymer is identified as a polypyrrole (PPy)-like plasma polymer, as shown by molecular optical absorption spectroscopy and GC–MS. FT-IR spectra confirm that the surface films are composed of the same plasma polymer. Inert gas plasmas produce higher-molecular weight plasma polymers, while O2 plasma treatments produce over-oxidized polypyrrolic-plasma polymer films.

Probing plasma–surface interactions with the transmission electron microscope or the Si–collector interface of the plasma bipolar junction transistor

Two platforms developed to probe the plasma–solid interface are briefly reviewed here. A sensitive diagnostic of the interaction between a low-temperature plasma and a silicon surface is provided by the plasma bipolar junction transistor (PBJT) in which e−–h+ (semiconductor) and e−–ion (gas phase) plasmas are separated by a nanoscale potential barrier but coupled by a strong (>1 V µm−1) electric field. Electrical properties of the Si base–collector plasma interface are controlled by the bias applied to the PBJT emitter-base junction, as well as the morphology and electronic structure of the base surface facing the collector plasma. Recent experiments are described in which the Si(100) surface of the PBJT base is transformed into black Si, a nanostructured array comprising ∼3 × 109 nanocones. Each cone is ∼100 nm in height and has a radius of curvature at its tip of <1 nm. Altering the base surface so as to intentionally enhance field emission results in burst-mode operation of the PBJT in which the collector current oscillates as a result of the periodic contraction (or collapse) and revival of the plasma sheath. The observed oscillation frequencies (3.6–13 kHz) are consistent with the transit time of ions across the sheath. Integration of a microplasma device with a transmission electron microscope has also been realized recently (Tai et al 2013 Sci. Rep. 3 1325). This diagnostic tool allows plasma–surface interactions to be observed in real-time with a spatial resolution <100 nm. Although initial experiments concerned the growth of Au islands in a dc plasma, the extension of this probe to nanostructured and spatially modulated surfaces is proposed.

Effects of hydrocarbon contamination on ozone generation with dielectric barrier discharges

The increasing usage of the feed gases of lower grade liquid oxygen (LOX) containing higher levels of trace hydrocarbon impurities in dielectric barrier discharge (DBD) for ozone generation requires a better understanding of the kinetics of the by-product formation resulting from reactions involving these hydrocarbon impurities. As a case study of hydrocarbon impurities, the kinetics of CH4 conversion in DBDs and the subsequent HNO3 formation were investigated by means of gas-phase plasma diagnostics, supported by detailed process modeling, and extensive in-situ and ex-situ by-product analysis. The by-products formation in the plasma with the presence of CH4, were found to differ significantly in oxygen-fed generators as compared to generators fed with oxygen/nitrogen mixtures. The amount of HNO3 formed depends on the concentration of NO x formed in the plasma and the amount of CH4 that is converted, but not on the O3 concentration. In the present work we have investigated CH4 concentrations of up to 1.95 wt% of the feed gas. The rate of deterioration of the overall ozone generator performance was found to be affected by the concentration of nitrogen in the oxygen/nitrogen mixture.

Functionalization of Multiwall Carbon Nanotubes by Ozone at Basic pH. Comparison with Oxygen Plasma and Ozone in Gas Phase

The selective functionalization of carbon nanotube surfaces is crucial for many potential applications of these materials. For this purpose several oxidants, among other substances, are used. The aim is to reach a large degree of functionalization which depends on the oxidant character of the reagent. For this reason the functionalization of multiwall carbon nanotubes (MWCNTs) by treatment with ozone in basic solution is studied. At basic pHs, ozone results into hydroxyl radicals whose reduction potential is very high (E° = 3.06 V). The results have been compared to those obtained by ozone in gas phase and with cold oxygen plasma. The oxidation with ozone in basic solution seems to be kinetically restricted. As a consequence, the degree of oxidation in this medium is smaller than this of ozone gas, in spite of the larger oxidation capacity of the former. The oxygen-containing groups fixed by these two treatments are mainly attached to defects of the nanotubes. Moreover, no modification of the graphene lay...

Electrical breakdown of microwave plasma in water

The electrical breakdown of microwave plasma in water was investigated between 1 and 30 kPa. The dependency of the ignition power for generating plasma on the size of coaxial electrode was measured. The ignition power decreases with a decrease of the diameter of the inner electrode. The behavior of microwave plasma in water was observed using a high-speed camera. The plasma ignites in a bubble generated by microwave heating. The model for calculating the electric field was created on the basis of the captured images of the bubble just before plasma ignition. The method presented can be used to visualize the electrical field distribution in the bubble. The electric field breakdown was calculated using the measured ignition power. The electric field breakdown of plasma in water is of the same order as gas phase plasma.

Reactive fluxes delivered by dielectric barrier discharge filaments to slightly wounded skin

The application of atmospheric-pressure plasmas to human tissue has been shown to have therapeutic effects for wound healing and in treatment of skin diseases. In this paper, we report on a computational study of the intersection of plasma filaments in a dielectric barrier discharge (DBD) with a small wound in human skin in the context of plasma medicine. The wound is represented as a small cut in the epidermal layer of cells. Intracellular structures and their electrical properties were incorporated into the two-dimensional computational mesh in order to self-consistently couple gas phase plasma transport with the charging of the surface of the wound. We quantify the fluxes of reactive oxygen and nitrogen species, ions and photons produced in or diffusing into the wound as might occur during the first few discharge pulses of treatment. Comparison is made to fluxes predicted by global modelling. We show that the relative location of the plasma filament with respect to the wound is important on plasma time scales (ns) for ions and photons, and for radicals directly produced by electron impact processes. On the longer-term diffusion time scales (ms) the position of the plasma filament relative to the wound is not so critical. For typical DBD conditions, the magnitude of these fluxes to the cellular surfaces corresponds to fluences of radicals nearly equal to the surface site density. These results imply that the biological reactivity is limited by reaction probabilities and not the availability of radical fluxes.

Characterization of the Chemical Kinetics in an O2/HMDSO RF Plasma for Material Processing

Experimental study of the plasma gas phase in low-pressure radiofrequency discharges of oxygen and hexamethyldisiloxane is presented. The plasma phase has been studied by means of optical emission spectroscopy. Mass spectroscopy of the neutral and of the charged species has been performed too, directly sampling the plasma gas phase, by a dedicated spectrometer. We also measured the ion energy distribution. We have studied the influence of the operating conditions on the plasma gas-phase composition which plays a primary role in the formation process of SiO2 films, which are known for their important applicative uses.

Atmospheric-Pressure Plasma-Enhanced Chemical Vapor Deposition of a-SiCN:H Films: Role of Precursors on the Film Growth and Properties

Atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) using Surfx Atomflow(TM) 250D APPJ was utilized to synthesize amorphous silicon carbonitride coatings using tetramethyldisilizane (TMDZ) and hexamethyldisilizane (HMDZ) as the single source precursors. The effect of precursor chemistry and substrate temperature (T(s)) on the properties of a-SiCN:H films were evaluated, while nitrogen was used as the reactive gas. Surface morphology of the films was evaluated using atomic force microscopy (AFM); chemical properties were determined using Fourier transform infrared spectroscopy (FTIR); thickness and optical properties were determined using spectroscopic ellipsometry and mechanical properties were determined using nanoindentation. In general, films deposited at substrate temperature (T(s)) < 200 °C contained organic moieties, while the films deposited at T(s) > 200 °C depicted strong Si-N and Si-CN absorption. Refractive indices (n) of the thin films showed values between 1.5 and 2.0, depending on the deposition parameters. Mechanical properties of the films determined using nanoindentation revealed that these films have hardness between 0.5 GPa and 15 GPa, depending on the T(s) value. AFM evaluation of the films showed high roughness (R(a)) values of 2-3 nm for the films grown at low T(s) (<250 °C) while the films grown at T(s) ≥ 300 °C exhibited atomically smooth surface with R(a) of ~0.5 nm. Based on the gas-phase (plasma) chemistry, precursor chemistry and the other experimental observations, a possible growth model that prevails in the AP-PECVD of a-SiCN:H thin films is proposed.

Development of a laser-induced plasma probe to measure gas phase plasma signals at high pressures and temperatures

The ability of laser induced breakdown spectroscopy (LIBS) technique for on line simultaneous measurement of elemental concentrations has led to its application in a wide number of processes. The simplicity of the technique allows its application to harsh environments such as present in boilers, furnaces and gasifiers. This paper presents the design of a probe using a custom optic which transforms a round beam into a ring (Donut) beam, which is used for forming a plasma in an atmosphere of nitrogen at high pressure (20bar) and temperature (200°C). The LIBS experiments were performed using a high pressure cell to characterize and test the effectiveness of the donut beam transmitted through the LIBS probe and collect plasma signal in back scatter mode. The first tests used the second harmonic of a Nd:YAG laser, pulse width 7ns, to form a plasma in nitrogen gas at five different pressures (1, 5, 10, 15 and 20bar) and three different gas temperatures (25, 100 and 200°C). The uniqueness of this probe is the custom made optic used for reshaping the round laser beam into a ring (Donut) shaped laser beam, which is fed into the probe and focused to form a plasma at the measurement point. The plasma signal is collected and collimated using the laser focusing lens and is reflected from the laser beam axis onto an achromatic lens by a high reflection mirror mounted in the center section of the donut laser beam. The effect of gas pressure and temperature on N(I) lines in the high pressure cell experiment shows that the line intensity decreases with pressure and increases with temperature. Mean plasma temperature was calculated using the ratios of N(I) line intensities ranging from 7400K to 8900K at 1bar and 2400K to 3200K at 20bar for the three different gas temperatures. The results show that as a proof of principle the donut beam optics in combination with the LIBS probe can be used for performing extensive LIBS measurements in well controlled laboratory environment as well as harsh and demanding environments of practical devices at both high pressures and temperatures.

Multi-Layered Plasma-Polymerized Chips for SPR-Based Detection

The surface functionalization of a noble metal is crucial in a surface plasmon resonance-based biomolecular detection system because the interfacial coating must retain the activity of immobilized biomolecules while enhancing the optimal loading. We present here a one-step, room-temperature, high-speed, gas-phase plasma polymerization process for functionalizing gold substrates using siloxane as an adhesion layer and acrylic acid as a functional layer. Siloxane- and thiol-based coatings were compared for their performance as adhesion and the interfacial layer for subsequent functionalization. An in situ sequential deposition of siloxane and acrylic acid resulted in a 7-fold increase in carboxylic functionality surfacial content compared to films deposited with thiol-containing precursors. Grading of the layer composition achieved as a consequence of ion-induced mixing on the surface coating under the application of the plasma is confirmed through secondary ion mass spectroscopic studies. DNA hybridization assays were demonstrated on gold/glass substrates using surface plasmon enhanced ellipsometry and the applicability of this coating for protein immunoassays were demonstrated with plasma functionalized gold/plastic substrates in Biacore 3000 SPR instrument.