Comparison of Plasma-Polymerized Thin Films Deposited from 2-Methyl-2-oxazoline and 2-Ethyl-2-oxazoline: I Film Properties.

Poly(2-oxazoline) is a promising new class of polymeric materials due to their antibiofouling properties and good biocompatibility. Poly(2-oxazoline) coatings can be deposited on different substrates via plasma polymerization, which can be more advantageous than other coating methods. The aim of this study is to deposit poly(2-oxazoline) coatings using a surface dielectric barrier discharge burning in nitrogen at atmospheric pressure using 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline vapours as monomers and compare the film properties. For the comparison, the antibacterial and cytocompatibility tests were peformed according to ISO norms. The antibacterial tests showed that all the deposited films were highly active against Staphylococcus aureus and Escherichia coli bacteria. The chemical composition of the films was studied using FTIR and XPS, and the film surface's properties were studied using AFM and surface energy measurement. The cytocompatibility tests showed good cytocompatibility of all the deposited films. However, the films deposited from 2-methyl-2-oxazoline exhibit better cytocompatibility. This difference can be explained by the different chemical compositions and surface morphologies of the films deposited from different monomers.

Optical characterization of inhomogeneous thin films with randomly rough boundaries.

An inhomogeneous polymer-like thin film was deposited by the plasma enhanced chemical vapor deposition onto silicon single-crystal substrate whose surface was roughened by anodic oxidation. The inhomogeneous thin film with randomly rough boundaries was created as a result. This sample was studied using the variable-angle spectroscopic ellipsometry and spectroscopic reflectometry. The structural model including the inhomogeneous thin film, transition layer, and identically rough boundaries was used to process the experimental data. The scalar diffraction theory was used to describe the influence of roughness. The influence of the scattered light registered by the spectrophotometer due to its finite acceptance angle was also taken into account. The thicknesses and optical constants of the inhomogeneous thin film and the transition layer were determined in the optical characterization together with the roughness parameters. The determined rms value of the heights of roughness was found to be in good agreement with values obtained using AFM. The results of the optical characterization of the studied inhomogeneous thin film with rough boundaries were also verified by comparing them with the results of the optical characterization of the inhomogeneous thin film prepared using the same deposition conditions but onto the substrate with a smooth surface.

Optical characterization of inhomogeneous thin films with randomly rough boundaries exhibiting wide intervals of spatial frequencies.

Results concerning the optical characterization of two inhomogeneous polymer-like thin films deposited by the plasma enhanced chemical vapor deposition onto silicon single crystal substrates are presented. One of these films is deposited onto a smooth silicon surface while the latter film is deposited on a randomly rough silicon surface with a wide interval of spatial frequencies. A combination of variable-angle spectroscopic ellipsometry and spectroscopic reflectometry applied at near-normal incidence are utilized for characterizing both the films. An inhomogeneity of the films is described by the method based on multiple-beam interference of light and method replacing inhomogeneous thin films by multilayer systems. Homogeneous transition layers between the films and substrates are considered. The Campi-Coriasso dispersion model is used to express spectral dependencies of the optical constants of the polymer-like films and transition layers. A combination of the scalar diffraction theory and Rayleigh-Rice theory is used to include boundary roughness into formulae for the optical quantities of the rough polymer-like film. Within the optical characterization, the spectral dependencies of the optical constants at the upper and lower boundaries of both the polymer-like films are determined together with their thickness values and profiles of the optical constants. Roughness parameters are determined for the rough film. The values of the roughness parameters are confirmed by atomic force microscopy. Moreover, the optical constants and thicknesses of both the transition layers are determined. A discussion of the achieved results for both the polymer-like films and transition layers is performed.

Ellipsometric characterization of inhomogeneous thin films with complicated thickness non-uniformity: application to inhomogeneous polymer-like thin films.

The method of variable angle spectroscopic ellipsometry usable for the complete optical characterization of inhomogeneous thin films exhibiting complicated thickness non-uniformity together with transition layers at their lower boundaries is presented in this paper. The inhomogeneity of these films is described by means of the multiple-beam interference model. The thickness non-uniformity is taken into account by averaging the elements of the Mueller matrix along the area of the light spot of the ellipsometer on the films. The local thicknesses are expressed using polynomials in the coordinates along the surfaces of the films. The efficiency of the method is illustrated by means of the optical characterization of a selected sample of the polymer-like thin film of SiOxCyHz prepared by plasma enhanced chemical vapor deposition onto the silicon single crystal substrate. The Campi-Coriasso dispersion model is used to determine the spectral dependencies of the optical constants at the upper and lower boundaries of this film. The profiles of these optical constants are determined too. The thickness non-uniformity is described using a model with local thicknesses given by the polynomial with at most quadratic terms. In this way it is possible to determine the geometry of the upper boundary. The thickness and spectral dependencies of the optical constants of the transition layer are determined as well. Imaging spectroscopic reflectometry is utilized for confirming the results concerning the thickness non-uniformity obtained using ellipsometry.

Ellipsometric characterization of highly non-uniform thin films with the shape of thickness non-uniformity modeled by polynomials.

A common approach to non-uniformity is to assume that the local thicknesses inside the light spot are distributed according to a certain distribution, such as the uniform distribution or the Wigner semicircle distribution. A model considered in this work uses a different approach in which the local thicknesses are given by a polynomial in the coordinates x and y along the surface of the film. An approach using the Gaussian quadrature is very efficient for including the influence of the non-uniformity on the measured ellipsometric quantities. However, the nodes and weights for the Gaussian quadrature must be calculated numerically if the non-uniformity is parameterized by the second or higher degree polynomial. A method for calculating these nodes and weights which is both efficient and numerically stable is presented. The presented method with a model using a second-degree polynomial is demonstrated on the sample of highly non-uniform polymer-like thin film characterized using variable-angle spectroscopic ellipsometry. The results are compared with those obtained using a model assuming the Wigner semicircle distribution.

Spectroscopic ellipsometry of inhomogeneous thin films exhibiting thickness non-uniformity and transition layers.

In this paper the complete optical characterization of an inhomogeneous polymer-like thin film of SiOxCyHz exhibiting a thickness non-uniformity and transition layer at the boundary between the silicon substrate and this film is performed using variable angle spectroscopic ellipsometry. The Campi-Coriasso dispersion model was utilized for describing the spectral dependencies of the optical constants of the SiOxCyHz thin film and transition layer. The multiple-beam interference model was used for expressing inhomogeneity of the SiOxCyHz thin film. The thickness non-uniformity of this film was taken into account by means of the averaging of the elements of the Mueller matrix performed using the thickness distribution for the wedge-shaped non-uniformity. The spectral dependencies of the optical constants of the SiOxCyHz thin film at the upper and lower boundaries together with the spectral dependencies of the optical constants of the transition layer were determined. Furthermore, the thickness values of the SiOxCyHz film and transition layer, profiles of the optical constants of the SiOxCyHz thin film and the rms value of local thicknesses corresponding to its thickness non-uniformity were determined. Thus, all the parameters characterizing this complicated film were determined without any auxiliary methods.

Laser ablation synthesis of new gold carbides. From gold-diamond nano-composite as a precursor to gold-doped diamonds. Time-of-flight mass spectrometric study.

RATIONALE: Gold carbides can be produced via laser ablation synthesis (LAS) from mixtures of nano-gold (NG) and various carbonaceous materials. The nano-composite of nano-gold (NG) and nano-diamond (ND) might represent a promising precursor for the generation of new gold carbides. METHODS: Time-of-flight mass spectrometry (TOF MS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX) were used. The stoichiometry of clusters was determined via modelling of the isotopic patterns and MS(n) analysis. RESULTS: A simple procedure for the preparation of ND-NG nano-composite was developed using NG and ND. The formation of AuCn(+) (n = 1-11, 18), Au2Cn(+) (n = 1-16) and Au3Cn(+) (n = 1-10) clusters during LAS of the nano-composite was proved. Structures of gold carbides are proposed and discussed. Diamonds-containing AumCn(+) (m = 1-3, n = 10, 14, 18, 22) clusters might be not carbides but endohedral supramolecular complexes Aum@Cn(+) i.e., 'gold-doped' diamonds. CONCLUSIONS: TOF MS was shown to be a useful technique for following the formation of gold carbides in the gas phase. Clusters and 'gold-doped' diamonds generated might inspire synthesis of new Au-C materials with hardly predictable, unusual properties.

Optical characterization of inhomogeneity of polymer-like thin films arising in the initial phase of plasma-enhanced chemical vapor deposition.

In this study, an optical investigation in a wide spectral range of polymer-like (SiOxCyHz) thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) is presented. The primary focus is on assessing the homogeneity of the grown films. Within the PECVD, it is possible to alter the properties of the deposited material by continually adjusting deposition process parameters and hence allow for the growth of inhomogeneous layers. However, as shown in this study, the growth of homogeneous layers could be similarly challenging. This challenge is especially pronounced at the beginning of the deposition process, where it is necessary to consider the influence of the substrate among other factors, as even slight variations in the deposition conditions can lead to the formation of inhomogeneous layers. Several series of polymer-like thin films were deposited onto silicon substrates with the goal of producing homogeneous layers, i.e. all deposition parameters were held constant. These samples were optically characterized with a special interest in homogeneity, especially at the beginning of the growth. It was found that initial inhomogeneous growth is always present. The thickness of the initial inhomogeneous part was found to be surprisingly large.

A Long-Term Study on the Bactericidal Effect of ZrN-Cu Nanostructured Coatings Deposited by an Industrial Physical Vapor Deposition System.

ZrN-Cu coatings containing two different amounts of Cu (~11 at.% and ~25 at.%) were deposited using an industrial physical vapor deposition (PVD) system. The as-deposited coatings exhibited 100% bactericidal efficiency against Escherichia coli CCM 3988 for an exposure time of 40 min. Subsequently, the samples were attached onto our faculty's door handles for six months to study the coatings' long-term effectiveness and durability under actual operational conditions. The samples were periodically evaluated and it was observed that the coatings with 25 at.% Cu performed better than the ones with 11 at.% Cu. For example, following 15 days of being touched, the bactericidal effectiveness of the sample containing 25 at.% Cu dropped to 65% while it fell to 42% for the sample containing 11 at.%. After 6 months, however, both samples showed bactericidal efficiency of ~16-20%. The bactericidal efficiency of the samples touched for 6 months was successfully restored by polishing them. Furthermore, a group of samples was kept untouched and was also evaluated. The untouched samples with Cu content of ~25 at.% did not show any drop in their bactericidal properties after 6 months. ZrN-Cu coatings were concluded to be promising materials for self-sanitizing application on high-touch surfaces.

The Effect of a Taper Angle on Micro-Compression Testing of Mo-B-C Coatings.

This research was devoted to studying the influence of the taper angle on the micro-compression of micro-pillars fabricated from near-amorphous and nanocrystalline Mo-B-C coatings. A series of micro-pillars with a taper angle between 4-14° was fabricated by focused ion beam technique. The deformation mechanism was found to be dependent on the taper and, also, on the crystallinity of the coating. In order to obtain correct values of yield strength and Young's modulus, three empirical models of stress correction were experimentally tested, and the results were compared with nanoindentation measurements. It was shown that the average stress correction model provided comparable results with nanoindentation for the yield strength for taper angles up to ~10°. On the other hand, the average radius or area model gave the most precise results for Young's modulus if the taper angle was <10°.

Characterization of Platinum-Based Thin Films Deposited by Thermionic Vacuum Arc (TVA) Method.

The current work aimed to characterize the morphology, chemical, and mechanical properties of Pt and PtTi thin films deposited via thermionic vacuum arc (TVA) method on glass and silicon substrates. The deposited thin films were characterized by means of a scanning electron microscope technique (SEM). The quantitative elemental microanalysis was done using energy-dispersive X-ray spectroscopy (EDS). The tribological properties were studied by a ball-on-disc tribometer, and the mechanical properties were measured using nanoindentation tests. The roughness, as well as the micro and nanoscale features, were characterized using atomic force microscopy (AFM) and transmission electron microscopy (TEM). The wettability of the deposited Pt and PtTi thin films was investigated by the surface free energy evaluation (SFE) method. The purpose of our study was to prove the potential applications of Pt-based thin films in fields, such as nanoelectronics, fuel cells, medicine, and materials science.

Atmospheric Pressure Plasma Polymerized 2-Ethyl-2-oxazoline Based Thin Films for Biomedical Purposes.

Polyoxazoline thin coatings were deposited on glass substrates using atmospheric pressure plasma polymerization from 2-ethyl-2-oxazoline vapours. The plasma polymerization was performed in dielectric barrier discharge burning in nitrogen at atmospheric pressure. The thin films stable in aqueous environments were obtained at the deposition with increased substrate temperature, which was changed from 20 ∘C to 150 ∘C. The thin film deposited samples were highly active against both S. aureus and E. coli strains in general. The chemical composition of polyoxazoline films was studied by FTIR and XPS, the mechanical properties of films were studied by depth sensing indentation technique and by scratch tests. The film surface properties were studied by AFM and by surface energy measurement. After tuning the deposition parameters (i.e., monomer flow rate and substrate temperature), stable films, which resist bacterial biofilm formation and have cell-repellent properties, were achieved. Such antibiofouling polyoxazoline thin films can have many potential biomedical applications.

Fast mechanical model for probe-sample elastic deformation estimation in scanning probe microscopy.

We present a numerical approach for estimation of the probe-sample elastic deformation for higher contact forces and/or smaller probe apex radii in Scanning Probe Microscopy (SPM) measurements. It is based on a mass-spring model implemented on a graphics card in order to perform very high numbers of individual force-distance curves calculations in reasonable time, forming virtual profiles or virtual SPM images. The model is suitable for predicting the mechanical response of the probe and sample in SPM mechanical properties mapping regimes and for estimating the uncertainty sources related to probe-sample elastic deformation in dimensional nanometrology. As the model is based on using regular orthogonal mesh formed from the scanned surface topography, it can be also used as preprocessor for various pixel by pixel physical quantities calculations using Finite Difference Method, namely for the energy transfer between probe and sample, where a realistic probe-sample contact formation needs to be taken into account. Model performance is demonstrated via comparison to analytical solutions for simple contact mechanics tasks and its possibilities for SPM data interpretation are illustrated on measurements on simple reference structures, such as step edges or quantum dots.

Fast Surface Hydrophilization via Atmospheric Pressure Plasma Polymerization for Biological and Technical Applications.

Polymeric surfaces can benefit from functional modifications prior to using them for biological and/or technical applications. Surfaces considered for biocompatibility studies can be modified to gain beneficiary hydrophilic properties. For such modifications, the preparation of highly hydrophilic surfaces by means of plasma polymerization can be a good alternative to classical wet chemistry or plasma activation in simple atomic or molecular gasses. Atmospheric pressure plasma polymerization makes possible rapid, simple, and time-stable hydrophilic surface preparation, regardless of the type and properties of the material whose surface is to be modified. In this work, the surface of polypropylene was coated with a thin nanolayer of plasma-polymer which was prepared from a low-concentration mixture of propane-butane in nitrogen using atmospheric pressure plasma. A deposition time of only 1 second was necessary to achieve satisfactory hydrophilic properties. Highly hydrophilic, stable surfaces were obtained when the deposition time was 10 seconds. The thin layers of the prepared plasma-polymer exhibit highly stable wetting properties, they are smooth, homogeneous, flexible, and have good adhesion to the surface of polypropylene substrates. Moreover, they are constituted from essential elements only (C, H, N, O). This makes the presented modified plasma-polymer surfaces interesting for further studies in biological and/or technical applications.

Atmospheric Pressure Plasma Polymerized Oxazoline-Based Thin Films-Antibacterial Properties and Cytocompatibility Performance.

Polyoxazolines are a new promising class of polymers for biomedical applications. Antibiofouling polyoxazoline coatings can suppress bacterial colonization of medical devices, which can cause infections to patients. However, the creation of oxazoline-based films using conventional methods is difficult. This study presents a new way to produce plasma polymerized oxazoline-based films with antibiofouling properties and good biocompatibility. The films were created via plasma deposition from 2-methyl-2-oxazoline vapors in nitrogen atmospheric pressure dielectric barrier discharge. Diverse film properties were achieved by increasing the substrate temperature at the deposition. The physical and chemical properties of plasma polymerized polyoxazoline films were studied by SEM, EDX, FTIR, AFM, depth-sensing indentation technique, and surface energy measurement. After tuning of the deposition parameters, films with a capacity to resist bacterial biofilm formation were achieved. Deposited films also promote cell viability.

Cell proliferation on modified DLC thin films prepared by plasma enhanced chemical vapor deposition.

Recently, diamondlike carbon (DLC) thin films have gained interest for biological applications, such as hip and dental prostheses or heart valves and coronary stents, thanks to their high strength and stability. However, the biocompatibility of the DLC is still questionable due to its low wettability and possible mechanical failure (delamination). In this work, DLC:N:O and DLC: SiOx thin films were comparatively investigated with respect to cell proliferation. Thin DLC films with an addition of N, O, and Si were prepared by plasma enhanced CVD from mixtures of methane, hydrogen, and hexamethyldisiloxane. The films were optically characterized by infrared spectroscopy and ellipsometry in UV-visible spectrum. The thickness and the optical properties were obtained from the ellipsometric measurements. Atomic composition of the films was determined by Rutherford backscattering spectroscopy combined with elastic recoil detection analysis and by x-ray photoelectron spectroscopy. The mechanical properties of the films were studied by depth sensing indentation technique. The number of cells that proliferate on the surface of the prepared DLC films and on control culture dishes were compared and correlated with the properties of as-deposited and aged films. The authors found that the level of cell proliferation on the coated dishes was high, comparable to the untreated (control) samples. The prepared DLC films were stable and no decrease of the biocompatibility was observed for the samples aged at ambient conditions.