Composite SiOx/hydrocarbon plasma polymer films prepared by RF magnetron sputtering of SiO2 and polyethylene or polypropylene

Composite SiO_x/hydrocarbon plasma polymer films have been prepared by RF sputtering of silica and hydrocarbon polymer (polyethylene (PE) or polypropylene (PP)) targets placed on two balanced magnetrons. The morphology and composition of the composite films have been analysed by means of AFM, RBS/ERDA, FTIR, and XPS. The obtained films demonstrated wide range of wettability and hardness in dependence on the preparation conditions. When the ratio of RF powers delivered to the individual targets P_SiO2/P_PE(P_PP) changed from 0.1 to 10 the static contact angles of water varied from 75° to 25° and from 80° to 33° for composite films obtained from PE and PP, respectively. The hardness of the composite films varied from 2400 to 3400 N/mm² and from 1600 to 2000 N/mm² for the above-mentioned cases, respectively. Peculiar properties of the composite SiO_x/hydrocarbon plasma polymer films have been discussed with respect to the elemental composition and nature of the chemical bonds established on the surface of the films.     

Influence of substrate temperature on N-doped ZnO films deposited by RF magnetron sputtering

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N₂ / (Ar + N₂) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (T_s). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing T_s. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing T_s to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing T_s from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing T_s. The negative sign of Hall coefficients confirmed the n-type conducting.     

Plasma polymer films rf sputtered from PTFE under various argon pressures

Fluorocarbon plasma polymer films were prepared by radio-frequency (rf) sputtering of polytetrafluoroethylene (PTFE). Their wettability decreased with the increase in pressure of argon working gas. The films deposited at 70 Pa were found to be superhydrophobic plasma polymers with a static contact angle 146° for water. Sputtered fluorocarbon plasma polymer films were characterized by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. The paper shows that the surface composition and chemical structure of the films vary with altering the argon gas pressure.     

Indium phosphide films prepared by flash evaporation technique: Synthesis and characterization

Indium phosphide films were deposited by flash evaporating InP powder (99.995%) on glass substrates. Microstructural information was obtained from transmission electron microscope and atomic force microscope (AFM) studies. The average value (~ 0.33 nm) of surface roughness of the films was determined by AFM. X-ray diffraction traces indicated reflections from (111), (220) and (311) planes only. The band gap was found to vary between ~ 1.94 eV and 1.96 eV. ε_∞ varied between 11.58 and 11.89 while the plasma frequency (ω_p,) were seen to vary between 8.52 and 8.59 × 10¹⁴ s^− 1. The bonding environment in the films was determined from Raman and Fourier transformed infrared measurements. The experimental absorption spectra could be faithfully described by considering the effect of scattering by the ultra small crystallites in the film alone. Photoluminescence peak located at ~ 1.5 eV may be ascribed due to transitions from states arising out of phosphorous vacancy to the valance band. The shoulders of the peak ~ 1.5 eV may originate from the DA transitions between V_P and In_P.     

Effect of annealing temperature on growth of Ce-ZnO nanocomposite thin films: X-ray photoelectron spectroscopy study

Ce-doped ZnO nanocomposite thin films with Ce/Zn ratio fixed at optimum value (10 at.%) have been prepared via sol-gel method at different annealing temperatures varied from 180 to 500 °C. The synthesized samples were characterized employing atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) techniques. According to AFM analysis, the average grain size increased from about 70 nm to 150 nm by increasing the annealing temperature from 300 to 500 °C. Moreover, based on the XPS data analysis, it was found that three major metal ions namely Ce³⁺, Ce⁴⁺, and Zn²⁺ coexist on the surface of the nanocomposite films. XPS data analysis also revealed that Ce³⁺ ion is oxidized to Ce⁴⁺ ion with increasing annealing temperature. Due to oxidation, the ratio of [Ce^3±]/[Ce total] changed from 68.8 to 38.1% by increasing the annealing temperature from 180 to 500 °C. In addition, the Ce/Zn ratio increased from 0.21 to 0.42 when increasing the annealing temperature from 180 to 500 °C indicating migration of Ce ions toward the surface at higher temperatures. Finally, the XRD measurements determined that the ZnO thin films have a hexagonal wurtzite structure and CeO₂ crystallites are formed at 500 °C in the Ce-doped ZnO nanocomposite thin films.     

Carbon films deposited by MCECR plasma sputtering

The mirror-confinement-type electron cyclotron resonance (MCECR) plasma source has high plasma density and high electron temperature, and it is quite useful in many plasma processing, and has been used for etching and thin-film deposition. In this paper, the carbon films about 50 nm thickness were deposited on Si (1 0 0) by MCECR plasma sputtering the sintered carbon target with the argon plasma, and its properties were studied. The bonding structure of the film was analyzed by using the X-ray photoelectron spectropscopy (XPS) and the nanostructure was evaluated with the high-resolution transmission electron microscopy (HRTEM). The tribological properties (friction coefficient, wear rate, and wear life) of the film was investigated by using the pin-on-disk tribometer under the conditions that the normal load is 1 N and the sliding velocity is 0.05 m/s. The nanohardness of the films was measured by using the nanoindenter under conditions that the maximum displacement is 30 nm and the maximum load is 500 μN. The optical properties were measured by using the ellipsometer. The residual stress was measured with a surface profilometer. The surface morphology was studied by using the atomic force microscope (AFM).     

X-Ray photoelectron spectroscopy analysis of plasma-polymer interactions for development of low-damage plasma processing of soft materials

Plasma-polymer interactions have been investigated using atomic force microscopy (AFM) and x-ray photoelectron spectroscopy (XPS) of polyethyleneterephthalate (PET) films, which have been exposed to argon plasmas driven by low-inductance antenna modules as a parameter of ion energy. The AFM images indicated that the argon plasma exposure exhibited a significant change in surface roughness. The XPS analyses suggested that the degradation of chemical bonding structure and/or bond scission of PET could be effectively suppressed in the plasma exposures with ion energies below 6 eV. However, significant degradations of O = C-O bond, C-O bond and phenyl group were observed with increasing ion energy above 6 eV.     

Spray pyrolysis deposition of indium sulphide thin films

In₂S₃ thin films were grown by the chemical spray pyrolysis (CSP) method using the pneumatic spray set-up and compressed air as a carrier gas. Aqueous solutions containing InCl₃ and SC(NH₂)₂ at a molar ratio of In/S = 1/3 and 1/6 were deposited onto preheated glass sheets at substrate temperatures T_s = 205-410 °C. The obtained films were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM,) optical transmission spectra, X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS). According to XRD, thin films deposited at T_s = 205-365 °C were composed of the (0 0 12) orientated tetragonal β-In₂S₃ phase independent of the In/S ratio in the spray solution. Depositions performed at T_s = 410 °C led to the formation of the In₂O₃ phase, preferably when the 1/3 solution was sprayed. Post-deposition annealing in air indicated that oxidation of the sulphide phase has a minor role in the formation of In₂O₃ at temperatures up to 450 °C. In₂S₃ films grown at T_s below 365 °C exhibited transparency over 70% in the visible spectral region and E_g of 2.90-2.96 eV for direct and 2.15-2.30 eV for indirect transitions, respectively. Film thickness and chlorine content decreased with increasing deposition temperatures. The XPS study revealed that the In/S ratio in the spray solution had a significant influence on the content of oxygen (Me-O, BE = 530.0 eV) in the In₂S₃ films deposited in the temperature range of 205-365 °C. Both XPS and EDS studies confirmed that oxygen content in the films deposited using the solution with the In/S ratio of 1/6 was substantially lower than in the films deposited with the In/S ratio of 1/3.     

Surface characteristics of parylene-C films in an inductively coupled O2/CF4 gas plasma

In this article, we report the results obtained from a study carried out on the inductively coupled plasma (ICP) etching of poly-monochloro-para-xylylene (parylene-C) thin films using an O₂/CF₄ gas mixture. The effects of adding CF₄ to the O₂ plasma on the etch rates were investigated. As the CF₄ gas fraction increases up to approximately 16%, the polymer etch rate increases in the range of 277-373 nm/min. In this work, the atomic force microscopy (AFM) analysis indicated that the surface roughness was reduced by the addition of CF₄ to the O₂ plasma. Contact angle measurements showed that the surface energy decreases with increasing CF₄ fraction. At the same time, X-ray photoelectron spectroscopy (XPS) demonstrated the increase in the relative F atomic content on the surface.     

Contact angle analysis of low-temperature cyclonic atmospheric pressure plasma modified polyethylene terephthalate

Polyethylene terephthalate (PET) films are modified by cyclonic atmospheric pressure plasma. The experimentally measured gas phase temperature was around 30 °C to 90 °C, indicating that this cyclonic atmospheric pressure plasma can treat polymers without unfavorable thermal effects. The surface properties of cyclonic atmospheric pressure plasma-treated PET films were examined by the static contact angle measurements. The influences of plasma conditions such as treatment time, plasma power, nozzle distance, and gas flow rate on the PET surface properties were studied. It was found that such cyclonic atmospheric pressure plasma is very effective in PET surface modification, the reduced water contact angle was observed from 74° to less than 37° with only 10 s plasma treatment. The chemical composition of the PET films was analyzed by X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) was used to study the changes in PET surface feature of the polymer surfaces due to plasma treatment. The photoemission plasma species in the continuous cyclone atmospheric pressure plasma was identified by optical emission spectroscopy (OES). From OES analysis, the plasma modification efficiency can be attributed to the interaction of oxygen-based plasma species in the plasma with PET surface. In this study, it shows a novel way for large scale polymeric surface modification by continuous cyclone atmospheric pressure plasma processing.     

Effect of oxygen plasma treatment on bonding states for columnar structured a-CNx thin films prepared by reactive sputtering

Amorphous carbon nitride (a-CN) thin films were deposited on silicon single crystal substrates by rf-reactive sputtering method using a graphite target and nitrogen gas. The substrate temperature was varied from room temperature (RT) to 853 K. After deposition, the effect of oxygen plasma treatment on bonding structures of the film surface has been studied by using an oxygen discharge at 16 Pa and rf power of 85 W. The chemical bonding states and film composition were analyzed by X-ray photoelectron spectroscopy (XPS), while film thickness was obtained from scanning electron microscopy (SEM) and ellipsometer. XPS study revealed that the films have NO₂ and NO₃ bonding structures when the films are deposited at temperatures higher than 673 K. After exposure to oxygen plasma, carbon in the film surface was etched selectively and this phenomenon was observed in all films. In contrast, the surface concentration of nitrogen was ket at constant values before and after oxygen plasma treatment. The NO₃ bonding state had dramatically increased after oxygen plasma treatment for films deposited at higher deposition temperatures. The film surfaces have been observed to change the function from hydrophobic to hydrophilic after oxygen plasma treatment.     

Low-voltage characteristics of MgO-CaO films as a protective layer for AC plasma display panels by e-beam evaporation

The MgO-CaO composites films were prepared by e-beam evaporation to improve both operating voltages and memory coefficient of a protective layers for AC plasma display panels (PDPs). The effects of CaO addition to the conventional MgO films on both the electrical properties and the structural changes of the Mg_1–xCa_xO thin films deposited on the slide glass substrates were investigated. Atomic force microscopy (AFM) results revealed that the Mg_0.8Ca_0.2O film had a very rough surface due to the formation of a second phase on the surface. By adding controlled amount of CaO, the Mg-Ca-O films showed a firing voltage of 176 V that is lower than that of the conventional 100% MgO film. The deposition rates of 40–100 nm/min were obtained as a function of [CaO/(MgO+CaO)] ratio of the evaporation source materials.     

Thickness effect on properties of titanium film deposited by d.c. magnetron sputtering and electron beam evaporation techniques

This paper reports effect of thickness on the properties of titanium (Ti) film deposited on Si/SiO₂ (100) substrate using two different methods: d.c. magnetron sputtering and electron beam (e-beam) evaporation technique. The structural and morphological characterization of Ti film were performed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). XRD pattern revealed that the films deposited using d.c. magnetron sputtering have HCP symmetry with preferred orientation along (002) plane, while those deposited with e-beam evaporation possessed fcc symmetry with preferred orientation along (200) plane. The presence of metallic Ti was also confirmed by XPS analysis. FESEM images depicted that the finite sized grains were uniformly distributed on the surface and AFM micrographs revealed roughness of the film. The electrical resistivity measured using four-point probe showed that the film deposited using d.c. magnetron sputtering has lower resistivity of ～13 μΩcm than the film deposited using e-beam evaporation technique, i.e. ～60 μΩcm. The hardness of Ti films deposited using d.c. magnetron sputtering has lower value (～7·9 GPa) than the film deposited using e-beam technique (～9·4 GPa).     

On the zinc nitride properties and the unintentional incorporation of oxygen

Zinc nitride films were prepared by radio-frequency magnetron sputtering in N₂/Ar ambient using different substrates (glass and thermally-oxidized-Si) and buffer layers (low-temperature Zn₃N₂ and ZnO). Resonant Rutherford backscattering (RBS) allowed determining Zn_xN_y stoichiometry and thickness. Despite the sputtering system was operated in high vacuum conditions, unintentional oxygen incorporation during growth was detected. Calculations of the relative oxygen concentration showed that the oxygen content was very dependent on the growth rate. Ex-situ oxidation was also analyzed by resonant RBS and compared with the results of as-grown layers. Scanning electron microscopy and X-ray diffraction revealed that surface morphology and crystal orientation were strongly dependent on the substrate temperature (T_s). In addition, optical transmission measurements show a reduction of the optical energy band gap from 1.46 to 1.25 eV as T_s increased. The electrical properties were examined as a function of growth rate, total working gas flux and T_s aiming to maximize electron mobility. From those studies, it was found that Hall mobility increased significantly as the growth rate decreased. A maximum mobility of 100 cm²/Vs and a minimum carrier concentration of 3.2 × 10¹⁸ cm⁻³ were achieved at a T_s of 423 K and a growth rate of 4.44 nm/min.     

Composite SiOx/fluorocarbon plasma polymer films prepared by r.f. magnetron sputtering of SiO2 and PTFE

Composite films SiO_x/fluorocarbon plasma polymers were prepared by r.f. sputtering from two balanced magnetrons equipped with polytetrafluoroethylene (PTFE) and silica (SiO₂) targets. Argon was used as the working gas. The obtained films were characterised by means of XPS, RBS, FTIR, AFM, TEM, microhardness and static contact angle measurements. The obtained SiO_x/fluorocarbon plasma polymer films reveal different wettability (static contact angle of water ranges from 68° to 40°) and hardness (ranges from 720 to 3200 N/mm²) when the volume fraction ratio (filling factor) of SiO₂ changes from 0.01 to 0.7. The concentration of elements determined by RBS/ERDA varies strongly over this range of filling factors. The heterogeneous structure of the composite films is indicated by TEM at high SiO_x contents.     

Tungsten oxides as interfacial layers for improved performance in hybrid optoelectronic devices

Tungsten oxide (WO₃) films with thicknesses ranging from 30 to 100 nm were grown by Hot Filament Vapor Deposition (HFVD). Films were studied by X-Ray Photoemission Spectroscopy (XPS) and were found to be stoichiometric. The surface morphology of the films was characterized by Atomic Force Microscopy (AFM). Samples had a granular form with grains in the order of 100 nm. The surface roughness was found to increase with film thickness. HFVD WO₃ films were used as conducting interfacial layers in advanced hybrid organic-inorganic optoelectronic devices. Hybrid-Organic Light Emitting Diodes (Hy-OLEDs) and Organic Photovoltaics (Hy-OPVs) were fabricated with these films as anode and/or as cathode interfacial conducting layers. The Hy-OLEDs showed significantly higher current density and a lower turn-on voltage when a thin WO₃ layer was inserted at the anode/polymer interface, while when inserted at the cathode/polymer interface the device performance was found to deteriorate. The improvement was attributed to a more efficient hole injection and transport from the Fermi level of the anode to the Highest Occupied Molecular Orbital (HOMO) of a yellow emitting copolymer (YEP). On the other hand, the insertion of a thin WO₃ layer at the cathode/polymer interface of Hy-OPV devices based on a polythiophene-fullerene bulk-heterojunction blend photoactive layer resulted in an increase of the produced photogenerated current, more likely due to improved electron extraction at the Al cathode.     

Evaluation of microstructures and mechanical properties of diamond like carbon films deposited by filtered cathodic arc plasma

Diamond-like carbon (DLC) films were deposited by a cathodic arc plasma evaporation (CAPD) process, using a mechanical shield filter combined with a magnetic filter with enhanced arc structure at substrate-bias voltage ranging from − 50 to − 300 V. The film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). The mechanical properties were investigated by using a nanoindentation tester, scratch test and ball on disc wear test. The Raman spectra of the films showed that the wavenumber ranging from 900 to 1800 cm^− 1 could be deconvoluted into 1140 cm^− 1, D band and G band. The bias caused a significant effect on the sp³ content which was increased with the decreasing of I_D/I_G ratio. The XPS spectra data of the films which were etched by H⁺ plasma indicated the sp³ content are higher than those of the as-deposited DLC films. This implied that there is a sp²-rich layer present on the surface of the as-deposited DLC films. The nanoindentation hardness increased as the maximum load increased. A 380 nm thick and well adhered DLC film was successfully deposited on WC-Co substrate above a Ti interlayer. The adhesion critical load of the DLC films was about 33 N. The results of the wear tests demonstrated that the friction coefficient of the DLC films was between 0.12 and 0.2.     

Deposition of diamond-like carbon films on the inner surface of narrow stainless steel tubes

Diamond-like carbon (DLC) films were deposited on the inner surface of 304-type stainless steel tube with an inner diameter of 10 mm by DC glow discharge plasma. The influence of the deposition time, pressure and the ratios of CH₄ in CH₄/Ar gas mixture on the DLC film deposition were investigated. The images of Scanning Electron Microscopy (SEM) show that the DLC films are featureless and free of porosity. Fibre-like structure was recognized on the film surface by Atomic Force Microscopy (AFM). The film deposition rate decreases with increasing the deposition time. Relative higher deposition rate (40 nm/min) can be obtained at 20-30 Pa, higher and lower pressure will significantly decrease the deposition rate. Raman spectrum analysis shows that the films deposited in 30 min at 20-30 Pa have more sp³ content. The corrosion resistance of the films was measured by potentiodynamic polarization test. The DLC films deposited on the inner surface of the 304-type stainless steel tube significantly improve its corrosion resistance.     

Characterization of nanocrystalline indium tin oxide thin films prepared by ion beam sputter deposition method

Indium tin oxide (ITO) thin films were deposited on glass substrates by ion beam sputter deposition method in three different deposition conditions [(i) oxygen (O₂) flow rate varied from 0.05 to 0.20 sccm at a fixed argon (1.65 sccm) flow rate, (ii) Ar flow rate changed from 1.00 to 1.65 sccm at a fixed O₂ (0.05 sccm) flow rate, and (iii) the variable parameter was the deposition time at fixed Ar (1.65 sccm) and O₂ (0.05 sccm) flow rates]. (i) The X-ray diffraction (XRD) patterns show that the ITO films have a preferred orientation along (400) plane; the orientation of ITO film changes from (400) to (222) direction as the O₂ flow rate is increased from 0.05 to 0.20 sccm. The optical transmittance in the visible region increases with increasing O₂ flow rate. The sheet resistance (R_s) of ITO films also increases with increasing O₂ flow rate; it is attributed to the decrease of oxygen vacancies in the ITO film. (ii) The XRD patterns show that the ITO film has a strong preferred orientation along (222) direction. The optical transmittance in the visible spectral region increases with an increase in Ar flow rate. The R_s of ITO films increases with increasing Ar flow rate; it is attributed to the decrease of grain size in the films. (iii) A change in the preferred orientations of ITO films from (400) to (222) was observed with increasing film thickness from 314 to 661 nm. The optical transmittance in the visible spectral region increases after annealing at 200 °C. The R_s of ITO film decreases with the increase of film thickness.     

Improved impermeability of PET substrates using oxygen and hydrogen plasma

A considerable decrease in permeability of polyethylene terephthalate (PET) films by means of surface plasma treatment in a reactive ion etching system is reported. The effects of oxygen and hydrogen radio frequency plasma on the surface properties of PET polymers are investigated by infrared spectroscopy, scanning electron microscopy (SEM), and X-ray photon spectroscopy (XPS). The surface morphology of the samples has been investigated using SEM and atomic force microscopy (AFM). The optical transmission spectroscopy has been studied further confirming the significant effect of O-plasma. Also the penetration of air through the treated substrates was investigated using a vacuum test. It is found that oxygen and hydrogen plasmas lead to about four-fold reduction in the penetration of air through the PET films, while the effect of hydrogen plasma has been more significant. In addition, oxygen plasma results in a rougher surface as observed both by AFM and SEM analyses. The formation of nanostructures on PET surfaces has been observed at plasma powers of 0.3 W/cm².