Reactive sputter-deposition of oxygenated amorphous carbon thin films in Ar/O2

Oxygenated amorphous carbon thin films were deposited by DC magnetron sputtering using various argon and oxygen process gas mixtures. The X-ray diffraction data indicated that the predominantly amorphous films had more defined peaks with a higher partial pressure of oxygen. Results indicated that use of oxygen in the working gas enhanced the crystalline nature of the films. Scanning electron and atomic force microscopy revealed that the surface roughness and film topography differed with the oxygen process gas variations. X-ray photoelectron spectroscopy revealed increased surface oxygen content with higher oxygen concentration in the working gas. Raman spectroscopy results suggested that the increased oxygen in the films may have led to a higher percentage of sp³-bonded carbon atoms. The growth rate (deposition rate) of the films decreased as the amount of oxygen increased. This decreased deposition rate was associated with an oxygen etching of the film.     

Mechanical characterization of ultra-thin fluorocarbon films deposited by R.F. magnetron sputtering

Fluorocarbon films were deposited on silicon substrate by R.F. magnetron sputtering using a polytetrafluoroethylene (PTFE) target. Structure of the deposited films was studied by X-ray photoelectron spectroscopy (XPS). Hardness, elastic modulus and scratch resistance were measured using a nanoindenter with scratch capability. -CF_x (x = 1, 2, 3) and C-C units were found in the deposited fluorocarbon films. The hardness and elastic modulus of the films are strongly dependent on the R.F. power and deposition pressure. The film hardness is in the range from 0.8 GPa to 1.3 GPa while the film elastic modulus is in the range from 8 GPa to 18 GPa. Harder films exhibit higher scratch resistance. Differences in nanoindentation behavior between the deposited fluorocarbon films, diamond-like carbon (DLC) films and PTFE were discussed. The fluorocarbon films should find more applications in the magnetic storage and micro/nanoelectromechanical systems.     

Surface Modification of Poly(Tetrafluoroethylene) Films by Graft Copolymerization for Adhesion Improvement with Sputtered In-Sn Oxides

Surface modification of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) films was carried out via UV-induced graft Copolymerization with glycidyl methacrylate (GMA), acrylamide (AAm) and hydroxylethylacrylate (HEA) to improve the adhesion strength with sputtered indium-tin-oxide (ITO). The surface compositions of the graftcopolymerized PTFE films were studied by X-ray photoelectron spectroscopy (XPS). The graft yield increases with increasing monomer concentration and Ar plasma pre-treatment time of the PTFE films. The T-peel adhesion strength was affected by the type of monomer used for graft Copolymerization, the graft concentration, and the thermal post-treatment after ITO deposition. A double graft-copolymerization process, which involved initially the graft copolymeri/ation with AAm or HEA, followed by graft Copolymerization with GMA. was also employed to enhance the adhesion of sputtered ITO to PTFE. T-peel adhesion strengths in excess of 8 N cm were achieved in the ITO graft-modified PTFE laminates. The adhesion failure of the ITO/PTFE laminates in T-peel tests was found to occur inside the PTFE films. The electrical resistance of ITO on all graft-modified PTFE surfaces before and after thermal post-treatment remained conslant at about 30 Ω square, suggesting that the graft layer did not have any significant effect or. the electrical properties of the deposited ITO.     

Low surface temperature synthesis and characterization of diamond thin films

Polycrystalline diamond films are deposited on p-type Si(100) and n-type SiC(6H) substrates at low surface deposition temperatures of 370–530 °C using a microwave plasma enhanced chemical vapor deposition (MPECVD) system. The surface temperature during deposition is monitored by an IR pyrometer capable of measuring temperature between 250 and 600 °C in a microwave environment. The lower deposition temperature is achieved by using an especially designed cooling stage. The influence of the deposition conditions on the growth rate and structure of the diamond film is investigated. A very high growth rate up to 1.3 μm/h on SiC substrate at 530 °C surface temperature is attributed to an optimized Ar-rich Ar/H₂/CH₄ gas composition, deposition pressure, and microwave power. The structure and microstructure of the films are characterized by X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. A detailed stress analysis of the deposited diamond films of grain sizes between 2 and 7 μm showed a net tensile residual stress and predominantly sp³-bonded carbon in the deposited films.     

Processing and characterization of multilayer films of poly(ethylene terephthalate) and surface-modified poly(tetrafluoroethylene)

Multilayer films were prepared from poly(tetrafluoroethylene) (PTFE) and poly(ethylene terephthalate) (PET) films together with using an adhesion promoting layer (tie-layer) consisting of ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and low density polyethylene (LDPE) blend. Na/naphthalene treatment and subsequent acrylic acid grafting were applied on the surfaces of PTFE for chemical modification. FT-IR spectroscopy, XPS analysis and surface energy measurements were performed to characterize the modified PTFE films. The analyses showed defluorination and oxidation of PTFE surface, and supported the acrylic acid grafting. The surface energy of modified surfaces enhanced with respect to unmodified one, which promoted adhesion. The multilayers were subjected to T-peel tests to measure the adhesion strength between PET and modified PTFE. Peel strength between the films increased with increasing E-MA-GMA amount in the tie-layer. A proportional dependence of peel strength on Na/naphthalene treatment time was observed for multilayers containing acrylic acid grafted or ungrafted PTFE. From SEM analysis, it was observed that the texture of the PTFE surface after modifications became rougher when compared to untreated PTFE. The peeled surfaces were also analyzed by SEM. The micrographs evidence that the energy absorbing mechanism is the plastic deformation of the tie-layer, which is responsible for obtaining high peel strengths.     

Reactions in Vapor-Phase Electrolytic Deposition for Preparing Yttria-Stabilized Zirconia Thin Films

The process of vapor-phase electrolytic deposition (VED) for the formation of yttria-stabilized zirconia (YSZ) films has been studied. This technology, which is similar to the electrochemical vapor deposition (EVD) process, is based on electrolytic deposition, using a glow-discharge plasma as the conductive medium. Radio-frequency (rf) glow-discharge plasma is generated in the vapor phase of a metal chloride (ZrCl₄ or YCl₃). A porous electrode layer, which is deposited on the stabilized zirconia layer, is connected to a dc power source. The grounded electrode, which is located in the plasma, is used as a counter electrode to complete the dc circuit. X-ray photoemission spectroscopy and electron probe microanalysis measurements identify the deposited layer to be YSZ that contains 8 mol% of Y₂O₃. This layer is free from pores and cracks, within the scale of scanning electron microscopy observation. The conductivities of the YSZ films that are prepared at different current densities via the VED process are almost equal, and the conductivity values of these thin films are very similar to that of the sintered YSZ pellet. The dependence of the current efficiency on the dc current density is investigated. The current efficiency decreases as the current density increases.     

Adhesion enhancement of thermally evaporated aluminum to surface graft copolymerized poly(tetrafluoroethylene) film

Surface modifications of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) film via UV-induced graft copolymerization with glycidyl methacrylate (GMA) and 1-vinylimidazole (VIDz) were carried out to improve the adhesion with evaporated aluminum metal. The surface compositions of the graft copolymerized PTFE films were studied by X-ray photoelectron spectroscopy (XPS). The adhesion strength of the evaporated aluminum to the surface graft copolymerized PTFE film was affected by the type of monomer used for graft copolymerization, the graft concentration, the plasma post-treatment of the graft copolymerized PTFE surface prior to metallization, and the extent of thermal treatment after metallization. The optimum T-peel adhesion strengths of the Al/PTFE laminates were in excess of 10 and 5 N/cm, respectively, for the GMA and VIDz graft copolymerized PTFE films. These adhesion strengths are significantly higher than those obtained between the evaporated aluminum and the pristine or plasma-pretreated PTFE film. The mechanism of adhesion enhancement and the failure of the metal-polymer assembly were also investigated. It was observed that the failure occurred within the PTFE film. The strong adhesion between Al and PTFE arises from the charge-transfer interaction between the Al atom and the epoxide moiety of the grafted GMA polymer, as well as from the fact that the graft chains are covalently tethered on the PTFE film surface as a result of the grafting process.     

Thermal imidization of poly(amic acid) precursors on surface-modified poly(tetrafluoroethylene) films via graft copolymerization with glycidyl methacrylate

A novel method for preparing composites of polyimides (PI) laminated to poly(tetrafluoroethylene) (PTFE) films is reported. PI/PTFE composites were developed through thermal imidization of poly(amic acid) (PAA) precursors on surface-modified PTFE films. Surface modification of PTFE films was carried out via Ar plasma pretreatment of the films, followed by UV-induced graft copolymerization with glycidyl methacrylate (GMA). The surface composition and topography of the graft copolymerized PTFE films and the delaminated PI and PTFE surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. The adhesion strengths of the PI (imidized PAA) on the GMA graft copolymerized PTFE films were evaluated as a function of various thermal imidization schedules. The adhesion reliability of the PI/PTFE composites was tested by a series of hydrothermal cycles. The development of strong Tpeel adhesion strengths of about 8 N/cm with excellent reliability for the PI/PTFE composites was attributable to the synergistic effect of coupling the curing of the epoxide functional groups of the grafted GMA chains with the imidization process of the PAA and the fact that the GMA chains were covalently tethered onto the PTFE surface. The PI/PTFE composites delaminated via cohesive failure inside the PTFE substrates. The delaminated PI film with a covalently adhered 'rough' PTFE surface layer exhibited a water contact angle as high as 140°.     

射频磁控溅射法制备FC/ZnO杂化材料及其基本性质

采用射频磁控溅射法,首先以聚四氟乙烯（PTFE）为靶,氩气为载气,在聚对苯二甲酸乙二醇酯（PET）基底上沉积氟碳（FC）膜;然后以金属锌为靶,氩气为载气,氧气为反应气体,在FC膜上再沉积一层ZnO膜而形成FC/ZnO有机-无机纳米杂化材料。用AFM、XPS、UV以及静态接触角测定仪对杂化材料的基本性质进行了研究。结果表明,该法制得的杂化材料是由纳米粒子组成的岛状结构,岛的表面起伏不平。其生长模式是一种依附于有机核的沉积-扩张生长。杂化材料具有较好的紫外吸收特性,这是由于其分子结构中含有π-π共轭双键、表面的不平整性以及纳米氧化锌粒子对紫外光的吸收共同作用的结果。静态水接触角均大于90°,呈现出良好的疏水性。     

Molecular beam mass spectrometry and modelling of CH4–CO2 plasmas in relation with polycrystalline and nanocrystalline diamond deposition

CH₄–CO₂ microwave plasmas have been studied by optical emission spectroscopy, microwave interferometry, Langmuir probing and molecular beam mass spectrometry. The variations of plasma parameters and the concentration variations of both stable species and radicals in the plasma had been reported previously as a function of the power density; the influence of the total inlet flow rate is reported here. While the power density influences directly the plasma kinetics, the flow rate changes the residence time in the plasma and then the degree of conversion of the chemical system that is the extent to which the gas composition moves toward its steady-state composition. This is studied by modelling of plasma kinetics taking into account the coupled fluid dynamics of the gaseous species and the gas-phase chemistry including electron dissociation and surface recombination at the reactor wall. The experimental and modelling studies are used for correlating: – the relative concentration of important hydrocarbon radicals and etching radicals in the plasma and the gradients of all these species in front of the surface; – to the deposition domain, the structure (polycrystalline or nanocrystalline) and the quality of diamond films, which is the ratio of sp³ to (sp³ + sp²)-hybridized carbon in the film. All results evidence the plasma kinetic effect on the diamond deposition domain and the diamond deposition quality and structure, due to different degrees of conversion of the chemical system. The deposition of diamond coating from CH₄–CO₂ is shown to be a versatile process that permits deposition of a great variety of diamond films. However it requires particular attention because of the variation of the deposition conditions and then diamond quality and structure of the deposits depending on the extent of conversion of the inlet species to various intermediate and finally stable species formed in the plasma chemical system.     

Surface-initiated ring opening polymerization of N-carboxy anhydride of benzyl-l-glutamate monomers on soft flexible substrates

The potential of pulsed plasma deposited polyallylamine (PAA) adlayer has been successfully demonstrated for fabrication of polypeptide brushes functionalized soft flexible polymeric surfaces. Polymeric substrates functionalized with the plasma deposition PAA adlayer resulted in polymeric surfaces functionalized with amino groups, which are the suitable initiating moieties for ring-opening polymerization (ROP) of N-carboxy anhydride of benzyl-l-glutamate (NCA-BLG) monomer. Poly(γ-benzyl-l-glutamate) (PBLG) brushes were grown on PAA functionalized polypropylene (PP), and polytetrafluoroethylene (PTFE) polymeric substrates. These substrates were intentionally chosen for their inert chemical nature towards most wet chemical surface modification reactions. Surface grafted thin films of poly(γ-benzyl-l-glutamate) PBLG on both the PP and PTFE polymeric substrates yielded high density PBLG brushes. PBLG chain orientation, secondary structure and grafting density were characterized by infra-red spectroscopy. The synthesis of PBLG brushes on a flexible polymeric substrate is unprecedented and technologically important, since PBLG possess good electro-optical activity. Analysis of brush layers by Attenuated Total Reflectance Infra-Red (ATR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) as well as atomic force microscopy (AFM) fully corroborated the success of the plasma activated soft surface grafting approach.     

Interfacial adhesion between polyurethane binder and poly(tetrafluoroethylene) powder in bonded solid lubricant films

Poly(tetrafluoroethylene) (PTFE) powder was irradiated with ⁶⁰Co γ-rays to improve its dispersing ability in polyurethane (PU) as a binder. The bonded solid lubricant films of the irradiated PTFE were prepared on an AISI 1045 steel block by spraying and curing at ambient temperature, with PU as the binder. The tribological properties of bonded solid lubricant films with the PTFE pigment volume fraction were examined on a ring-on-block friction and wear tester. The interfacial adhesion between the PU binder and PTFE powder was investigated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), immersion heat, and X-ray photoelectron spectroscopy (XPS). It was found that γ-ray irradiation increases the activity of the PTFE powder surface and improves the interfacial adhesion between the PTFE powder and the PU binder, which is helpful for improving the wear resistance of the corresponding bonded solid lubricant films.     

Molecule structure variations in friction of stainless steel/PTFE and its composite

The friction and wear characteristics of PTFE and one of its composites, JS material rubbing against stainless steel, were determined with a pin-disk tester in this study. The JS material is a multilayer composite composed of PTFE layer containing metal oxide and others, porous bronze layer, copper-plating layer and steel back. The submicroscopic features of frictional surfaces of stainless steel and JS materials were observed with an electron probe microanalyzer (EPM). By analysis of fractional surfaces of stainless steel pins in various operating stages with X-ray photoelectron spectroscopy (XPS), chemical shifts of C_ls, O_ls, and F_ls peaks, F-ion gathering in surface transfer films, and generation of a metal fluoride and an unknown compound containing oxygen were found. The determination of JS material wear debris with electron spin resonance spectroscopy (ESR) showed that polymeric radicals different in structure and stable in air existed. The authors consider that these PTFE molecule structure variations might be of benefit to the adhesion of PTFE transfer film to the rubbed stainless steel surface, which is important to improve the friction and wear performance of PTFE.     

Surface structures and adhesion enhancement of poly(tetrafluoroethylene) films after modification by graft copolymerization with glycidyl methacrylate

Surface modifications of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) film were carried out via near-UV light-induced graft copolymerization with glycidyl methacrylate (GMA). The structure and chemical composition of the copolymer surface and interface were studied by angle-resolved X-ray photoelectron spectroscopy (XPS). For PTFE substrate with a substantial amount of grafting, the grafted GMA polymer penetrates or becomes partially submerged beneath a thin surface layer of dense substrate chains to form a stratified surface microstructure. The concentration of the surface-grafted GMA polymer increases with the plasma pretreatment time, the near-UV light illumination time, and the monomer concentration. The GMA graft copolymerized PTFE surfaces adhere strongly to one another when brought into direct contact and cured (i) in the presence of a diamine alone or (ii) in the presence of an epoxy adhesive (epoxy resin plus diamine curing agent). In the presence of diamine alone, failure occurs in the interfacial region. For epoxy adhesive-promoted adhesion, the failure mode is cohesive, i.e. it takes place in the bulk of one of the delaminated PTFE films. The lap shear strengths in both cases increase with the amount of surface-grafted epoxide polymer. The development of the adhesion strength depends on the concentration of the surface graft, the microstructure of the graft copolymerized PTFE surface, the interfacial reactions, and the nature of the bonding agent.     

Hydrophobicity and transparency of Al2O3-based poly-tetra-fluoro-ethylene composite thin films using aerosol deposition

Alumina and polytetrafluoroethylene (Al₂O₃-PTFE) composite films were fabricated by a simple aerosol deposition (AD) process, to confirm its applicability for various display screens requiring water resistant, anti-smudge and easy-to-clean properties. The surface morphologies, hydrophobic properties, and transparencies of the composite films with different PTFE contents, varying from 0.01 to 1?wt% were investigated. As a result, the composite films with over 0.3?wt% PTFE showed a sudden rise in surface roughness and low transmittance, despite having the highest contact angle of 128° at a PTFE content of 0.3?wt%. From the energy dispersive spectrometer analysis, the crash-cushioning effect of PTFE and agglomerated PTFE particles were determined to be major causes of surface roughness and opacity. In contrast, the transmittance showed a tendency to be enhanced, with an increasing PTFE content in the range of 0.01, 0.05, and 0.1?wt% PTFE, respectively. Especially, the film with 0.1?wt% of PTFE had contact angle of 111° and exhibited a high transmittance of over 75%, which was inferred to be an appropriate amount of PTFE, with a high elongation filling up the surface and the internal defects, leading to an enhancement of transparency. Consequently, these results implied that the AD-prepared Al₂O₃-PTFE composite coatings are promising candidates for various display applications.     

Pore Narrowing and Formation of Ultrathin Yttria-Stabilized Zirconia Layers in Ceramic Membranes by Chemical Vapor Deposition/Electrochemical Vapor Deposition

Chemical vapor deposition (CVD) and electrochemical vapor deposition (EVD) have been applied to deposit yttria-stabilized-zirconia (YSZ) on porous ceramic media. The experimental results indicate that the location of YSZ deposition can be varied from the surface of the substrates to the inside of the substrates by changing the CVD/EVD experimental conditions, i.e., the concentration ratio of the reactant vapors. The deposition width is strongly dependent on the deposition temperature used. The deposition of YSZ inside the pores resulted in pore narrowing and eventually pore closure, which was measured by using permpor-ometry. However, deposition of YSZ on top of porous ceramic substrates (outside the pores) did not result in a reduction of the average pore size. Ultrathin, dense YSZ layers on porous ceramic substrates can be obtained by suppressing the EVD layer growth process after pore closure.     

Porous polytetrafluoroethylene (PTFE) electret films: porosity and time dependent charging behavior of the free surface

Electrically charged porous polytetrafluoroethylene (PTFE) films are often discussed as active layers for electromechanical transducers. Here, the electric charging behavior of open-porous PTFE films with different porosities is investigated. Optimized electric charging of porous PTFE films is determined by variation of charging parameters such as electric fields and charging times. Maximum surface potentials are depending on the porosity of the PTFE films. Suitable charging leads to high surface potentials observed on non-stretched or slightly stretched porous PTFE films. Further increase of charging fields yields decreasing values of the surface potential accompanied with an increase of conductivity.     

Structural and Optical Properties of Nanoscale Galinobisuitite Thin Films

Galinobisuitite thin films of (Bi₂S₃)(PbS) were prepared using the chemical bath deposition technique (CBD). Thin films were prepared by a modified chemical deposition process by allowing the triethanolamine (TEA) complex of Bi³⁺ and Pb²⁺ to react with S²⁻ ions, which are released slowly by the dissociation of the thiourea (TU) solution. The films are polycrystalline and the average crystallite size is 35 nm. The composition of the films was measured using the atomic absorption spectroscopy (AAS) technique. The films are very adherent to the substrates. The crystal structure of Galinobisuitite thin films was calculated by using the X-ray diffraction (XRD) technique. The surface morphology and roughness of the films were studied using scanning electron microscopes (SEM), transmission electron microscopes (TEM) and stylus profilers respectively. The optical band gaps of the films were estimated from optical measurements.     

Ag/PAMAM树形分子纳米复合材料对PTFE膜性能的影响

以第4.0代端氨基聚酰胺-胺型树形分子(G4.0-NH2PAMAM)为模板制备Ag/PAMAM纳米复合材料(Ag·DENPs), 利用了Ag·DENPs与聚四氟乙烯(PTFE)膜表面的氢键作用,通过超声沉积的方法制备出了PTFE-Ag/PAMAM复合膜.通过研究沉积时间对Ag·DENPs在PTFE膜表面沉积量的影响,得到饱和沉积时间是60min,沉积量约为2.32mg.通过UV-vis光谱和SEM对其化学组成和微观形貌进行了表征.复合膜的水接触角为105.3°,较纯PTFE膜降低了23.6°,显著改善PTFE膜表面亲水性.复合膜对水和牛血清白蛋白的通量比纯PTFE膜低,但傅立叶变换衰减全反射红外光谱(FRR)为88.2%,比纯PTFE膜的35.4%高出了52.8%,且对大肠杆菌及金黄色葡萄球菌具有抑菌作用.表明Ag·DENPs的引入可以改善PTFE的抗污染性及抑菌性.     

Surface and bulk compositional characterization of plasma-polymerized fluorocarbons prepared from hexafluoroethane and acetylene or butadiene reactant gases

The surface tension and surface and bulk composition of plasma-polymerized fluorocarbon films (PPFCs) prepared from hexafluoroethane (HFE) and either acetylene or butadiene reactant gases were determined. Increasing the HFE reactant gas content from 0 to 100% gave an increase in the amount of fluorine incorporated in the films and a shift to incorporation of more highly fluorinated species at the film surface, according to X-ray photoelectron spectroscopy (XPS) data. Hydrogen levels in the films were determined by forward recoil spectrometry (FRS) and were shown to be inversely dependent on HFE concentration in the reactant gas feed and dependent on hydrocarbon co-reactant type. The compositional changes were mirrored by changes in the surface tension from 52 to 20 mN/m. XPS and surface tension results demonstrated that fluorine incorporation at the surface of the PPFCs is significantly reduced when butadiene, rather than acetylene, is used as a co-reactant gas with HFE. The differences are attributed to higher concentrations of hydrogen, which acts as a scavenger for reactive fluorine atoms and as an inhibitor in the CF_x → CF_x+1 reaction, and of carbon, decreasing the F/C ratio, when butadiene is used as the hydrocarbon source. Furthermore, potential changes in surface composition due to energetic ion bombardment are discussed. Three factors were suggested as strongly influencing the composition and the properties of the PPFCs: 1) the energy input into the plasma polymerization reaction, 2) the amount and type of fluorine scavenging reagent introduced with the HFE, and 3) the elemental composition of the reactant gases. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 409–421, 1997