Modification of surface properties of polyamide 6 films with atmospheric pressure plasma

To investigate the effect of the different plasma gases treatment on the surface modification of atmospheric pressure plasma, polyamide 6 films were treated using pure helium (He), He/O₂ and He/CF₄, respectively. Atomic force microscopy (AFM) showed rougher surface, while X-ray photoelectron spectroscopy (XPS) revealed increased oxygen and fluorine contents after the plasma treatments. The plasma treated samples had lower water contact angles and higher T-peel strength than that of the control. The addition of small amount of O₂ or CF₄ to He plasma increases the effectiveness of the plasma treatment in polymer surface modification in terms of surface roughness, surface hydrophilic groups, etching rate, water contact angle and bonding strength.     

The effect of fluorine-based plasma treatment on morphology and chemical surface composition of biocompatible silicone elastomer

X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) have been used to investigate the effect of reactive ion etching (RIE) on poly(methylhydrogensiloxane-co-dimethylsiloxane) surface in fluorine-based plasmas. Polysiloxane layers supported on the standard silicon wafers were etched using SF₆ + O₂ or CF₄ + O₂ plasmas. SEM studies show that the polysiloxane morphology depends on plasma chemical composition strongly. Presence of a columnar layer likely covered with a fluorine rich compound was found on the elastomer surface after the CF₄ + O₂ plasma exposure. After the SF₆ + O₂ or CF₄ + O₂ plasma treatment the polysiloxane surface enriches with fluorine or with fluorine and aluminum, respectively. Different morphologies and surface chemical compositions of the silicone elastomer etched in both plasmas indicate different etching mechanisms.     

Surface morphology changes of poly(ethyleneterephthalate) fabrics induced by cold plasma treatments

Some selective cold plasma processing modify specific surface properties of textile polymeric materials such as their dyeability, wettability and hydrorepellence. To correlate the sample surface changes with the acquired surface properties allows one to obtain information on the chemical and physical processing involved in plasma treatment. In this work, atomic force microscopy (AFM) has been applied to investigate the morphological and topographical surface modifications induced by RF cold plasma processing of poly(ethyleneterephthalate) (PET) fabrics. Rms surface roughness and surface area of the samples are measured before and after the treatments. The morphology changes have been analysed as a function of the treatment time and air gas pressure. Measurements have been performed also using plasmas produced by different gases such as He, Ar, SF₆ and CF₄. The PET shows different behaviour with different gas plasmas. In the case of air, He and Ar gases the sample surface modifications seem to be mainly due to etching effects, while the fluorine atoms grafting probably is responsible for surface rearrangement process using SF₆ and CF₄ gases. As a consequence different surface properties are produced in the plasma treated samples. Article presented at the International Conference on the Frontiers of Plasma Physics and Technology, 9–14 December 2002, Bangalore, India.     

Surface modification of a polyamide 6 film by He/CF4 plasma using atmospheric pressure plasma jet

Polyamide 6 (PA 6) films are treated with helium(He)/CF₄ plasma at atmospheric pressure. The samples are treated at different treatment times. The surface modification of the PA 6 films is evaluated by water contact angle, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The etching rate is used to study the etching effect of He/CF₄ plasma on the PA 6 films. The T-peel strengths of the control and plasma treated films are measured to show the surface adhesion properties of the films. As the treatment time increases, the etching rate decreases steadily, the contact angle decreases initially and then increases, while the T-peel strength increases first and then decreases. AFM analyses show that the surface roughness increases after the plasma treatment. XPS analyses reveal substantial incorporation of fluorine and/or oxygen atoms to the polymer chains on the film surfaces.     

Morphology and electronic properties of carbon nanotubes synthesized by arc discharge in CF4gas

The morphology of carbon nanotubes synthesized by arc discharge in a CF₄gas atmosphere was investigated by scanning electron microscopy and transmission electron microscopy. The electronic properties of these nanotubes were investigated by electron spin resonance. The synthesis conditions in CF₄gas were then compared with those in CH₄, H₂and He based on these results. Furthermore, the mechanism of tube growth in CF₄gas was discussed briefly.     

RF-CF4 plasma surface modification of paper: Chemical evaluation of two sidedness with XPS/ATR-FTIR

The study was performed to examine the correlation between the initial roughness and surface fluorination of paper under RF-CF₄ plasma environment.Based on the experimental observations, a correlation was observed between surface fluorination and plasma parameters, e.g. RF-power, treatment time and gas pressure. The level of fluorination with RF-CF₄ plasma treatment was found to be extensive in both side of paper. Even very short treatment time, as low as 1 min at 300 W power, provides effective implantation of fluorine (38.7%) on surfaces. It was observed that, CF₄ plasma treatment had a significant effect on the molecular fragmentation on both side of paper. However, the felt side have a much stronger effect on plasma-induced dissociation and fluorination than in the wire side of paper.     

Influence of carrier gas pressure and flow rate on atomic layer deposition of HfO2 and ZrO2 thin films

Influence of the carrier gas on HfCl₄-H₂O and ZrCl₄-H₂O atomic layer processes was investigated. The growth rates of HfO₂ and ZrO₂ decreased with increasing flow rate and pressure of the N₂ carrier gas. Data of real-time quartz crystal microbalance measurements demonstrated that the effect observed was mainly due to influence of carrier gas on surface reactions and the role of overlapping the precursor pulses was negligible. At the same increase of the carrier gas mass flow, the increase of the linear flow rate led to more significant changes of thin-film properties than the increase of the carrier gas pressure did. Thin films with higher density, higher refractive index and, particularly, lower concentration of residual chlorine were obtained at higher carrier gas flow rates. Increase of the carrier gas flow rate also resulted in a higher concentration of a metastable phase in HfO₂ thin films deposited at 300 °C.     

Activation Energy for the Glass Transition of a Confined Elastomer in HDPE/PP Blends

Blends of two highly crystalline polymers containing an elastomer were prepared to study the glass transition of the confined elastomer. The polymers chosen were high density poly ethylene (HDPE), polypropylene (PP), and two elastomers of a different nature: natural number (NR) and EPDM. The dynamic mechanical analyzer (DMA) technique was used to analyze the storage modulus of blends with elastomer content from 0% to 30% by weight, with the remainder made up of equal amounts of HDPE and PP, and blends with 10% of the elastomer, but varied ratios of polyolefins. We used the differentiation modification of the Arrhenius method in the kinetic analysis assuming an n‐order relaxation mechanism, which allowed detecting the percolation threshold of NR. Results indicate that both temperature and activation energy for glass transition (T _g ) are dependent on the types of polymers in the blend and blend composition. The T _g and E values of the unblended elastomers are higher than those in blends; this behavior is associated with the elastomer confinement and blend morphology.     

Chemical sputtering,a discussion of mechanisms

Sputtering can be defined as the process whereby particles leave the surface as a direct consequence of the presence of incident radiation. When particles leave the surface as a result of receiving momentum from the collision cascade induced by the incident radiation, the process is called “physical sputtering”. If the incoming radiation (ions, electrons, or photons) induces a chemical reaction which leads to the subsequent desorp-tion of particles, the process could be classified as “chemical sputtering”. There are a number of molecules such as CH₄, CF₄, CF₃H, CF₃CI, etc., whose binding energy to a large variety of surfaces is believed to be only a few kcal/mole. Therefore, these molecules will not remain absorbed at room temperature. Consequently, if they are generated from surface atoms by radiation-induced processes, they will almost immediately desorb into the gas phase. This process is one type of chemical sputtering. Recent data obtained in plasma environments suggest that this type of reaction is a widely occurring phenomena: however, few systematic quantitative investigations of the subject have been completed. In this paper we will review the evidence for chemical sputtering and discuss mechanisms based on experimental information obtained for the chemical sputtering of silicon and SiO₂ under argon ion bombardment in the presence of a molecular beam of XeF2. Under these conditions, 25 or more silicon atoms can leave the surface per incident argon ion. About 75% of the silicon is emitted as SiF₄ (gas) and the rest leaves as silicon atoms or SiFx radicals. The total yield (silicon plus fluorine) is greater than 100 atoms/ion. The measured yields are a strong function of XeF₂ flux and a much weaker function of ion energy in the range 500-5000 eV. The chemical-sputtering yield for SiO₂ is smaller than that of silicon by about an order of magnitude, but it is still larger than the physical-sputtering yield. Moreover, SiO₂ is also sputtered by electrons. These results indicate that the incident radiation induces a chemical reaction between silicon and adsorbed fluorine which produces SiF₄, and the SiF4 is subsequently desorbed into the gas phase. We define this process as chemical sputtering. The large yields are probably a consequence of weak binding between the surface and the SiF₄ molecule.     

Annealing and oxidation effects after CF4/H2 dry etching for damage recovery

When a Si substrate, just after SiO₂ etching, is exposed to an additional etch using CF₄ + H₂ reactive sputter etching, carbon and fluorine atoms penetrate into the Si substrate to a depth of ≈ 100–150 Å. The effects of an annealing and oxidation atmosphere for this damage recovery and impurity redistribution in the Si substrate are investigated using IMA and Secco etching. Annealing in N₂ gas is only effective for removing fluorine atoms. After dry O₂ oxidation, though the carbon atoms are removed, the fluorine atoms are still confined in the oxidized layer. Under wet oxidation, carbon and fluorine atoms are removed as soon as the damaged layer is oxidized. Moreover, after 300 Å wet oxidation, no impurity atoms or defects are observed. Wet oxidation may serve as a pretreatment for Si selective epitaxial growth on a dry etched Si substrate.     

The formation of an intense secondary pulsed molecular beam and obtaining accelerated molecules and radicals in it

A method for obtaining an intense secondary pulsed molecular beam is described. The kinetic energy of molecules in the beam can be controlled by vibrational excitation of the molecules in the source under high-power IR laser radiation. A compression shock (shock wave) is used as a source of secondary beams. The shock wave is formed in interaction between an intense pulsed supersonic molecular beam (or flow) and a solid surface. The characteristics of the secondary beam were studied. Its intensity and the degree of gas cooling in it were comparable with the corresponding characteristics of the unperturbed primary beam. Vibrational excitation of molecules in the shock wave and subsequent vibrational-translational relaxation, which occurs when a gas is expanded in a vacuum, allow the kinetic energy of molecules in the secondary beam to be substantially increased. Intense [≥10²⁰ molecules/(sr s)] beams of SF₆ and CF₃I molecules with kinetic energies approximately equal to 1.5 and 1.2 eV, respectively, were generated in the absence of carrier gases, and SF₆ molecular beams with kinetic energies approximately equal to 2.5 and 2.7 eV with He (SF₆/He=1/10) and H₂ (SF₆/H₂=1/10) as carrier gases, respectively, were obtained. The spectral and energy characteristics of acceleration of SF₆ molecules in the secondary beams were studied. The optimal conditions were found for obtaining high-energy molecules. The possibility of accelerating radicals in secondary molecular beams was demonstrated.     

Carrier gas effects on the SiGe quantum dots formation

SiGe quantum dots (QDs) grown by ultra-high vacuum chemical vapor deposition using H₂ and He carrier gases are investigated and compared. SiGe QDs using He carrier gas have smaller dot size with a better uniformity in terms of dot height and dot base as compared to the H₂ carrier gas. There is a higher Ge composition and less compressive strain in the SiGe QDs grown in He than in H₂ as measured by Raman spectroscopy. The Ge content is higher for He growth than H₂ growth due to hydrogen induced Si segregation and the lower interdiffusivity caused by the more strain relaxation in the He-grown SiGe dots. The photoluminescence also confirms more compressive strain for H₂ growth than He growth. Hydrogen passivation and Ge-H cluster formation play an important role in the QDs growth.     

Medium effects on the fluorine chemical shifts of non-polar molecules in liquids

The gas-to-infinite dilution fluorine chemical shifts of CF₄, SiF₄, SF₆, C₆F₆, p-fluorotoluene and p-difluorobenzene have been measured for a series of non-polar solvents. Downfield displacements ranging from 3–16 p.p.m. have been observed. Comparisons with proton solvent shifts make it evident that the London dispersion forces are the principal agent in causing the shifts. However, unlike proton resonance where the local diamagnetic shielding is mostly affected, it is probably through the local paramagnetic shielding that solvents alter fluorine chemical shifts.     

K-shell and valence shell excitations in CF4 by 2.5 keV electron impact

Energy loss spectra of 2.5 keV electrons, scattered through small angles by CF₄, have been obtained in the region of valence, carbon K- and fluorine K-shell excitations. The carbon K-shell spectrum has features which may be associated with the existence of an effective potential barrier in the CF₄ molecule.     

Room Temperature Solution ENDOR of some Super Stable Fluorocarbon Radicals

Room temperature fluorine electron nuclear double resonance (ENDOR) has been successfully observed for several superstable fluorocarbon radicals ·C(C₂F₄R)(i-C₃F₇)₂ in solution. Three radicals were employed in which CF₃, F, and O-c-C₆F₁₀SO₃C₂F₅ were introduced as R, and all the hyperfine couplings (hfcs) obtained by ENDOR were assigned with the help of ESR simulation and ab initio MO calculation. In case of ·C(i-C₃F₇)₃ large ¹³C and considerable β-fluorine couplings suggest the nonplaner arrangement for the central and three carbons at the β-position, in spite of the fact that all the methyl fluorine show the same hfc. Therefore, a rapid puckering motion along the C₃ axis together with the methyl rotation should average the hfc’s of the 18 fluorine nuclei to give the same value. When one of the CF₃ groups is substituted with an F nucleus, the five CF₃ groups give two hfc values, suggesting some dynamics still exists for the molecular frame. When a large group, O-c-C₆F₁₀SO₃C₂F₅, is substituted for CF₃, all the five CF₃ groups become nonequivalent and the ENDOR signal becomes intensive and sharp even at 290 K, indicating that the molecular frame becomes rigid. The relation between the ENDOR spectra of these systems and the intramolecular dynamics is discussed.     

Investigations of self-, H2- and He-broadening for rotational transitions of HCCC15N,CF3D and CF3CCH by the microwave transient emmission technique

The pressure dependence of coherent dephasing time T₂ has been determined by investigating transient emission signals of molecular gas samples, following pulsed microwave excitation. Experimental results on cyanoacetylene (HCCC¹⁵N), deuterated fluoroform (CF₃D) and 3,3,3-trifluoropropyne (CF₃CCH) are reported for the pure gas and also for mixtures with H₂ and He for rotational transitions in the frequency range from 5.8 GHz to 19.6 GHz.     

E.S.R. spectra of SiF3 radicals produced in a single crystal of SiF4

E.S.R. spectra of a γ-irradiated single crystal of SiF₄ were investigated. The spectra observed were attributed to SiF₃ radicals having ²⁸Si (I=0) and ²⁹Si (I=1/2) atoms. From the angular dependence of the spectral lines on rotation of the single crystal, hyperfine tensors were determined for three fluorine atoms and the ²⁹Si atom of the SiF₃ radical. The three fluorine atoms in the radical are equivalent, whereas the directions of their hyperfine tensors are different from one another owing to the pyramidal structure of the radical. In addition to the hyperfine analysis, the analysis of the superhyperfine structure due to neighbouring fluorine atoms gave information on the orientation of the radicals in the crystal and the mechanism of radical formation. The structure of the radical is discussed in comparison with that of the CF₃ radical.     

Wettability modification of electrospun poly(?-caprolactone) fibers by femtosecond laser irradiation in different gas atmospheres

The effect of femtosecond laser irradiation in air and in O₂ and CF₄ gas flows on the wettability of electrospun poly(?-caprolactone) fiber tissue scaffolds was studied. Laser power, focus spot size, raster scan spacing and gas atmosphere were varied in experiments. SEM imaging showed the average fiber diameter and surface porosity sizes were both altered by ablation. The micro-scale surface roughness measured by scanning laser profilometry was found to have a non-monotonic relationship to the surface wettability measured by the contact angle of sessile water droplets. In contrast, surface water contact angle continuously decreased with increased oxygen atomic percentage and oxygen-containing group fraction as measured by XPS. Further, the oxygen content was larger for more extensively ablated fiber surfaces, regardless of whether the increased ablation was caused by high laser power, smaller scanning space or smaller defocusing distance. Of the three gas atmospheres, O₂ gas flow was the most favorable environment for increasing surface oxidization, resulting in the largest water contact angle decrease for given laser power. For CF₄ gas flow, the least oxidization occurred, and the magnitude of water contact angle decrease was smallest for treatment at a given laser power.     

Microstructure of stomaflex based magnetic elastomers

Stomaflex elastomers filled with two types of magnetic particles (nano- and micro-sized) were investigated. It was observed that doping with Fe₃O₄ nanoparticles and applying a magnetic field during the polymerisation process led to a significant change in the local structure of the elastomer. Decreases in the quasi-crystalline phase concentration, in the average size of the crystalline blocks, and in the ordering distance were observed after doping the elastomer with magnetite nanoparticles. After filling the polymer with Fe₃O₄ nanoparticles, yet the elastomer fractal dimension changes. For the elastomer filled with a large amount of Fe microparticles (75% particle concentration) a texture effect is observed, and this effect is larger for the samples polymerised in a magnetic field. At all microparticle concentrations, these elastomers exhibit surface fractal structure.     

Asymmetric surface modification of poly(ethylene terephthalate) film by CF4 plasma immersion

Poly(ethylene terephthalate) (PET) films were treated with CF₄ plasma immersion. The samples were processed at different RF powers and treatment time. The surface modification of PET films was evaluated by water contact angle (CA), X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). Decrease in contact angle of both sides of PET films was observed under mild treatment conditions. However, as raising treatment power and/or time, the change in contact angle between the two sides of PET films was different. The relatively hydrophobic and hydrophilic surfaces were being in situ formed on the two sides of PET films, respectively. And the extreme values of water contact angle reached 108.63 and 7.56°, respectively. XPS analyses revealed that there was a substantial incorporation of fluorine and/or oxygen atoms in both side surfaces. The relative chemical composition of the C (ls) spectra's showed the incorporation of non-polar fluorine-based functionalities (i.e. CFCF_n, CF₂ or CF₃ groups) and polar oxygen-based functionalities (i.e. COOH or OH groups) in the surfaces. Correlation between the plasma parameters and the surface modification of PET films is also discussed.