Characteristics of a cylindrical magnetron and reactive sputtering of binary compound films

The characteristics of a cylindrical magnetron, such as the dependences of the discharge voltage, chamber pressure, and plasma radiation intensity on the reactive gas flow rate and discharge current, are studied. In this magnetron, titanium nitride (TiN) and titanium dioxide (TiO₂) films are obtained by reactive magnetron sputtering. The transmission and reflection spectra of the films in the visual range are taken. From the transmission data for the TiO₂ films, their refractive index and absorption factor in the wavelength range 350–800 nm, as well as the porosity, are found by the Valeev method. The variation of the fundamental absorption edge with film thickness is determined with the Urbach formula.     

Formation of nanostructured carbon films in gas-discharge plasmas

Deposition of carbon materials from methane-hydrogen gas mixtures in a DC gas discharge is investigated. Parameters ensuring stable discharge conditions and synthesis of diamond and graphite-like films are determined. Optical emission spectroscopy is used to analyze the composition of the activated gas phase in the course of carbon film deposition. Synthesis of graphite-like carbon nanotubes and nanocrystallites is shown to correlate with the presence of C₂ dimers in the plasma. A noncatalytic mechanism of synthesis of nanostructured graphite in a carbon-containing gas phase is proposed.     

Preparation of N-doped TiO<Subscript>2</Subscript> photocatalyst by atmospheric pressure plasma process for VOCs decomposition under UV and visible light sources

The nitrogen doped (N-doped) titanium dioxide (TiO₂) photocatalyst was prepared by the atmospheric-pressure plasma-enhanced nanoparticles synthesis (APPENS) process operated under normal temperature, i.e. the dielectric barrier discharge plasma process. The N₂ carrier gas is dissociated in the AC powered nonthermal plasma environment and subsequently doped into the TiO₂ photocatalyst that was capable of being induced by visible light sources. The APPENS process for producing N-doped TiO₂ showed a higher film deposition rate in the range of 60–94 nm/min while consuming less power (<100 W) as compared to other plasma processes reported in literatures. And the photocatalytic activity of the N-doped TiO₂ photocatalyst was higher than the commercial ST01 and P25 photocatalysts in terms of toluene removals in a continuous flow reactor. The XPS measurement data indicated that the active N doping states exhibited N 1s binding energies were centered at 400 and 402 eV instead of the TiN binding at 396 eV commonly observed in the literature. The light absorption in the visible light range for N-doped TiO₂ was also confirmed by a clear red shift of the UV-visible spectra.     

Spectroscopic diagnostics of barrier discharge plasmas in mixtures of zinc diiodide with inert gases

The spectral characteristics of the emission of gas discharge atmospheric pressure plasmas in mixtures of zinc diiodide vapor with inert gases (He, Ne, Ar, Kr, and Xe) are investigated. The formation of a gas discharge plasma and the excitation of the components of a working mixture were performed in a high-frequency (with a repetition frequency of sinusoidal voltage pulses of 100 kHz) barrier discharge. The gas discharge emission was analyzed in the spectral range 200–900 nm with a resolution of 0.05 nm. Emission bands of ZnI(B-X) exciplex molecules and I₂* excimer molecules, lines of inert gases, and emission bands of XeI* exciplex molecules (in Xe-containing mixtures) were revealed. It is ascertained that the strongest emission of ZnI* molecules is observed in ZnI₂/He(Ne) mixtures. The regularities in the spectral characteristics of the gas discharge plasma emission are considered.     

TiO2/polyaniline nanocomposite films prepared by magnetron sputtering combined with plasma polymerization process

Radiofrequency plasma polymerization in combination with direct current reactive magnetron sputtering is utilized for the synthesis of TiO₂/plasma polymerized aniline nanocomposite thin films. In the composite film, X-ray diffraction measurements reveal formation of nanocrystalline rutile TiO₂ of crystallite size 3.6 nm. Due to continuous bombardment of plasma species during simultaneous magnetron sputtering and plasma polymerization, the precursors of polymerization are broken and few functional groups are retained in the composite film. The plasma polymerized aniline has the direct optical band gap of 3.55 eV and the nanocrystalline rutile TiO₂ is wide gap semiconductor with indirect gap of 3.20 eV which suggests the existence of an energy barrier at the interface in the composite form. The ac conductivity of composite film shows significant improvement as compared to plasma polymerized aniline film and sputtered rutile TiO₂ film. The composite film may find potential application as antistatic coatings.     

Investigation on surface properties of TiO2 films modified by DC glow discharge plasma

In the present work, TiO₂ films deposited on polyethylene terephthalate substrates by dip coating technique were subsequently treated by DC glow discharge plasma as a function of discharge potential. Hydrophilicity of these TiO₂ film surfaces was analyzed by contact angle measurements. Atomic force microscopy (AFM) revealed changes in surface morphology of the plasma treated TiO₂ films. Modifications in structural and chemical composition of the TiO₂ films were detected by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The blood compatibility of TiO₂ films was studied by in vitro investigation which includes thrombus formation and whole blood clotting time analysis (WBCT). It was found that the plasma treatment results in blood compatibility enhancement attributed to the structural, chemical and morphological properties of the modified film surfaces.     

Influence of the oxygen concentration on the formation of crystalline phases of TiO<Subscript>2</Subscript> during the low-pressure arc-discharge plasma synthesis

The synthesis of titanium dioxide (TiO₂) nanoparticles with different percentage of anatase and rutile phases is investigated. The synthesis is performed by controlling the oxygen percentage in the gas mixture in the plasmachemical evaporation–condensation process employing a low-pressure arc discharge. In all our experiments, the pressure in the plasmachemical reactor and the average size of particles remain constant and are 60 Pa and 6 nm, respectively. The crystal structure of synthesized TiO₂ is studied using X-ray diffraction; the morphology of the particles is analyzed employing transmission electron microscopy. Using X-ray phase analysis, it is established that the concentration of the TiO₂ anatase phase decreases upon a decrease in the oxygen concentration in the gas mixture. It is shown that the TiO₂ anatase phase is more efficient for photocatalytic decomposition of methylene blue than the rutile phase.     

The effect of surface modification by nitrogen plasma on photocatalytic degradation of polyvinyl chloride films

The solid-phase photocatalytic degradation of poly(vinyl chloride) (PVC) films was investigated under the ambient air in order to assess the feasibility of developing photodegradable polymers. Nitrogen plasma was used to modify PVC films to enhance the photocatalytic degradation of PVC with nano-sized anatase TiO₂. The plasma parameter varied in this study is discharge power from 30 to 120 W for a constant treatment time of 60 s and a constant gas pressure of 10 Pa. The photodegradation of the plasma-treated PVC-TiO₂ films was compared with that of pure PVC films and PVC-TiO₂ films performing weight loss monitoring, scanning electron microscopy (SEM) analysis, contact angle measurements, electron spin resonance (ESR), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The wettability of the plasma-treated PVC is improved significantly. ESR revealed that the signal of radicals on the surface of the plasma-treated PVC film was enhanced after the treatment. Furthermore, the weight loss indicated that TiO₂ speeds up the photocatalytic degradation of PVC chains. The SEM image of the plasma-treated PVC-TiO₂ film showed a lot of crack on the film surface after irradiation. XPS indicated that the C and Cl atomic concentration reached minimum values on the surface of plasma-treated PVC-TiO₂ under identical photocatalytic condition. The experimental results reveal that plasma treatment can obviously enhance the photocatalytic degradation of PVC.     

Analysis of TiO2 photocatalysis in a pulsed discharge system for phenol degradation

Photocatalysis of supported TiO₂ film photocatalyst in a pulsed discharge system for phenol degradation was studied in this paper. The obtained results revealed that the supported TiO₂ film with anatase structure had preferable photocatalytic activity in the pulsed discharge system. Phenol degradation and main byproduct generation were better in the discharge/TiO₂ system. The photocatalyst prepared with eight times dipping process had higher photocatalytic activity than other photocatalysts and testified a preferable photocatalyst condition in the pulsed discharge system. Furthermore, the supported TiO₂ photocatalyst kept photocatalytic activity after using five times in the pulsed discharge system.     

Output characteristics and parameters of the plasma from a gas-discharge low-pressure ultraviolet source using helium-iodine and xenon-iodine mixtures

The output characteristics and parameters of the plasma of a powerful gas-discharge source of UV radiation are studied. The UV source uses He-I₂ and Xe-I₂ mixtures and is excited by a longitudinal glow discharge. The pressure of the gas mixtures is varied from 100 to 1500 Pa, and the discharge power falls into the range 15–250 W. The source (lamp) emits in the spectral interval 200–390 nm, which covers the spectral line of the iodine atom at 206.2 nm, the spectral band of XeI(B-X) with a maximum at 253 nm, and the spectral band of with a maximum at 342 nm. For He(Xe)-I₂ mixtures at a pressure of 800–1000 Pa (this pressure range is near-optimal according to our experimental data), the electron energy distribution functions and the electron kinetic coefficients as functions of parameter E/N (E is the electric field strength, and N is the particle concentration in the discharge) are calculated. The calculated plasma parameters are used in the qualitative analysis of key electronic processes in the plasma of an exciplex halogen UV source and will be subsequently employed in numerical simulation of the process kinetics and output characteristics of a UV source based on helium-iodine or xenon-iodine mixtures.     

Photocatalytic performance of TiO2/V2O5 nanocomposite powder prepared by DC arc plasma

TiO₂/V₂O₅ nanocomposite powder was synthesized by the DC arc plasma, and its photocatalytic activity was examined by decompositions of Rhodamine B solution and toluene gas. In the synthesis of TiO₂/V₂O₅ nanocomposite powder, TiCl₄ and VOCl₃ precursors were introduced into thermal plasma flame with argon carrier gases through separated two gas bubblers. They were decomposed by Ar–N₂ thermal plasma generating Ti and V vapors, followed by the formation of oxides with the injection of additional oxygen into a plasma reactor. Nanocomposite composed of relatively small size V₂O₅ nanoparticles on a spherical TiO₂ nanoparticle which was about 250 nm in diameter was identified by X-ray diffractometry, electronic microscopy, and energy dispersive spectroscopy when the ratio of carrier gas flow rates for TiCl₄ to VOCl₃ was 1:4 or 1:5. In ultraviolet–visible absorption spectroscopy, the absorbed wavelength of light for synthesized TiO₂/V₂O₅ nanocomposite powder was wider than that for commercially available TiO₂ nanopowder. Therefore, Rhodamine B solution exposed to visible light was decomposed by TiO₂/V₂O₅ nanocomposite, whereas it was not decomposed by TiO₂ nanopowder. In addition, toluene decomposition in a dielectric barrier discharge reactor was carried out with nano-sized photocatalysts of TiO₂ nanopowder and TiO₂/V₂O₅ nanocomposite. Relatively higher removal rate of toluene was found in the case of TiO₂/V₂O₅ nanocomposite in virtue of improved photocatalytic performance.     

Emission characteristics of a high-power glow discharge plasma in a mixture of inert gases with bromine and iodine vapor

The results of an investigation of the UV radiation from the plasma of a dc glow discharge in mixtures of inert gases with bromine and iodine molecules are presented. The current-voltage and spectral characteristics of a longitudinal glow discharge with a power of 10–250 W are studied. The power and the efficiency of the total UV radiation of the plasma, as well as the power of radiation at the spectral line of the iodine atom at 206.2 nm, are optimized as functions of the power deposited into the plasma and the composition of the gas mixture. In active media based on Kr-Br₂ mixtures, the molecular emission of the plasma was represented by bands at 207 (KrBr(B-X)) and 289 nm (Br ₂ ^* ), while, in He-Xe-I₂ mixtures, it was represented by bands at 253 (XeI(B-X)) and 342 nm (I₂).     

Thickness dependent optical properties of titanium oxide thin films

TiO₂ thin films of different thickness were prepared by the Electron Beam Evaporation (EBE) method on crystal silicon. A variable angle spectroscopic ellipsometer (VASE) was used to determine the optical constants and thickness of the investigated films in the spectral range from 300 to 800 nm at incident angles of 60°, 70°, and 75°, respectively. The whole spectra have been fitted by Forouhi–Bloomer (FB) model, whose best-fit parameters reveal that both electron lifetime and band gap of TiO₂ thin film have positive correlation to the film thickness. The refractive indices of TiO₂ thin film increase monotonically with an increase in film thickness in the investigated spectral range. The refractive index spectra of TiO₂ thin films have maxima at around 320 nm and the maxima exhibit a marginally blue-shift from 327.9 to 310.0 nm with an increase in film thickness. The evolution of structural disorder in the TiO₂ thin film growth can be used to explain these phenomena.     

Characteristics of a high-frequency barrier discharge in mixtures of mercury diiodide vapor with gases

The spectral and electric characteristics of atmospheric-pressure high-frequency barrier discharge plasma based on mixtures of mercury diiodide with neon and admixtures of argon, xenon, and nitrogen are analyzed. A repetition rate of sinusoidal voltage pulses of about 100 kHz is used both to produce the gas discharge plasma and to excite the components of the working mixture. The radiation of the discharge in the range 200–900 nm is analyzed with a high resolution. It is found that, in the range 400–900 nm, the system of bands of excimer molecules HgI(B → X) emits 85% of the barrier discharge radiation. It is established that the radiation intensity of HgI(B → X) molecules is maximal in the mixture HgI₂/Xe/Ne = 0.6/10/90 kPa. In this mixture, UV radiation of molecules XeI(B → X) and XeI(B → A) is observed. The regular features of the spectral and electric characteristics of the gas discharge plasma are discussed. An atmospheric-pressure high-frequency barrier discharge in mixtures of mercury diiodide with gases is of interest for use in a selective (Δλ = 438–446 nm) excilamp with a cylindrical working aperture.     

The Influence of Molecular Gas on the Apokamp Discharge Formation

Emission spectra of apokamp discharge plasma jets in CO₂, Ar, Kr, N₂, and their mixtures have been studied. It has been shown that the emission spectra of the Kr–N₂ mixture contain N₂ and \(\rm{N_2^+}\) bands, as well as Kr lines. The spectrum of the Ar–CO₂ mixture is presented by bands of the Fox–Duffendack–Barker system and lines of the exited argon atom. In all gas media under study, the reduction of the molecular gas quantity leads to the transition from an apokampic discharge in the form of a diffusion jet developing from the current channel to a volume discharge with a strong transverse glowing. The experimental apparatus described in this work is proposed for use in laboratory investigations of spectral characteristics of transient luminous events observed in atmospheres of planets of the Solar System.     

Photocatalytic hydroxyapatite/titanium dioxide multilayer thin film deposited onto glass using an rf magnetron sputtering technique

Hydroxyapatite (HA)/titanium dioxide (TiO₂) thin film was deposited on glass using a radio frequency magnetron sputtering. X-ray diffraction (XRD), Fourier-transform infrared spectrometry, ultraviolet-visible spectroscopy and measurement of its photocatalytic activity by the decomposition of formaldehyde gas and the bacterial survival test of Escherichia coli (E. coli) cells were applied to characterize the film. After heat treatment (at 500 °C), XRD analysis of the HA/TiO₂ film showed a crystalline TiO₂ crystal structure with anatase phase. The transmittance of the HA/TiO₂ film decreased after the heat treatment, however, the average transmittance remained at 87% in the visible light range.In the decomposition of formaldehyde gas, the HA/TiO₂ film showed a higher decomposition rate than either the TiO₂ or the HA film alone. However, in the bacterial survival test, survival of cells on the HA/TiO₂ film was higher than that on the TiO₂ film, which indicates the HA/TiO₂ film has a lower bactericidal effect than the TiO₂ film alone.     

Development of rf plasma sputtered Al2O3-TiO2 multilayer broad band antireflecting coatings and its correlation with plasma parameters

TiO₂/Al₂O₃/TiO₂/Al₂O₃ multilayer structures were obtained at different oxygen:argon gas ratios of 20:80, 30:70, 50:50 and 60:40 sccm and constant rf power of 200 W using reactive magnetron sputtering. Grain size and elemental distribution in the films were studied from AFM image and XPS spectra respectively. The deposited grain size increased with increasing oxygen:argon gas ratio. The optical band gap, refractive index, extinction coefficient were calculated from UV-vis transmittance and reflectance spectra. It was observed that the value of refractive index, extinction coefficient and band gap increased with increasing oxygen. These variations are due to the defects levels generated by the heterostructure and explained by the PL spectrum. The antireflecting (AR) efficiency of the films was estimated from the reflectance spectra of the films. Broad band antireflecting coating for the visible range was achieved by varying oxygen content in the film. The plasma chemistry controlled the antireflecting property by the interface interdiffusion of atoms during layer transition in multilayer deposition. The in situ investigation of the plasma chemistry was performed using optical emission spectroscopy. The plasma parameters were estimated and correlated with the characteristics of the films.     

Deodorisation effect of diamond-like carbon/titanium dioxide multilayer thin films deposited onto polypropylene

Many types of plastic containers have been used for the storage of food. In the present study, diamond-like carbon (DLC)/titanium oxide (TiO₂) multilayer thin films were deposited on polypropylene (PP) to prevent flavour retention and to remove flavour in plastic containers.For the flavour removal test, two types of multilayer films were prepared, DLC/TiO₂ films and DLC/TiO₂/DLC films. The residual gas concentration of acetaldehyde, ethylene, and turmeric compounds in bottle including the DLC/TiO₂-coated and the DLC/TiO₂/DLC-coated PP plates were measured after UV radiation, and the amount of adsorbed compounds to the plates was determined. The percentages of residual gas for acetaldehyde, ethylene, and turmeric with the DLC/TiO₂ coated plates were 0.8%, 65.2% and 75.0% after 40 h of UV radiation, respectively. For the DLC/TiO₂/DLC film, the percentages of residual gas for acetaldehyde, ethylene and turmeric decreased to 34.9%, 76.0% and 85.3% after 40 h of UV radiation, respectively. The DLC/TiO₂/DLC film had a photocatalytic effect even though the TiO₂ film was covered with the DLC film.     

Investigations of Pulse‐Plasma‐Polymer Coating on TiO2 Nanoparticles and Their Dispersion

An amorphous acrylic acid (AA) polymer coating was generated on TiO₂ nanoparticles through pulse radio frequency (RF) plasma polymerization. The AA plasma synthesis mechanism was studied by its optical emission spectrum. The chemical structures of AA–plasma‐polymer were carefully investigated by Fourier transform infrared spectroscopy (FTIR). The dispersion behaviors of AA‐coated and uncoated TiO₂ nanoparticles in glycol solution were characterized by ultraviolet absorbency and particle size distribution measurements. The results showed that the aggregation of TiO₂ nanoparticles in glycol solution was effectively lowered and the dispersion was improved a lot after AA–plasma‐polymer coating. The pulse plasma coating parameters played an important role in the dispersion enhancement of TiO₂ nanoparticles. By properly regulating the pulse discharge parameters, the system could gain the highest radical–monomer reactions rate, the most compatible functional groups on the nanoparticles, and the best dispersion in the background media.     

Applications of vertically oriented TiO2 micro-pillars array on the electrode of dye-sensitized solar cell

In this research, dye-sensitized solar cells based on TiO₂ micro-pillars fabricated by inductive couple plasma etcher were investigated by analyses of X-ray diffraction (XRD), scanning electron microscopy (SEM), contact angle, ultraviolet-visible absorption spectra (UV-vis), and current-voltage characteristics. X-ray diffraction patterns show that the TiO₂ anatase phase forms while sintering at 450 °C for 30 min. The SEM images reveal that the diameter and height of TiO₂ micro-pillars are about 3 and 0.8 μm, respectively. The measurements of contact angle between TiO₂ micro-pillars and deionized water (DI water) reveal that the TiO₂ micro-pillars is super-hydrophilic while annealed at 450 °C for 30 min.The absorption spectrum of TiO₂ micro-pillars is better than TiO₂ thin film and can be widely improved in visible region with N3 dye adsorbed. The results of current-voltage (I-V) characteristics analysis reveal that dye-sensitized solar cell with TiO₂ micro-pillars electrode has better I-V characteristics and efficiency than TiO₂ film electrodes. This result may be due to the annealed TiO₂ micro-pillars applied on the electrode of dye-sensitized solar cell can increase the contact area between TiO₂ and dye, resulting in the enhancement of I-V characteristics and efficiency for dye-sensitized solar cell.