A combined sensor for the diagnostics of plasma and film properties in magnetron sputtering processes

A combined sensor for the simultaneous measurement of plasma and deposition parameters has been designed and built. It comprises (i) a quartz crystal microbalance, (ii) a planar Langmuir probe and (iii) a calorimetric (Gardon) probe, which allows to measure the deposition rate, typical plasma parameters (plasma density and electron temperature) and the total energy input into a growing film. The combined sensor is electrically insulated against ground, allowing these measurements also for floating or substrate-bias conditions. These parameters are measured (nearly) simultaneously, controlled by a specific measurement and analysis program. The operation of this combined sensor is demonstrated for the deposition of copper and tungsten films with a 2 inch planar magnetron.     

Effect of argon and substrate bias on diamond thin film surface morphology

Nanocrystalline materials are of high interest, because mechanical and physical properties of such materials are different from those or coarse-grained type. Continuous and smooth nanocrystalline diamond (NCD) thin films were successfully grown on mirror polished silicon substrates, using double bias plasma-enhanced hot filament chemical vapour deposition technique. A gas mixture of Ar:CH₄:H₂ and CH₄:H₂ was used as the precursor gas. The effect of the gas composition, flow rate and substrate bias during deposition on diamond crystallite size was investigated. Changing the growth parameters facilitates control of grain size of polycrystalline diamond thin films from microcrystalline to nanocrystalline. The structure of fine-grained NCD films has been studied with scanning electron microscopy and Raman spectroscopy.     

Preparation and characterization of ethylenediamine and cysteamine plasma polymerized films on piezoelectric quartz crystal surfaces for a biosensor

This paper describes a method for the modification of quartz crystal surfaces to be used as a transducer in biosensors that allow recognition and quantification of certain biomolecules (antibodies, enzymes, proteins, etc). Quartz crystal sensors were modified by a plasma based electron beam generator in order to detect the level of the toxin histamine within biological liquids (blood, serum) and food (wine, cheese, fish etc.). Cysteamine and ethylenediamine were used as precursors in the plasma. After each modification step, the layers on the quartz crystal were characterized by frequency measurements. Modified surfaces were also characterized by contact angle, X-ray photoelectron spectroscopy and atomic force microscopy to determine the physical and chemical characteristics of the surfaces after each modification. Finally, the performance of the sensors were tested by the response to histamine via frequency shifts. The frequency shifts of the sensors prepared by plasma polymerization of ethylenediamine and cysteamine were approximately 3230 Hz and 5630 Hz, respectively, whereas the frequency change of the unmodified crystal surface was around 575 Hz.     

Influences of argon plasma cleaning on the die-shear force of chip and copper/polyimide flexible substrate assembly using a non-conductive film

Abstract

A non-conductive film (NCF) and a thermal compression process were combined to assemble a chip onto a flexible substrate. To achieve direct bonding and to enhance the adhesion of a chip on the flexible substrate with NCF, argon plasma was used to clean copper electrodes over a flexible substrate. For flexible substrates which received argon plasma cleaning, low contact angles were obtained, and gold bumps directly contacted copper electrodes to form active input/output (I/O) paths, indicating the contaminants on the flexible substrate were removed and a clean bonding surface could be achieved. Neither delamination nor porosity was observed at the bonding interface between the NCF and copper electrodes. A sound bonding interface with satisfactory die-shear force was achieved. The argon plasma cleaning led to a significant improvement of the die-shear force of a chip bonded onto the flexible substrate using NCF.     

Effects of RF bias power on electron energy distribution function and plasma uniformity in inductively coupled argon plasma

Changes in the plasma non-uniformity and the electron energy distribution function (EEDF) by increasing RF bias power were observed in inductively coupled plasma using spatially resolved radial EEDF measurements. As the bias power was increased at a fixed ICP power at a low gas pressure, The EEDF was evolved from a bi-Maxwellian to a Maxwellian distribution. The plasma density was decreased in all radial positions and thus plasma non-uniformity was slightly changed. However, strongly improved plasma spatial non-uniformity was observed at a high gas pressure with a decrease in the center-plasma density and an increase in the radial edge-plasma density. This result could be understood by combined effects of the ion acceleration loss and the non-uniform power deposition due to the RF bias power.     

Distributions of dusts in the plasma column sheath

Dust crystal and void were simulated with a two-dimensional fluid model and a three-dimensional molecular dynamic model. The distributions of dust particles are obtained and these distributions are one-layer or two-layer dust crystals, conversely cone-shaped, and formulation of a cylindrical dust void without ion drag is complex. It is due to a gentle potential bump in the central region of the electrode caused by the cylindrical geometry. It can be concluded that it is the potential well of the central region of the electrode bottom established by lower ion density that contributes to the formation of dust voids.     

Modeling of the supersonic argon plasma jet at low gas pressure environment

Numerical simulation results are presented concerning the heat transfer and fluid flow within the supersonic argon plasma jet encountered in low pressure (or soft vacuum) plasma spraying (LPPS). The plasma parameters at the inlet section of the plasma jet are taken from our modeling results of the subsonic-to-supersonic d.c. arc plasma torch. The mach number, temperature and static pressure at the center of the plasma jet on the torch exit section are 2.8, 13 200 K and 6000 Pa, respectively, whereas the environment (i.e. vacuum chamber) pressure is 0.1 atm. Those parameters are typical for LPPS. The plasma jet is assumed to be axi-symmetrical and in local thermodynamic equilibrium state. The All-Speed SIMPLE algorithm is coupled with the FAST-2D program to simulate the whole plasma jet containing both the supersonic and subsonic flow regions. Modeling results clearly show that there exist several successive temperature, velocity and static wave crests and troughs. The fluctuation magnitudes of those parameters reduce rapidly in the flow direction, along with the flow transformation from the supersonic flow regime into the subsonic flow regime. The existence of a series of compression and expansion waves in the region near the torch nozzle exit shows clearly the over-expanded characteristics of the supersonic plasma flow.     

Modification of low temperature deposited LiMn2O4 thin film cathodes by oxygen plasma irradiation

Lithium manganese oxides have been deposited by radio frequency magnetron sputter deposition with relatively lower annealing temperatures and then post-treated with a radio frequency (rf) driven oxygen plasma. Following oxygen plasma irradiation, the film properties were modified, and the performance of the thin film cathode has been enhanced. The electrochemical properties of the treated thin-film cathodes were characterized and compared. The results showed that the samples with moderate plasma treatment also maintained good cyclic properties as cycled at a wide range potential window of 2.0 V-4.5 V. Its electrochemical properties were significantly improved by this process, even though the films were prepared under low annealing temperature.     

Development of an intelligent model to optimize heat-affected zone,kerf, and roughness in 309 stainless steel plasma cutting by using experimental results

Plasma cutting is an effective way to cut hard metals. In this process, three output parameters cutting width (kerf), surface roughness (Ra) and heat-affected zone (HAZ) are critical factors which affect the quality and efficiency of the cutting. In this paper, an experimental study was conducted to investigate the cutting quality in terms of kerf, Ra, and HAZ for the 309 stainless steel plasma cutting. First, the research tested the effect of input parameters including current, gas pressure, and cutting speed on the process outputs. Then, the results were used to develop three predictive models by intelligent systems based on genetic algorithm (GA) and artificial neural network (ANN). Finally, a hybrid technique of genetically optimized neural network systems (GONNs) was designed and employed to simultaneously optimize the process outputs. The results show that the implemented strategy is an effective method for optimizing the output parameters in the plasma cutting process.     

Effect of oxygen exposure on the electrical conductivity and gas sensitivity of nanostructured ZnO films

Nanostructured ZnO films (undoped and Ga, Co, Mn doped) were exposed to oxygen (1-80 vol.%) at temperature range of 300-500 °С in order to reveal the ambience-temperature effect on the electrical conductivity. The dominant effect of ambient influence via oxygen absorption was observed: the intensity of conductivity decrease was found to be proportional with temperature and tends to saturate with time. It is demonstrated that oxygen absorption occurs accordingly to diffusion law and the quantifying of oxygen diffusion was realized for different samples. It is revealed that the type of dopant affects the diffusion in ZnO and the tendency to increase the diffusion intensity with dopant content has been observed. After oxygen saturation the reversible effect of oxygen adsorption became dominant and contributed to the film's conductivity. Oxygen exposure undoped ZnO films revealed high sensitivity for oxygen content change in the ambience therefore they have been preceded further for gas sensor design and the detailed investigation of film's sensing properties has been carried out.     

The behaviour of minor and trace elements in coal in an argon plasma

The occurrence of the elements Co, U, Dy, Eu, Ba, Ti, Sr, I, Br, Mg, Cu, Na; V, AI, Mn, Cl and Ca in coal is reviewed. An experimental technique is described in which the concentration of these elements is reduced. The technique consists of treating the coal in an argon plasma, which is formed by injecting argon into a carbon arc through axial holes drilled in graphite electrodes. The coal samples are contained in graphite crucibles and thus the carbon activity is one. The rate and the mechanism of removal of these elements is reported. The concentration of the elements was determined by instrumental neutron activation analysis.     

Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

The characteristics of the multi-hole RF capacitively coupled plasma discharged with neon, argon and krypton

The characteristics of the multi-hole electrode RF capacitively coupled plasma are experimented and analyzed. Neon, argon and krypton are discharged with various pressures, powers and electrode hole diameters. The relationship of plasma density and hole diameter of the electrode is compared in various gas plasma discharges. The data can be a reference for the design of a multi-hole electrode for high density RF capacitively coupled plasma discharge.     

Analysis of rat plasma proteins desorbed from gold and methyl- and hydroxyl-terminated alkane thiols on gold surfaces

It is believed that adsorbed blood or plasma components, such as water, peptides, carbohydrates and proteins, determine key events in the concomitant inflammatory tissue response close to implants. The aim of the present study was to develop a procedure for the collection and analysis of minor amounts of proteins bound to solid metal implant surfaces. The combination of a sodium dodecyl sulfate washing method coupled with a polyacylamide gel electrophoretic protein separation technique (SDS–PAGE), Western blot and image analysis enabled the desorption, identification and semiquantification of specific proteins. The analyzed proteins were albumin, immunoglobulin G, fibrinogen and fibronectin. Concentration procedures of proteins were not required with this method despite the small area of the test surfaces. The plasma proteins were adsorbed to pure gold and hydroxylated and methylated gold surfaces, which elicit different tissue responses in vivo and plasma protein adsorption patterns in vitro. The image analysis revealed that the pure gold surfaces adsorbed the largest amount of total and specific proteins. This is in accordance with previous ellipsometry/antibody experiments in vitro. Further, the principles described for the protein analysis can be applied on implant surfaces ex vivo. ©©2000 Kluwer Academic Publishers     

Influence of the luminous gas phase on direct current plasma polymerized hydrocarbon film growth

The characteristics of the glow created in plasma polymerization systems are notably different from inert gas plasmas such as argon, in which the well-known negative glow is the primary glow. The study of direct current (DC) glow discharges of a series of saturated hydrocarbon monomers indicated that cathode glow forms the distinctive glow in plasma polymerization systems. It forms a strong contrast to characteristic negative ionization glow of glow discharges of inert gases that do not polymerize. Optical emission analysis results obtained from these plasma deposition systems indicated that polymerizable species are mainly formed in cathode glow region. The growth of direct current plasma polymerized hydrocarbon film clearly showed the dominating effects of luminous gas phases on the polymerizable tendency in plasma polymerization system.     

Nanosize stabilization of cubic and tetragonal phases in reactive plasma synthesized zirconia powders

Pure zirconium oxide powders with particle size 2–33 nm are synthesized by reactive plasma processing. Transmission electron microscopy investigation of these particles revealed size dependent behavior for their phase stabilization. The monoclinic phase is found to be stable when particle size is ≥20 nm; Tetragonal is found to be stabilized in the range of 7–20 nm and as the particle size decreases to 6 nm and less, the cubic phase is stabilized.     

Preparation of thermosensitive gold nanoparticles by plasma pretreatment and UV grafted polymerization

This work is to develop an easy method of plasma treatment and graft polymerization to prepare thermosensitive gold nanoparticles. Gold nanoparticles (Nano-Au) were reduced by trisodium citrate combined with hydrogen tetrachloroaurate(III) tetrahydrate (chloroauric acid) and modified with 11-mercaptoundecanoic acid (MUA) by the self-assembly monolayers (SAM). The surface graft polymerization of N-isopropylacrylamide (NIPAAm) was carried out by two steps, using O₂ plasma pretreatment of the surface on MUA SAM modified Nano-Au to form the peroxide groups on Nano-Au(MUA), and then subsequently using UV light to induce grafting with thermosensitive polymer. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to direct investigation of the particle size and morphology in situ. The diameters of the gold nanoparticles measured from the TEM images are in good agreement with data measured at room temperature which is about 15 nm. The thermosensitive gold nanoparticles were characterized by chemical structure of surface (ESCA) and Fourier-transform infrared spectroscopy (FTIR). ESCA result suggests that plasma treatments can be employed to generate peroxides on the Nano-Au(MUA) for the subsequent UV graft polymerization of PNIPAAm.     

The study of adsorption characteristics Cu and Pb ions onto PHEMA and P(MMA-HEMA) surfaces from aqueous single solution

The adsorption characteristics of Cu²⁺ and Pb²⁺ ions onto poly2-hydroxyethyl methacrylate (PHEMA) and copolymer 2-hydroxyethyl methacrylate with monomer methyl methacrylate P(MMA-HEMA) adsorbent surfaces from aqueous single solution were investigated with respect to the changes in the pH of solution, adsorbent composition (changes in the weight percentage of MMA copolymerized with HEMA monomer), contact time and the temperature in the individual aqueous solutions. The linear correlation coefficients of Langmuir and Freundlich isotherms were obtained. The results revealed that the Langmuir isotherm fitted the experimental results better than the Freundlich isotherm. Using the Langmuir model equation, the monolayer adsorption capacity of PHEMA surface was found to be 0.840 and 3.037 mg/g for Cu²⁺ and Pb²⁺ ions and adsorption capacity of (PMMA-HEMA) was found to be 31.153 and 31.447 mg/g for Cu²⁺ and Pb²⁺ ions, respectively. Changes in the standard Gibbs free energy (ΔG⁰), standard enthalpy (ΔH⁰) and standard entropy (ΔS⁰) show that the adsorption of mentioned ions onto PHEMA and P(MMA-HEMA) are spontaneous and exothermic at 293–323 K.     

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.     

The effect of argon dilution on deposition of microcrystalline silicon by microwave plasma enhanced chemical vapor deposition

Microwave plasma-enhanced chemical vapor deposition (PECVD) is a very promising method for industrial scale fabrication of microcrystalline silicon solar cells since the technique is well applicable for large areas, and high deposition rates can be obtained. We have investigated the effect of Ar dilution on the growth process and the material properties of microcrystalline silicon. The major benefit of Ar addition in the MWPECVD process, using H₂ and SiH₄ as reactant gases, is an improved stabilization of the plasma, in particular at low pressure and MW power. We show, however, that material properties of the microcrystalline silicon layers deteriorate if we partly substitute H₂ by Ar during the deposition. The density of the layers - as expressed by the refractive index - decreases, and the defect density (measured by Fourier transform photocurrent spectroscopy) increases with increasing Ar flow. Investigation of the plasma by optical emission study shows that Ar atoms play a very active role in the dissociation processes of H₂ and SiH₄. Substitution of H₂ by Ar decreases the SiH^? emission and increases the Si^? emission. On the other hand, the H_α/H_β ratio increases upon substitution of H₂ by Ar. The latter effect shows that Ar addition does not lead to higher electron temperatures and we conclude that the changes of SiH^? and Si^? emissions are due to dissociation of SiH₄ by Ar^? (quenching reactions). The precise role of Ar in MWPECVD of microcrystalline silicon needs further investigation, but we conclude that the usage of this gas should be minimized in order to maximize the quality of the silicon layers.