Thermally and chemically non-equilibrium modelling of Ar-N2-H2 inductively coupled plasmas at reduced pressure

A two-dimensional thermally and chemically non-equilibrium model was developed for Ar-N₂-H₂ inductively coupled plasmas (ICP) at reduced pressure. The Ar-N₂-H₂ or Ar-NH₃ plasmas at reduced pressure has been widely used for nitriding processing of materials. Totally 164 reactions including 82 forward reactions and their backward reactions were taken into account. Spatial particle composition distribution in the plasma torch as well as in the reaction chamber was derived by solving simultaneously the mass conservation equation of each particle, considering diffusion, convection and production terms.     

Two-temperature non-chemical equilibrium analysis of Ar-CH4-O2 ICTP at reduced pressure

In present work, a two-temperature chemically non-equilibrium (2T-NCE) model has been studied for Ar-CH₄-O₂ inductively coupled thermal plasma (ICTP) at reduced pressure from the viewpoint of interaction between plasma and fuel combustion. Chemically non-equilibrium effects have been taken into account by solving mass conservation equations for each of 22 particles considering convection, diffusion and net production effects. Species density of each particle or simply particle composition was also derived from the mass conservation equation of each one taking the non chemical equilibrium effect into account. For the net production term, totally 196 chemical reactions were taken into account including dissociation, ionization and other chemical reactions and their backward reactions. Finally, heat profile due to individual reaction and the total contribution of all reactions to the heat generated has been observed.     

Synthesis of carbon-doped TiO2 nanoparticles using CO2 decomposition by thermal plasma

This study examined the synthesis of carbon-doped titanium dioxide using TiCl₄ and CO₂ as titanium and carbon sources, respectively, by thermal plasma at atmospheric pressure. The effect of the CO₂ gas flow rate on the preparation of TiO₂ was investigated. The results showed that the decomposition rate of CO₂ was 90% at a CO₂ gas flow rate of 1 L/min. When TiCl₄ was added to produce TiO₂, the decomposition rate of CO₂ reached 95% at a CO₂ gas flow rate of 1 L/min. The resulting powders contained mixed anatase and rutile phases with particle sizes ranging from 20 to 50 nm. The carbon in the CO₂ acted as a dopant to produce the carbon-doped TiO₂. The prepared samples were mainly characterized by X-ray diffraction, X-ray photoelectron spectroscopy, specific surface area measurements and ultraviolet-visible spectroscopy.     

Defect passivation by O2 plasma treatment on high-k dielectric HfO2 films at room temperature

Oxygen plasma treatment process was used to passivate the non-stoichiometric HfO₂ films deposited by magnetron sputtering. After optimal oxygen plasma treatment, the gate leakage of HfO₂ films would be reduced and dielectric breakdown voltage would be improved to 30 percentage. XPS spectrum was used to analysis the non-stoichiometric HfO₂ films after oxygen plasma treatment which demonstrate a higher concentration of incorporated oxygen atoms at the surface in comparison to the bulk HfO₂. This simple method can maintain high-k dielectric deposition process at room temperature by sputtering. It would be useful for fabrication thin film transistor on polymer based substrate in the future.     

Effect of N2/H2 plasma treatment on the moisture adsorption of MOCVD-TiN films

In the application of contact glue layer for semiconductor devices, a nitrogen/hydrogen (N₂/H₂) plasma treatment is usually used to reduce the amount of C and O impurities of metallorganic chemical vapor deposition titanium nitride (MOCVD-TiN) films. This study found that the sheet resistance of as-deposited MOCVD-TiN film without N₂/H₂ plasma treatment dramatically increased with exposure time due to moisture adsorption. Increasing plasma treatment power and time was able to retard the increase in sheet resistance. From residue gas analysis at 200 °C, it was found that the amount of H₂O outgases from the MOCVD-TiN films decreased with increasing plasma treatment power and time. TEM images reveal that the surface of the MOCVD-TiN films became compact as it received more plasma treatment energy, making it difficult for the external moisture to diffuse into and react with the MOCVD-TiN films.     

Synthesis of nano-sized Al doped TiO2 powders using thermal plasma

High quality nano-sized Al doped TiO₂ powders were prepared using a DC plasma jet. Titanium tetrachloride (TiCl₄) and aluminum chloride (AlCl₃) were fed into the plasma flame as starting materials, and the ratio of Al to TiO₂ was varied from 1 to 8 wt.%. We investigated the effect of process parameters on phase composition, particle size, and optical property by using XRD, SEM/EDX, TEM, UV/Vis spectroscope. The powders collected at the reaction tube were dominated by anatase. The size of synthesized powder decreased by increasing the amount of Al because doped Al species inhibited the particle growth. For the optical property, the absorption band of synthesized powders shifted from the UV region to the visible region according to the increase of the amount of Al dopant.     

Influence of plasma heating of wafer substrates on SiO2 deposition rate in a TEOS/O2 high-density plasma CVD system

The influence of plasma heating of the Si and glass wafer substrates on silicon dioxide (SiO₂) deposition rates by a tetraethylorthosilicate/O₂ supermagnetron (high-density) plasma CVD were investigated. With a fixed RF power of 100 W supplied to both upper and lower electrodes, the SiO₂ deposition rate on the Si wafer substrate decreased with increasing wafer-stage temperature, showing a negative activation energy for the deposition rate. When Si and glass wafers were attached to the electrode using adherent thermal conductors, the film thickness increased almost linearly with regard to the deposition time, and both deposition rates became almost the same (about 310 Å/min). When both wafers were simply laid on the electrode without an adhesive bond and hence with poor thermal contact, the film thickness increased nonlinearly with deposition time, showing a gradual decrease in deposition rate with time, being as low as 80 and 150 Å/min, respectively for Si and glass wafers, for a deposition time of 15 min. The difference between the two deposition rates on Si and glass wafers in the case of poor thermal contact to the lower electrode is thought to be caused by plasma heating and related mainly to differences in optical absorption characteristics of the two wafer substrates. Variations in measured thickness distributions across the substrate surface were attributed to an antisymmetric plasma density distribution in the direction perpendicular to the magnetic field lines caused by E×B electron drift.     

Inductively coupled Cl2/O2 plasma: experimental investigation and modelling

In this work, we investigated the influence of the Cl₂/O₂ mixing ratio on both the plasma parameters and the volume densities of the neutral and the charged particles in inductively coupled plasma system. The change in the gas mixture composition from pure Cl₂ to O₂ was found to lead to an increase in the electron density and in the electron temperature. Accordingly, the addition of oxygen to chlorine influences electron-impact dissociation kinetics as well as it can cause a stepwise dissociation of Cl₂ molecules through their interaction with oxygen atoms. As a result, in Cl₂-rich plasma, a non-monotonic behaviour of the Cl atom density is possible.     

Controlled modification of octadecyltrichlorosilane self-assembled monolayer by CO2 plasma

CO₂-plasma is used to introduce functional groups on the uppermost surface of an alkoxysilane self-assembled monolayer (SAM). The structural and chemical modifications of the material surface were monitored by X-ray reflectometry, atomic force microscopy, X-ray photoelectrons spectroscopy and water contact angle measurements. Optimization of the plasma parameters is performed in order to achieve a maximum functionalization and to prevent degradation of the SAM. Finally, the ability of grafting organic compounds onto the plasma modified SAMS was demonstrated by the formation of an alkoxysilane bilayer.     

Modeling of high frequency atmospheric pressure Ar/H2/SiH4 glow discharges

In this paper, a one-dimensional self-consistent fluid model is applied to simulate high frequency atmospheric pressure glow discharges. The results show that the plasma density and current density depend strongly on the excitation frequency. When the excitation frequency is below 13.56 MHz, the discharge operates in the α mode, and when the excitation frequency is above 13.56 MHz, the discharge operates in a γ-like mode. The densities of species including SiH₃⁺, SiH₃⁻, SiH₃, SiH₂, H, Ar⁺, Ar^? and electron are enhanced with the frequency increasing from 6.78 to 27.12 MHz. Similar discharge mode transition was observed experimentally in radio frequency atmospheric pressure He glow discharges. The effects of excitation frequency on plasma characteristics and densities of precursors for μc-Si:H film are further discussed. This study reveals that an appropriate excitation frequency is important for the growth of μc-Si:H film.     

Modification of low temperature deposited LiMn2O4 thin film cathodes by oxygen plasma irradiation

Lithium manganese oxides have been deposited by radio frequency magnetron sputter deposition with relatively lower annealing temperatures and then post-treated with a radio frequency (rf) driven oxygen plasma. Following oxygen plasma irradiation, the film properties were modified, and the performance of the thin film cathode has been enhanced. The electrochemical properties of the treated thin-film cathodes were characterized and compared. The results showed that the samples with moderate plasma treatment also maintained good cyclic properties as cycled at a wide range potential window of 2.0 V-4.5 V. Its electrochemical properties were significantly improved by this process, even though the films were prepared under low annealing temperature.     

Effect of doping elements on ZnO etching characteristics with CH4/H2/Ar plasma

Effect of doping elements on the etching characteristics of doped-ZnO (Ag, Li, and Al) thin films, etched with a positive photoresist (PR) mask, and an etch process window for infinite etch selectivity were investigated by varying the CH₄ flow ratio and self-bias voltage, V_dc, in inductively coupled CH₄/H₂/Ar plasmas. Increased doping of ZnO films decreased the etch rates significantly presumably due to lower volatility of reaction by-products of doped Li, Ag, and Al in CH₄/H₂/Ar plasmas. The etch rate of AZO (Al-doped ZnO) was most significantly decreased as the doping concentration is increased from 4 to 10 wt%. It was found that process window for infinite etch selectivity of the doped ZnO to the PR is closely related to a balance between deposition and removal processes of a-C:H (amorphous hydrogenated carbon) layer on the doped-ZnO surface. Measurements of optical emission of the radical species in the plasma and surface binding states by optical emission spectroscopy (OES) and X-ray photoelectron spectroscopy (XPS), respectively, implied that the chemical reaction of CH radicals with Zn atoms in doped-ZnO play an important role in determining the doped-ZnO etch rate together with an ion-enhanced removal mechanism of a-C:H layer as well as Zn(CH_x)_y etch by-products.     

Influence of SiO2 interlayer on the hydrophilicity of TiO2/SiO2/glass produced by RF-magnetron sputtering

The effect of silicon dioxide (SiO₂) on the hydrophilicity of the TiO₂ thin film is investigated. SiO₂ and TiO₂ films were deposited on the glass by RF-magnetron sputtering. Heat-treatment for 15 h at 573 K on TiO₂/glass and TiO₂/SiO₂/glass is carried out to make Na⁺-ion diffused from the glass to the TiO₂ thin film, which results in no band-gap change but instead the enhanced crystallinity of the anatase phase-TiO₂. This in turn leads to the improvement in hydrophilicity. Irrespective of the SiO₂ interlayer, the anatase phase-TiO₂ thin film with enhanced crystallinity shows outstanding super-hydrophilicity. Consequently, under the heat-treatment condition, the SiO₂ interlayer played an important role in improving the crystallinity of the anatase phase-TiO₂ rather than preventing Na⁺-ion diffusion.     

Low-temperature growth of ZnO nanostructures by oxygen plasma oxidation of ZnCl2

The thermodynamically forbidden reaction between ZnCl₂ and O₂ was able to take place by using oxygen plasma, yielding cone-shaped ZnO nanostructure. In situ optical emission spectroscopy was used to identify the excited species during the plasma enhanced reaction. The determination of excited temperature suggested that the addition of O₂ had great contribution to the enhanced dissociation of ZnCl₂. The successful synthesis of ZnO indicates that the chlorides may replace the organometallics as a new precursor in thin film preparation industry.     

The cryogenic thermal expansion and mechanical properties of plasma modified ZrW2O8 reinforced epoxy

In this article, epoxy resin reinforced by negative thermal expansion material, ZrW₂O₈, was fabricated. The surface modification of ZrW₂O₈ particles was performed via plasma enhanced chemical vapor deposition (PECVD) process. As a result, a thin film was uniformly deposited on the surfaces of the ZrW₂O₈ particles, leading to an improvement of compatibility and dispersion of ZrW₂O₈ fillers inside epoxy matrix. Moreover, the coefficients of thermal expansion (CTEs) of the composite material containing 0-40 vol.% fillers were studied under cryogenic temperatures. The results showed a significant reduction in thermal expansion with increasing ZrW₂O₈ content. The cryogenic mechanical properties of ZrW₂O₈/epoxy composites were also investigated, showing the properties were improved by adding ZrW₂O₈ to certain content. In addition, the mechanical strength and modulus of the composite were observed significantly higher at cryogenic temperature than that at room temperature because of the thermal shrink effect and the frozen epoxy matrix.     

Deoxidisation and phase analysis of plasma sprayed TiO2 by X-ray Rietveld method

It is fundamentally important to determine the deoxidisation and phase compositions of plasma sprayed TiO₂ coatings containing anatase. In the present study, plasma sprayed porous TiO₂ coatings containing anatase were prepared using anatase powder and both Ar-He-H₂ and Ar-He-N₂ plasma gases. The deoxidisation of TiO₂ and phase compositions of the starting powder and the prepared coatings were examined using X-ray Rietveld method by refining their crystalline parameters and scale factors. The refined oxygen occupancies showed that there were about 0.08 and 0.1 formula units of oxygen deficiencies for the rutile and anatase phases of the coatings, respectively. Such degrees of deoxidisation and the other crystalline parameters appeared independent of the plasma spraying process parameters. With considerations of the presence of organic adhesive in the starting powder and the formation of titanium ethoxide in the coatings, the degrees of deoxidisation estimated by the X-ray Rietveld method were slightly higher than those quantified by the thermogravimetry curves. The phases of the coatings determined from the refined scale factors were mainly composed of rutile with 10.0% to 22.5% anatase by weight, and the latter content increased with decreasing the intensity of the plasma jet.     

CF4 plasma effect combined with rapid thermal annealing for high-k Er2O3 dielectrics

In this study, the influence of the duration of CF₄ plasma treatment of rapid thermal annealing on high-k Er₂O₃ dielectrics deposited on polycrystalline silicon was investigated using electrical and material analyses. Results demonstrate that Er₂O₃ dielectric films annealed at 800 °C and plasma treated with CF₄ for a period of 1 min exhibited excellent dielectric performance, including a higher breakdown electric field, lower charge trapping rate, and a larger charge-to-breakdown than the as-deposited sample. Performance improvements were caused by the incorporation of fluorine atoms and the reduction of dangling bonds and defect traps.     

Formation of nanoparticles and nanorods in a N2-C2H4-H2 atmospheric pressure dielectric barrier Townsend discharge

In the present publication, the effect of the addition of H₂ in an atmospheric pressure Townsend Dielectric Barrier Discharge in an atmosphere of N₂-C₂H₄ is examined with an emphasis put on the evaluation of the surface chemistry and growth mechanisms. Scanning Electron Microscopy, Atomic Force Microscopy, X-Ray Photoelectron Spectroscopy and Fourier Transform Infrared Spectroscopy were used to characterize the coatings. For all H₂ concentrations, films obtained present high N/C ratio (∼ 0.8) with high NH_x and nitrile content. However, when H₂ is added in the discharge, nanoparticles/nanorods are formed imbedded in a smooth film. The average size of the nanorods is 100-200 nm in diameter with length from 1 to 10 μm. A growth mechanism is proposed to explain the formation of the nanorods on the surface of the coating in the presence of H₂.     

Consolidation of Sm5Fe17 powder by spark plasma sintering method

Sm₅Fe₁₇ bulk materials, one of the newer permanent magnetic materials, were successfully produced by the spark plasma sintering method. The resultant bulk materials had high densities of 85–98%. When obtained by sintering at relatively lower temperatures, the Sm₅Fe₁₇ bulk materials consisted of the Sm₅Fe₁₇ and SmFe₃ phases, whereas they contained some -Fe phase together with the Sm₅Fe₁₇ and SmFe₃ phases when obtained by sintering at relatively high temperatures. High coercivity values, exceeding 2 MAm⁻¹, were found in the Sm₅Fe₁₇ bulk materials consisting of the Sm₅Fe₁₇ and SmFe₃ phases.     

Synthesis and characterization of HfO2 and ZrO2 thin films deposited by plasma assisted reactive pulsed laser deposition at low temperature

A plasma assisted reactive pulsed laser deposition process was demonstrated for low-temperature deposition of thin hafnia (HfO₂) and zirconia (ZrO₂) films from metallic hafnium or zirconium with assistance of an oxygen plasma generated by electron cyclotron resonance microwave discharge. The structure and the interface of the deposited films on silicon were characterized by means of Fourier transform infrared spectroscopy, which reveals the monoclinic phases of HfO₂ and ZrO₂ in the films with no interfacial SiO_x layer between the oxide film and the Si substrate. The optical properties of the deposited films were investigated by measuring the refractive indexes and extinction coefficients with the aid of spectroscopic ellipsometry technique. The films deposited on fused silica plates show excellent transparency from the ultraviolet to near infrared with sharp ultraviolet absorption edges corresponding to direct band gap.