Electron Cyclotron Wave Resonance Plasma Research Articles

Deposition of Fe2O3:Sn semiconducting thin films by reactive pulsed HiPIMS + ECWR co-sputtering from Fe and Sn targets

Semiconducting Fe2O3 thin films were deposited on SnO2:F (FTO) and Pt substrates by reactive high-power impulse magnetron sputtering combined with electron cyclotron wave resonance plasma (HiPIMS + ECWR). Fe2O3 films were fabricated either by sputtering from a single Fe target or by co-sputtering from an additional Sn target. Plasma parameters during co-sputtering were measured by an RF probe system enabling the comparison between HiPIMS + ECWR and only HiPIMS conditions used for the film deposition. As deposited Fe2O3 films were post-annealed in air at 450 °C and 650 °C, respectively. It was shown that as deposited Fe2O3 films were amorphous but became crystalline after post-annealing at 450 °C. Further increase of annealing temperature to 650 °C did not improve significantly the crystalline structure of the Fe2O3 film. All post-annealed Fe2O3 films exhibited photocurrents in the anodic region; generally, hematite films annealed at 650 °C exhibited higher photocurrents than those annealed at 450 °C. Films doped by Sn co-sputtering had higher photocurrents than films only doped by Sn diffusion during post-annealing from the FTO substrate. Hematite films on Pt substrate doped by Sn co-sputtering and post-annealed at 650 °C exhibited the highest photocurrents. It was verified by XPS analysis with ion sputtering depth profiling that Pt atoms also diffuse from the Pt substrate into the Fe2O3 film during the post-annealing at 650 °C and can, similar to Sn in the case of an FTO substrate, act as a dopant.

High-quality dense ZnO thin films: work function and photo/electrochemical properties

AbstractCompact ZnO (wurtzite) thin films are prepared on four different substrates by (i) spray pyrolysis or (ii) pulsed reactive magnetron sputtering combined with a radio frequency electron cyclotron wave resonance plasma. Films are characterized by AFM, XRD, Kelvin probe, cyclic voltammetry, electrochemical impedance spectroscopy, and UV photoelectrochemistry. Film morphologies, defect concentrations, crystallite size, and orientation provided specific fingerprints for the electronic structure of ZnO close to the conduction band minimum. Fabricated films are referenced, if relevant, to a model system based on a wurtzite single crystal with either Zn-face or O-face termination. Kelvin probe measurements of the ZnO/air interface distinguished effects of annealing and UV excitation, which are attributed to removal of oxygen vacancies close to the surface. In turn, the work function, at the electrochemical interface, specifically addressed the growth protocol of the ZnO electrodes but not the effects of crystallinity and annealing. Finally, high photocurrents of water oxidation are observed exclusively on virgin films. This effect is then discussed in terms of photocorrosion, and work function changes due to UV light. Graphical Abstract

Anatase TiO2 deposited at low temperature by pulsing an electron cyclotron wave resonance plasma source

Photocatalytic surfaces have the potentiality to respond to many of nowadays societal concerns such as clean H2 generation, CO2 conversion, organic pollutant removal or virus inactivation. Despite its numerous superior properties, the wide development of TiO2 photocatalytic surfaces suffers from important drawbacks. Hence, the high temperature usually required (> 450 °C) for the synthesis of anatase TiO2 is still a challenge to outreach. In this article, we report the development and optimisation of an ECWR-PECVD process enabling the deposition of anatase TiO2 thin films at low substrate temperature. Scanning of experimental parameters such as RF power and deposition time was achieved in order to maximise photocatalytic activity. The careful selection of the deposition parameters (RF power, deposition time and plasma gas composition) enabled the synthesis of coatings exhibiting photocatalytic activity comparable to industrial references such as P25 Degussa and Pilkington Activ at a substrate temperature below 200 °C. In addition, to further decrease the substrate temperature, the interest of pulsing the plasma RF source was investigated. Using a duty cycle of 50%, it is thus possible to synthesise photocatalytic anatase TiO2 thin films at a substrate temperature below 115 °C with a deposition rate around 10 nm/min.

Electron beam injection from a hollow cathode plasma into a downstream reactive environment: Characterization of secondary plasma production and Si3N4 and Si etching

A material etching system was developed by combining beam electron injection from a direct current hollow cathode (HC) electron source with the downstream reactive environment of a remote CF4/O2 low temperature plasma. The energy of the injected beam electrons is controlled using an acceleration electrode biased positively relative to the HC argon discharge. For an acceleration voltage greater than the ionization potential of Ar, the extracted primary electrons can produce a secondary plasma in the process chamber. The authors characterized the properties of the secondary plasma by performing Langmuir probe measurements of the electron energy probability function (EEPF) 2.5 cm below the extraction ring. The data indicate the existence of two major groups of electrons, including electrons with a primary beam electron energy that varies as the acceleration voltage is varied along with low energy electrons produced by ionization of the Ar gas atoms in the process chamber by the injected beam electrons. When combining the HC Ar beam electron with a remote CF4/O2 electron cyclotron wave resonance plasma, the EEPF of both the low energy plasma electron and beam electron components decreases. Additionally, the authors studied surface etching of Si3N4 and polycrystalline Si (poly-Si) thin films as a function of process parameters, including the acceleration voltage (0–70 V), discharge current of the HC discharge (1–2 A), pressure (2–100 mTorr), source to substrate distance (2.5–5 cm), and feed gas composition (with or without CF4/O2). The direction of the incident beam electrons was perpendicular to the surface. Si3N4 and polycrystalline silicon etching are seen and indicate an electron-neutral synergy effect. Little to no remote plasma spontaneous etching was observed for the conditions used in this study, and the etching is confined to the substrate area irradiated by the injected beam electrons. The electron etched Si3N4 surface etching rate profile distribution is confined within a ∼30 mm diameter circle, which is slightly broader than the area for which poly-Si etching is seen, and coincides closely with the spatial profile of beam electrons as determined by the Langmuir probe measurements. The magnitude of the poly-Si etching rate is by a factor of two times smaller than the Si3N4 etching rate. The authors discuss possible explanations of the data and the role of surface charging.

Semiconducting p-Type Copper Iron Oxide Thin Films Deposited by Hybrid Reactive-HiPIMS + ECWR and Reactive-HiPIMS Magnetron Plasma System

A reactive high-power impulse magnetron sputtering (r-HiPIMS) and a reactive high-power impulse magnetron sputtering combined with electron cyclotron wave resonance plasma source (r-HiPIMS + ECWR) were used for the deposition of p-type CuFexOy thin films on glass with SnO2F conductive layer (FTO). The aim of this work was to deposit CuFexOy films with different atomic ratio of Cu and Fe atoms contained in the films by these two reactive sputtering methods and find deposition conditions that lead to growth of films with maximum amount of delafossite phase CuFeO2. Deposited copper iron oxide films were subjected to photoelectrochemical measurement in cathodic region in order to test the possibility of application of these films as photocathodes in solar hydrogen production. The time stability of the deposited films during photoelectrochemical measurement was evaluated. In the system r-HiPIMS + ECWR, an additional plasma source based on special modification of inductively coupled plasma, which works with an electron cyclotron wave resonance ECWR, was used for further enhancement of plasma density ne and electron temperature Te at the substrate during the reactive sputtering deposition process. A radio frequency (RF) planar probe was used for the determination of time evolution of ion flux density iionflux at the position of the substrate during the discharge pulses. Special modification of this probe to fast sweep the probe system made it possible to determine the time evolution of the tail electron temperature Te at energies around floating potential Vfl and the time evolution of ion concentration ni. This plasma diagnostics was done at particular deposition conditions in pure r-HiPIMS plasma and in r-HiPIMS with additional ECWR plasma. Generally, it was found that the obtained ion flux density iionflux and the tail electron temperature Te were systematically higher in case of r-HiPIMS + ECWR plasma than in pure r-HiPIMS during the active part of discharge pulses. Furthermore, in case of hybrid discharge plasma excitation, r-HiPIMS + ECWR plasma has also constant plasma density all the time between active discharge pulses ni ≈ 7 × 1016 m−3 and electron temperature Te ≈ 4 eV, on the contrary in pure r-HiPIMS ni and Te were negligible during the “OFF” time between active discharge pulses. CuFexOy thin films with different atomic ration of Cu/Fe were deposited at different conditions and various crystal structures were achieved after annealing in air, in argon and in vacuum. Photocurrents in cathodic region for different achieved crystal structures were observed by chopped light linear voltammetry and material stability by chronoamperometry under simulated solar light and X-ray diffraction (XRD). Optimization of depositions conditions results in the desired Cu/Fe ratio in deposited films. Optimized r-HiPIMS and r-HiPIMS + ECWR plasma deposition at 500 °C together with post deposition heat treatment at 650 °C in vacuum is essential for the formation of stable and photoactive CuFeO2 phase.

Ion optical effects in a low pressure rf plasma

Ion optical effects in low pressure gas discharges are introduced as a novel input into low pressure plasma technology. They are based on appropriate geometrical plasma confinements which enable a control of the shape of internal density and potential distributions and, hence, the ion motion in the plasma bulk. Such effects are exemplified for an electron cyclotron wave resonance plasma in Ar at 1–5 × 10−3 millibars. The geometry of the plasma chamber is modified by a conical and a cylindrical insert. Computer simulations display spherical plasma density contours to be formed around the conical confinement. This effects an increase of the ratio of the ion currents into the conical and the cylindrical inserts which depends on the fourth power of the plasma electron temperature. A quantitative understanding of this behavior is presented. As another essential result, the shape of the internal plasma contours is found to be independent of the pressure controlled plasma parameters.

Plasma diagnostics of low pressure high power impulse magnetron sputtering assisted by electron cyclotron wave resonance plasma

This paper reports on an investigation of the hybrid pulsed sputtering source based on the combination of electron cyclotron wave resonance (ECWR) inductively coupled plasma and high power impulse magnetron sputtering (HiPIMS) of a Ti target. The plasma source, operated in an Ar atmosphere at a very low pressure of 0.03 Pa, provides plasma where the major fraction of sputtered particles is ionized. It was found that ECWR assistance increases the electron temperature during the HiPIMS pulse. The discharge current and electron density can achieve their stable maximum 10 μs after the onset of the HiPIMS pulse. Further, a high concentration of double charged Ti++ with energies of up to 160 eV was detected. All of these facts were verified experimentally by time-resolved emission spectroscopy, retarding field analyzer measurement, Langmuir probe, and energy-resolved mass spectrometry.

Simulation of cylindrical electron cyclotron wave resonance argon discharges

A fluid model of a cylindrical electron cyclotron wave resonance (ECWR) argon discharge is presented. The results for a 1 mTorr argon discharge were checked against the analytical theory, simulation and experimental data. The basic plasma properties as power dissipation, magnetic field, electric potential, electron density and temperature were very well reproduced using predefined boundary conditions for the magnetic potential. The results of this model were further used as inputs for the simulation of plasma expansion into a diffusion region, allowing thus fast and complete modelling of a typical ECWR plasma reactor.

Large area deposition of hydrogenated amorphous carbon films for optical storage disks

Homogenous wear resistant carbon coatings with an optical gap of 3 eV but low stress are needed to increase the storage density in optical storage disks in order to reach 100 GB in 12-cm diameter disks. Here, hydrogenated amorphous carbon (a-C:H) films are deposited at room temperature using a large area electron cyclotron wave resonance plasma beam source of 14.2-inch diameter. Methane is used as the precursor. The ion flux and energy, plasma pressure, distance between the extraction grid and the substrate were varied. The films are characterized in terms of hydrogen content, stress, optical gap, refractive index, wear resistance, surface roughness and homogeneity by a variety of characterization techniques. Resonant Raman spectroscopy is used in order to non-destructively monitor the disk quality. We show how it is possible to produce homogenous, wear resistant a-C:H coatings with an optical gap of 3 eV and low stress (<500 MPa), without damaging the plastic disks.

Ion energy dependence of film properties for diamond-like carbon prepared with plasma-assisted deposition

Hydrogen-free diamondlike carbon films were prepared on Si(100) with electron cyclotron wave-resonance plasma, which serves to sputter the graphite target and to simultaneously bombard the growing surface. Direct penetration of postionized carbon atoms (up to 140 eV) in addition to the momentum transfer from Ar plasma facilities the formation of the Ta–C structure. Surface morphology, mechanical, and optical properties of the deposits were examined with respect to the ion energy. Atomic force microscope images revealed island morphology in deposits with a typical root-mean-square roughness of 20 nm. A maximum content of about 70% for the fourfold-bonded structure was estimated from the Raman profiles, giving rise to a micro hardness of 60 ± 5 GPa.

The Preparation, Characterization and Tribological Properties of TA-C:H Deposited Using an Electron Cyclotron Wave Resonance Plasma Beam Source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 900 Å/min over a 4″ diameter and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized in terms of its sp3 content, mass density, intrinsic stress, hydrogen content, C–H bonding, Raman spectra, optical gap, surface roughness and friction coefficient. The results obtained indicated that the film properties were maximized at an ion energy of approximately 167 eV, corresponding to an energy per daughter carbon ion of 76 eV. The relationship between the incident ion energy and film densification was also explained in terms of the subsurface implantation of carbon ions into the growing film.

High rate deposition of ta-C:H using an electron cyclotron wave resonance plasma source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 1.5 nm/s over a 4-inch diameter and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized as having an sp 3 content of up to 77%, plasmon energy of 27 eV, refractive index of 2.45, hydrogen content of about 30%, optical gap of up to 2.1 eV and RMS surface roughness of 0.04 nm.

High Rate Deposition of Ta-C:H Using an Electron Cyclotron Wave Resonance Plasma Source

ABSTRACTA compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 900 A/mm and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized in terms of its bonding, stress and friction coefficient. The results indicated that the ta-C:H produced using this source fulfills the necessary requirements for applications requiring enhanced tribological performance.