Surface energy modification of SiOxCyHz film using PECVD by controlling the plasma processes for OMCTS (Si4O4C8H24) precursor

SiO_x films produced from octamethylycyclodisiloxane (Si₄O₄C₈H₂₄, OMCTS) with oxygen carrier gas have a low contact angle. The surface energy of the SiO_x films can be changed by controlling the plasma process. SiO_xC_yH_z films were deposited on polycarbonate substrates by plasma enhanced chemical vapor deposition using OMCTS without oxygen carrier gas. The input power in the radio frequency plasma was changed to optimize the surface energy of the resulting SiO_xC_yH_z film. The plasma diagnostics, surface energy and surface morphology were characterized by optical emission spectrometry, contact angle measurements and atomic force microscopy, respectively. The chemical properties of the coatings were examined by Fourier transform infrared spectroscopy. The surface energy of the SiO_xC_yH_z films produced using a room temperature plasma process could be controlled by employing the appropriate intensity of excited neutrals, ionized atoms, molecules and energy (input rf power and bias), as well as the suitable dissociation of OMCTS.     

Deposition of hydrophobic nano-coatings with low-pressure radio frequency CH2F2/Ar plasma processing

In an attempt to perform hydrophobic nano-coating, this investigation examined various operational parameters including in RF plasma power, system gas pressure, and CH₂F₂:Ar ratio of low-pressure plasma processing. The low-pressure plasma, generated with radio frequency power at 13.56 MHz, was fed difluoromethane (CH₂F₂)/Ar gas mixture. The surface characteristics of the plasma polymerized films were studied by static contact angle measurement (CA) and atomic force microscopy (AFM). As a result, increasing deposition of CH₂F₂ plasma polymerized films was achieved in enhanced RF plasma power input. The CH₂F₂ plasma polymerized films also were conducted in a varying system gas pressure with enhanced hydrophobic surface property. The effects of CH₂F₂/Ar plasma on the surface characteristics of the plasma polymerized films were investigated as a function of the Ar content. The super hydrophobic coating under optimized operational parameters prepared in this study obtained water contact angles greater than 150°. It was found that the maximum water contact angles (161°) was obtained at 1.5:1 (CH₂F₂: Ar) ratio. In addition, AFM analysis shows that possible ion bombardment from CH₂F₂/Ar plasma can increase surface roughness, and effectively form a hydrophobic coating on the surface of heat sensitive materials.     

Comparison of fluorocarbon film deposition by pulsed/continuous wave and downstream radio frequency plasmas

Fluorocarbon (FC) films have been deposited using pulsed and continuous wave (cw) radio frequency (rf) plasmas fed with hexafluoroethane (C₂F₆), octafluoropropane (C₃F₈), or octafluorocyclobutane (C₄F₈). The effects of feed gases used, discharge pressure, rf power, substrate positions and discharge modes (pulsed or cw) on the deposited films are examined. Film properties are determined using X-ray photoelectron spectroscopy, atomic force microscopy, and static contact angle measurements. The contact angles of FC films are well related to their compositions and structures. Feed gases used, discharge pressure, rf power, substrate positions and discharge modes strongly affect the morphology of the resulting film, as revealed by atomic force microscopy. Optical emission spectrometry measurements were performed to in-situ characterize the gas-phase compositions of the plasmas and radicals’ emission intensities during film deposition. Correlations between film properties, gas-phase plasma diagnostic data, and film growth processes were discussed. The film growth in pulsed or downstream plasmas was controlled by the surface migration of radicals, such as CF₂ towards nucleation centers, which result in the deposition of FC films with less cross-linked nature and rougher surfaces. These results demonstrate that it is possible to control film compositions and surface structure by changing deposition parameters.     

Inductively coupled plasma reactive ion etching of titanium thin films using a Cl2/Ar gas

Inductively coupled plasma reactive ion etching of titanium thin films patterned with a photoresist using Cl₂/Ar gas was examined. The etch rates of the titanium thin films increased with increasing the Cl₂ concentration but the etch profiles varied. In addition, the effects of the coil rf power, dc-bias voltage and gas pressure on the etch rate and etch profile were investigated. The etch rate increased with increasing coil rf power, dc-bias voltage and gas pressure. The degree of anisotropy in the etched titanium films improved with increasing coil rf power and dc-bias voltage and decreasing gas pressure. X-ray photoelectron spectroscopy revealed the formation of titanium compounds during etching, indicating that Ti films etching proceeds by a reactive ion etching mechanism.     

Etch characteristics of indium zinc oxide thin films in a C2F6/Ar plasma

Dry etching of indium zinc oxide (IZO) thin films was performed using inductively coupled plasma reactive ion etching in a C₂F₆/Ar gas. The etch characteristics of IZO films were investigated as a function of gas concentration, coil rf power, dc-bias voltage to substrate, and gas pressure. As the C₂F₆ concentration was increased, the etch rate of the IZO films decreased and the degree of anisotropy in the etch profile also decreased. The etch profile was improved with increasing coil rf power and dc-bias voltage, and decreasing gas pressure. An X-ray photoelectron spectroscopy analysis confirmed the formation of InF₃ and ZnF₂ compounds on the etched surface due to the chemical reaction of IZO films with fluorine radicals. In addition, the film surfaces etched at different conditions were examined by atomic force microscopy. These results demonstrated that the etch mechanism of IZO thin films followed sputter etching with the assistance of chemical reaction.     

Chemical vapor deposition of SiO2 films by TEOS/O2 supermagnetron plasma

A TEOS/O₂ supermagnetron double electrode plasma system was used to deposit SiO₂ films. Deposition rates were measured as a function of rf power and substrate stage temperature. With an increase of rf power on both electrodes from 40 to 80W, the deposition rate increased; however, with a further increase of rf power from 80 to 120W, the deposition rate ceased to increase or decreased only a small amount. The presence of O-H bonds from bonded water in the film was evaluated using buffered HF (BHF) etching solution. With an increase of rf power from 40 to 120W, the BHF etch rate decreased; i.e., the number of O-H bonds were reduced. A minimum BHF etch rate was observed at a rf phase difference of 180° between the two rf power sources. A SiO₂ film was deposited on a trench-patterned quartz substrate. A flat surface SiO₂ layer with air gaps (voids) was formed on the high-aspect ratio (depth/width=1.5-2) trench area.     

Fabrication of thromboresistant multilayer thin film on plasma treated poly (vinyl chloride) surface

Layer-by-layer deposited anticoagulant multilayer films were prepared on ammonia plasma treated poly (vinyl chloride) (PVC). Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) and contact angle results revealed the presence of –NH₂ on the ammonia plasma treated PVC surfaces and the layer-by-layer self-assembly process. The stability of multilayer film was studied with the radio labeled method. The remainder bovine serum albumin (BSA) in cross-linked 5(heparin/BSA) multilayer films dipped in phosphate buffered saline (PBS, pH 7.4) was more than 90% in 40 days. The static platelet adhesion result indicated the anticoagulant multilayer films deposited on the plasma treated PVC reduced platelet adhesion drastically and no thrombus forming. The plasma recalcification time revealed that the multilayer modified surfaces greatly prolonged the plasma recalcification time. Such an easy processing and shape-independent method may have good potential for surface modification of cardiovascular devices.     

Planar plasma etching of chromium

We have investigated the plasma etching characteristics of chromium thin films in an rf planar (parallel plate) reactor. The experimental work was performed using a commercial reactor operating at 13.56 MHz with power variable up to 500 W. The etch rate of the Cr films deposited on glass substrates by e-beam evaporation was measured as a function of the concentration of O₂ in a CCl₄/O₂ gas mixture, the total flow rate of input gases and the rf power density. Using a total gas flow of 15 sccm and an input power density of 0.4 W cm^?2, the maximum etch rate was obtained in CCl₄ plasma containing 40% O₂. It was found that doubling the number of the substrates in the reactor decreased the etch rate by 20%. Also, the etch rate at the back of the reactor was twice that at the front. Methods to alliviate non-uniformity and loading effects are discussed and the mechanism of plasma etching of Cr is examined through the effect of various processing parameters on the etching characteristics.     

Indium tin oxide films deposited on polyethylene naphthalate substrates by radio frequency magnetron sputtering

Indium tin oxide (ITO) thin films were deposited on unheated polyethylene naphthalate substrates by radio-frequency (rf) magnetron sputtering from an In₂O₃ (90 wt.%) containing SnO₂ (10 wt.%) target. We report the structural, electrical and optical properties of the ITO films as a function of rf power and deposition time. Low rf power values, in the range of 100-130 W, were employed in the deposition process to avoid damage to the plastic substrates by heating caused by the plasma. The films were analyzed by X-ray diffraction and optical transmission measurements. A Hall measurement system was used to measure the carrier concentration and electrical resistivity of the films by the Van der Pauw method. The X-ray diffraction measurements analysis showed that the ITO films are polycrystalline with the bixbite cubic crystalline phase. It is observed a change in the preferential crystalline orientation of the films from the (222) to the (400) crystalline orientation with increasing rf power or deposition time in the sputtering process. The optical transmission of the films was around 80% with electrical resistivity and sheet resistance down to 4.9 × 10^- 4 Ωcm and 14 Ω/sq, respectively.     

Structures and N2-sorption properties of carbonaceous films prepared by high-powered sputtering of d-phenylalanine

Amino acid-based carbonaceous films were prepared by the radio-frequency (rf) sputtering of d-phenylalanine under the rf power density from 0.18 to 0.53 W/cm². As the rf power was increased, the deposition rate tended to increase, especially for 120-W sputtering. The surface of carbonaceous films prepared by high rf power have rugged surfaces following their storage in a vacuum box. The carbonization of the sputtered films progressed with rf power; the oxygen and nitrogen content in the films decreased as rf power increased, as well as the content of CH moieties decreased. Increasing the rf sputtering power enhanced the N₂-sorption capability and the viscous character of the carbonaceous films. The quartz crystal resonators coated with the carbonaceous films by the highest rf sputtering power had superior resonance signals toward the N₂ sorption-desorption measurement with suppressed noise.     

Electric properties and surface characterization of transparent Al-doped ZnO thin films prepared by pulsed laser deposition

We grew 2 wt.% Al-doped ZnO (AZO) films on 5.08 cm-diameter polymer substrates at room temperature by the pulsed laser deposition (PLD) technique added the beam-rastering function. The structural properties, surface morphology, resistivity, mobility and chemical bonding states of AZO/polymer films were measured. The structuring of polymer surface by atmospheric plasma can occur at nm scales and can influence adhesion, optical and wettability properties of the materials. With increasing plasma treatment power, surface hydrophilicity and roughness for PET and PES polymer increased, respectively.     

Low temperature atomic layer deposition of titania thin films

This paper presents a comprehensive study of atomic layer deposition of TiO₂ films on silicon and polycarbonate substrates using TiCl₄ and H₂O as precursors at temperatures in the range 80-120 °C. An in-situ quartz crystal microbalance was used to monitor different processing conditions and the resultant films were characterised ex-situ using a suite of surface analytical tools. In addition, the contact angle and wettability of as-deposited and UV irradiated films were assessed. The latter was found to reduce the contact angle from ≥ 80° to < 10°. Finally, the effect of surface pre-treatment on film toughness and adhesion was investigated and the results show a significant improvement for the pre-treated films.     

Characterisation of SiOxCyHz thin films deposited by low-temperature PECVD

SiO_xC_yH_z thin films were deposited from hexamethyldisiloxane (HMDSO)/O₂ mixtures in a parallel plate, capacitively coupled, RF plasma reactor. Polyethylene terephthalate (PET), Si(1 0 0) wafers and KBr tablets were chosen as substrates. Effect of HMDSO/O₂ ratio, total treatment pressure and power input on the properties of the deposited films were investigated. The structure and bondings were studied by means of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Wettability characteristics of the deposited thin films were investigated by means of water droplet contact angle measurements. Surface morphology was investigated with atomic force microscopy. Barrier properties of the SiO_xC_yH_z thin films were investigated by measuring the water vapour transmission rate of the coated PET substrates. Correlations between the characteristics of the deposited film and their barrier properties were discussed.     

Effects of rf power on the structural properties of carbon nitride thin films prepared by plasma enhanced chemical vapour deposition

Carbon nitride (CN_x) thin films were deposited by radio frequency plasma enhanced chemical vapour deposition (rf PECVD) technique from a gas mixture of methane (CH₄), hydrogen (H₂) and nitrogen (N₂). The effects of rf power on the structural properties of CN_x thin films were discussed in this paper. It was found that rf power had significant effects on the growth rate, structural and morphological properties of the deposited films. The point of transition of the growth rate trend marked the equilibrium condition for primary and secondary reactions in growth kinetics of the film with respect to rf power. The films grown at this optimum rf power were most ordered in structure with high surface roughness and had the lowest N incorporation. This work showed that H etching effects and ion bombardment effects increase with increase in rf power and strongly influenced the structure of the CN_x films.     

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.     

Optical and hydrophilic properties of nanostructure Cu loaded brookite TiO2 thin film

Copper loaded TiO₂ brookite thin films were deposited on glass substrates using the dip-coating method. The crystalline structure of the films was characterized by X-ray diffraction analysis. X-ray photoelectron spectroscopy was used to evaluate the properties of the film surfaces. The transmittance spectra of the films were obtained by the Shimadzu multi-purpose spectrophotometer. The water contact angle on the film surfaces during irradiation and storage in a dark place was measured by a contact angle analyzer. The results indicate that Cu loading did not affect the transmittance spectra, whereas it had a significant effect on the hydrophilicity of the TiO₂ film surface.     

Comparison of their electrical,optical, and electrochemical properties of as-grown plasma polymerized organic thin films by PECVD

Plasma polymerized organic thin films have been deposited on Si(100), glass and metal substrates at 25∼100 °C using thiophene and toluene precursors by plasma enhanced CVD method. In order to compare physical and electrochemical properties of the as-grown thin films, the effect of the RF (13.56 MHz) plasma power in the range of 30∼100 W and the deposition temperature on the corrosion protection efficiency and optical property were mainly studied in this work. Corrosion protection efficiency (P_k), which is one of important factors for corrosion protection in the interlayer dielectrics of microelectronic devices application, provided an increasing tendency with increasing RF power. The highest P_k value of plasma polymerized toluene film (85.27% at 70 W) was higher than that of the plasma polymerized thiophene film (65.17% at 100 W). The result of contact angle measurement showed that the plasma polymerized toluene films have more hydrophobicity than that of the plasma polymerized thiophene films.     

Etch characteristics of IrMn thin films using an inductively coupled plasma of CH3OH/Ar

An inductively coupled plasma reactive ion etching of IrMn magnetic thin films patterned with Ti hard mask was studied in a CH₃OH/Ar gas mix. As the CH₃OH concentration increased, the etch rates of IrMn thin films and Ti hard mask decreased, while the etch profiles improved with high degree of anisotropy. The effects of coil rf power, dc-bias voltage to substrate and gas pressure on the etch characteristics were investigated. The etch rate increased and the etch profile improved with increasing coil rf power, dc-bias voltage and decreasing gas pressure. X-ray photoelectron spectroscopy revealed that the chemical reaction between IrMn films and CH₃OH gas occurred, leading to the clean and good etch profile with high degree of anisotropy of 90°.     

Comparison of hydrophilic properties of TiO2 thin films prepared by sol-gel method and reactive magnetron sputtering system

This article reports on preparation, characterization and comparison of TiO₂ films prepared by sol-gel method using the titanium isopropoxide sol (TiO₂ coating sol 3%) as solvent precursor and reactive magnetron sputtering from substoichiometric TiO_2 − x targets of 50 mm in diameter. Dual magnetron supplied by dc bipolar pulsed power source was used for reactive magnetron sputtering. Depositions were performed on unheated glass substrates. Comparison of photocatalytic properties was based on measurements of hydrophilicity, i.e. evaluation of water contact angle on the film surface after UV irradiation. It is shown, that TiO₂ films prepared by the sol-gel method exhibited higher hydrophilicity in the as-deposited state but has significant deterioration of hydrophilicity during aging, compared to TiO₂ films prepared by magnetron sputtering. To explain this effect AFM, SEM and high resolution XPS measurements were performed. It is shown that the deterioration of hydrophilicity of sol-gel TiO₂ films can be suppressed if as-deposited films are exposed to the plasma of microwave oxygen discharge.     

Enhanced adhesion of osteoblastic cells on polystyrene films by independent control of surface topography and wettability

We independently controlled surface topography and wettability of polystyrene (PS) films by CF₄ and oxygen plasma treatments, respectively, to evaluate the adhesion and proliferation of human fetal osteoblastic (hFOB) cells on the films. Among the CF₄ plasma-treated PS films with the average surface roughness ranging from 0.9 to 70 nm, the highest adhesion of hFOB cells was observed on a PS film with roughness of ~ 11 nm. When this film was additionally treated by oxygen plasma to provide a hydrophilic surface with a contact angle less than 10°, the proliferation of bone-forming cell was further enhanced. Thus, the plasma-based independent modification of PS film into an optimum nanotexture for human osteoblast cells could be appplied to materials used in bone tissue engineering.