Zdeněk Navrátil

Deposition of thin organosilicon polymer films in atmospheric pressure glow discharge

The atmospheric pressure glow discharge burning in nitrogen with small admixture of organosilicon compounds such as hexamethyldisilazane or hexamethyldisiloxane was used for the deposition of thin organosilicon polymer films. The properties of the discharge were studied by means of optical emission spectroscopy and electrical measurements. The deposited films were characterized by atomic force microscopy, x-ray photoelectron spectroscopy, infrared transmission measurements, ellipsometry, depth sensing indentation technique and contact angle measurements. The films were polymer-like, transparent in the visible range, with uniform thickness and without pinholes. The film hardness varied from 0.3 to 0.6 GPa depending on deposition conditions, the elastic modulus was in the range 15-28 GPa and the surface free energy was in the range 26-45 mJ m-2. The studied films exhibited good adhesion to the substrate.

Surface modification of polyethylene and polypropylene in atmospheric pressure glow discharge

An atmospheric pressure glow discharge (APGD) was used for surface modification of polyethylene (PE) and polypropylene (PP). The discharge was generated between two planar metal electrodes, with the top electrode covered by a glass and the bottom electrode covered by the treated polymer sample. The discharge burned in pure nitrogen or in nitrogen–hydrogen or nitrogen–ammonia mixtures. The surface properties of both treated and untreated polymers were characterized by scanning electron microscopy, atomic force microscopy, surface free energy measurements and x-ray photoelectron spectroscopy. The influence of treatment time and power input to the discharge on the surface properties of the polymers was studied. The ageing of the treated samples was investigated as well. The surface of polymers treated in an APGD was homogeneous and it had less roughness in comparison with polymer surfaces treated in a filamentary discharge. The surface free energy of treated PE obtained under optimum conditions was 54 mJ m−2 and the corresponding contact angle of water was 40°; the surface free energy of treated PP obtained under optimum conditions was 53 mJ m−2 and the contact angle of water 42°. The maximum decrease in the surface free energy during the ageing was about 10%.

The transition between different modes of barrier discharges at atmospheric pressure

Barrier discharges (BDs) can be operated in so-called diffuse modes. In contrast to the usual filamentary regime, which is characterized by a large number of individual microdischarges, the plasma of a diffuse BD covers the entire electrode area uniformly. Depending on the operation conditions (gas composition, amplitude and frequency of applied voltage), different diffuse modes can be investigated, namely, the atmospheric pressure Townsend discharge (APTD) and the atmospheric pressure glow discharge (APGD). The subject of the paper is the study of the transition between APTD and APGD as well as between diffuse and filamentary BD modes. Therefore, BDs were studied in the gas mixtures N2/H2, N2/He, N2/Ne and N2/Ar. It is shown that APGD in the noble gases helium and neon is formed due to high ionization rate at a comparatively low electric field, assisted by indirect ionization mechanisms involving metastable states of inert gases and nitrogen impurities, while the existence of APTD is coupled to the existence of metastable states of molecular nitrogen. Furthermore, a similar memory effect of residual surface charges on the dielectric barriers as described for filamentary BDs was observed in diffuse BDs.

Comparative study of diffuse barrier discharges in neon and helium

Diffuse dielectric barrier discharges in neon and helium at atmospheric pressure were studied. The discharges were generated between two metal electrodes, both covered by an alumina layer and driven by ac voltage of frequency 10 kHz. The discharge gap was 2.2 mm and 5 mm, respectively. The discharges were investigated by electrical measurements and by temporally and spatially resolved optical emission spectroscopy. The experimental results revealed similar discharge behaviour in both gases being considered. Although the discharges were ignited at slightly different electric field strengths, their evolutions were found to be similar. At maximum discharge current the spatial light intensity distribution was characterized by the formation of a cathode fall. A difference was observed in the magnitudes of the current density only. In addition to the regime with a single discharge pulse per voltage half period T/2, a discharge mode with two and more subsequent current pulses per T/2 (also referred to as the pseudoglow discharge regime in the literature) was obtained due to an increase in the voltage amplitude or an admixture of nitrogen.

Deposition of hard thin films from HMDSO in atmospheric pressure dielectric barrier discharge

An atmospheric pressure dielectric barrier discharge burning in nitrogen with a small admixture of hexamethyldisiloxane (HMDSO) was used for the deposition of thin organosilicon films. The thin films were deposited on glass, silicon and polycarbonate substrates, and the substrate temperature during the deposition process was increased up to values within the range 25 - 150 C in order to obtain hard SiOx-like thin films.

An investigation of dielectric barrier discharge in Ar and Ar/NH3 mixture using cross-correlation spectroscopy

Dielectric barrier discharges (BDs) are known to operate in two distinctive modes. The filamentary mode of BD is characterized by a large number of short lasting spatially bounded microdischarges. This type of discharge is typical for most cases of BDs at atmospheric pressure. Under some specific conditions another form of BD may arise. In this mode plasma uniformly covers the whole electrode area. This mode is usually referred to as the diffuse or homogeneous mode of BD.This work presents studies of the filamentary mode of BD in argon and its transition to the diffuse mode by ammonia addition. The discharges were investigated by means of cross-correlation spectroscopy. Particularly, the influence of electrode shape, discharge gap and the influence of ammonia admixture on discharge development were studied. The measurement offers results with high temporal and spatial resolution which are useful for comparison with results of numerical models.The obtained results include the electrical current measurement of discharge in several ammonia admixtures to argon. The diffuse discharge appeared at ammonia admixture above 3 vol%. The observed propagation of streamer in discharge in pure argon for two different electrode configurations is presented. When compared with discharge in pure argon the streamer velocity is decreased for 0.1 vol% ammonia admixture. With increasing ammonia concentration the streamer velocity increases again. The behaviour of presented impurities was observed and the results are included in this report. The basic model of the discharge kinetic is included. For reduced electric field below 10 Td the electron drift is much higher in argon–ammonia mixture than in pure argon.

Surface modification of polycarbonate in homogeneous atmospheric pressure discharge

A homogeneous atmospheric pressure dielectric barrier discharge was used for the surface modification of polycarbonate (PC). The discharge was generated between two planar metal electrodes, the top electrode was covered by glass and the bottom electrode was covered by a polymer sample. The discharge burned in pure nitrogen or in a mixture of nitrogen and hydrogen. The surface properties of both treated and untreated polymers were characterized by atomic force microscopy, surface free energy (SFE) measurements and x-ray photoelectron spectroscopy. The influence of the treatment time and power input to the discharge on the surface properties of polymers was studied. The ageing of treated samples was also investigated. The treatment of polymers in the homogeneous atmospheric pressure discharge was homogeneous and the polymer surfaces showed a smaller degree of roughness in comparison with the polymer surfaces treated in a filamentary discharge. The SFE of the treated PC obtained at optimum conditions was 53 mJ cm-2 and the corresponding contact angle of water was 38deg . The maximum decrease in the SFE during ageing was about 13%. The analysis of the chemical composition showed an increase in the nitrogen concentration in the surface layer, but almost a zero increase in the oxygen concentration. This result was discussed concerning the measured values of the SFE measurement.

On the analysis of surface free energy of DLC coatings deposited in low pressure RF discharge

The results of statistical study of acid-base approach to the determination of the surface free energy are presented. Plasma enhanced chemical vapour deposition (PECVD) in low pressure RF discharge was used to prepare diamond-like carbon (DLC) coatings. The plasma deposited films were investigated by means of contact angle technique in order to determine their surface free energy. Drops of various liquids were set on the film surface and the drop profiles were snapped with CCD camera. The obtained contact angle data using several testing liquids were analyzed by threeliquid acid-base method and the results retrieved on the basis of different liquid triplets used were compared.A multiple regression method for a determination of the surface energy from more than three liquids is suggested and its outputs are compared with the results obtained by standard three-liquid acid-base approach.

Investigation of helium barrier discharges with small admixtures of oxygen

Barrier discharges in helium and in helium with small admixtures of oxygen were investigated by electrical measurements, the spatiotemporally resolved optical emission spectroscopy and surface charge diagnostics via the electro-optic Pockels effect. As already known, in pure helium a diffuse discharge is typically formed because of the significant role of the metastable species. However, even a very small oxygen admixture (0.025 vol.%) causes the transition to a filamentary mode as a result of the effective quenching of helium metastables by oxygen molecules. This effect was indicated by a significant decrease of N-2(+) the first negative system emission. The transition region was characterized by several Townsend-like discharge breakdowns becoming more and more unstable with an increasing O-2 admixture. The formation of the atmospheric pressure Townsend-like discharge was confirmed by the spatiotemporally resolved emission. The development of the surface charges agrees qualitatively and quantitatively well with the transported charge during the discharge breakdown calculated from the discharge current.

Determination of electron density and temperature in a capacitively coupled RF discharge in neon by OES complemented with a CR model

A method of determination of electron temperature and electron density in plasmas based on optical emission spectroscopy complemented with collisional-radiative modelling (OES/CRM) was studied in this work. A radiofrequency (13.56 MHz) capacitively coupled discharge in neon at 10 Pa was investigated by intensity calibrated optical emission spectroscopy. The absolute intensities of neon transitions between 3p and 3s states were fitted with a collisional-radiative (CR) model in order to determine the electron temperature and electron density. Measuring techniques such as imaging with an ICCD camera were adopted for supplementary diagnostics. The obtained results were compared with the results of compensated Langmuir probe measurement and one-dimensional particle-in-cell/Monte Carlo (PIC/MC) simulation. The results of OES/CRM and PIC/MC method were in close agreement in the case of electron temperature in the vicinity of a driven electrode. The determined value of electron temperature was about 8 eV. In bulk plasma, the measured spectra were not satisfactorily fitted. In the case of electron density only relative agreement was obtained between OES/CRM and Langmuir probe measurement; the absolute values differed by a factor of 5. The axial dependence of electron density calculated by PIC/MC was distinct from them, reaching the maximum values between the results of the other two methods. The investigation of power dependence of plasma parameters close to the driven electrode showed a decrease in electron temperature and an increase in electron density together with increasing incoming RF power. The calculated spectra fitted very well the measured spectra in this discharge region.