Low Pressure Radio Frequency Research Articles

Synthesis of Composition-Tunable Ag-Cu Bimetallic Nanoparticles Through Plasma-Driven Solution Electrolysis.

Bimetallic nanomaterials have shown great potential across various fields of application. However, the synthesis of many bimetallic particles can be challenging due to the immiscibility of their constituent metals. In this study, we present a synthetic strategy to produce compositionally tunable silver-copper (Ag-Cu) bimetallic nanoparticles using plasma-driven liquid surface chemistry. By using a low-pressure nonthermal radiofrequency (RF) plasma that interacts with an Ag-Cu precursor solution at varying electrode distances, we identified that the reduction of Ag and Cu salts is governed by two "orthogonal" parameters. The reduction of Cu2+ is primarily influenced by plasma electrons, whereas UV photons play a key role in the reduction of Ag+. Consequently, by adjusting the electrode distance and the precursor ratios in the plasma-liquid system, we could control the composition of Ag-Cu bimetallic nanoparticles over a wide range.

Investigating instabilities in magnetized low-pressure capacitively coupled RF plasma using particle-in-cell (PIC) simulations

The effect of a uniform magnetic field on particle transport in low-pressure radio frequency (RF) capacitively coupled plasma (CCP) has been studied using a particle-in-cell model. Three distinct regimes of plasma behavior can be identified as a function of the magnetic field. In the first regime at low magnetic fields, asymmetric plasma profiles are observed within the CCP chamber due to the effect of E→×B→ drift. As the magnetic field increases, instabilities develop and form self-organized spoke-shaped structures that are distinctly seen within the bulk plasma closer to the sheath. In this second regime, the spoke-shaped coherent structures rotate inside the plasma chamber in the −E→×B→ direction, where E→ and B→ are the DC electric and magnetic field vectors, respectively, and the DC electric field exists in the sheath and pre-sheath regions. The spoke rotation frequency is in the megahertz range. As the magnetic field strength increases further, the rotating coherent spokes continue to exist near the sheath. The coherent structures are, however, accompanied by new small-scale incoherent structures originating and moving within the bulk plasma region away from the sheath. This is the third regime of plasma behavior. The threshold values of the magnetic field between these regimes were found not to vary with changing plasma reactor geometry (e.g., area ratio between ground and powered electrodes) or the use of an external capacitor between the RF-powered electrode and the RF source. The threshold values of the magnetic field between these regimes shift toward higher values with increasing gas pressure. Analysis of the results indicates that the rotating structures are due to the lower hybrid instability driven by density gradients and electron-neutral collisions. This paper provides guidance on the upper limit of the magnetic field for instability-free operation in low-pressure CCP-based semiconductor deposition and etch systems that use the external magnetic field for plasma uniformity control.

Optical actinometry for number density measurements in low-pressure plasmas: Advantages, error sources, and method validation

Number density of plasma-generated atoms or molecules is an important parameter for both fundamental research and applications. It can be measured in a straightforward manner, using vacuum-ultraviolet absorption spectroscopy, which is mainly possible in laboratory conditions as it may require bulky equipment, such as lasers. By contrast, optical actinometry is an alternative approach that only uses spontaneous emission from the plasma. This technique relies on the so-called corona excitation and uses emission line ratios between the gases with unknown and known concentrations (called actinometer in the last case). As a result of using line ratios, the additional density calibration is not required if the excitation cross sections are known. This study discusses Ar-based actinometry in low-pressure (roughly <1 kPa) plasma discharges with an emphasis on multiple line ratios. The work is particularly focused on the method’s applicability, the choice of Ar cross sections, and potential error sources. The influence of the additional excitation mechanisms is analyzed based on both experiments and modeling. The optical transitions for F, O, H, N, and P atoms along with expressions for their number density are presented, not requiring high optical resolution for measurements. For the sake of method validation, it is shown that in low-pressure radiofrequency discharges, a nearly excellent agreement between the actinometry data and the calibrated measurements can be achieved by careful selection of optical transitions.

Abnormal transition of the electron energy distribution with excitation of the second harmonic in low-pressure radio-frequency capacitively coupled plasmas

The self-excited second harmonic in radio-frequency capacitively coupled plasma was significantly enhanced by adjusting the external variable capacitor. At a lower pressure of 3 Pa, the excitation of the second harmonic caused an abnormal transition of the electron energy probability function, resulting in abrupt changes in the electron density and temperature. Such changes in the electron energy probability function as well as the electron density and temperature were not observed at the higher pressure of 16 Pa under similar harmonic changes. The phenomena are related to the influence of the second harmonic on stochastic heating, which is determined by both amplitude and the relative phase of the harmonics. The results suggest that the self-excited high-order harmonics must be considered in practical applications of low-pressure radio-frequency capacitively coupled plasmas.

A game-changing equation during the etching of tuning forks and its verification through experiments

Quartz tuning fork (QTF) sensors, characterized by simplicity, low cost, and high-quality factor, represent a significant subset. This study delves into the etching dynamics of QTF systems, crucial for sensor applications like quartz crystal microbalance (QCM). Both theoretical and experimental investigations into QTF etching, via methods like electro-etching for large-scale tuning forks (TF) and low-pressure radio frequency (RF) plasma treatment for QTFs, have been conducted. Surprisingly, post-etching measurements reveal a lower vibrational frequency for both large-scale TFs and QTFs compared to their bare counterparts, unlike QCM sensors. A novel formula correlating this frequency reduction to mass loss has been proposed and validated through lots of experiments. Notably, longitudinal homogeneity emerges as a pivotal factor influencing the accuracy of the proposed formula. In summary, the novel mathematical framework presented herein is poised to catalyze the widespread adoption of low-cost QTFs as mass-sensitive biosensors, marking a significant advancement in the field.

Study of the Gelatinization, Fatty Acid Profiles and the Conversion of Ergosterol into Vitamin D in Wheat Shorts by Optimization of Low-pressure Radiofrequency Cold Plasma Treatment Conditions

Study of the Gelatinization, Fatty Acid Profiles and the Conversion of Ergosterol into Vitamin D in Wheat Shorts by Optimization of Low-pressure Radiofrequency Cold Plasma Treatment Conditions

Effect of Intermittent Low-Pressure Radiofrequency Helium Cold Plasma Treatments on Rice Gelatinization, Fatty Acid, and Hygroscopicity.

To establish the safe and reproducible effects of cold plasma (CP) technology on food products, this study evaluated the gelatinization parameters, fatty acid profile, and hygroscopic properties of rice grains repeatedly treated with low-pressure radiofrequency (RF) helium CP (13.56 MHz, 140 Pa, 120 W-20s, 0-4 times, and 300 g sample). Compared with the untreated (zero times) sample, with an increase in CP treatment times from one to four on rice, the water contact angle and cooking time decreased, while the water absorption rate and freshness index increased, and the pH value remained unchanged. CP repeating treatments essentially had no effect on the gelatinization enthalpy, but significantly increased the peak temperature of gelatinization. From the pasting profile of rice that has been repeatedly CP treated, the peak, breakdown, and setback viscosities in flour paste decreased. CP repeating treatments on rice did not change the short-range molecular order of starch. Compared with the untreated sample, the first helium CP treatment maintained the content of C18:1n9c, C18:2n6c, and C18:3n3, but the second to fourth CP treatment significantly decreased contents of these fatty acids (FAs) as the C18:0 content increased. The first three CP treatments can increase the water and sucrose solvent retention capacity in rice flours. CP repeatedly treated rice first exhibits the similar monolayer water content and solid surface area of water sorption. Principal component analysis shows that contact angle, pasting parameters, and fatty acid profile in milled rice are quite sensitive to CP treatment. Results support that the effect of low-pressure RF 120W helium CP treatment 20 s on rice grains is perdurable, and the improvement of CP intermittent treatments on rice cooking and pasting properties is an added benefit, and the hygroscopic properties of rice was kept.

Drug release control and anti-inflammatory effect of biodegradable polymer surface modified by gas phase chemical functional reaction

The plasma technique has been widely used to modify the surfaces of materials. The purpose of this study was to evaluate the probability of controlling the prednisolone delivery velocity on a polylactic acid (PLA) surface modified by plasma surface treatment. Surface modification of PLA was performed at a low-pressure radio frequency under conditions of 100 W power, 50 mTorr chamber pressure, 100–200 sccm of flow rate, and Ar, O2, and CH4 gases. The plasma surface-modified PLA was characterized using scanning emission microscope, x-ray photoelectron spectroscopy (XPS), and contact angle measurements. In vitro evaluations were performed to determine cellular response, drug release behavior, and anti-inflammatory effects. The PLA surface morphology was changed to a porous structure (with a depth of approximately 100 μm) and the surface roughness was also significantly increased. The XPS results demonstrated higher oxygenized carbon contents than those in the non-treated PLA group. The prednisolone holding capacity increased and the release was relatively prolonged in the surface-modified PLA group compared to that in the non-treated PLA group. In addition, cell migration and proliferation significantly increased after PLA treatment alone. The activity of cytokines such as cyclooxygenase-2 (COX-2), tumor necrosis factor-a (TNF-α), interleukin (IL-1β), and IL-6 were considerably reduced in the plasma-treated and prednisolone holding group. Taken together, surface-modified PLA by plasma can provide an alternative approach to conventional physicochemical approaches for sustained anti-inflammatory drug release.

Similarity laws for two-dimensional simulations of low-pressure capacitively coupled radio-frequency discharges

Similarity laws (SLs) for low-pressure capacitive radio-frequency plasmas are generalized from one- to two-dimensional (2D) frameworks based on kinetic particle-in-cell simulations. Fundamental discharge parameters, such as the 2D distributions of electron densities and electric fields, are examined to assess the applicability of SLs to such discharges. The discharge characteristics are found to remain invariant when external control parameters are changed according to SLs. Even under conditions where nonlinear electron resonance heating caused by the self-excitation of the plasma series resonance due to the geometric reactor asymmetry plays an important role, the electron kinetics are shown to be invariant. Moreover, the validity of SLs for the ion dynamics is demonstrated. The results advance the applicability of SLs to a 2D cylindrical reactor geometry with azimuthal symmetry, indicating broad application prospects in practice.

First-principles simulation of optical emission spectra for low-pressure argon plasmas and its experimental validation

Various spectral line emissions are often used for the experimental characterization of low-temperature plasmas. For a better understanding of the relation between the plasma characteristics and optical emission spectra, first-principle numerical simulations for low-pressure radio-frequency driven capacitively-coupled plasmas (CCPs) of argon have been performed by coupling one-dimensional particle-in-cell/Monte Carlo collision (PIC/MCC) simulations with a global collisional-radiative model (CRM). The only ionization and excitation mechanisms included in the PIC/MCC simulations of this study are the electron-impact ionization and excitations of the ground-state Ar atoms, as done commonly, whereas the electron-impact ionization of metastable states and other ionization mechanisms are also included in the CRM to account for the optical emission spectra. The PIC/MCC coupled CRM provides the emission spectra, which are then compared with experimental data obtained from the corresponding Ar CCPs with a gas pressure ranging from 2 Pa to 100 Pa. The comparison has shown good agreement for pressures up to about 20 Pa but increasingly notable deviations at higher pressures. The deviation is ascribed to the missing consistency between the PIC/MCC simulations and CRM at higher pressures, where the ionization from the metastable states is more dominant than that from the ground states, indicating a significant change in the electron energy distribution function due to the electron collisions with excited Ar atoms at higher pressures.

Transition in radio frequency gas breakdown with a transverse magnetic field

This paper presents the quantification of gas breakdown voltages in low-pressure argon capacitive radio frequency (rf) discharges in the presence of an external transverse magnetic field via fully kinetic particle-in-cell/Monte Carlo collision simulations. It is found that as the magnetic field increases, the left branch of the breakdown curve, a double-valued rf breakdown voltage regime, shifts toward a lower-pressure region. A split of the breakdown curve into lower and upper branches occurs when the external magnetic field rises to a critical value. The observed abrupt transition of rf breakdown behaviors can be understood based on the electron kinetics behaviors, with the consideration of the enhanced ionization and electron confinement induced by drift motions. An improved analytical model is developed, which can estimate the critical magnetic field required for the occurrence of the transition.

Model of the Interaction of Reactive Gases with Polymer Materials in Low-Pressure Radio-Frequency Plasma

Model of the Interaction of Reactive Gases with Polymer Materials in Low-Pressure Radio-Frequency Plasma

Band Alignment of β-Ga2O3 with BaTiO3, SrTiO3, and Related Composites

Integrating perovskite oxides BaTiO3 (BTO), SrTiO3(STO) with β-Ga2O3 is of great interest for developing β-Ga2O3 power devices due to its promotion for improving uniformity in the electric field profile and breakdown characteristics. In this work, β-Ga2O3/BaTiO3 (BTO), β-Ga2O3/SrTiO3 (STO), β-Ga2O3/Ba0.5Sr0.5TiO3 (BSTO) heterojunction were epitaxially grown on sapphire substrates by low-pressure chemical vapor deposition (LPCVD) and radio frequency physical vapor deposition (RF PVD). The energy band alignment of β-Ga2O3/BaTiO3, β-Ga2O3/SrTiO3, β-Ga2O3/Ba0.5Sr0.5TiO3 (BSTO) heterojunction have been analyzed by X-ray photoemission spectroscopy and UV–visible transmittance spectrum. The conduction band offsets (∆E c ) of β-Ga2O3/BTO, β-Ga2O3/STO, β-Ga2O3/BSTO is found to be 0.32 ± 0.05, 1.15 ± 0.05, 0.78 ± 0.05 eV, respectively; and the valence band offsets (∆E v ) of these heterojunction is 0.76 ± 0.05 eV, 0.55 ± 0.05 eV, and 0.73 ± 0.05 eV, respectively. Our results indicate that type-I band alignment respectively form at these heterojunction, in which the valence and conduction bands of β-Ga2O3 are concomitantly higher than those of BTO, STO, and BSTO. The accurate determination of ∆E c and ∆E v is important for the design of β-Ga2O3/ferroelectric heterojunction multifunctional devices.

On the importance of excited state species in low pressure capacitively coupled plasma argon discharges

In the past three decades, first principles-based fully kinetic particle-in-cell Monte Carlo collision (PIC/MCC) simulations have been proven to be an important tool for the understanding of the physics of low pressure capacitive discharges. However, there is a long-standing issue that the plasma density determined by PIC/MCC simulations shows quantitative deviations from experimental measurements, even in argon discharges, indicating that certain physics may be missing in previous modeling of the low pressure radio frequency (rf) driven capacitive discharges. In this work, we report that the energetic electron-induced secondary electron emission (SEE) and excited state atoms play an important role in low pressure rf capacitive argon plasma discharges. The ion-induced secondary electrons are accelerated by the high sheath field to strike the opposite electrode and produce a considerable number of secondary electrons that lead to additional ionizing impacts and further increase of the plasma density. Importantly, the presence of excited state species even further enhances the plasma density via excited state neutral and resonant state photon-induced SEE on the electrode surface. The PIC/MCC simulation results show good agreement with the recent experimental measurements in the low pressure range (1–10 Pa) that is commonly used for etching in the semiconductor industry. At the highest pressure (20 Pa) and driving voltage amplitudes 250 and 350 V explored here, the plasma densities from PIC/MCC simulations considering excited state neutrals and resonant photon-induced SEE are quantitatively higher than observed in the experiments, requiring further investigation on high pressure discharges.

Mass spectroscopy of oxygen plasmas with energetic ions

An experimental study of the plasma gas phase in low pressure radiofrequency discharges of oxygen is presented. The plasma phase has been studied by means of mass spectroscopy of the neutral and of the charged species, directly sampling the plasma gas phase. We also measured the ion energy distributions. We have studied the influence of the operating conditions on the plasma gas-phase composition. Ion density and energy have been measured as a function of discharge parameters. In particular, we have identified operating conditions in low pressure discharges allowing the extraction of ions from the plasma state with energies exceeding 50 eV. This makes plasma processing with energetic oxygen ions feasible in our device.

The Sensitivity of Fungi Colonising Buckwheat Grains to Cold Plasma Is Species Specific.

Fungi are the leading cause of plant diseases worldwide and are responsible for enormous agricultural and industrial losses on a global scale. Cold plasma (CP) is a potential tool for eliminating or inactivating fungal contaminants from biological material such as seeds and grains. This study used a low-pressure radiofrequency CP system with oxygen as the feed gas to test the decontamination efficacy of different genera and species commonly colonising buckwheat grains. Two widely accepted methods for evaluating fungal decontamination after CP treatment of seeds were compared: direct cultivation technique or contamination rate method (%) and indirect cultivation or colony-forming units (CFU) method. For most of the tested fungal taxa, an efficient decrease in contamination levels with increasing CP treatment time was observed. Fusarium graminearum was the most susceptible to CP treatment, while Fusarium fujikuroi seems to be the most resistant. The observed doses of oxygen atoms needed for 1-log reduction range from 1024-1025 m-2. Although there was some minor discrepancy between the results obtained from both tested methods (especially in the case of Fusarium spp.), the trends were similar. The results indicate that the main factors affecting decontamination efficiency are spore shape, size, and colouration.

Boron carbide thin film surface characterization after graphitic carbon removal using low-pressure oxygen gas RF plasma.

B 4 C-coated thin film mirrors are used in high brilliance synchrotron and x-ray free electron laser beamlines due to their low absorption coefficient and high thermal stability. As in the case of gold, platinum, and other thin film mirrors, B 4 C-coated mirrors also are affected due to synchrotron radiation-induced carbon contaminations in beamlines. In the present study, a graphitic carbon (C) layer deposited on top of boron carbide (B x C) thin film surface is removed by five successive oxygen radio frequency (RF) plasma exposures (RF power, 10W; O 2 flow, 30sccm; exposure time, 10min each). Before and after the carbon layer removal, structural and compositional properties of the B x C/C bilayer are characterized by soft x-ray reflectivity, x-ray photoelectron spectroscopy, grazing angle x-ray diffraction, and Raman spectroscopy techniques. Characterization results reveal that in the first four exposures the carbon layer thickness decreases continuously without affecting the B x C layer properties; however, in the fifth exposure, the carbon layer is completely removed along with a partial etching of the B x C layer too.

A study of plasma−porous carbon−CO2 interactions: Ammonia plasma treatment and CO2 capture

Owing to its high porosity and tunable surface chemistry activated carbon (AC) is considered a promising material for CO2 adsorption. Functionalising porous materials by plasma is challenging but if successful, it could enhance the CO2 uptake capacity of AC via chemisorption. This work presents an in-depth analysis of the interactions between ammonia plasmas and the porous surface of AC monolithic samples. The treatment involved an ammonia based atmospheric-pressure dielectric barrier discharge and a low-pressure radio frequency plasma. Unique plasma reactor designs for treating 3-dimensional, electrically conducting and non-conducting monolithic structures at atmospheric pressure with versatile applications are presented. The plasma-surface interactions were analysed using emission spectroscopy and X-ray photoelectron spectroscopy. High surface N containing AC samples were then used to assess the treatment effect on the subsurface. A much lower although a still significant amount of N was found at depths of ∼30 µm. A simple fit of the results showed that the ratio of plasma species reaching the surface with higher to lower sticking probability was 4:1. A slight decrease in the microporosity of the plasma treated samples was found and attributed to pore blocking by the grafted N species. Plasma treated AC with high N showed an improved CO2 adsorption capacity of up to 14 % and selectivity against CH4 and N2 adsorption showed that the treatment was selective primarily towards CO2.

An Experimental Anodized Titanium Surface for Transgingival Dental Implant Elements-Preliminary Report.

The characteristics such as microtopography, physical and chemical properties influence the behavior of an implant in a soft tissue. Anodization-as a potent method of titanium alloy surface modification-of the transgingival abutment or healing screw, has achieved some improvement. One of the possible surface treatment method is low-pressure radiofrequency oxygen plasma treatment. The aim of the study was to evaluate the chemical properties and cytocompatibility of the experimental surface. Titanium discs made of grade-23 titanium alloy (Ti-6Al-4V) anodized (A sample) with different voltage parameters (28, 67, 78, and 98 V) were included in the study. Half of the samples regarded as the "S" group were additionally treated with low-pressure radiofrequency oxygen plasma treatment. The surfaces were characterized using scanning electron microscopy, X-ray spectroscopy and Raman spectroscopy, and electrochemically investigated via a corrosion test. Furthermore, two cell lines were used, including the CHO-compatible reference line and a primary human fibroblast line for the MTT assay; direct (contact) cytotoxicity of the materials was tested with the cells, and the growth of fibroblasts on the surfaces of the different materials was tested. The morphology of the "S"-treated samples did not differ from the morphology of only-anodized samples. However, the oxygen concentration on the surface in that group slightly increased by about 1% as a result of post-trial treatment. The highest corrosion resistance was observed for both A-78 V and S-78 V samples. The cytotoxicity assay revealed no changes in cell morphology or vitality. The MTT test proved comparable culture viability among all groups; however, the "S" samples showed statistically significantly higher fibroblast proliferation and adhesion scores compared to the "A" samples. Through the in vitro study, the low-pressure radiofrequency oxygen plasma treatment of the anodized Ti-6Al-4V alloy presented itself as an auspicious option in the field of transgingival element surface modification of implants.

Морфология поверхности и структурные свойства кристаллов GaTe после ионно-плазменной обработки

The effect of ion-plasma treatment on the physical properties of the surface of GaTe crystals is investigated. Gallium telluride crystals were grown by vertical zone melting under the pressure of an inert argon gas of 10.0 MPa at a temperature of 1000 °C and a zone displacement velocity of 9 mm/hr. The treatment was carried out in argon plasma in a high-density low-pressure radio frequency (RF) inductively coupled plasma reactor at an argon ion energy of 100-200 eV for 15-120 s. Using scanning electron microscopy methods, it was shown that the formation of nano- and submicron structures of various architectures (nanohillocks, nanocones, droplet structures) occurred on the surface during processing. It is shown that the sputtering processes are accompanied by enrichment of the near-surface layer with metal atoms and a decrease in oxygen content. The formation of nano- and submicron gallium droplets on the surface has been proved by X-ray diffractometry. The analysis of the raman scattering spectra showed a decrease in the oxide phases of tellurium after plasma treatment. It is established that modification of the GaTe surface leads to suppression of specular optical reflection in the range of 0.4-6.2 eV.