Atmospheric Pressure Plasma Discharge for Polysiloxane Thin Films Deposition and Comparison with Low Pressure Process

An atmospheric pressure dielectric barrier plasma discharge has been used to study a thin film deposition process. The DBD device is enclosed in a vacuum chamber and one of the electrodes is a rotating cylinder. Thus, this device is able to simulate continuous processing in arbitrary deposition condition of pressure and atmosphere composition. A deposition process of thin organosilicon films has been studied reproducing a nitrogen atmosphere with small admixtures of hexamethyldisiloxane (HMDSO) vapours. The plasma discharge has been characterized with optical emission spectroscopy and voltage-current measurements. Thin films chemical composition and morphology have been characterized with FTIR spectroscopy, atomic force microscopy (AFM) and contact angle measurements. A strong dependency of deposit character from the HMDSO concentration has been found and then compared with the same dependency of a typical low pressure plasma enhanced chemical vapour deposition process.     

Surface characterization of the SiOx films prepared by a remote atmospheric pressure plasma jet

The deposition rate and surface properties of SiO_x films were prepared and investigated using remote atmospheric pressure plasma (APP) jet. The APP, generated with low frequency power at 16 kHz, was fed with tetraethoxysilane (TEOS)/air gas mixture. After deposition, the SiO_x films were analyzed for chemical characteristics, elemental composition, surface morphology, and hardness. It was found that the deposition substrate temperature is the key factor to affect the deposition rate of remote APP chemical vapor deposition process. Fourier transform infrared (FTIR) spectra indicated that APP deposited SiO_x films are an inorganic feature. XPS examination revealed that the SiO_x films contained approximately 30% silicon, 58% oxygen and 12% carbon. Atomic forced microscopy (AFM) analysis results indicated a smooth surface of SiO_x films in deposition under higher substrate temperature. Also, pencil hardness tests indicated that the hardness of APP deposited SiO_x films was greatly improved with increasing substrate temperatures. Copyright © 2008 John Wiley & Sons, Ltd.     

UV Absorptance of Titanium Dioxide Thin Films by Plasma Enhanced Deposition from Mixtures of Oxygen and Titanium-Tetrakis-Isopropoxide

A low pressure radio frequency discharge was used to deposit films by mixtures of oxygen and titanium (IV) isopropoxide (TTIP) at powers of 200 W on films of polyethylene-terephthalat and samples of quartz glass. In the non-thermal plasma, films of rather pure TiO₂ could be deposited as revealed by X-ray photo-electron spectroscopy. Besides the film growth rate and the chemical composition, the spectral behaviour of the spectral transmittance of visually transparent films was determined in the range from 200 to 500 nm. Furthermore, the absorptance of films has been derived at characteristic spectral positions of the transmission spectra of the films. Accordingly, cut-off wavelength was found to increase with deposition time from 5 to 10 min as well as with the concentration of TTIP in a range below 1.7%. At 310 nm, the spectral absorption coefficient (extinction coefficient × concentration) was 12 μm⁻¹. While keeping other parameters constant, this coefficient decreased by 4 μm⁻¹ due to an increase of the concentration of TTIP from 1.7% to 8%. Simultaneously, the surface roughness increased as revealed by profilometry. Thus, since the chemical structure of films was found to change only marginally, a decrease of the film density is likely to cause the observed dependence of the absorption coefficient with increasing precursor concentration.     

Influence of Plasma Treatment on the Electroless Deposition of Copper on Carbon Fibers

Air and nitrogen glow discharge were used to replace chromic acid pretreatment to deposit copper film on carbon fiber surfaces from an CuSO₄‐HCHO electroless system. A greater copper uptake and a more uniformly coated copper film were obtained for plasma‐treated carbon fibers. The adhesion between the copper film and the carbon fibers was also improved. An orthogonal table L₉(3⁴) was used to study the effects of discharge pressure, discharge power, time and gas type on the copper uptake. Scanning electron microscopy (SEM), reflection absorption infrared spectroscopy (RAIR) and X‐ray photoelectron spectroscopy (XPS) at different depths were applied to characterize the physical and chemical changes of the surface of the carbon fibers. The results showed that after plasma treatment, the carbon fiber surface became rough and several types of polar oxygen groups, such as carboxylic acid COOH, esters COOC, quinones Ph?O, etc., were introduced into the carbon fiber surface. A mechanism of plasma treatment effects on copper electroless deposition on the carbon fiber surface is also suggested.     

Surface Properties of Low Density Polyethylene upon Low-Temperature Plasma Treatment with Various Gases

The surface of a LDPE was modified by Ar, O₂, N₂, CO₂ gaseous plasma. The changes in surface morphology and surface wettability were investigated using AFM and SEM. The surface chemical changes of LDPE were also characterized by FTIR-ATR. The SEM and AFM results demonstrated variable changes in surface roughness for different types of plasma gas used, the changes being more for the Ar and N₂ plasma treatments. Considering the nature of the LDPE film, XRD studies were carried out to determine changes in the percentage crystalinity. The results showed that all low pressure O₂, Ar, N₂, CO₂ gas plasmas improved the wettability of LDPE films. Contact angles decreased significantly depending on the discharge powers and exposure times. Surface morphology was also found to vary with plasma discharge powers, exposure times, and the type of gas being used. Ar and N₂ gas plasmas in general produced more superior results.     

Nitrogen-doped TiO2 from TiN and its visible light photoelectrochemical properties

Homogeneous titanium nitride (TiN) thin film was produced by simple electrophoreic deposition process on Ti substrate in an aqueous suspension of nanosized TiN powder. Nitrogen-doped titanium dioxide (TiO_2−xN_x) was synthesized by oxidative annealing the resulted TiN thin film in air. Photoelectrochemical measurements demonstrated visible light photoresponse for the electrode of annealed electrophoreic deposited TiN samples. It is found that the synthesized TiO_2−xN_x electrode showed higher photo potential under white and visible light illumination than the pure TiO₂ electrode. The photocurrent under visible light illumination was also observed, which increased with the increase of deposition time of TiN thin films.     

Influence of Vapor Phase Pretreatments of Epoxy Surfaces on the Nucleation of MOCVD Copper Thin Films

Vapor phase pretreatments of epoxy composite material reinforced with carbon fibers were carried out prior to the growth of Cu thin films by metal-organic chemical vapor deposition (MOCVD) using Cu (hfa)(COD) as copper precursor. These dry surface oxidation processes include H₂O/UV, O₂/UV and O₂/Plasma treatments. Oxygen plasma method is the most efficient to oxidize the surface and it has the greatest effect to improve the wettability of epoxy samples. As a consequence, the higher hydrophilicity of the plasma-modified epoxy surface induces a higher nucleation density in the Cu film. Furthermore, this treatment reduces drastically the induction period observed for the growth of the metal. Even though the O₂/UV pretreatment incorporates almost the same amount of oxygen in the epoxy surface than the plasma treatment, the functional groups are different, as revealed by XPS analyses, and the surface is less hydrophilic. Correlations between oxidation, wettability and nucleation density of the Cu films are discussed.     

Silicon Dioxide Coating of Titanium Dioxide Nanoparticles from Dielectric Barrier Discharge in a Gaseous Mixture of Silane and Nitrogen

The coating of titanium dioxide nanoparticles with silicon dioxide has been carried out by dielectric barrier discharge (DBD) plasma treatments to enhance the thermostability of Titania for applications at high temperature processes. During the first coating processing step, a closed film of silicon nitride was produced via plasma treatment in a gaseous mixture of silane and nitrogen, while atmospheric surface contaminations got mainly removed. In the second processing step, the DBD plasma treatment in oxygen or air was used to convert the silicon nitride mainly into silicon dioxide. Remaining carbon impurities at the interfaces between titanium dioxide and silicon nitride after the nitrogen/silane plasma treatment were subsequently removed simultaneously. Atomic force microscopy and X-ray photoelectron spectroscopy were employed to study the DBD plasma treatments of the TiO₂ nanoparticles.     

Reusable thin film photocatalyst of Fe‐doped TiO2 deposited by ECR plasma

The paper presents an improved method of depositing nanocrystalline thin films of Fe‐doped TiO₂ to be used as a reusable cyclic photocatalyst for degrading the organic pollutants. The technique of electron cyclotron resonance plasma‐enhanced chemical vapor deposition was employed with titanium tetra‐isopropoxide (C₁₂H₂₈O₄Ti) and ferrocene (C₁₀H₁₀Fe) as precursors of Ti and Fe, respectively. Optical emission spectroscopy was used to identify the reactive species, to determine the electron temperature and the ion density during deposition. The films were characterized using optical absorption and photoluminescence spectra, whereas the morphological analysis was carried out with scanning electron microscopy. Strong adhesion of the deposited films with the substrate ruled out any possibility of TiO₂ particles being leached out. It was confirmed by observing the degradation rate of the same film repeatedly. Cyclic use of the film for the catalytic reactions thus makes the process much user friendly for the water treatment. Copyright © 2014 John Wiley & Sons, Ltd.     

Single‐phase TiO2 formation by plasma oxidation of titanium thin films

Synthesis of titanium oxide film by plasma oxidization of the metallic films is investigated. Argon/oxygen gas mixture in the pressure range 30 × 10^?2 mbar is used for plasma processing at a frequency of 250 kHz. The plasma‐oxidized films are annealed in a tube furnace in argon atmosphere to establish crystalline‐phase formation. X‐ray diffraction and Raman spectroscopic results manifest peaks corresponding to rutile TiO₂. Ultraviolet‐Visible (UV‐Vis) spectroscopic analysis confirms the bandgap of rutile TiO₂, and photoluminescence spectra exhibit peaks due to oxygen defects. Homogeneity across the film's thickness and the nature of the film substrate interface is studied by depth profiling acquired using secondary ion mass spectrometry. Copyright © 2015 John Wiley & Sons, Ltd.     

含二氮杂萘酮结构聚醚砜酮膜的微波等离子体处理研究

含二氮杂萘酮结构型聚醚砜酮(ＰＰＥＳＫ)是近年来本研究组开发成功的新型耐高温聚合物[1].该聚合物具有优异的力学性能和突出的耐热性,玻璃化转变温度(Ｔｇ)为265～305℃(随砜酮比不同而变化),其结构式如下:ＯＮＮＯＳＯＯＯＮＮＯＣＯ　　研究表明,用ＰＰＥＳＫ制成的气体分离膜对Ｏ2/Ｎ2、ＣＯ2/Ｎ2有良好的气体渗透性和透过选择性[2,3],但由于其亲水性不高进而限制了它在纳滤膜和反渗透膜等方面的应用,因此有必要对其进行改性.目前,常用的膜及膜材料改性的方法有磺化、氯甲基化季胺化、接枝等化学改性和低温等离子体与辐射等物理改性.其…     

Surface chemical composition and fibrinogen adsorption-retention of fluoropolymer films deposited from an RF glow discharge

Fluoropolymer films have been deposited in the glow and afterglow regions of radio frequency glow discharges fed with C₂F₆−H₂ mixtures. Structure, growth rate, composition, and wettability of the films have been investigated by means of atomic force microscopy, electron spectroscopy for chemical analysis, secondary ion mass spectrometry, and water contact angle measurements.¹²⁵I labeled baboon fibrinogen in baboon plasma has been used to study the adsorption of the protein onto the films. Protein retention, i.e., the binding affinity of the adsorbed protein, has been examined by elution with a sodium dodecyl sulfate solution. Adsorption and retention of fibrinogen were correlated using multivariate statistical methods with the wettability, the degree of film fluorination, and the CF _x (1≤x≤3) group distribution of the coatings. This correlation identified the influence of each variable on the adsorption and retention of fibrinogen onto these substrates. These variables or surface properties can be easily balanced by properly tuning the experimental conditions of the glow discharge deposition process.     

Influence of High-energy electron-beam on photocatalytic activity of TiO2 films on carbon-fiber deposited by atomic layer deposition

High-energy electron-beam with energy of 1 MeV was used for modifying surface structure of TiO₂ thin films on carbon fiber prepared by using atomic layer deposition under atmospheric pressure. TiO₂ nanoparticles (∼20 nm) on carbon fiber underwent structural modification of the surface upon electron-beam treatment, resulting in enhanced photocatalytic activity. In contrast, a thicker film of TiO₂ did not show such changes in surface structure and photocatalytic activity by electron-beam treatment. We demonstrate that electron-beam can be used for modifying surface structure of photocatalysts consisting of nanoparticles for improvement of their activity.     

Plasma surface modification of poly (l-lactic acid) and poly (lactic-co-glycolic acid) films for improvement of nerve cells adhesion

Radio frequency (RF) plasma treatment in O₂ was applied to modify the surface of poly (l-lactic acid) (PLLA) and poly (d,l-lactic acid-coglycolic acid) (PLGA) as biodegradable polymers. The surface structure, morphology, wettability and surface chemistry of treated films were characterized by water drop contact angle measurement, scanning electron microscope (SEM), optical invert microscope, differential scanning calorimetry (DSC) and ATIR–FTIR spectroscopy. The cell affinity of the oxygen plasma treated film was evaluated by nervous tissue B65 cell culture in stationary conditions. The results showed that the hydrophilicity increased greatly after O₂ plasma treatment. The results showed that improved cell adhesion was attributed to the combination of surface chemistry and surface wettability during plasma treatment. Cell culture results showed that B65 nervous cell attachment and growth on the plasma treated PLLA was much higher than an unmodified sample and PLGA. Surface hydrophilicity and chemical functional groups with high polar component play an important role in enhancing cell attachment and growth.     

Photo-Induced Hydrophilicity of TiO<Subscript>2</Subscript> Films Deposited on Stainless Steel via Sol-Gel Technique

The photo-induced hydrophilicity of TiO₂ films deposited on stainless steel substrates and silicon wafers using two different sol-gel routes has been investigated. The results indicate that crystalline titanium oxide films with excellent hydrophilic properties can be obtained on silicon wafer with both routes. XPS and XRD data reveal that films deposited on stainless steel exhibit crystallization features similar to those of films deposited on silicon wafers, and only differ by their oxidation degree owing to a TiO₂ reduction process associated to a diffusion of iron ions during deposition of the acidic sol and/or high temperature post-treatment. Consequently, hydrophilic properties of films deposited on stainless steel are inhibited. The deposition of a SiO_x barrier layer at the film/substrate interface allows preventing such a detrimental substrate influence. A low temperature deposition route of the TiO₂ film associated to the presence of a barrier layer yields best results in preventing iron contamination of the films.     

The Role of Dielectric Barrier Discharge Atmosphere and Physics on Polypropylene Surface Treatment

Dielectric barrier discharge (DBD) is the discharge involved in corona treatment, widely used in industry to increase the wettability or the adhesion of polymer films or fibers. Usually DBD's are filamentary discharges but recently a homogeneous glow DBD has been obtained. The aim of this paper is to compare polypropylene surface transformations realized with filamentary and glow DBD in different atmospheres (He, N₂, N₂ + O₂ mixtures) and to determine the relative influence of both the discharge regime and the gas nature, on the polypropylene surface transformations. From wettability and XPS results it is shown that the discharge regime can have a significant effect on the surface transformations, because it changes both the ratio of electrons to gas metastables, and the space distribution of the plasma active species. This last parameter is important at atmospheric pressure because the mean free paths are short (m). These two points explain why in He, polypropylene wettability increase is greater by a glow DBD than by a filamentary DBD. In N₂, no significant effect of the discharge regime is observed because electrons and metastables lead to the same active species throughout the gas bulk. The specificity of a DBD in N₂ atmosphere compared to an atmosphere containing oxygen is that it allows very extensive surface transformations and a greater increase of the polypropylene surface wettability. Indeed, even in low concentration and independently of the discharge regime, when O₂ is present in the plasma gas, it controls the surface chemistry and degradation occurs.     

Computational investigation of the adsorption and reactions of SiHx (x = 0–4) on TiO2 anatase (101) and rutile (110) surfaces

The adsorption and reactions of the SiH_x (x = 0–4) on Titanium dioxide (TiO₂) anatase (101) and rutile (110) surfaces have been studied by using periodic density functional theory in conjunction with the projected augmented wave approach. It is found that SiH_x (x = 0–4) can form the monodentate, bidentate, or tridentate adsorbates, depending on the value of x. H coadsorption is found to reduce the stability of SiH_x adsorption. Hydrogen migration on the TiO₂ surfaces is also discussed for elucidation of the SiH_x decomposition mechanism. Comparing adsorption energies, energy barriers, and potential energy profiles on the two TiO₂ surfaces, the SiH_x decomposition can occur more readily on the rutile (110) surface than on the anatase (101) surface. The results may be used for kinetic simulation of Si thin‐film deposition and quantum dot preparation on titania by chemical vapor deposition (CVD), plasma enhanced CVD, or catalytically enhanced CVD. © 2013 Wiley Periodicals, Inc.     

The Effects of Cold Plasma Treatments on LDPE Wettability and Curing Kinetic of a Polyurethane Adhesive

A cold plasma feed with either oxygen or nitrogen was used to modify thin Low Density Polyethylene films. The treatment improved both the surface wettability and the curing kinetic of a polyurethane based adhesive spread on the surface. The chemical functionalities responsible of the observed behaviours were investigated and monitored over time by high resolution x-ray photoelectron spectroscopy. Atomic force microscopy were used to compare the effects of the two feeding gases on the surface morphology of films exposed (to the plasma) for equal times. The effect on the treated films of the atmosphere exposure and of the aging time were also considered.     

Effect of heat treatment on electrochromic properties of TiO<Subscript>2</Subscript> thin films

Electrochromic titanium oxide (TiO₂) films were deposited on ITO/glass substrates by chemical solution deposition (CSD). The stock solutions were spin-coated onto substrates and then heated at various temperatures (200–500 °C) in various oxygen concentrations (0–80%) for 10 min. The effects of the processing parameters on the electrochromic properties of TiO₂ films were investigated. X-ray diffraction measurements demonstrated that the amorphous TiO₂ films were crystallized to form anatase films above 400 °C. The electrochromic properties and transmittance of TiO₂ films were measured in 1 M LiClO₄–propylene carbonate (PC) non-aqueous electrolyte. An amorphous 350 nm-thick TiO₂ film that was heated at 300°C in 60% ambient oxygen exhibited the maximum transmittance variation (ΔT%), 14.2%, between the bleached state and the colored state, with a ΔOD of 0.087, Q of 10.9 mC/cm², η of 7.98 cm²/C and x in Li _x ClO₄ of 0.076 at a wavelength (λ) of 550 nm.     

Atmospheric Pressure Plasma Deposition of Polyfuran

The atmospheric pressure radiofrequency (RF) plasma polymerization of furan was carried out with the objective of synthesizing polyfuran thin film. The structure, compositions and morphology of the plasma deposited polyfuran film were investigated by Fourier transform infrared (FTIR), atomic force microscopy (AFM), ultraviolet‐visible absorption spectroscopy (UV‐vis) and thermogravimetric analysis (TGA). The formation of polyfuran was confirmed using FTIR and UV‐visible analysis. The properties of plasma‐deposited polyfuran were compared with those of chemically synthesized polyfuran. Although the plasma deposited thin film polyfuran shows lower thermal stability than that of chemically synthesized polyfuran. It has better solubility in CHCl₃, also. Thin uniform polyfuran films are obtained in plasma assisted polyfuran deposition, while particles are obtained in chemical polyfuran polymerization.