Electron Cyclotron Resonance Microwave Research Articles

Plasma assisted pulsed laser deposition of WO3 films for thermochromism

Tungsten trioxide (WO3) is one of the extensively investigated transition metal oxides. Its excellent chromogenic properties make WO3 promising for a variety of scientific and technological applications. We report a new method for reactively depositing WO3 films by plasma assisted pulsed laser deposition that combines electron cyclotron resonance microwave discharge and pulsed laser ablation. The plasma formed during film deposition was spectroscopically characterized by optical emission measurement, revealing that the plasma contains high density of reactive gaseous oxygen and tungsten species which are essential for efficiently synthesizing WOx precursors and depositing WO3 films. The structure of the deposited films and the effect of post-deposition thermal annealing on the film structure were characterized by X-ray diffraction and Raman spectroscopy. The as-deposited WO3 film appears amorphous in nature. Annealing resulted in the growth of crystalline grains and the improvement in the crystallinity of monoclinic WO3. Optical properties of the prepared WO3 films were studied by measuring ultraviolet–visible–near infrared transmission spectra. With the increase of annealing temperature, the WO3 films show a continuous change in color, decline in transmittance, red shift in absorption edge, and narrowing in band gap, clearly manifesting the thermochromic features of the deposited WO3 films.

Ion concentration ratio measurements of ion beams generated by a commercial microwave electron cyclotron resonance plasma source.

A commercially available electron cyclotron resonance (ECR) plasma source (GenII Plasma Source, tectra GmbH) is widely used for surface processing. This plasma source is compatible with ultrahigh vacuum systems, and its working pressure is relatively low, around 10-6-10-4 Torr even without differential pumping. Here, we report ion flux concentration ratios for each ion species in an ion beam from this source, as measured by a mass/energy analyzer that is a combination of a quadrupole mass spectrometer, an electrostatic energy analyzer, and focusing ion optics. The examined beams were those arising from plasmas produced from feed gases of H2, D2, N2, O2, Ar, and dry air over a range of input power and working pressures. H2(D2) plasmas are widely used for nuclear fusion applications and, hence, the ion concentration ratios of H+, H2+, and H3+ reported here will be useful information for research that applies this plasma source to well-controlled plasma-material interaction studies. Ion energy distributions, stability of operation, and impurity concentrations were also assessed for each of the plasma species investigated.

Self-mode transition, oscillation and inverse hysteresis in ECR discharges

Positive and negative feedback of microwave (MW) ECR (electron cyclotron resonance) discharges in cross magnetic field were manipulated by a three-stub coaxial tuner. Unstable ECR discharges in the positive feedback region, such as the self-mode transition between the ordinary (O)-wave mode and extraordinary (X) one, inverse hysteresis, and oscillation, were investigated using a time-resolved MW power meter, high speed camera, and thermocouple. In the positive feedback region, the self-O → X wave mode discharge transition can be driven under the “hot” wall condition, while the counterpart, namely the self-X → O wave mode transition, is observable for the “cold” wall; the inverse hysteresis and oscillation take place at low and moderate gas flow rates, respectively. The mechanism underlying the self-mode transitions and instabilities is the discharge shift due to the gas heating effect. For MW ECR discharges to become stable, as indicated in previous experiments, they should be mismatched in the negative feedback region.

Paper-based ZnO self-powered sensors and nanogenerators by plasma technology

Nanogenerators and self-powered nanosensors have shown the potential to power low-consumption electronics and human-machine interfaces, but their practical implementation requires reliable, environmentally friendly and scalable processes for manufacturing and processing. Furthermore, the emerging flexible and wearable electronics technology demands direct fabrication onto innovative substrates such as paper and plastics typically incompatible with high process temperatures. This article presents a plasma synthesis approach for the fabrication of piezoelectric nanogenerators (PENGs) and self-powered sensors on paper substrates. Polycrystalline ZnO nanocolumnar thin films are deposited by plasma-enhanced chemical vapour deposition on common paper supports using a microwave electron cyclotron resonance reactor working at room temperature yielding high growth rates and low structural and interfacial stresses. Applying Kinetic Monte Carlo simulation, we elucidate the basic shadowing mechanism behind the characteristic microstructure and porosity of the ZnO thin films, relating them to an enhanced piezoelectric response to periodic and random inputs. The piezoelectric devices are assembled by embedding the ZnO films in polymethylmethacrylate (PMMA) and using Au thin layers as electrodes in two different configurations, namely laterally and vertically contacted devices. We present the response of the laterally connected devices as a force sensor for low-frequency events with different answers to the applied force depending on the impedance circuit, i.e. load values range, a behaviour that is theoretically analyzed. The characterization of the vertical devices in cantilever-like mode reaches instantaneous power densities of 80 nW/cm2 with a mean power output of 20 nW/cm2. Besides, we analyze their actual-scenario performance by activation with a fan and handwriting. Overall, this work demonstrates the advantages of implementing plasma deposition for piezoelectric films to develop robust, flexible, stretchable, and enhanced-performance nanogenerators and self-powered piezoelectric sensors compatible with inexpensive and recyclable supports.

Simple experimental and analytical methods to estimate the power coupling efficiency in plasma discharges

AbstractA simple experimental method to estimate the power effectively absorbed by a plasma is presented. It relies on a thermal management study that is applied to the whole discharge system, providing the energy released by the plasma and lost by convection and radiation at the reactor walls. The methodology is illustrated in the case of H2 Electron Cyclotron Resonance microwave plasma. Nevertheless, this method can be extended to a variety of electrical discharge or feed gases. Using this method, an experimental coupling efficiency of ∼22 ± ∼8% was derived. In comparison, an analytical balance of the plasma power absorption yields a theoretical coupling efficiency of ∼28 ± ∼9%.

A comprehensive study on the electron cyclotron resonance effect in a weakly magnetized capacitively coupled RF plasma: experiment, simulation and modeling

The electron cyclotron resonance (ECR) effect in a weakly magnetized capacitively coupled radio frequency (RF) plasma was previously observed with optical emission spectroscopy (OES) in experiments and analyzed by particle-in-cell/Monte Carlo collision (PIC/MCC) simulations (Zhang et al 2022 Plasma Sources Sci. Technol. 31 07LT01). When the electron cyclotron frequency equals the RF driving frequency, the electron can gyrate in phase with the RF electric field inside the plasma bulk, being continuously accelerated like microwave ECR, leading to prominent increases in the electron temperature and the excitation or ionization rate in the bulk region. Here, we study further the basic features of the RF ECR and the effects of the driving frequency and the gas pressure on the RF ECR effect by OES and via PIC/MCC simulations. Additionally, a single electron model is employed to aid in understanding the ECR effect. It is found that the maximum of the measured plasma emission intensity caused by ECR is suppressed by either decreasing the driving frequency from 60 MHz to 13.56 MHz or increasing the gas pressure from 0.5 Pa to 5 Pa, which shows a qualitative agreement with the change of the excitation rate obtained in the simulations. Besides, the simulation results show that by decreasing the driving frequency the electron energy probability function (EEPF) changes from a convex to a concave shape, accompanied by a decreased electron temperature in the bulk region. By increasing the gas pressure, the EEPF and the electron temperature show a reduced dependence on the magnitude of the magnetic field. These results suggest that the ECR effect is more pronounced at a higher frequency and a lower gas pressure, primarily due to a stronger bulk electric field, together wih a shorter gyration radius and lower frequency of electron–neutral collisions.

Qualification of uniform large area multidipolar ECR hydrogen plasma

The design and characterization of a multi-dipolar microwave electron cyclotron resonance (ECR) hydrogen plasma reactor are presented. In this configuration, 16 ECR sources are disposed uniformly along the azimuthal direction at a constant distance from the center of a cylindrical reactor. Several plasma diagnostics have been used to determine key parameters such as neutral species temperature; electron density and temperature; and H+, H2+, and H3+ ion energy distributions. The experimental characterization is supported by electromagnetic and magnetostatic field simulations as well as Particle In-Cell Monte Carlo Collisions simulations to analyze the observed ion energy distribution functions. Especially, we show that both electron density and temperature are spatially uniform, i.e., 1011 cm−3 and 3 eV, respectively. This plasma enables generating ion flux and energy in the ranges 1019–1022 ions m−2 s−1 and few keVs, respectively. The H2+ ion distribution function shows two populations which were attributed to surface effects. These features make this reactor particularly suitable for studying hydrogen plasma surface interaction under controlled conditions.

Comparative studies of cold/hot probe techniques for accurate plasma measurements

The emissive probe technique and the cold Langmuir probe technique for the plasma potential measurement are compared in microwave electron cyclotron resonance plasmas. With different results of plasma potential, discrepant results of electron temperature and electron density are obtained from a hot emissive probe I–V curve and a cold Langmuir probe I–V curve, respectively. A comparison of the experimental data shows that the plasma parameters obtained from the cold Langmuir probe I–V curve are always grossly underestimated, while the results determined from the hot emissive probe I–V curve are much more reliable. Additionally, based on the experimental results, a novel emissive probe technique named the hot probe with zero emission limit method is proposed to easily obtain the accurate plasma potential and other reliable plasma parameters.

Structure and optical properties of ZrxHf1-xO2 films deposited by pulsed laser co-ablation of Zr and Hf targets with the assistance of oxygen plasma

Group IVB metal oxides have demonstrated many potential applications in a variety fields owing to their excellent optical, mechanical, electrical, chemical and thermal properties. In this work, ternary oxides ZrxHf1-xO2 films with variable compositions were deposited by pulsed laser co-ablation of a Zr target and a Hf target in an oxygen plasma generated by electron cyclotron resonance microwave discharge of O2 gas. The oxygen plasma provided an environment containing a high concentration of reactive oxygen species for synthesizing oxides with the Zr and Hf species ablated from the Zr and Hf targets. The structure of the deposited films was characterized and the optical properties were evaluated together with the examination of the effects of post-deposition annealing on the structure and optical properties. The ternary ZrxHf1-xO2 films are much alike with binary ZrO2 and HfO2 films in structure and optical properties. They have a monoclinic structure and are highly transparent in a wide spectral region from mid-ultraviolet to mid-infrared. The ultraviolet absorption edge and optical band gap vary slightly with the pulse energies of the laser beams ablating the targets. Annealing in N2 resulted in the improvement in the film structure.

Microwave preionization and electron cyclotron resonance plasma current startup in the EXL-50 spherical tokamak

Preionization has been widely employed to create initial plasma and help the toroidal plasma current formation. This research focuses on implementing a simple, economical and practical electron cyclotron resonance (ECR) preionization technique on the newly constructed EXL-50 spherical tokamak, and evaluating the effectiveness on improving the plasma current startup. Two types ECR microwave preionization experiments for the plasma initialization without the central solenoid are reported: (1) 2.45 GHz microwave preionization and current startup with 2.45 GHz ECR source; (2) 2.45 GHz microwave preionization and current startup with 28 GHz ECR source. Application of the 2.45 GHz ECR microwave preionization to the experiments has contributed to (1) getting rid of the plasma breakdown delay; (2) the significant improvement of the discharge quality: the discharge is much longer and more stable while the driven plasma current is larger, compared to the discharge without preionization.

Comparative study of high temperature anti-oxidation property of sputtering deposited stoichiometric and Si-rich SiC films

Stoichiometric and silicon-rich (Si-rich) SiC films were deposited by microwave electron cyclotron resonance (MW-ECR) plasma enhanced RF magnetron sputtering method. As-deposited films were oxidized at 800 °C, 900 °C, and 1000 °C in air for 60 min. The chemical composition and structure of the films were analyzed by x-ray photoelectron spectroscopy (XPS), Raman spectroscopy and Fourier transform infrared spectroscopy (FT-IR). The surface morphology of the films before and after the high temperature oxidation was measured by atomic force microscopy. The mechanical property of the films was measured by a nano-indenter. The anti-oxidation temperature of the Si-rich SiC film is 100 °C higher than that of the stoichiometric SiC film. The oxidation layer thickness of the Si-rich SiC film is thinner than that of the stoichiometric SiC film in depth direction. The large amount of extra silicon in the Si-rich SiC film plays an important role in the improvement of its high temperature anti-oxidation property.

Characterization of the combination of microwave and laser ablation plasmas

The main aim of the present work is to report on the study of the combination of continuous plasma, formed by a microwave electron cyclotron resonance (ECR) discharge and the pulsed plasma obtained by the laser ablation of a solid target. Such arrangement allows studying the formation of materials in the form of thin films making use of the relatively high densities of the microwave discharge and the wide range of ion energies produced in the pulsed laser ablation plasmas. With this arrangement it is possible to deposit thin films of materials that in the usual microwave discharge require the use of dangerous and corrosive substances, as the required element is obtained from a pure solid target. Moreover, as the laser ablation process is carried out in plasma as the background gas, instead of a neutral gas, the presence of contaminants, such as oxygen can be significantly reduced. For the purpose of the present paper a nitrogen microwave ECR discharge was combined with the plasma created during the ablation of an aluminum target, in order to deposit AlN thin films. Plasma parameters were measured by a Langmuir probe, and the chemical species contained in the plasma were analyzed by optical emission spectroscopy (OES). The optical properties and chemical composition of the AlN thin films are reported.

Mechanism of highly selective etching of SiCN by using NF3/Ar-based plasma

As part of the self-aligned processes to fabricate a 3D device, highly selective SiCN etching using NF3/Ar-based gas plasma generated by microwave electron-cyclotron resonance was investigated. The etching rate of SiCN etched by NF3/Ar plasma was higher than that of various other materials, namely, SiO2, Si3N4, poly-Si, TiN, and Al2O3. Extremely highly selective etchings of SiCN with regard to various materials are possible by forming protective layers on nonetched materials by adding gases to the NF3/Ar plasma. The effects of adding gases to the NF3/Ar plasma on various other materials were studied by analysis using optical emission spectroscopy and x-ray photoelectron spectroscopy (XPS). The three key findings of these analyses are summarized as follows. First, highly selective etching of SiCN to poly-Si was achieved by adding oxygen to the NF3/Ar etching plasma. This etching was made possible because poly-Si etching was inhibited by forming a 1.0-nm-thick oxidized layer to protect the poly-Si surface from the etching reaction with fluorine radicals. Second, highly selective etching of SiCN to SiO2 and Si3N4 was achieved by using NF3/Ar-based plasma with added SiCl4. In this etching, silicon-containing deposited layers were formed on the SiO2 and Si3N4 surfaces. The deposited layers protected the surfaces from being etched by reacting with fluorine radicals. Third, highly selective etching over TiN was achieved by using hydrogen-added plasma. The XPS results show that a thin protective layer containing TiNxFy and ammonium fluoride was formed on the TiN surface. The protective layer formed on the TiN surface effectively protects the TiN from being etched by fluorine radicals.

Elastic loading enhanced NH3 sensing for surface acoustic wave sensor with highly porous nitrogen doped diamond like carbon film

We proposed a surface acoustic wave (SAW) NH3 gas sensor based on nitrogen doped diamond like carbon (N-DLC) film. The N-DLC film, prepared using a microwave electron cyclotron resonance plasma chemical vapor deposition (ECR-PECVD) method, is highly porous and physically and chemically stable, and have active polar groups on its surface, which can selectively absorb polar NH3 gas molecules. These features of the film lead to the high sensitivity, low noise and excellent stability of the sensor. The sensor can achieve capabilities of in-situ monitoring NH3 in a concentration range from 100 ppb to 100 ppm with fast response (∼5 s) and recovery (∼29 s) at room temperature. The NH3 sensing mechanism is attributed to the decreased porosity of the N-DLC film caused by adsorbed NH3 molecules on its polar groups, which leads an increase of the elastic modulus of the film.

Development, design, and testing of a microwave-driven compact rotating-target D-D fast neutron generator for imaging applications

A compact D-D fast neutron generator system was developed with an emphasis on imaging applications. It is equipped with an electron cyclotron resonance microwave ion source, an electric field method electron suppression electrode, and a rotating beam target. The design, mechanical assembling, and initial performance of the system is presented in this work. Electrostatics and charged particle tracing simulations were employed to dimension components in the vacuum system and estimate the size of the ion beam spot on the target surface. Stable operation of the neutron generator was possible with accelerating potentials of up to −120 kV and an estimated averaged ion beam current of around 0.5 mA. At these conditions, the neutron yield was estimated to 6 ⋅ 107 s−1 based on a combination of detailed Monte Carlo MCNP6 models and the ambient dose rate reading of an LB6411 neutron probe. The neutron emitting spot size was compared to the ion beam spot size and experimentally determined with an attenuating edge technique to be between 1.7 and 2.6 mm. With these neutron yield and emitting spot size values, the system compares favorably with commercially available neutron generators, and this context is also presented.

Effect of nitrogen flow on the properties of carbon nitride films deposited by electron cyclotron resonance plasma-enhanced chemical vapor deposition

Amorphous hydrogenated carbon nitride (a-CNx:H) films were fabricated via electron cyclotron resonance microwave plasma-enhanced chemical vapor deposition technology using N2 and C2H2 as nitrogen and carbon sources, respectively. The effects of the N2/C2H2 gas flow ratio on the composition, bond structure, scratch resistance, and optical properties of the a-CNx:H films were investigated. X-ray photoluminescence spectroscopy and Raman spectroscopy results indicated that the N/C atomic ratio, carbon 1s sp3/sp2 ratio, and nitrogen 1s sp3/sp2 ratio increased with increasing N2/C2H2 gas ratio. Pin-on-disk wear tests conducted with a pin made of ultrahigh-molecular weight polyethylene indicated that all the a-CNx:H films exhibited good scratch resistance; however, rubbing with a stainless-steel ball weakened the wear resistance of the a-CNx:H films as the N2/C2H2 gas ratio changed from 5/30 to 30/30. The measured transmittance spectra showed that nitrogen incorporation into the carbon films increased their transmittance in the visible to near-infrared regions. The optical bandgap of the a-CNx:H films was obtained by the Tauc method, which demonstrated that when the N2/C2H2 gas flow ratio changed from 0/30 to 30/30, the optical bandgap increased from 1.18 to 1.86 eV. Our results suggest that a-CNx:H films can be used as optical and protective coatings.

AlGaN/GaN metal–insulator–semiconductor high electron mobility transistors (MISHEMTs) using plasma deposited BN as gate dielectric

AlGaN/GaN metal–insulator–semiconductor high electron mobility transistors (MISHEMTs) were fabricated on Si substrates with a 10 nm boron nitride (BN) layer as a gate dielectric deposited by electron cyclotron resonance microwave plasma chemical vapor deposition. The material characterization of the BN/GaN interface was investigated by X-ray photoelectric spectroscopy (XPS) and UV photoelectron spectroscopy. The BN bandgap from the B1s XPS energy loss is ∼5 eV consistent with sp2 bonding. The MISHEMTs exhibit a low off-state current of 1 × 10−8 mA/mm, a high on/off current ratio of 109, a threshold voltage of −2.76 V, a maximum transconductance of 32 mS/mm at a gate voltage of −2.1 V and a drain voltage of 1 V, a subthreshold swing of 69.1 mV/dec, and an on-resistance of 12.75 Ω·mm. The interface state density (Dit) is estimated to be less than 8.49 × 1011 cm−2 eV−1. Gate leakage current mechanisms were investigated by temperature-dependent current–voltage measurements from 300 K to 500 K. The maximum breakdown electric field is no less than 8.4 MV/cm. Poole–Frenkel emission and Fowler–Nordheim tunneling are indicated as the dominant mechanisms of the gate leakage through the BN gate dielectric at low and high electric fields, respectively.

Engineering high-defect densities across vertically-aligned graphene nanosheets to induce photocatalytic reactivity

The fabrication of graphene nanostructures, with a variety of morphologies and densities of defective sites, can be a promising tool to tune their characteristics towards photocatalytic applications, without the need for external dopants. In this study, the impact of morphological properties in terms of the orientation and defect concentrations of graphene nanostructures is demonstrated to support the development of active photocatalytic sites across graphitic structures. Vertically-aligned graphene nanosheets were grown across carbon fibres via electron cyclotron resonance microwave plasma chemical vapour deposition, to yield a range of different wall densities and edge functionalities. The variation of growth conditions was correlated to the photocatalytic activity for the degradation of methylene blue dye under ultra-violet and visible light. The chemical state of oxygen content hybridized with nanosheets was studied by X-ray photoelectron spectroscopy and correlated to the growth conditions and photocatalytic performance. The fastest degradation rate of dye was found on the graphene samples which were grown at 800 °C for 240 min, with a kinetic constant of 46.6 × 10−4 min−1. Such performance has not been observed to date for any graphitic materials and is shown to be on the same order of performance as the conventional photocatalytic materials.

Cutting performance of cubic boron nitride-coated tools in dry turning of hardened ductile iron

A novel cubic boron nitride (cBN)-coated silicon nitride(Si3N4) cutting tool was fabricated via the diamond interlayers by electron cyclotron resonance (ECR) microwave plasma chemical vapor deposition (MPCVD) technique. The cutting performance of cBN-coated tools was evaluated by dry turning of hardened ductile iron in comparison with the commercially available titanium aluminum nitride (TiAlN)-coated tools. The effects of cutting parameters on the cutting force and cutting temperature were studied. The results showed that the cutting forces increased with the increase of depth of cut but decreased with the increase of cutting speed, while the cutting temperature increased with the increase of cutting speed. Compared to the TiAlN-coated tools under identical turning conditions, the cBN-coated tools had lower cutting force and cutting temperature, and smaller tool wear. The cBN-coated tools delivered excellent cutting performance and prolonged tool life. Furthermore, the wear patterns and wear mechanisms of cBN-coated tools were investigated. It was found that the dominant wear patterns were crater wear on rake face and flank wear land, and the wear mechanisms were demonstrated to be abrasion wear and diffusion wear. The cutting experiments verified that the cBN-coated tools had attractive potentials in the applications for dry turning of refractory metals and hardened ferrous materials.

Synergistic passivation effects of nitrogen plasma and oxygen plasma on improving the interface quality and bias temperature instability of 4H-SiC MOS capacitors

Interface properties and bias temperature instability (BTI) determine the performance and stability of SiC metal-oxide semiconductor (MOS) devices. In this work, we propose an electron cyclotron resonance microwave nitrogen–oxygen (NO) mixed plasma post-oxidation annealing (POA) process to improve the interface properties and BTI of 4H-SiC MOS capacitors. Results showed that the NO mixed plasma POA reduces the density of interface traps, maintains the stability of the flat band voltage (Vfb) hysteresis under four successive cycles of positive bias temperature stress (PBTS) and negative bias temperature stress (NBTS) at 423 K, and significantly reduces the Vfb hysteresis under alternating PBTS and NBTS at 100 K. The oxide traps remarkably decreased to 2.27 × 1012 cm−2 after NO mixed plasma POA. The related passivation and improvement mechanisms were further studied by secondary ion mass spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. The synergistic effects of highly reactive N and O plasma promoted the considerable absorption of N at the interface and prevented further oxidation of the SiC substrate. We also elaborate on the effects of N, O, and NO plasma on the elimination and passivation of O vacancy defects, C-related defects (SiOxCy and C dimer), and Si interstitial defects and discuss implications of the simultaneous suppression of electron and hole trapping.