Characterization of diamond fluorinated by glow discharge plasma treatment

The surface fluorination of diamond by treatment in glow discharge plasmas of CF₄ for different times has been investigated. High quality diamond films were deposited onto silicon substrates using hot filament chemical vapor deposition (HFCVD). Subsequently, the films were exposed to a radiofrequency glow discharge plasma of CF₄ for times ranging from 5 min to 1 h. The effects of the plasma treatment on the surface morphology, diamond quality and elemental composition were investigated using atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. Differences in film roughness caused by the plasma treatment were detected by AFM and confirmed by scanning electron microscopy (SEM). Raman spectroscopic analyses showed that the original diamond was of high quality and that the bulk of each film was unchanged by the plasma treatment. Analyses using XPS revealed increased surface fluorination of the films at longer treatment times. In addition, the density of free radicals in the films was probed using electron paramagnetic resonance spectroscopy (EPRS), revealing that untreated diamond possesses an appreciable density of free radicals (6×10¹² g⁻¹) which initially falls with treatment time in the CF₄ plasma but increases for long treatment times.     

Surface energy of the plasma treated Si incorporated diamond-like carbon films

Surface energy and surface chemical bonds of the plasma treated Si incorporated diamond-like carbon films (Si-DLC) were investigated. The Si-DLC films were prepared by r.f. plasma assisted chemical vapor deposition using benzene and diluted silane (SiH₄/H₂ = 10:90) as the precursor gases. The Si-DLC films were subjected to plasma treatment using various gases like N₂, O₂, H₂ and CF₄. The plasma treated Si-DLC films showed a wide range of water contact angles from 13.4° to 92.1°. The surface energies of the plasma treated Si-DLC films revealed a high polar component for O₂ plasma treated Si-DLC films and a low polar component for CF₄ plasma treated Si-DLC films. The CF₄ plasma treated Si-DLC films indicated the minimum surface energy. X-ray photoelectron spectroscopy (XPS) revealed that the polarizability of the bonds present on the surface explains the hydrophilicity and hydrophobicity of the plasma treated Si-DLC films. We also suggest that the O₂ plasma treated surface can provide an excellent hemocompatible surface from the estimated interfacial energy between the plasma treated Si-DLC surface and human blood.     

Effects of CF4 plasma on the field emission properties of aligned multi-wall carbon nanotube films

We present a simple method to functionalize the surface and to modify the structures of aligned multi-wall carbon nanotube (CNT) arrays grown on silicon substrates using CF₄ plasma produced by reactive ion etching (RIE). Field emission (FE) measurements showed that after 2 min of plasma treatment, the emission currents were enhanced compared with as-grown CNTs; however, extended treatment over 2 min was found to degrade the FE properties of the film. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy have been employed to investigate the mechanism behind the modified FE properties of the CNT film. The FE enhancement after 2 min of etching could be attributed to favorable surface morphologies, open-ended structures and a large number of defects in the aligned CNT films. On the other hand, deposition of an amorphous layer comprising carbon and fluorine during extended CF₄ plasma treatment may hamper the field emission of CNT films.     

Hydrophobic properties of ethylene–vinyl alcohol copolymer treated with plasma source ion implantation

The industrial use of ethylene–vinyl alcohol copolymer (EVOH) film is limited because it is easily degraded by moisture. The plasma source ion implantation (PSII) technique with CF₄ or CH₄ gas was used for the EVOH film to improve the surface hydrophobic properties. Variables examined in implantation were ion energy (0–10 keV), treatment time (5 s–5 min), and ion species. The hydrophobic properties of EVOH films were greatly enhanced after a CF₄ PSII treatment, as evidenced by an increased contact angle from 66° to above 100° at ‐5 keV, and remained relatively unchanged during the period of 28 days. X‐ray photoelectron spectroscopy, atomic force microscopy, and O₂ permeability were used to characterize the surface properties of EVOH films treated with PSII. The improved hydrophobic properties were closely related to the formation of fluorine‐containing functional groups such as CF, CF_2, and CF₃ on the modified surface. The percentage distribution of carbon functional groups supports the role of CF₂ and CF₃ groups in surface modification. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2069–2075, 2004     

Surface modification of nanofibrillated cellulose films by atmospheric pressure dielectric barrier discharge

A dielectric barrier discharge in a gas mixture of tetrafluoromethane (CF₄) and O₂ was used for tailoring the surface properties of nanofibrillated cellulose (NFC) films. The surface chemical composition of plasma-modified NFC was characterized by means of X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, while surface morphology was illustrated by atomic force microscopy. Wettability was characterized through the static sessile drop method. The adhesion between NFC and polylactide (PLA) laminated films was tested by the double cantilever beam technique. As a result of atmospheric pressure plasma treatment, the water contact angle of NFC films increased and the values were comparable with those of PLA films. On the other hand, surface chemical characterization revealed inhomogeneity of the plasma treatment and limited improvement in adhesion between NFC and PLA films. Further research in this direction is required in order to enhance the uniformity of the plasma treatment results.     

Hydrophobic polymer films plasma-polymerized from CF4/hydrocarbon and hexafluroacetone/hydrocarbon mixtures

Polymer films were deposited from the plasma polymerization of the mixtures of hydrocarbons, ethane, ethylene, and acetylene, and tetrafluoromethane (CF₄) or hexafluoroacetone (HFA). The surface properties, the advancing contact angle of water, and surface energy of the films deposited and the chemical composition at the outermost layer of the films are discussed from the data of the angular XPS measurements. The plasma polymers deposited from the CF₄/hydrocarbon and HFA/hydrocarbon mixtures contained fluorine atoms whose content depended on the CF₄ or HFA concentration of the mixtures. The hydrophobicity of the films deposited could not be determined by the fluorine content of the films but by the chemical composition of the fluorine moieties at the outermost layer of the films. The CF₃ moieties rather than the CF₂ and CF moieties contribute largely to the hydrophobicity of the films. The plasma polymer films deposited from the HFA/acetylene (87.5 mol % HFA) showed higher hydrophobicity (the surface energy is 9.7 mJ/m²) than those from the CF₄/acetylene mixture (87.5 mol % CF₄) (the surface energy is 13 mJ/m²).     

Plasma polymerization of perfluoro-2-butyltetrahydrofuran/methane and perfluorobezene/tetrafluoromethane mixtures and gas permeation properties of the plasma polymers

Plasma polymer films prepared from perfluoro-2-butyltetrahydrofuran (PFBTHF) and perfluorobenzene (PFB) were investigated by elemental analysis, infrared spectroscopy, and ESCA. The gas separation properties were also investigated to seek plasma polymer films with good permselectivity. Plasma polymer films from PFBTHF and PFB were composed of polymer chains with fluorinated moieties such as C –CF_n, C F, C F–CF_n, C F₂, and C F₃ groups. Changes in the afcurrent as an operating condition for plasma polymerization showed less influence on the distribution of the fluorinated moieties but more influence on the permselectivity of the plasma polymer films formed. The permselectivity was improved by plasma polymerization in the PFBTHF/CH₄ or PFB/CF₄ mixture systems. The P_O2/P_N2 ratio for the plasma polymer films prepared from PFBTHF/CH₄ and PFB/CF₄ mixtures increased from 3.1 at 0 mol % CH₄ to 4.0 at 50 mol % CH₄ addition, and from 4.1 at 0 mol % CF₄ to 5.0 at 25 mol % CF₄ addition, respectively. The permselectivity of the plasma polymer films may be related to the crosslinkage and aggregation of polymer chains rather than the elemental composition.     

Characterization and electrochemical properties of CF4 plasma-treated boron-doped diamond surfaces

The effect of CF₄ plasma etching on diamond surfaces, with respect to treatment time, was investigated using scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. SEM observations and Raman spectra indicated an increase in surface roughening on a scale of 10–20 nm, and an increase in crystal defect density was apparent with treatment time in the range of 10 s to 30 min. In contrast, alteration of the diamond surface terminations from oxygen to fluorine was found to be rather rapid, with saturation of the F/C atomic ratio estimated from XPS analysis after treatment durations of 1 min and more. The redox kinetics of Fe(CN)₆^3−/4− was also found to be significantly modified after 10 s of CF₄ plasma treatment. This behavior shows that C–F terminations predominantly affect the redox kinetics compared to the effect on the surface roughness and crystal defects. The double-layer capacitance (C_dl) of the electrolyte/CF₄ plasma-treated boron-doped diamond interface was found to show a minimum value at 1 min of treatment. These results indicate that a short-duration CF₄ plasma treatment is effective for the fabrication of fluorine-terminated diamond surfaces without undesirable surface damage.     

Cyclophosphazene-containing Polymers as Imprint Lithography Resists

We present the evaluation of a cyclophosphazene-containing polymer as a patternable resist for imprint lithography. Hexamethacryloxybutoxycyclotriphosphazene layers containing small amounts of photoinitiator can be applied to silicon wafers substrates by spin coating techniques and cured photochemically to give tough, network polymer thin films. The films were characterized by FT-IR. Thin films approximately 200 nm in thickness were subjected to anisotropic O₂ and CF₄ plasmas and the etch rates were determined. The polymer films etch at a rate of 21 Å/s in CF₄ plasma, and as low as 1.6 Å/s in O₂ plasma, which is comparable or lower than the rates observed with commercially available silicon-containing photoresists. The surface chemical composition was surveyed by X-ray photoelectron spectroscopy, which gave results consistent with the formation of an etch resistant phosphorus-rich layer during reaction with O₂ plasma. The polymer was processed by nano-contact molding imprint lithography and replicated 200 nm period test patterns. This report is the first demonstration of a cyclophosphazene-containing polymer as a resist candidate for high-resolution lithography.     

Ta and TaN adhesion to high-temperature fluorinated polyimides. Surface and interface chemistry

The practical adhesion of Cu/Ta to high-temperature fluorinated polyimides (FPIs) was initially good but failed after the reliability test involving treatment under the FPI curing condition five times (T₅). But a thin layer (40 nm) of TaN greatly improved the reliability of the Cu/Ta-to-FPI adhesion. Both CF₄ and in situ Ar plasma treatments of FPIs prior to metal deposition enhanced the metal-to-FPI adhesion strength. CF₄ plasma enriches the FPI surface with fluorine atoms and most of fluorine is bound to carbon as CF₃, CF₂, and CF. Ar plasma first destroys CF₃ and then C=O groups of the FPIs to yield a polar surface. The locus of failure by a 90° peel test was found to be within the Ar-plasma-modified FPI layer but it moved toward the bulk of FPI, i.e. away from the metal-polymer interface, after the T₅ reliability test. The locus of failure in the case of weak adhesion where no plasma treatment was done on FPI films was in the near-interface region within the FPI layer, and the failure seemed to occur in the weak boundary layers of FPI surfaces. Plasma treatment removes weak boundary layers and also increases FPI surface roughness. These two effects combined improved the metal-to-FPI practical adhesion.     

Diamond-like carbon thin films prepared by ECR argon plasma assisted pulsed laser deposition

Diamond-like carbon films were prepared by pulsed laser ablation of graphite target in argon plasma produced from electron cyclotron resonance (ECR) microwave discharge and analyzed by Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The analysis shows that the films prepared with argon plasma assistance have different chemical structure compared with the films prepared in vacuum without plasma assistance. The structure of the films prepared with plasma assistance depends strongly on the bias voltages applied on the substrate. Surface morphology observation shows that the films prepared with argon plasma assistance have a smoother surface than the films prepared without plasma assistance. The re-sputtering of the growing film due to the bombardment of the plasma stream results in reduction of the deposition rate. The ablation plumes during film preparation with and without plasma assistance were examined through optical emission spectroscopy. In vacuum, emission lines from mono-atomic carbons and carbon ions dominate the plume emission. In argon plasma, the plume emission exhibits different behavior in its temporal and spatial evolution. It is initially dominated by strong lines from mono-atomic carbons and carbon ions and then evolves to consist mainly of emissions from C₂ molecules superposed on a featureless continuum. It is also found that the emission intensity of the C₂ molecules as well as the continuum varies with the bias voltages.     

Microstructure of c-BN thin films deposited on diamond films

Diamond films were used as substrates for cubic boron nitride (c-BN) thin film deposition. The c-BN films were deposited by ion beam assisted deposition (IBAD) using a mixture of nitrogen and argon ions on diamond films. The diamond films exhibiting different values of surface roughness ranging from 16 to 200 nm (in R_rms) were deposited on Si substrates by plasma enhanced chemical vapor deposition. The microstructure of these c-BN films has been studied using in situ reflexion electron energy loss spectroscopy analyses at different primary energy values, Fourier transform infrared spectroscopy and high resolution transmission microscopy. The fraction of cubic phase in the c-BN films was depending on the roughness of the diamond surface. It was optimized in the case of the smooth surface presenting no particular geometrical effect for the incoming energetic nitrogen and argon ions during the deposition. The films showed a nanocrystalline cubic structure with columnar grains while the near surface region was sp² bonded. The films exhibit the commonly observed layered structure of c-BN films, that is, a well textured c-BN volume lying on a h-BN basal layer with the (00.2) planes perpendicular to the substrate. The formation mechanism of c-BN films by IBAD, still involving a h-BN basal sublayer, does not depend on the substrate nature.     

Surface characterization of nickel alloy plasma-treated by O2/CF4 mixture

The micro- or nano-structured mold used for polymer embossing typically must be coated with an anti-adhesion material to reduce its interaction with the embossing. The mold is typically made by nickel sulphamate electroforming. For the anti-adhesion coating to adhere to the mold, the nickel mold surface must be clean and preferably unoxidized or possess reactive groups suitable for covalent bonding with the anti-adhesion coating. The effectiveness of plasma cleaning using mixtures of oxygen (O₂) and tetrafluoromethane (CF₄) with varying ratios versus liquid-only cleaning was investigated. To simulate the nickel mold, Ni200 alloy was used. Plasma treatment using mixtures of O₂ and CF₄ was found to be more effective in cleaning the Ni200 surface than liquid-only cleaning or pure O₂ or pure CF₄ plasma treatment. Using a 1 : 1 O₂ /CF₄ mixture plasma, the contact angles of water, glycerol and diiodomethane on Ni200 were the lowest and the calculated surface energy was the highest among the investigated treatments. From X-ray photoelectron spectroscopy (XPS), the amount of organic contamination on Ni200 was significantly reduced with plasma treatment. For liquid-only cleaned samples, metallic nickel, NiO and Ni(OH)₂ are present on the surface. With pure O₂ or pure CF₄ or 1 : 1 O₂ /CF₄ mixture plasma, both oxidation and fluorination occur and the surface contains combinations of NiF₂, Ni(OH)₂, Ni(OH)F, Ni₂O₃ and NiO₁₅F instead (without metallic nickel and NiO). The proportions of these different compounds vary according to the O₂/CF₄ ratio; O/Ni ratio is highest for pure O₂ plasma treatment, whilst F/Ni is highest for pure CF₄ plasma treatment.     

Simultaneous graft copolymerization of 2‐hydroxyethyl methacrylate and acrylic acid onto polydimethylsiloxane surfaces using a two‐step plasma treatment

Acrylic acid (AAc) and 2‐hydroxyethyl methacrylate (HEMA) mixtures were simultaneously grafted onto the surfaces of polydimethylsiloxane (PDMS) films using a two‐step oxygen plasma treatment (TSPT). The first step of this method includes: oxygen plasma pretreatment of the PDMS films, immersion in HEMA/AAc mixtures, removal from the mixtures, and drying. The second step was carried out by plasma copolymerization of preadsorbed reactive monomers on the surfaces of dried pretreated films. The effects of pretreatment and polymerization time length, monomer concentration, and ratio on peroxide formation and graft amount were studied. The films were characterized by attenuated total reflection Furrier transformer infrared (ATR‐FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), zeta potential, surface tension, and water contact angle measurements. The ATR‐FTIR spectrum of the modified film after alkaline treatment showed the two new characteristic bands of PHEMA and PAAc. Both increase the polar part of surface tension (γ_p) after grafting and the evaluation of surface charge at pH 1.8, 7, and 12 confirmed the presence of polar groups on the surface of grafted films with a mixture of HEMA/AAc. Morphological studies using both AFM and SEM evaluation illustrated various amounts of grafted copolymer on the surface of PDMS films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Plasma modification on a Nafion membrane for direct methanol fuel cell applications

This research focuses on Nafion modification using plasma techniques for direct methanol fuel cell applications. The results indicated the both argon (Ar) and carbon tetrafluoride (CF₄) plasma treatments modified the Nafion surface substantially without altering the bulk properties. The Nafion surface exposed to CF₄ plasma resulted in a more hydrophobic layer and an even lower MeOH permeability than the Ar-treated membrane. The plasma operating conditions using CF₄ were optimized by utilizing an experimental design. The minimum MeOH permeability was reduced by 74%. The conductivity was 1–2×10^-3 S/cm throughout the entire experimental range. Suppressed MeOH permeability can be achieved while maintaining the proton conductivity at a satisfactory level by adjusting the plasma operating conditions.     

Adhesion of copper to poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) surfaces modified by vacuum UV photo-oxidation downstream from Ar microwave plasma

Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) surfaces were exposed to vacuum UV (VUV) photo-oxidation downstream from Ar microwave plasma. The modified surfaces showed the following: (1) an improvement in wettability as observed by water contact angle measurements; (2) surface roughening; (3) defluorination of the surface; and (4) incorporation of oxygen as CF—O—CF₂, CF₂—O—CF₂ and CF—O—CF₃ moieties. With long treatment times, a cohesive failure of copper sputter-coated onto the modified surface occurred within the modified FEP and not at the Cu–FEP interface.     

Influence of substrate material and ion bombardment on plasma-deposited fluorocarbon thin films

The influence of substrate material and ion bombardment on fluorocarbon thin films deposited using a C₂F₆ glow discharge in an rf, parallel plate reactor was investigated. Monitoring of the plasma process by optical emission spectroscopy indicated that the dominant species in the glow discharge was CF₂. Studies of bulk polytetrafluoroethylene (PTFE) and plasma-polymerized fluorocarbon thin-film samples in an XPS system demonstrated that the formation of non-CF₂ species can be induced by ion bombardment of CF₂ molecules. Characterization of the deposited fluorocarbon films by XPS found that the F/C ratio and CF_x distribution (0 < x < 3) in the films were dependent on processing conditions. Fluorocarbon films deposited simultaneously onto Al, glass, steel, and PTFE substrates using a C₂F₆ plasma and a graphite sputter target had measurably different F/C ratios, with the F/C ratio of the films deposited onto the Al substrates consistently lower than the F/C ratios of the films deposited onto the other substrates. When a C₂F₆ plasma was used without a graphite target, the F/C ratio in the film was constant, but the CF_x distribution was different for each of the substrate materials. Analysis of the plasma-polymerized films by TEM revealed that localized growth of fluorocarbon particles occurred during the initial stages of deposition, consistent with an activated growth mechanism. Differences in the F/C ratio for films deposited onto the various substrate materials were attributed to the interaction of the fluorocarbon plasma with the exposed surface of the substrate prior to complete coverage by the polymeric film. © 1994 John Wiley & Sons, Inc.     

Surface modification of tetrafluoroethylene–perfluoroalkyl vinylether copolymer (PFA) by plasmas for copper metallization

Tetrafluoroethylene–perfluoroalkyl vinylether copolymer (PFA) sheet surfaces were modified with argon, helium, oxygen, and hydrogen plasmas. How the four plasmas modified the PFA sheet surfaces was investigated. All plasmas modified the PFA surfaces and at the same time initiated degradation of the PFA polymer chains. The balance between modification and degradation was strongly influenced by the magnitude of the discharge current in the plasmas. Efficiency of the plasmas in modification was hydrogen plasma > oxygen plasma > argon plasma > helium plasma. The modification involved defluorination of CF₂ carbons into CHF and CH₂ carbons and oxidation into O? CH₂, O? CHF, and O? CF₂ groups. The surface‐modification technique (a combination of hydrogen plasma treatment and silane coupling treatment) proposed in this study was applied for copper metallization of the PFA surface. The utility of the technique was confirmed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1087–1097, 2002     

Plasma treatment of polymethyl methacrylate to improve surface hydrophilicity and antifouling performance

Surface modification of polymethyl methacrylate (PMMA) by O₂/CF₄ plasma is investigated to improve hydrophilicity and antifouling performance of PMMA. The PMMA surface before and after treatment is characterized by atomic force microscopy, contact angle measurement, and X-ray photoelectron spectroscopy. Antifouling properties are evaluated by protein adsorption and bacterial adhesion experiments using Staphylococcus aureus in vitro. Higher O₂ content in the mixture gas promotes hydrophilicity of the plasma-treated PMMA, while a hydrophobic surface forms at higher CF₄ content. Modifying PMMA improves antifouling performance regardless of the O₂/CF₄ volume ratio, and this improvement increases with rising CF₄ content in O₂/CF₄ plasma working gas. Functional groups C O and C F are detected in O₂/CF₄ plasma-treated PMMA surface and the ratio of C O to C F can be controlled by the O₂/CF₄ volume ratio in the plasma working gas.     

Surface properties of polymers treated with tetrafluoromethane plasma

Polymer films of poly(ethylene terephthalate), polypropylene, and cellophane were surface treated with tetrafluoromethane plasma under different time, power, and pressure conditions. Contact angles for water and methylene iodide and surface energy were analyzed with a dynamic contact angle analyzer. The stability of the treated surfaces was investigated by washing them with water or acetone, followed by contact angle measurements. The plasma treatments decreased the surface energies to 2–20 mJ/m² and consequently enhanced the hydrophobicity and oleophobicity of the materials. The treated surfaces were only moderately affected after washing with water and acetone, indicating stable surface treatments. The chemical composition of the material surfaces was analyzed with X-ray photoelectron spectroscopy (XPS) and revealed the incorporation of about 35–60 atomic % fluorine atoms in the surfaces after the treatments. The relative chemical composition of the C ls spectra's showed the incorporation of —CHF— groups and highly nonpolar —CF₂— and —CF₃ groups in the surfaces and also —CH₂—CF₂— groups in the surface of polypropylene. The hydrophobicity and oleophobicity improved with increased content of nonpolar —CF₂—, —CF₃, and —CH₂—CF₂— groups in the surfaces. For polyester and polypropylene, all major changes in chemical composition, advancing contact angle, and surface energy are attained after plasma treatment for one minute, while longer treatment time is required for cellophane. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1591–1601, 1997