Physical and electrical characteristics of Ba(Zr0.1Ti0.9)O3 thin films under oxygen plasma treatment for applications in nonvolatile memory devices

In this study, the effects of oxygen gas plasma treatment on the surface of Ba(Zr_0.1Ti_0.9)O₃ (BZT) films are investigated. The influence of oxygen plasma treatment on the crystal structure is developed by X-ray diffraction patterns and on the electrical characteristics are measured by the Al/BZT/Pt capacitor (metal–dielectric–metal) structure. Experimental results show that the capacitance increases and the leakage current density decreases as the oxygen plasma is treated on the BZT films. These results clearly indicate that the electrical characteristics of BZT films have effectively improved by means of the oxygen plasma surface treatment process. PACS 77.84.-s; 81.15.Cd; 73.40.Qv; 77.22.Ej; 51.50.+v     

Effect of O2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO2 thin films

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage (C-V) measurements to investigate the variation of structure, surface morphology, thickness of SiO₂-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO₂ growth has taken place above approximately 51%. The best C-V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.     

The influence of the structures and compounds of DLC coatings on the barrier properties of PET bottles

To reduce the oxygen transmission rate through a polyethylene terephthalate (PET) bottle (an organic plastic) diamond-like carbon (DLC) coatings on the inner surface of the PET bottle were deposited by radio frequency plasma-enhanced chemical vapour deposition (RF-PECVD) technology with C₂H₂ as the source of carbon and Ar as the diluted gas. As the barrier layer to humidity and gas permeation, this paper analyses the DLC film structure, composition, morphology and barrier properties by Fourier transform infrared, atomic force microscopy, scanning electron microscopy and oxygen transmission rate in detail. From the spectrum, it is found that the DLC film mainly consists of sp³ bonds. The barrier property of the films is significantly relevant to the sp³ bond concentration in the coating, the film thickness and morphology. Additionally, it is found that DLC film deposited in an inductively coupled plasma enhanced capacitively coupled plasma source shows a compact, homogeneous and crack-free surface, which is beneficial for a good gas barrier property in PET bottles.     

Improvement of hydrophilic properties of electrospun polyamide-imide fibrous mats by atmospheric-pressure plasma treatment

Polyamide-imide (PAI) fibrous mats were fabricated through electrospinning and further treated with atmospheric-pressure plasma. The surface characteristics of the PAI fibrous mats were examined to determine the effect of plasma treatment on the hydrophilic properties. FT-IR, X-ray photoelectron spectroscopy, and contact-angle analysis indicated that the hydrophilicity of the PAI fibrous mats increased upon the introduction of hydrophilic groups by plasma treatment. The concentration of functional groups, including oxygen, and the surface roughness of the PAI fibrous mats increased with increasing treatment time. The optimum plasma treatment time for surface modification of the PAI fibrous mats under atmospheric pressure was 120 s.     

Formation of functional groups on graphite during oxygen plasma treatment

Improved sample wettability was obtained by oxygen plasma functionalization of pyrolytic graphite. The samples were exposed to highly dissociated oxygen plasma with the density of 1 × 10¹⁶ m⁻³, the electron temperature of about 5.5 eV and the density of neutral oxygen atoms of 8 × 10²¹ m⁻³ for 20 s. The surface wettability was measured by a contact angle of water drop. The contact angle dropped from original 112° down to about 1°. The functional groups were detected by XPS analyses. The survey spectrum showed a substantial increase of oxygen concentration on the surface, while high-resolution analyses showed additional oxygen was bonded onto the graphite surface in the form of C-O polar functional group responsible for the increase of the surface energy.     

Initial stages of hydrogen reduction of NiO(100)

The reduction of single crystal NiO(100) under hydrogen has been followed by AES, XPS and LEED for the pressure range of 1.0 × 10^?7 to 1.3 × 10^?6 Torr and for substrate temperatures of 150–350°C. The kinetics of reduction are controlled both by the rate of removal of lattice oxide at the surface and by the diffusion of subsurface oxygen to the oxygen-depleted surface. The rate of oxygen removal is first-order in surface oxide concentration and in hydrogen pressure. An induction period precedes the reduction reaction and its length is postulated to be controlled by surface defect concentration. The stoichiometric and reduced lattice oxygen species appear to be chemically identical and give a single symmetric XPS peak at 529.4 eV. Nickel spectra indicate a shift in XPS binding energies from those expected of the oxide to those of nickel metal early in the reduction process, although LEED indicates the NiO(100) surface lattice to remain the stable structure for surface reduced to approximately 20% of the stoichiometric oxygen concentration. Ni(100) island formation is observed, with Ni 〈010〉 and 〈001〉 directions along the NiO 〈010〉 and 〈001〉, respectively, but only after the NiO surface is severely depleted in oxygen.     

Long-distance oxygen plasma sterilization: Effects and mechanisms

The distribution of electrons, ions and oxygen radicals in long-distance oxygen plasma and the germicidal effect (GE) of Escherichia coli on the surface of medical poly(tetrafluoroethylene) (PTFE) film were studied. The quantity of protein leakage and the production of lipid peroxide in bacterial suspension as well as the state of DNA were measured after sterilization to analyse the inactivation mechanisms. The results showed that the concentration of electrons and ions decreased rapidly with increasing the distance from the center of induction coil, which approximated to 0 at 30 cm, whereas the concentration of oxygen radicals reduced slowly, i.e. decreased 30% within 40 cm. GE value reached 3.42 in the active discharge zone (0 cm) and exceeded 3.32 within 40 cm when plasma treatment parameters were set as follows: plasma rf power at 100 W, treatment time at 60 s and oxygen flux at 40 cm³/min. Fast etching action on cell membrane by electrons, ions and attacking polyunsaturation fatty acid (PUFA) in cell membrane by oxygen radicals are primary reasons of oxygen plasma sterilization in the active discharge and the afterglow zone, respectively. The GE of UV radiation in long-distance oxygen plasma is feebleness.     

Surface modification of medical PVC by remote oxygen plasma

Surface modification of medical PVC by remote oxygen plasma has been studied: surface structure and performance of treated material are analyzed by weight loss rate, contact angle measurement and XPS. With the increase of sample distance from the plasma source, weight loss rate drops, electrons and ions and etching action are restrained; and C=O groups are found in the treated PVC surface. The surface wettability of PVC film can be improved by remote low-temperature plasma and the radical reaction is intensified.     

Effects of atomic oxygen irradiation on the surface properties of phenolphthalein poly(ether sulfone)

To study the effects of low earth orbit environment on the surface properties of polymers, phenolphthalein poly(ether sulfone) (PES-C) blocks were irradiated by atomic oxygen in a ground-based simulation system. The surface properties of the pristine and irradiated blocks were studied by attenuated total-reflection FTIR (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). It was found that atomic oxygen irradiation induced the destruction of PES-C molecular chains, including the scission and oxidation of PES-C molecular chains, as evidenced by FTIR and XPS results. The scission of PES-C molecular chains decreased the relative concentration of C in the surface, while the oxidation increased the relative concentration of O in the surface. The changes in surface chemical structure and composition also changed the surface morphology of the block, which shifted from smooth structure before irradiation to “carpet-like” structure after irradiation.     

Influence of ethylene glycol pretreatment on effectiveness of atmospheric pressure plasma treatment of polyethylene fibers

For atmospheric pressure plasma treatments, the results of plasma treatments may be influenced by liquids adsorbed into the substrate. This paper studies the influence of ethylene glycol (EG) pretreatment on the effectiveness of atmospheric plasma jet (APPJ) treatment of ultrahigh molecular weight polyethylene (UHMWPE) fibers with 0.31% and 0.42% weight gain after soaked in EG/water solution with concentration of 0.15 and 0.3 mol/l for 24 h, respectively. Scanning electron microscopy (SEM) shows that the surface of fibers pretreated with EG/water solution does not have observable difference from that of the control group. The X-ray photoelectron spectroscopy (XPS) results show that the oxygen concentration on the surface of EG-pretreated fibers is increased less than the plasma directly treated fibers. The interfacial shear strength (IFSS) of plasma directly treated fibers to epoxy is increased almost 3 times compared with the control group while that of EG-pretreated fibers to epoxy does not change except for the fibers pretreated with lower EG concentration and longer plasma treatment time. EG pretreatment reduces the water contact angle of UHMWPE fibers. In conclusion, EG pretreatment can hamper the effect of plasma treatment of UHMWPE fibers and therefore longer plasma treatment duration is required for fibers pretreated with EG.     

Low-pressure plasma cleaning of Au and PtIr noble metal surfaces

The effect of low-pressure hydrogen and oxygen plasma cleaning of Au and PtIr was investigated by X-ray photoelectron spectroscopy. Hydrocarbon contamination was efficiently removed by hydrogen and oxygen plasma. Hydrogen plasma additionally reduces oxygen compounds, especially metal oxides, while oxygen plasma results in the formation of a surface layer of Au₂O₃ and PtO, respectively. Both noble metal oxides are unstable and decompose with time. The decomposition of metal oxides occurs in parallel with the recontamination of the surface. Metal oxides can be removed completely for Au and partially for PtIr by an additional cleaning with hydrogen plasma. Hydrogen plasma treatment is very promising for noble metal surface cleaning.     

Leakage current and sub-bandgap photo-response of oxygen-plasma treated GaN Schottky barrier diodes

The effect of oxygen plasma treatment on the performance of GaN Schottky barrier diodes is studied. The GaN surface is intentionally exposed to oxygen plasma generated in an inductively coupled plasma etching system before Schottky metal deposition. The reverse leakage current of the treated diodes is suppressed in low bias range with enhanced diode ideality factor and series resistance. However, in high bias range the treated diodes exhibit higher reverse leakage current and corresponding lower breakdown voltage. The X-ray photoelectron spectroscopy analysis reveals the growth of a thin GaO_x layer on GaN surface during oxygen plasma treatment. Under sub-bandgap light illumination, the plasma-treated diodes show larger photovoltaic response compared with that of untreated diodes, suggesting that additional defect states at GaN surface are induced by the oxygen plasma treatment.     

Surface analysis of oxygen plasma treated poly(p-phenylene benzobisoxazole) fibers

The influence of oxygen plasma treatment on surface properties of poly(p-phenylene benzobisoxazole) (PBO) fibers and aging effect of the oxygen plasma modified PBO fiber surfaces were investigated by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and dynamic contact angle analysis (DCAA), respectively. The results indicated that the oxygen plasma treatment introduced some polar groups to PBO fiber surfaces, enhanced surface roughness and changed surface morphologies of PBO fibers by plasma etching and oxidative reactions. Surface wettability of PBO fibers may be significantly improved by increasing surface free energy of the fibers via oxygen plasma treatment. Aging effect of the oxygen plasma treated PBO fibers showed that the fiber surface wettability degraded in the first several days after the plasma treatment, and it was found to be changeless as the aging time continued as long as 30 days.     

Surface modification of polytetrafluoroethylene film using single liquid electrode atmospheric- pressure glow discharge

Polytetrafluoroethylene films are treated by room temperature helium atmospheric pressure plasma plumes, which are generated with a home-made single liquid electrode plasma device. After plasma treatment, the water contact angle of polytetrafluoroethylene film drops from 114°to 46°and the surface free energy increases from 22.0 mJ/m2 to 59.1 mJ/m2. The optical emission spectrum indicates that there are reactive species such as O2+ , O and He in the plasma plume. After plasma treatment, a highly crosslinking structure is formed on the film surface and the oxygen element is incorporated into the film surface in the forms of -C-O-C-, -C=O, and -O-C=O groups. Over a period of 10 days, the contact angle of the treated film is recovered by only about 10 , which indicates that the plasma surface modification is stable with time.     

Improvement of aramid fiber III reinforced bismaleimide composite interfacial adhesion by oxygen plasma treatment

Domestic Aramid Fiber III (DAF III) was modified by oxygen plasma treatment. The effects of oxygen plasma treatment power on fiber surface and DAF III reinforced bismaleimides (BMI) composite interfacial properties were investigated, respectively. The fiber surface characteristics were analyzed by X-ray photoelectron spectroscopy, Scanning Electron Microscopy, Atomic Force Microscopy and Dynamic Contact Angles Analysis, respectively. The results showed that oxygen plasma treatment introduced new oxygen containing groups such as C=O and –COO on to the fiber surfaces, changed the fiber surface morphologies and enhanced surface roughness by oxidative reactions and plasma etching. Finally, the fiber surface wettability was effectively improved. The total free energy increased from 49.8 to 71.7 mJ/m2 at maximum with 300 W oxygen plasma treatment. The composite interlaminar shear strength (ILSS) was evaluated by short beam shear measurement. The ILSS value increased from 49.3 to 59.8 MPa (by 21.3%) within 300 W plasma treatment.     

Oxygen-mediated suppression of twinning in gas-phase prepared FePt nanoparticles

We report on the influence of oxygen on the morphology and crystal structure of gas-phase prepared FePt nanoparticles. The particles are prepared by DC-sputtering in an Ar/He gas mixture. Without any oxygen, the obtained particles are predominantly icosahedra. The additional supply of oxygen leads to significant changes in both the crystal structure and morphology of the FePt nanoparticles. With increasing oxygen concentration, we observe the onset of particle agglomeration and a drop of the particle size. In addition, the crystal structure changes from icosahedral to fcc. These results are ascribed to oxygen mediated changes of the surface properties of the FePt nanoparticles such as the surface diffusivity and the surface free energy.     

The research on the interfacial compatibility of polypropylene composite filled with surface treated carbon fiber

Dielectric barrier discharges (DBD) in ambient air are used on carbon fiber to improve the fiber surface activity. Carbon fibers with length of 75 μm are placed into the plasma configuration. The interaction between modified carbon fibers and polypropylene (PP) was studied by three-point bending (TPB) test. The chemical changes induced by the treatments on carbon fiber surface are examined using X-ray photoelectron spectroscopy (XPS). XPS results reveal that the carbon fiber modified with the DBD at atmospheric pressure show a significant increase in oxygen and nitrogen concentration. These results demonstrate that the surface of the carbon fiber is more active and hydrophilic after plasma treatments using a DBD operating in ambient air.     

Organic contaminants removal by oxygen ECR plasma

Recently electron cyclotron resonance (ECR) plasma have been explored for wafer cleaning applications, since it is known to do less damage to silicon surface than conventional plasma. Organic contaminants removal efficiency and plasma radiation damage of the ECR plasma cleaning have been investigated. In oxygen ECR plasma cleaning, the plasma exposure time needed to remove the organic contaminants on the silicon surface down to the detection limit is 40 s, but the one to reach the lowest surface roughness is 10 s. The leakage current level of the MOS capacitor made using the Si substrate exposed to oxygen ECR plasma for 40 s is 8 × 10⁻⁹ A. The optimum exposure time determined by considering the contaminants removal efficiency and the plasma radiation damage (or the leakage current level) is 40 s. Organic contaminants seem to be removed through both sputter-off mechanism by oxygen ion bombardment and evaporation mechanism by chemical reactions with excited oxygen atoms.     

The surface chemistry resulting from low-pressure plasma treatment of polystyrene: The effect of residual vessel bound oxygen

The surface chemistry of plasma treated polystyrene samples has been studied in a specially designed low-pressure argon discharge system incorporating in situ XPS analysis. By using an electrostatic grid biasing technique, the plasma source can also be used in a mode preventing ion interactions with the sample.The system, which utilizes a vacuum transfer chamber between plasma and XPS analysis has allowed us to differentiate between the level of oxygen incorporated at the polystyrene surface from residual gas during treatment and that from the exposure of the treated sample to the laboratory atmosphere. Using typical base pressures of about 5 × 10⁻³ Pa (4 × 10⁻⁵ Torr) the XPS results show that significant oxygen surface incorporation resulted from oxygen containing species in the plasma itself (i.e. water vapour with 2 × 10⁻³ Pa partial pressure). The surface concentration of O was measured at 7.6 at.%. Subsequent atmospheric exposure of the treated samples resulted in only a small increase (of 0.6 at.%) in oxygen incorporation in the form of acid anhydride functionalities.XPS measurements of PS samples exposed to plasmas with no ion-surface component (i.e. exposure from VUV, UV and excited neutral species only) showed no appreciable change in oxygen incorporation compared to those with low-energy ion bombardment from the plasma (<20 eV). Given the energetics of the remaining bombarding species, it indicates that VUV radiation may be chiefly responsible for the production of free radical sites in this discharge regime.     

Plasma treatment of carbon fibers: Non-equilibrium dynamic adsorption and its effect on the mechanical properties of RTM fabricated composites

The effect of oxygen plasma treatment on the non-equilibrium dynamic adsorption of the carbon fabric reinforcements in RTM process was studied. 5-Dimethylamino-1-naphthalene-sulfonylchloride (DNS-Cl) was attached to the curing agent to study the change of curing agent content in the epoxy resin matrix. Steady state fluorescence spectroscopy (FS) analysis was used to study this changes in the epoxy resin at the inlet and outlet of the RTM mould, and XPS was used to study the chemical changes on the carbon fiber surfaces introduced by plasma treatment. The interlaminar shear strength (ILSS) and flexural strength were also measured to study the effects of this non-equilibrium dynamic adsorption progress on the mechanical properties of the end products. FS analysis shows that the curing agent adsorbed onto the fiber surface preferentially for untreated carbon fiber, the curing agent content in the resin matrix maintain unchanged after plasma treatment for 3 min and 5 min, but after oxygen plasma treatment for 7 min, the epoxy resin adsorbed onto the fiber surface preferentially. XPS analysis indicated that the oxygen plasma treatment successfully increased some polar functional groups concentration on the carbon fiber surfaces, this changes on the carbon fiber surfaces can change the adsorption ability of carbon fiber to the resin and curing agent. The mechanical properties of the composites were correlated to this results.