Low-damage surface modification of polymethylmethacrylate with argon-oxygen mixture plasmas driven by multiple low-inductance antenna units

Surface modification of polymethylmethacrylate (PMMA) films has been investigated with argon-oxygen mixture plasmas sustained with multiple low-inductance antenna units. PMMA films were exposed to argon-oxygen mixture (20%) plasmas on a water-cooled substrate holder. Average ion energies bombarding onto the PMMA films was estimated to be as low as 6 eV, which was evaluated from the gap between plasma potential and floating potential. The etching depth of PMMA surface increased linearly with increasing plasma-exposure time and the etching rate was 170 nm/min. Surface roughness of PMMA slightly increased from 0.3 nm to 1.4 nm with increasing exposure time. Hard X-ray photoelectron spectroscopy (HXPES) was carried out to examine chemical bonding states of the PMMA surface in deeper regions (about 54 nm) as compared with those observed in shallower regions (27 nm).     

X-ray photoelectron spectroscopy for analysis of plasma-polymer interactions in Ar plasmas sustained via RF inductive coupling with low-inductance antenna units

Plasma-polymer interactions have been investigated on the basis of hard X-ray photoelectron spectroscopy (HXPES) together with conventional X-ray photoelectron spectroscopy (XPS) for analysis of chemical bonding states in the surface nano-layers of polymethylmethacrylate (PMMA) films, which were exposed to argon plasmas sustained via RF inductive coupling with multiple low-inductance antenna units. The PMMA films were exposed to argon plasmas on a water-cooled substrate holder. Average ion energies bombarding onto PMMA films were varied in the range of 6-16 eV, which were evaluated as ion kinetic energies at the sheath edge to the ground potential using a mass-separated ion-energy analyzer. The etching of PMMA surface after Ar plasma exposure with an ion dose of 3.4 × 10¹⁸ ions/cm² was measured to be insignificant (less than 20 nm). Surface roughness of PMMA slightly increased from 0.3 nm to 0.4 nm with increasing ion bombardment energy from 6 eV to 16 eV. HXPES was carried out together with conventional XPS to examine chemical bonding states of the PMMA surface in deeper regions (about 54 nm) with HXPES as compared to those observed in shallower regions (8 nm) with the conventional XPS.     

Plasma processing of soft materials for development of flexible devices

Plasma-polymer interactions have been studied as a basis for development of next-generation processing of flexible devices with soft materials by means of low-damage plasma technologies (soft materials processing technologies). In the present article, interactions between argon plasmas and polyethylene terephthalate (PET) films have been examined for investigations of physical damages induced by plasma exposures to the organic material via chemical bonding-structure analyses using hard X-ray photoelectron spectroscopy (HXPES) together with conventional X-ray photoelectron spectroscopy (XPS). The PET film has been selected as a test material for investigations in the present study not merely because of its specific applications, such as a substrate material, but because PET is one of the well defined organic materials containing major components in a variety of functional soft materials; C-C main chain, CH bond, oxygen functionalities (O=C-O bond and C-O bond) and phenyl group. Especially, variations of the phenyl group due to argon plasma exposures have been investigated in the present article in order to examine plasma interactions with π-conjugated system, which is in charge of electronic functions in many of the π-conjugated electronic organic materials to be utilized as functional layer for advanced flexible device formations. The PET films have been exposed to argon plasmas sustained via inductive coupling of RF power with low-inductance antenna modules. The HXPES analyses exhibited that the degradations of the oxygen functionalities and the phenyl group in the deeper regions up to 50 nm from the surface of the samples were insignificant indicating that the bond scission and/or the degradations of the chemical bonding structures due to photoirradiation from the plasma and/or surface heating via plasma exposure were relatively insignificant as compared with damages in the vicinity of the surface layers.     

Advanced research and development for plasma processing of polymers with combinatorial plasma-process analyzer

A plasma-process analyzer has been developed on the basis of combinatorial method, in which process examinations with continuous variations of plasma-process conditions can be carried out on a substrate holder with an inclined distribution of process parameters. Combinatorial plasma-process analyses have been demonstrated for examinations of plasma-polymer interactions in terms of etching characteristics and surface morphologies in order to show feasibility and effectiveness of the methodology as advanced research and development for next-generation plasma nano processes. The etching properties and surface morphologies have been investigated for polyethylene terephthalate (PET) films exposed to argon-oxygen mixture plasmas. The etching depth data obtained from three independent batches of the experiments showed universal and almost linear dependence with increasing product of (ion saturation current) × (exposure time); i.e. ion dose. Surface roughness of the polymer slightly increased with increasing ion dose, while the mean spacing after plasma exposure was found to decrease monotonically with increasing ion dose but was saturated at the level of approximately 250 nm.     

Effects of photoirradiation in UV and VUV regions during plasma exposure to polymers

Interactions between photons irradiated from Ar-O₂ mixture plasmas and polymer surfaces were investigated on the basis of depth analyses of chemical bonding states in the nano-surface layer of polyethylene terephthalate (PET) films via hard X-ray photoelectron spectroscopy (HXPES) and conventional X-ray photoelectron spectroscopy (XPS). The PET films were exposed to photons from the Ar-O₂ mixture plasmas by covering the PET samples with MgF₂ and quartz windows as optical filters for evaluation of photoirradiation effects in ultraviolet (UV) and vacuum ultraviolet (VUV) regions. The HXPES results indicated that the degradation of the chemical bonding states due to photoirradiation in regions was insignificant in deeper regions up to about 50 nm from the surface. Whereas, conventional XPS analysis showed that CO bond, OCO bond and CO bond increased after photoirradiation in UV and VUV regions. These results suggest that the increase in oxygen functionalities (CO bond, OCO bond and CO bond) may be attributed to chemical reactions and/or terminations of scissed bonds via photodecompositions of the polymer with oxygen and/or OH species (oxygen molecules and radicals during plasma exposure and/or oxygen molecules and moisture after taking the PET samples out of the plasma reactor to the ambient air) in the vicinity of the sample surface.     

Development of amorphous carbon protective coatings on poly(vinyl)chloride

The great versatility of polymers has promoted their application in a series of ordinary situations. The development of specific devices from polymers, however, requires modifications to fit specific stipulations. In this work the surface properties of thin films grown onto polyvinylchloride (PVC) were investigated. Hydrogenated amorphous carbon films were deposited onto commercial PVC plates from acetylene and argon plasmas excited by radiofrequency (13.56 MHz, 70 W) power. The proportion of acetylene in the gas feed was varied against that of argon, keeping the total pressure constant at 2.5 Pa. Deposition time was 1800 s. Film elemental composition was analyzed by X-ray photoelectron spectroscopy, XPS. Water contact angle measurements were performed using the sessile drop technique. The root mean squared roughness was derived from 50 × 50 µm² surface topographic images, acquired by scanning probe microscopy. Nanoindentation and pin-on-disk techniques were employed on the determination of film hardness and sliding wear, respectively. Oxidation resistance was obtained through the etching rate of the samples in oxygen radiofrequency (1.3 Pa, 50 W) plasmas. From XPS analysis it was detected oxygen and nitrogen contamination in all the samples. It was also found that sp³/sp² ratio depends on the proportion of argon in the plasma. At lower argon concentrations, hardness, wear and oxidation resistances were all improved with respect to the uncoated PVC. In such conditions, the surface wettability is low indicating a moderate receptivity to water. This combination of properties, ascribed to a balance between the ion bombardment and deposition processes, is suitable for materials exposed to rigorous weathering conditions.     

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

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

Improved impermeability of PET substrates using oxygen and hydrogen plasma

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

Using fast atomic source and low-energy plasma ions for polymer surface modification

A systematic study was carried out to characterize the effects of argon atomic beam irradiation and low-energy argon ions in plasma for polystyrene (PS) surface modification. The PS samples were exposed to a 1.5 keV, argon atomic beam from a fast atomic source (FAS) at different exposure times. The low-energy (1.5 eV) argon plasma ions were achieved in a two-stage RF discharge and PS samples were exposed to plasma for different times and powers. The surface characterization of these atomic beam and plasma modified PS samples was carried out using X-ray photoelectron spectroscopy. For FAS, the results showed a rapid increase (from 0.01 to 0.18) in oxygen-to-carbon ratio (O/C) at the surface of PS with first 10 s exposure time while further increase in exposure time up to 500 s showed about 50% decrease in O/C. Therefore, first few seconds of atomic beam irradiation useful to increase the O/C at the PS surface whereas at higher irradiation time the surface etching may took places and it could have advantage in surface cleaning. A comparison of O/C with FAS and plasma ions showed FAS is more effective way to achieve oxygen incorporation at PS surface relatively to low-energy flux plasma ions.     

Etch damage characteristics of TiO2 thin films by capacitively coupled RF Ar plasmas

Etch damage of TiO₂ thin films with the anatase phase by capacitively coupled RF Ar plasmas has been investigated. The plasma etching causes a mixed phase of anatase and rutile or the rutile phase. The effect of Ar plasma etching damage on degenerating TiO₂ thin films is dependent on gas pressure and etching time. The physical etching effect at a low gas pressure (1.3 Pa) contributes to the degradation: the atomic O concentration at the thin film surface is strongly increased. At a high gas pressure (13-27 Pa) and long etching time (60 min), there are a variety of surface defects or pits, which seem to be similar to those for GaN resulting from synergy effect between particle and UV radiation from the plasmas. For the hydrophilicity, the thin film etched at the high gas pressure and a short etching time (5 min) seems to have no etch damage: its contact angle property is almost similar to that for the as-grown thin film, and is independent of the black light irradiation. This result would probably result from formation of donor-like surface defects such as oxygen vacancy.     

Deep etch-induced damage during ion-assisted chemical etching of sputtered indium-zinc-oxide films in Ar/CH4/H2 plasmas

Plasma etch damage to sputtered indium-zinc-oxide (IZO) layers in the form of changes in the film stoichiometry was investigated using Auger Electron Spectroscopy (AES). While damage resulting from pure chemical etching processes is usually constrained to the surface vicinity, ion-assisted chemical etching of IZO in Ar/CH₄/H₂ plasmas produces a Zn-rich layer, whose thickness (∼ 50 nm) is well-above the expected stopping range of Ar ions in IZO (∼ 1.5 nm). Based on AES depth profiles as a function of plasma exposure time, it is concluded that the observed Zn enrichment and In depletion deep into the IZO film are driven by the implantation of hydrogen atoms.     

Comparison of dry etching of PMMA and polycarbonate in diffusion pump-based O2 capacitively coupled plasma and inductively coupled plasma

We report a comparison of dry etching of polymethyl methacrylate (PMMA) and polycarbonate (PC) in O₂ capacitively coupled plasma (CCP) and inductively coupled plasma (ICP). A diffusion pump was used as high vacuum pump in both cases. Experimental variables were process pressure (30-180 mTorr), CCP power (25-150 W) and ICP power (0-350 W). Gas flow rate was fixed at 5 sccm. An optimized process pressure range of 40-60 mTorr was found for the maximum etch rate of PMMA and PC in both CCP and ICP etch modes. ICP etching produced the highest etch rate of 0.9 μm/min for PMMA at 40 mTorr, 100 W CCP and 300 W ICP power, while 100 W CCP only plasma produced 0.46 μm/min for PMMA at the same condition. For polycarbonate, the highest etch rates were 0.45 and 0.27 μm/min, respectively. RMS surface roughnesses of PMMA and PC were about 2-3 nm after etching. Etch selectivity of PMMA over photoresist was 1-2 and that of PC was less than 1. When ICP power increased from 0 to 350 W, etch rates of PMMA and PC increased linearly from 0.47 to 1.18 μm/min and from 0.18 to 0.6 μm/min, while the negative self bias slightly reduced from 364 to 352 V. Increase of CCP power raised both self bias and PMMA etch rate. PMMA etch rates were about 3 times higher than those of PC at the same CCP conditions. SEM data showed that there was some undercutting of PMMA and PC after etching at 300 W ICP, 100 W CCP and 40 mTorr. The results also showed that the etched surface of PMMA was rough and that of PC was relatively smooth.     

Plasma etching of high-k and metal gate materials

Etching characteristics of high-k dielectric materials (HfO₂) and metal electrode materials (Pt, TaN) have been studied in high-density chlorine-containing plasmas at pressures around 10 mTorr. The etching of HfO₂ was performed in BCl₃ without rf biasing, giving an etch rate of about 5 nm/min with a high selectivity of >10 over Si and SiO₂. The etching of Pt and TaN was performed in Ar/O₂ with high rf biasing and in Ar/Cl₂ with low rf biasing, respectively, giving a Pt etch rate of about several tens nm/min and a TaN etch rate of about 200 nm/min with a high selectivity of >8 over HfO₂ and SiO₂. The etched profiles were outwardly tapered for Pt, owing to the redeposition of etch or sputter products on feature sidewalls, while the TaN profiles were almost anisotropic, probably owing to the ion-enhanced etching that occurred.     

Dry etching of AlN films using the plasma generated by fluoride

The plasma produced by the mixture of fluoride and argon (SF₆/Ar) was applied for the dry etching of AlN films. Very high etching rate up to 140 nm/min have been observed. The effects of the bias voltage and the plasma component on the etching results were investigated. It shows that AlN can be effectively etched by the plasma with the moderate SF₆ concentration and the etching rate varies linearly with the bias voltage. The FTIR spectra confirm that AlF₃ is formed due to the chemical reaction of Al and F atoms. The mechanism of AlN etching in F-based plasma is probably a combination between physical sputtering and chemical etching and can be briefly outlined: (i) F⁻ ions reacts with Al atoms to form low volatile product AlF₃ and passivate the surface, and (ii) at the same time the Ar⁺ ions sputter the reaction product from the surface and keep it fluoride free to initiate further reaction. AlF₃ formed on the patterned sidewall play a passivation role during the etching process. The etching process is highly anisotropic with quite smooth surface and vertical sidewalls.     

Surface modification of carbon electrodes using an argon plasma

In this work, an activated carbon sheet was modified, to improve capacitance and energy density of electric double layer capacitors (EDLCs). Surfaces were treated with plasma for selected times of 1, 5, 10, 20, and 30 min. The plasma source was a DC glow discharge in argon gas. The pressure was 20 Pa and the distance between positive and negative electrodes was 20 mm. DC power was 70 W. The activated carbon sheets were set up so that the sheets were covered with the DC glow discharge. The results showed that plasma treatment led to roughening of the surface of the activated carbon sheets which became more pronounced for increased time. This was attributed to an increased surface area caused by argon plasma etching. For discharge times greater than 10 min, contamination from sputtered PTEE in the chamber appeared to have a smoothing effect and led to a reduction of the measured surface area. Capacitance of the EDLCs cells with the activated carbon sheets after 1 min plasma surface treatment was increased by 2% compared to EDLCs cells with the original activated carbon sheet. The results have shown that the modification by plasma treatment of activated carbon sheets is a suitable technique for EDLCs used in high current applications.     

Etching process optimization using NH4Cl aqueous solution to texture ZnO:Al films for efficient light trapping in flexible thin film solar cells

0.5 μm-thick aluminum-doped zinc oxide (ZnO:Al) films were deposited at 100 °C on polyethylene terephthalate substrates by Radio Frequency magnetron sputtering. The as-deposited films were compact and dense, showing grain sizes of 32.0 ± 6.4 nm and resistivities of (8.5 ± 0.7) × 10^− 4 Ω cm. The average transmittance in the visible wavelength range of the structure ZnO:Al/PET was around 77%. The capability of a novel two-step chemical etching using diluted NH₄Cl aqueous solution to achieve efficient textured surfaces for light trapping was analyzed. The results indicated that both the aqueous solution and the etching method resulted appropriated to obtain etched surfaces with a surface roughness of 32 ± 5 nm, haze factors at 500 nm of 9% and light scattering at angles up to 50°. To validate all these results, a commercially ITO coated PET substrate was used for comparison.     

AES investigation of the stainless steel surface oxidized in plasma

Auger electron spectroscopy (AES) depth profiling was used to study the oxidation phenomena of AISI316L stainless steel during treatment with oxygen plasma. Samples were exposed to low-pressure RF plasma with a high dissociation degree, so that the flux of oxygen atoms onto the sample surface exceeded 10²⁴ m⁻² s⁻¹. A set of samples was oxidized 4 min at different temperatures up to 1300 K during plasma treatment. AES measurements showed that the oxide film thickness increased with the increasing temperature. The thickness of the oxide film on the samples oxidized in plasma at 300 K was nearly the same as for the untreated sample. The thickness of the oxide film of the samples which were oxidized at 1000 K was about 170 nm and it consisted of iron oxide. The thickest oxide film of about 350 nm was found on the samples heated in oxygen plasma to 1300 K. Depth profiling showed the uppermost layer of manganese oxide, followed by a mixture of chromium oxide and iron oxide. The scanning electron microscope analyses showed a dramatic increase of the surface roughness.     

Oxygen ion beam assisted etching of single crystal diamond chips using reactive oxygen gas

The etching characteristics of single crystal diamond chips processed using an oxygen ion beam with reactive oxygen gas flux were investigated. The specific etching rate increased linearly with increasing ion energy in the range of 250 to 1000 eV. The specific etching rates processed in a 1000-eV oxygen ion beam with oxygen gas was approximately twice that processed only in a 1000-eV oxygen ion beam. The angular dependences of only a 500-eV oxygen ion beam (no assist), and a 500-eV argon ion beam with oxygen gas were quite different from that of the other conditions. The specific etching rates were almost constant as a function of ion incident angle in the range of 0 to 50°. Those for the other conditions first increased with increasing ion incident angle, and reached a maximum rate at an ion incident angle of 40° or 50°, and then decreased gradually with further increase in ion incident angle. The specific etching rates using an argon ion beam with oxygen gas first increased with increasing gas partial pressure and then reached a saturation level at a gas partial pressure above 0.015 Pa, whereas those for the other conditions increased linearly with increasing gas partial pressure in the range of 0 to 0.06 Pa. The specific etching rates using an oxygen ion beam increased linearly with increasing substrate temperature in the range of 100 to 500 °C. The specific surface roughness was almost constant as a function of the substrate temperature, in the range of 100 to 500 °C. The specific surface roughness after assisted etching using oxygen or hydrogen gases was approximately half that processed in only oxygen or argon ion beams (no assist). © 2001 Kluwer Academic Publishers     

Characterization by optical emission spectroscopy of an oxygen plasma used for improving PET wettability

Polymers have excellent bulk physical and chemical properties but usually poor surface properties. For wettability improvement plasma technology is one of the most promising techniques. Several studies about surface modifications of polyethylene terephthalate (PET) exposed to an oxygen plasma have been already carried out. In this work an analysis of the plasma phase by optical emission spectroscopy (OES) has been employed in order to establish a correlation with the surface effects induced by plasma exposition on PET chemical composition and wettability, investigated by X-ray photoelectron spectroscopy (XPS) and water contact angle measurements, respectively. The treatment has been carried out for a time of 60 s at a constant pressure (15 Pa) and at different process powers ranging from 20 to 200 W. As expected, the best performance has been obtained at a power of 200 W due to the larger presence of oxygen radicals (OI) with the assistance of ionic species (OII, O₂⁺) which create dangling bonds on the substrate surface.     

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

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