Ellipsometric studies on TiO2 thin films synthesized by spray pyrolysis technique

TiO₂ thin films were synthesized on quartz substrates at substrate temperatures of 350 °C and 450 °C by thermal spray pyrolysis technique using titanium oxy-acetyl acetonate as a precursor. The optical properties of the thin films were characterized by a Spectroscopic Ellipsometer (SE). The surface morphology of the thin films was studied using Atomic Force Microscopy (AFM). The surface roughness values obtained using AFM and SE was compared. The refractive indices of the films were computed using a point by point ellipsometric data extraction procedure. The porosity of the films were modeled from the optical data by effective medium approximation and corroborated from empirical relations. Using Forouhi-Bloomer optical dispersion model, further treatment of SE data was carried out. The experimental investigations and modeling of the data were directed towards optical benchmarking of spray pyrolyzed titania thin films.     

Kinetic model of thin film growth by vapor deposition

A phenomenological kinetic model is proposed for describing the production of a thin film containing two components, A and B, by chemical and physical vapor deposition. The film was created by the “site-to-site” deposition of components A and B. The equations for the densities of components A and B in the surface layers were formed, and analytical and numerical solutions were obtained. The model includes the probabilities of different elementary processes for the interaction of gas phase components (molecules, radicals, atoms and ions) with those of A and B on the film surface. The deposition and erosion rates, the surface and volume densities of components A and B and the relative volume of micro-cavities inside the film were calculated as a function of the probabilities for the elementary processes of gas (plasma)-surface interactions. The experimental characteristics of a-Si: H thin films prepared by SiH₄ plasma deposition and those of carbon nitride thin films deposited from r.f. — magnetron sputtering and ion beam-assisted processes are compared with model calculations.     

Ionization effect to plasma expansion study during nanosecond pulsed laser deposition

The dynamic characteristic and effects of plasma play an important role in film growth process of pulsed laser deposition (PLD). Based on numerical hydrodynamic modeling, supposed the laser radiation and partial ionization of the plasma as a dynamic source, we deduce a set of new plasma expansion dynamics equations. Based on which, as an example of carbon target, using finite difference method, the plasma flow dynamics evolvement in vacuum is investigated. Our results show the dynamic partial ionization increases the expansion in all directions, which changes into a new dynamic source for plasma expansion. In the axial direction, because of the collisional interactions between particles, the plume density peak is in the vicinity of the target surface and the acceleration of plasma occurs mainly near the target surface too. In the transverse direction, the plume peak is not near the target, but at the surface. The space expansion distance is far less than the axial direction because there is no high initial velocity component in this direction. The predictions of the plasma expansion action based on the proposed dynamics source assumption are found to be in agreement with the experimental observation.     

Surface modification of a polyamide 6 film by He/CF4 plasma using atmospheric pressure plasma jet

Polyamide 6 (PA 6) films are treated with helium(He)/CF₄ plasma at atmospheric pressure. The samples are treated at different treatment times. The surface modification of the PA 6 films is evaluated by water contact angle, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The etching rate is used to study the etching effect of He/CF₄ plasma on the PA 6 films. The T-peel strengths of the control and plasma treated films are measured to show the surface adhesion properties of the films. As the treatment time increases, the etching rate decreases steadily, the contact angle decreases initially and then increases, while the T-peel strength increases first and then decreases. AFM analyses show that the surface roughness increases after the plasma treatment. XPS analyses reveal substantial incorporation of fluorine and/or oxygen atoms to the polymer chains on the film surfaces.     

Spectroscopic in situ diagnostics of boron nitride film growth in plasma-enhanced deposition

The development of in situ diagnostics of the most important species and reactions in the plasma and/or on the surface during thin-film growth is one of the current topics in plasma-enhanced vapor deposition. In situ thin film diagnostic methods which could be used in plasma processing are restricted due to the presence of electrons and ions. The advantages and disadvantages of different applicable methods will be discussed. The spectroscopic in situ control of boron nitride film growth is presented as an example of surface modification in low-temperature, low-pressure plasma processing. The growth of cubic and hexagonal boron nitride is observed by polarized infrared reflection spectroscopy in absorption and ellipsometric configurations as well as by single-wavelength ellipsometry in the visible spectral range. Modeling of the experimental results gives detailed information on growth conditions and internal stress of the films. Received: 8 August 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Polyethylene Oxide Films Polymerized by Radio Frequency Plasma-Enhanced Chemical Vapour Phase Deposition and Its Adsorption Behaviour of Platelet-Rich Plasma

We present polyethylene oxide (PEO) functional films polymerized by rf plasma-enhanced vapour chemical deposition (rf-PECVD) on p-Si (100) surface with precursor ethylene glycol dimethyl ether (EGDME) and diluted Ar in pulsed plasma mode. The influences of discharge parameters on the film properties and compounds are investigated. The film structure is analysed by Fourier transform infrared (FTIR) spectroscopy. The water contact angle measurement and atomic force microscope (AFM) are employed to examine the surface polarity and to detect surface morphology, respectively. It is concluded that the smaller duty cycle in pulsed plasma mode contributes to the rich C--O--C (EO) group on the surfaces. As an application, the adsorption behaviour of platelet-rich plasma on plasma polymerization films performed in-vitro is explored. The shapes of attached cells are studied in detail by an optic invert microscope, which clarifies that high-density C--O--C groups on surfaces are responsible for non-fouling adsorption behaviour of the PEO films.     

The effect of surface modification by nitrogen plasma on photocatalytic degradation of polyvinyl chloride films

The solid-phase photocatalytic degradation of poly(vinyl chloride) (PVC) films was investigated under the ambient air in order to assess the feasibility of developing photodegradable polymers. Nitrogen plasma was used to modify PVC films to enhance the photocatalytic degradation of PVC with nano-sized anatase TiO₂. The plasma parameter varied in this study is discharge power from 30 to 120 W for a constant treatment time of 60 s and a constant gas pressure of 10 Pa. The photodegradation of the plasma-treated PVC-TiO₂ films was compared with that of pure PVC films and PVC-TiO₂ films performing weight loss monitoring, scanning electron microscopy (SEM) analysis, contact angle measurements, electron spin resonance (ESR), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The wettability of the plasma-treated PVC is improved significantly. ESR revealed that the signal of radicals on the surface of the plasma-treated PVC film was enhanced after the treatment. Furthermore, the weight loss indicated that TiO₂ speeds up the photocatalytic degradation of PVC chains. The SEM image of the plasma-treated PVC-TiO₂ film showed a lot of crack on the film surface after irradiation. XPS indicated that the C and Cl atomic concentration reached minimum values on the surface of plasma-treated PVC-TiO₂ under identical photocatalytic condition. The experimental results reveal that plasma treatment can obviously enhance the photocatalytic degradation of PVC.     

Electronic structure of GaN(0001)‐2 × 2 thin films grown by PAMBE

Gallium nitride thin films were grown on silicon carbide (0001) by plasma‐assisted molecular beam epitaxy (PAMBE). The samples were cooled down in nitrogen plasma and characterized in situ by reflection high energy electron diffraction (RHEED), photoelectron spectroscopy (XPS/UPS), and atomic force microscopy (AFM) revealing stoichiometric and smooth GaN films virtually free of contaminations. We present valence band data obtained by UPS with strong emission from surface states inside the fundamental band gap. These states and the observed 2 × 2 surface reconstruction are highly sensitive towards residual molecules. Once these surface states have disappeared the original state could not be recovered by surface preparation methods underlining the necessity of in situ investigations on as‐grown surfaces. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of rf plasma nitriding time on electrical and optical properties of ZnO thin films

ZnO thin films were prepared by thermal oxidation of metallic Zn films and nitrided by an inductively coupled rf plasma. The effects of successive plasma processing cyclic times on structural and optical properties as well as electrical resistivity were examined by different characterization techniques. A small amount of nitrogen was detected at the film-substrate interface. The grain size decreased slightly as the treatment time increased. The surface roughness of examined films increased while the thickness decreased with increasing plasma treatment time. The electrical resistivity decreased about four orders of magnitude when the sample nitrided for 15 min. However, the transmittance increased as the plasma treatment time increased. The optical band gap increased from 2.76 to 3.02 eV with increasing plasma treatment time from 0 to 15 min.     

Modification of surface properties of polypropylene (PP) film using DC glow discharge air plasma

The industrial use of polypropylene (PP) films is limited because of undesirable properties such as poor adhesion and printability. In the present study, a DC glow discharge plasma has been used to improve the surface properties of PP films and make it useful for technical applications. The change in hydrophilicity of modified PP film surface was investigated by contact angle (CA) and surface energy measurements as a function of exposure time. In addition, plasma-treated PP films have been subjected to an ageing process to determine the durability of the plasma treatment. Changes in morphological and chemical composition of PP films were analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The improvement in adhesion was studied by measuring T-peel and lap shear strength. The results show that the surface hydrophilicity has been improved due to the increase in the roughness and the introduction of oxygen-containing polar groups. The AFM observation on PP film shows that the roughness of the surface increased due to plasma treatment. Analysis of chemical binding states and surface chemical composition by XPS showed an increase in the formation of polar functional groups and the concentration of oxygen content on the plasma-processed PP film surfaces. T-peel and lap shear test for adhesion strength measurement showed that the adhesion strength of the plasma-modified PP films increased compared with untreated films surface.     

In-situ diagnostics for plasma surface processing

A survey is given of in-situ diagnostics of plasma and surface for application in plasma etching and deposition. Especially those diagnostics that increase the fundamental understanding of the elementary processes occurring both within the plasma and at the surface are highlighted. In general, diagnostics are performed to determine the value of a physical parameter. This value is fed into models of plasma or surface, and in that way the understanding of the process is enhanced. In the paper first the most interesting physical parameters are defined. Subsequently the diagnostic techniques currently available to determine those parameters are reviewed.     

Lorentz magnetoresistance of thin films in the presence of surface scattering and domain structures

A modeling of ballistic electronic transport in thin films with diffuse surface scattering in the presence of a magnetic domain structure is performed. The conductance is obtained from the diffusive mean-square displacement of the conductance electrons. Lorentz magnetoresistance (LMR) effects for several domain structures are simulated and compared to corresponding experiments. We conclude that there is no reason to assume an intrinsic domain-wall resistance (DWR) in pure iron and cobalt films in order to explain experimental results. More generally, simulation results indicate that additional LMR related to the domain structure is best understood in terms of three separate effects, which all scale with the LMR of the homogenously magnetized film.     

Mechanical properties of sol-gel derived lead zirconate titanate thin films by nanoindentation

Lead zirconate titanate (PZT) thin films are deposited on platinized silicon substrate by sol-gel process. The crystal structure and surface morphology of PZT thin films are characterized by X-ray diffraction and atomic force microscopy. Depth-sensing nanoindentation system is used to measure mechanical characteristics of PZT thin films. X-ray diffraction analyses confirm the single-phase perovskite structures of all PZT thin films. Nanoindentation measurements reveal that the indentation modulus and hardness of PZT thin films are related with the grain size and crystalline orientation. The increases of the indentation modulus and hardness with grain size are observed, indicating the reverse Hall-Petch effect. Furthermore, the indentation modulus of (1 1 1)-oriented PZT thin film is higher than those of (1 0 0)- and random-oriented films. The consistency between experimental data and numerical results of the effective indentation moduli for fiber-textured PZT thin films using Voigt-Reuss-Hill model is obtained.     

Compositional analysis of ferroelectric films coated with carbon layer using laser-induced plasmas spectroscopy

An experimental investigation of the effect of different thickness of carbon layer coated on ferroelectric films on the atomic emission intensity using laser-induced plasmas spectroscopy technique with charge-coupled device (CCD) experimental system has been conducted. The experimental results show that the intensity of the spectra emitted with the carbon layer thickness of 15 μm is much higher than that of pure ferroelectric films. By using this best experimental condition, the atomic concentration ratios of ferroelectric films are evaluated by rationing the integrated intensities of selected spectral emission lines of the plasma produced from the films. And the experimental results show that N_La/N_Co and N_Sr/N_Co atomic concentration ratios are almost in agreement with the corresponding values obtained by traditional compositional analysis techniques of inductively coupled plasma (ICP).     

Solid state NMR study of carbon bonding in amorphous hydrogenated carbon films

Carbon bonding environments in hydrogenated amorphous carbon films (a-C:H) deposited from an rf-biased methane plasma onto various substrates have been quantified by application of solid state¹³C NMR. A family of films were prepared by systematically varying the substrate bias voltage. Quantitative data on carbon chemistry in these films is required for modeling the impact of structure on mechanical and optical properties. A variety of NMR acquisition pulse sequences have been investigated to determine the conditions under which quantitative¹³C NMR data can be acquired in this system. The results indicate that data acquisition from this material requires different protocols than for the study of polymeric hydrocarbon films. With proper experimental design, NMR is an excellent technique for structural studies of these materials.     

Passive films on stainless steels in aqueous media

The purpose of this paper is to provide a syntheses of experimental results regarding films formed on the surface of stainless steels. Such syntheses are attempted for the environments most studied. In each case the overview is presented with reference to the most important papers. Conflicting data are also presented and discussed. Based on the results of the prior studies, a four region model is proposed to describe the surface passive film and its breakdown.     

Influence of direct current plasma magnetron sputtering parameters on the material characteristics of polycrystalline copper films

Physical vapor processes using glow plasma discharge are widely employed in microelectronic industry. In particular magnetron sputtering is a major technique employed for the coating of thin films. This paper addresses the influence of direct current (DC) plasma magnetron sputtering parameters on the material characteristics of polycrystalline copper (Cu) thin films coated on silicon substrates. The influence of the sputtering parameters including DC plasma power and argon working gas pressure on the electrical and structural properties of the thin Cu films was investigated by means of surface profilometer, four-point probe and atomic force microscopy.     

Surface analytical studies of Ar-plasma etching of thin heptadecafluoro-1-decene plasma polymer films

An audio-frequency plasma polymerization set-up with a planar plasma source was used to deposit thin heptadecafluoro-1-decene (HDFD) plasma polymer films. The morphology and chemical structure of the films after deposition were compared with the state of the film after a subsequent Ar-plasma treatment by means of in situ Fourier transform infrared reflection absorbance spectroscopy (FT-IRRAS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and atomic force microscopy (AFM) as well as contact angle measurements. The results revealed the correlation of wettability of the model Teflon-like films with change of surface chemistry and surface topography as a result of Ar-plasma treatment.     

Plasma polymerization of styrene with carbon dioxide under glow discharge conditions

Plasma polymerization gains increasing interest for the deposition of films with functional properties suitable for a wide range of modern applications on account of its advantageous features. In this study, carbon dioxide (CO₂) was chosen as carrier gas at flow rates of 30 and 60 sccm, respectively and styrene vapor was used as the monomer to prepare polystyrene films on glass substrates. The structure and composition of the plasma polymerized films were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR) and compared with the film prepared by conventional thermal polymerization. The morphology information of the films was provided by optical microscopy. XPS and FT-IR results reveal that chemical composition of the plasma polymerized films is different from that of the thermal polymerized film and that oxygen content in the plasma polymerized films increases with the flow rate of CO₂. Furthermore, the presence of oxygen-containing groups on the surface of plasma polymerized polystyrene films is confirmed. It is also found that the composition and morphology of the plasma polymerized films are controlled by the flow rate of CO₂.