Short Plasma Exposure Research Articles

An Array of Micro-hollow Surface Dielectric Barrier Discharges for Large-Area Atmospheric-Pressure Surface Treatments

A robust, commercial micro-hollow plasma source was used to generate atmospheric-pressure plasma, of surface area 18 × 18 mm, in ambient air, nitrogen and argon. An electrode system consisting of 105 micro-hollow surface dielectric barrier discharges was powered by sinusoidal high-voltage at a frequency of 26.7 kHz. The influence of the plasmas on the polycarbonate surface was investigated by means of surface energy measurements and X-ray photoelectron spectroscopy. It emerged that short plasma exposures led to significant increases in surface energy. It is suggested that this may arise out of incorporation of polar groups on the polycarbonate surface. A thermal camera was used to monitor the plasma source surface temperatures for the gases at flow rates ranging from 0 to 5 L/min. It was found that the temperature of the micro-hollow ceramic when operated upon in ambient air decreased significantly from 147 °C at 0 L/min to 49 °C at 5 L/min. In order to investigate further the thermal properties of the plasma, optical emission spectroscopy was employed to monitor the vibrational and rotational temperatures of the plasma generated in ambient air. CCD camera spectroscopic measurements estimated plasma thickness and temperature distribution at high spatial resolution.

Towards the implementation of atomic layer deposited In2O3:H in silicon heterojunction solar cells

Hydrogen doped indium oxide (In2O3:H) with excellent optoelectronic properties, deposited using atomic layer deposition (ALD), has been made applicable as a window electrode material for silicon heterojunction (SHJ) solar cells. It is particularly challenging to integrate ALD In2O3:H into SHJ solar cells due to a low reactivity of the metalorganic precursor cyclopentadienyl indium (InCp) with the H-terminated surface of a-Si:H. This challenge has been overcome by a simple and effective plasma-based surface pretreatment developed in this work. A remote inductively coupled O2 or Ar plasma has been used to modify the surface of a-Si:H, thereby promoting the adsorption of InCp on the surface. The impact of the short plasma exposure on c-Si/a-Si:H interface passivation has also been studied. It has been found that the observed degradation of the interface is not due to ion bombardment, but rather due to ultraviolet emission from the plasma. Fortunately, these light-induced defects have been found to be metastable, and the interface passivation can thus easily be fully recovered by a short post-annealing. Using such a mild Ar plasma pretreatment, ALD In2O3:H has been successfully implemented in a SHJ solar cell. A short-circuit current density of 40.1mA/cm2, determined from external quantum efficiency, is demonstrated for a textured SHJ solar cell with an In2O3:H window electrode, compared to 38.5mA/cm2 for a reference cell that has the conventional Sn-doped indium oxide (In2O3:Sn, ITO) window electrode. The enhanced photocurrent stems from a reduced parasitic absorption of In2O3:H in the entire wavelength range of 400–1200nm.

A dislocation-based crystal viscoplasticity model with application to micro-engineered plasma-facing materials

Materials developed with special surface architecture are shown here to be more resilient to the transient thermomechanical environments imposed by intermittent exposures to high heat flux thermal loading typical of long-pulse plasma transients. In an accompanying article, we present experimental results that show the relaxation of residual thermal stresses in micro-engineered W surfaces. A dislocation-based model is extended here within the framework of large deformation crystal plasticity. The model is applied to the deformation of single crystals, polycrystals, and micro-engineered surfaces composed of a uniform density of micro-pillars. The model is utilized to design tapered surface micro-pillar architecture, composed of a Re core and W coatings. Residual stresses generated by cyclic thermomechanical loading of these architectures show that the surface can be in a compressive stress state, following a short shakedown plasma exposure, thus mitigating surface fracture.

Inactivation of Escherichia coli on PTFE surfaces by diffuse coplanar surface barrier discharge

The non-equilibrium plasma of diffuse coplanar surface barrier discharge (DCSBD) was tested for decontamination of bacteria Escherichia coli on polymer surfaces. We investigated the optical parameters of DCSBD plasma generated in synthetic air with different relative humidity. Our study was provided to estimate the main plasma components active during the DCSBD plasma degradation of E. coli contamination prepared on polytetrafluoroethylene (PTFE, Teflon) surface, in ambient air at atmospheric pressure. The DCSBD plasma was characterized by means of electrical measurements and optical emission spectroscopy. The inactivation of E. coli bacteria was evaluated by standard microbiological cultivation (CFU plate counting). The experimental results of the germicidal efficiency obtained for short plasma exposure times proved the effectiveness of DCSBD plasma for the polymer surface decontamination.

Non-thermal Plasma Exposure Rapidly Attenuates Bacterial AHL-Dependent Quorum Sensing and Virulence.

The antimicrobial activity of atmospheric pressure non-thermal plasma has been exhaustively characterised, however elucidation of the interactions between biomolecules produced and utilised by bacteria and short plasma exposures are required for optimisation and clinical translation of cold plasma technology. This study characterizes the effects of non-thermal plasma exposure on acyl homoserine lactone (AHL)-dependent quorum sensing (QS). Plasma exposure of AHLs reduced the ability of such molecules to elicit a QS response in bacterial reporter strains in a dose-dependent manner. Short exposures (30–60 s) produce of a series of secondary compounds capable of eliciting a QS response, followed by the complete loss of AHL-dependent signalling following longer exposures. UPLC-MS analysis confirmed the time-dependent degradation of AHL molecules and their conversion into a series of by-products. FT-IR analysis of plasma-exposed AHLs highlighted the appearance of an OH group. In vivo assessment of the exposure of AHLs to plasma was examined using a standard in vivo model. Lettuce leaves injected with the rhlI/lasI mutant PAO-MW1 alongside plasma treated N-butyryl-homoserine lactone and n-(3-oxo-dodecanoyl)-homoserine lactone, exhibited marked attenuation of virulence. This study highlights the capacity of atmospheric pressure non-thermal plasma to modify and degrade AHL autoinducers thereby attenuating QS-dependent virulence in P. aeruginosa.

Atmospheric pressure plasma treatment of flat aluminum surface

The atmospheric pressure ambient air and oxygen plasma treatment of flat aluminum sheets using the so-called Diffuse Coplanar Surface Barrier Discharge (DCSBD) were investigated. The main objective of this study is to show the possibility of using DCSBD plasma source to activate and clean aluminum surface. Surface free energy measurements, X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM/EDX) and Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) were used for the characterization of the aluminum surface chemistry and changes induced by plasma treatment. Short plasma exposure times (several seconds) led to a significant increase in the surface free energy due to changes of its polar components. Various ageing effects, depending on the storage conditions were observed and discussed. Effects of air and oxygen plasmas on the removal of varying degrees of artificial hydrocarbon contamination of aluminum surfaces were investigated by the means of EDX, ATR-FTIR and XPS methods. A significant decrease in the carbon surface content after the plasma treatment indicates a strong plasma cleaning effect, which together with high energy efficiency of the DCSBD plasma source points to potential benefits of DCSBD application in processing of the flat aluminum surfaces.

Nitrogen-doping of bulk and nanotubular TiO2 photocatalysts by plasma-assisted atomic layer deposition

Plasma-assisted atomic layer deposition (PA-ALD) was adopted to deposit TiO2-xNx ultrathin layers on Si wafers, calcined Ti foils and nanotubular TiO2 arrays. A range of N content and chemical bond configurations were obtained by varying the background gas (O2 or N2) during the Ti precursor exposure, while the N2/H2-fed inductively coupled plasma exposure time was varied between 2 and 20s. On calcined Ti foils, a positive effect from N doping on photocurrent density was observed when O2 was the background gas with a short plasma exposure time (5 and 10s). This correlates with the presence of interstitial N states in the TiO2 with a binding energy of 400eV (Ninterst) as measured by X-ray photoelectron spectroscopy. A longer plasma time or the use of N2 as background gas results in formation of N state with a binding energy of 396eV (Nsubst) and very low photocurrents. These Nsubst are linked to the presence of Ti3+, which act as detrimental recombination center for photo-generated electron-hole pairs. On contrary, PA-ALD treated nanotubular TiO2 arrays show no variation of photocurrent density (with respect to the pristine nanotubes) upon different plasma exposure times and when the O2 recipe was adopted. This is attributed to constant N content in the PA-ALD TiO2-xNx, regardless of the adopted recipe.

Plasma-mediated inactivation of Pseudomonas aeruginosa biofilms grown on borosilicate surfaces under continuous culture system.

Biofilms are microbial communities attached to a surface and embedded in a matrix composed of exopolysaccharides and excreted nucleic acids. Bacterial biofilms are responsible for undesirable effects such as disease, prostheses colonization, biofouling, equipment damage, and pipe plugging. Biofilms are also more resilient than free-living cells to regular sterilization methods and therefore it is indispensable to develop better ways to control and remove them. The use of gas discharge plasmas is a good alternative since plasmas contain a mixture of reactive agents well-known for their decontamination potential against free microorganisms. We have previously reported that Pseudomonas aeruginosa biofilms were inactivated after a 1-min plasma exposure. We determined that the adhesiveness and the thickness of Pseudomonas biofilms grown on borosilicate were reduced. We also reported sequential morphological changes and loss of viability upon plasma treatment. However, the studies were carried out in batch cultures. The use of a continuous culture results in a more homogenous environment ensuring reproducible biofilm growth. The aim of this work was to study plasma-mediated inactivation of P. aeruginosa biofilms grown on borosilicate in a continuous culture system. In this paper we show that biofilms grown on glass under continuous culture can be inactivated by using gas discharge plasma. Both biofilm architecture and cell culturabilty are impacted by the plasma treatment. The inactivation kinetics is similar to previously described ones and cells go through sequential changes ranging from minimal modification without loss of viability at short plasma exposure times, to major structure and viability loss at longer exposure times. We report that changes in biofilm structure leading to the loss of culturability and viability are related to a decrease of the biofilm matrix adhesiveness. To our knowledge, there has been no attempt to evaluate the inactivation/sterilization of biofilms grown in a continuous system.

Roles of plasma-generated vacuum-ultraviolet photons and oxygen radicals in damaging nanoporous low-k films

One important class of low-k materials used as interconnect dielectrics employs methyl groups added to nanoporous SiO2 matrices. These carbon-doped oxide materials are known to be susceptible to damage from plasma species during various stages of plasma processing. Two key active species generated in O2 plasma are oxygen (O) radicals and vacuum-ultraviolet (VUV) photons. These species are known to cause carbon loss, resulting in damaging increases in dielectric constant throughout the film. However, the mechanisms through which this damage is incurred are poorly understood. By capping the substrate in different ways during plasma exposure, it is possible to expose films to either photons alone or O atoms alone. The authors report measurements of damage induced by VUV photons only, O radicals only, and the combination of O radicals and photons. Through HF stripping, they note that carbon extraction from photons and from radicals yields different outcomes; the profile of carbon concentration within the modified region is different for each case. Damage from photons alone can be modeled and model predictions are in good agreement with measurements. Damage from O atoms alone can only be modeled if it is assumed that the near-surface region has a significantly reduced diffusivity compared to the bulk of the film. Experiment and model agree that both photons alone and O radicals alone damage the material by removing carbon. When radicals and photons are present simultaneously during plasma exposure, however, more C removal appears to be occurring in the model than experimentally observed. Remarkably, if only radicals are exposed to the film after short (10–30 s) plasma exposures, very little additional damage is incurred during this radical-only exposure. The most straightforward interpretation of these results appears to be that photons combine synergistically with radicals in the pores to narrow the pores, thereby reducing film diffusivity in the C-poor, plasma-damaged regions.

Human Mononuclear Cell Survival and Proliferation is Modulated by Cold Atmospheric Plasma Jet

AbstractCold plasma has become a promising application in the fields of biology and medicine. Its anti‐microbial effects and stimulating properties on eukaryotic cells make plasma an encouraging option in treatment of chronic wounds. Apart from fibroblasts or keratinocytes, immune cells have a major contribution in wound healing. In this study, human peripheral blood mononuclear cells (PBMC) were tested for viability and proliferation after treatment with an atmospheric pressure argon plasma jet. In a treatment time dependent manner compromised viability of PBMC and proliferation of T cells could be shown and was assigned to induced apoptosis. Negligible cell damage was observed after short plasma exposure. Finally, plasma did not cause loss of function and treated but viable T cells retained the ability to proliferate.

Process effects of copper film over a step etched with a plasma-based process

The additive gas effect of a new plasma-based process for etching the copper film over a dielectric step has been investigated. The addition of different gases, such as Ar, N2, and CF4, affected the copper vertical and lateral conversion rates, which are critical to the attack of the cusp region and the sidewall as well as the residue formation. This is due to changes of plasma phase chemistry and ion bombardment energy. Excessive attacks of the cusp region and the sidewall were observed when the chlorine radical concentration was high except for the short plasma exposure time or the sidewall passivation condition. When the slope angle of the dielectric step was small, the cusp structure of the copper film was barely visible; therefore, the excessive plasma attack of the cusp region was negligible. A two step etch process that minimizes excessive attacks of the cusp region and the sidewall as well as the residue formation has been developed. This new process is critical to the practical application of copper in microelectronic products.

Surface analysis of poly(ethylene naphthalate) (PEN) films treated at atmospheric pressure using diffuse coplanar surface barrier discharge in air and in nitrogen

Surface modification of poly(ethylene naphthalate) (PEN) films by Diffuse Coplanar Surface Barrier Discharge (DCSBD) in ambient air and nitrogen at atmospheric pressure was studied at short plasma exposure times from 1 s up to 10 s. Chemical changes in the surface composition after the plasma treatments were studied using a high resolution XPS (X-ray Photoelectron Spectroscopy). The water contact angle was reduced from an initial value of 79° to values of 31° and 20° for the ambient air and nitrogen plasma treatments. After 3 days of storage in ambient air the contact angles were still about 50° and 40°, respectively. The polar component of surface energy was changed by the aging significantly less than the total surface energy. Despite the marked increase in the surface energy, the plasma treatment had no significant influence on the surface morphology.The surface modification in air plasma resulted in significant reduction the OC bond formation on the treated surface. The concentration of oxygen on PEN surface was increased from an initial value of 22 at.% up to 45 at.% already after 5 s air plasma exposure, and this oxygen concentration remained constant for longer plasma treatments. A small presence of nitrogen under 1.5 at.% from the air was also found after the treatments. The nitrogen plasma modified surface composition only by implanted nitrogen up to 5 at.% when the ratio of CO and C–O was not significantly changed. But some new bonds are also expected to be formed in a very low number only.

Improved conductivity of ZnO thin films by exposure to an atmospheric hydrogen plasma

ABSTRACTAluminum-doped zinc oxide (ZnOx:Al) films have been deposited on a moving glass substrate by a high throughput metalorganic chemical vapor deposition process at atmospheric pressure. Thin (< 250 nm) ZnOx:Al films have a poor crystalline quality, due to a small grain size and the presence of different crystallographic orientations. The crystalline quality improves with increasing film thickness (from 50 nm to 1000 nm), resulting in a lower value of resistivity (from 100 Ohm cm to 1·10-3 Ohm cm, respectively). We have investigated the variation in the films’ conductivity and transparency induced by a post-deposition exposure to a He/H2 atmospheric plasma. The resistivity of thin (< 250 nm) films is found to decreased sharply from 100 Ohm cm to about 4·10-3 Ohm cm by a short (∼ seconds) plasma exposure, while the resistivity of thicker films remains unaffected.

Characterization of surface‐modified polyalkanoate films for biomedical applications

AbstractPoly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBHV) films prepared by solvent casting were treated with oxygen, argon, and nitrogen radiofrequency‐generated plasmas. The analysis by attenuated total reflectance infrared spectroscopy and X‐ray absorption near edge spectroscopy of modified surfaces showed an increase of hydroxyl and unsaturated groups, compared with unmodified surfaces. Water contact angles decreased after a short time of exposure (<30 s) for all types of plasma. At long exposure times (>30 s), the water contact angles appeared to be independent of treatment time for nitrogen and argon plasmas, whereas they continuously decreased for films treated with oxygen. HaCaT cultures on nontreated and treated PHBHV films showed that short plasma exposures of 10–20 s improve cell attachment to a greater extent than long exposure times habitually used in polymer surface plasma treatment. The film surface topology did not influence cell attachment. These results illustrate the importance of a detailed characterization of the surface physicochemistry in plasma‐modified substrates designed as part of a strategy to optimize specific cell–biomaterial interactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Impact of in situ oxygen plasma cleaning on the resistance of Ru and Au-Ru based rf microelectromechanical system contacts in vacuum

Contact resistance measurements are reported for radio frequency microelectromechanical system switches operating in an ultrahigh vacuum system equipped with in situ oxygen plasma cleaning capabilities. Ru-based contacts were prepared by means of standard sputtering techniques, sputtering followed by postdeposition oxidation, (surface RuO2) or reactive sputtering in the presence of oxygen (bulk RuO2). In situ oxygen plasma cleaning lowered the resistance of Ru contacts by two or more orders of magnitude but not lower than Au contacts, irrespective of whether the Au contacts were cleaned. The time dependence of the resistance was fit to power law extrapolations to infer contact creep properties and resistance values at t=∞. Time-dependent creep properties of mixed Au-Ru contacts were observed to be similar to those of Au-Au contacts, while the absolute value of the resistance of such contacts was more comparable to Ru-Ru contacts. Prior to, and for short oxygen plasma exposure times, bulk RuO2 resistance values exhibited much larger variations than values measured for surface RuO2. For O2 plasma exposure times exceeding about 5 min, the bulk and surface RuO2 resistance values converged, at both t=0 and t=∞, with the t=∞ values falling within experimental error of theoretical values predicted for ideal surfaces. The data strongly support prior reports in the surface science literature of oxygen plasma induced thickening of oxide layers present on Ru surfaces. In addition, they demonstrate that vacuum alone is insufficient to remove contaminants from the contact surfaces and/or prevent such contaminants from reforming after oxygen plasma exposure.

Is gas-discharge plasma a new solution to the old problem of biofilm inactivation?

Conventional disinfection and sterilization methods are often ineffective with biofilms, which are ubiquitous, hard-to-destroy microbial communities embedded in a matrix mostly composed of exopolysaccharides. The use of gas-discharge plasmas represents an alternative method, since plasmas contain a mixture of charged particles, chemically reactive species and UV radiation, whose decontamination potential for free-living, planktonic micro-organisms is well established. In this study, biofilms were produced using Chromobacterium violaceum, a Gram-negative bacterium present in soil and water and used in this study as a model organism. Biofilms were subjected to an atmospheric pressure plasma jet for different exposure times. Our results show that 99.6 % of culturable cells are inactivated after a 5 min treatment. The survivor curve shows double-slope kinetics with a rapid initial decline in c.f.u. ml(-1) followed by a much slower decline with D values that are longer than those for the inactivation of planktonic organisms, suggesting a more complex inactivation mechanism for biofilms. DNA and ATP determinations together with atomic force microscopy and fluorescence microscopy show that non-culturable cells are still alive after short plasma exposure times. These results indicate the potential of plasma for biofilm inactivation and suggest that cells go through a sequential set of physiological and morphological changes before inactivation.

Remote Plasma ALD of Platinum and Platinum Oxide Films

Platinum and platinum oxide films were deposited by remote plasma atomic layer deposition (ALD) from the combination of (methylcyclopentadienyl)trimethylplatinum precursor and plasma. A short plasma exposure (0.5 s) resulted in low resistivity , high density , cubic Pt films, whereas a longer plasma exposure (5 s) resulted in semiconductive films. In situ spectroscopic ellipsometry studies revealed no significant nucleation delay, different from the thermal ALD process with gas which was used as a benchmark. A broad temperature window for remote plasma ALD of Pt and was demonstrated.

Remote Plasma and Thermal ALD of Platinum and Platinum Oxide Films

Platinum and platinum oxide films were deposited using thermal and remote plasma ALD. The combination of MeCpPtMe3 precursor and O2 gas or a short (0.5 s) O2 plasma exposure resulted in high purity, low-resistivity (15 microOhm cm), high-density (21 g/cm3), cubic platinum films. The combination of MeCpPtMe3 precursor with a longer (5 s) O2 plasma exposure resulted in semi-conductive PtO2 films with a band gap of ~1.5 eV. The long nucleation delay observed with the thermal process could be overcome by using the remote plasma process where atomic oxygen is provided from the gas phase. The ALD process dependence on substrate temperature was investigated, where both the thermal and the remote plasma Pt process revealed a temperature window from 200 C to 300 C and the remote plasma PtO2 process had a temperature window from 100 C to 300 C.

Gravimetrical and chemical characterization of SiO x structures deposited on fine powders by short plasma exposure in a plasma down stream reactor

The surface of lactose particles was modified by a plasma-enhanced chemical vapor deposition process to improve the flow behavior of the powder. For this, the particulates were treated in a plasma down stream reactor which provides a short (50 ms) and homogeneous exposure to the capacitively coupled RF discharge. The organosilicon monomer hexamethyldisiloxane (HMDSO) was used as a precursor for the formation of SiO x which is deposited on the substrate particle surface. For varying process gas mixtures (O 2/Ar/HMDSO) and RF power applied, the amount of the deposited material was determined gravimetrically after dissolution of the lactose substrate particles and the chemical composition of the accumulated deposition material was investigated by means of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. The concentration of the deposited SiO x relating to the substrate material was found to be in the range of 0.1 wt.%. Based on the ATR-FTIR analysis, the inorganic, i.e. oxidic SiO x fraction of the obtained deposits was shown to be controllable by varying the process parameters, whilst a relatively large amount of organic structures must be considered.

Tunable hydrophilicity on a hydrophobic fluorocarbon polymer coating on silicon

An efficient, economic, reliable, and repeatable patterning procedure of hydrophobic surfaces was developed. A fluorocarbon polymer derived from the C4F8 gas in an inductively coupled plasma etcher was used as the hydrophobic coating. For a subsequent patterning of hydrophilic apertures on the polymer, a short O2 plasma exposure through a silicon shadow mask was utilized. The overall hydrophilicity of the patterned surface can be tuned by the duration of the O2 plasma exposure, and also by the density and the size of the hydrophilic apertures. The laborious photolithography and tricky lift-off procedures are avoided. Optimization of the whole patterning process is explained thoroughly and supported with experimental data. The hydrophilic adhesion of the patterned polymer was evaluated with aqueous droplets, which were studied on matrices of the hydrophilic apertures of different sizes. The deposition parameters of the fluorocarbon polymer, the size of the droplet required to enable rolling on the patterned surface, and the duration of the O2 plasma exposure were considered as the main parameters. To determine the achievable resolution of the patterning procedure, the subsurface etching beneath the shadow mask was evaluated. The results show that a resolution of less than 10μm can be achieved. The simple hydrophilic patterning procedure described here can be used for the production of on-plane microfluidics, where a controlled adhesion or decohesion of 8–50μl droplets on the surface with a variable hydrophilicity from one location to another can be achieved.