Effect of Low-Temperature Oxygen Plasma Treatment of Titanium Alloy Surface on Tannic Acid Coating Deposition.

In this study, the effect of low-temperature oxygen plasma treatment with various powers of a titanium alloy surface on the structural and morphological properties of a substrate and the deposition of a tannic acid coating was investigated. The surface characteristics of the titanium alloy were evaluated by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact angle measurements. Following this, the tannic acid coatings were deposited on the titanium alloy substrates and the structural and morphological properties of the tannic acid coatings deposited were subject to characterization by XPS, SEM, and spectroscopic ellipsometry (SE) measurements. The results show that the low-temperature oxygen plasma treatment of titanium alloys leads to the formation of titanium dioxides that contain -OH groups on the surface being accompanied by a reduction in carbon, which imparts hydrophilicity to the titanium substrate, and the effect increases with the applied plasma power. The performed titanium alloy substrate modification translates into the quality of the deposited tannic acid coating standing out by higher uniformity of the coating, lower number of defects indicating delamination or incomplete bonding of the coating with the substrate, lower number of cracks, thinner cracks, and higher thickness of the tannic acid coatings compared to the non-treated titanium alloy substrate. A similar effect is observed as the applied plasma power increases.

Optical Properties of Amorphous Carbon Thin Films Fabricated Using a High-Energy-Impulse Magnetron-Sputtering Technique.

This paper reports the results of amorphous carbon thin films fabricated by using the gas-impulse-injection magnetron-sputtering method and differing the accelerating voltage (1.0-1.4 kV). The obtained layers were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XRD), and spectroscopic ellipsometry (SE). The analysis of the Raman and XPS spectra point to the significant content of sp3 hybridization in the synthesized materials (above 54-73%). The refractive index of the films is very high-above 2.45 in the infrared spectral range. The band-gap energy (determined using the inversed-logarithmic-derivative method) depends on the discharging voltage and is in the range from 1.58 eV (785 nm) to 2.45 eV (506 nm). Based on the obtained results, we have elaborated a model explaining the a-C layers' formation process.

Study on New Dental Materials Containing Quinoxaline-Based Photoinitiators in Terms of Exothermicity of the Photopolymerization Process.

Modern dentistry places great demands on the dental composites used for filling tooth cavities or treating cavitated tooth decay. The aim of the work was to modify the properties of composites by changing the initiators and co-initiators. This was achieved by using initiators based on a quinoxaline skeleton and co-initiators that are derivatives of acetic acid, which is an advantage of these photoinitiating systems due to the elimination of aromatic amines from the photocurable composition. The composites also differed in dental fillers. The effect of the compounds on the exothermicity of the photopolymerization process, the surface morphology of the obtained materials and the maximum compressive strength were determined. The photoinitiating capacity of the two-component systems was tested by the microcalorimetric method using the multifunctional monomer TMPTA, typical for dental filler compositions. The new photoinitiating systems show particularly good efficiency of free radical polymerization initiation, which occurs by the photoinduced intermolecular electron transfer (PET) mechanism. The comparison of the tested systems with camphorquinone, a photoinitiator traditionally used in dentistry, made it possible to observe a decrease in temperature during photopolymerization without a significant decrease in the polymerization rate or increase in photocuring time, as well as a better homogeneity of the surface of the obtained polymeric materials. This indicates that dye-acetic acid derivative systems may be useful in dental applications.

Experimental and Theoretical Studies of the Optical Properties of the Schiff Bases and Their Materials Obtained from o-Phenylenediamine.

Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde L1 or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde L2, respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of L1 and L2 were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The 3D Hirschfeld analyses show that the most numerous interactions were found between hydrogen atoms. A considerable number of such interactions are justified by the presence of bulk tert-butyl groups in L2. The luminescence of L1 and L2 in various solvents and in the solid state was studied. In general, the quantum efficiency between 0.14 and 0.70 was noted. The increase in the quantum efficiency with the solvent polarity in the case of L1 was observed (λex = 350 nm). For L2, this trend is similar, except for the chloroform. In the solid state, emission was registered at 552 nm and 561 nm (λex = 350 nm) for L1 and L2, respectively. Thin layers of the studied compounds were deposited on Si(111) by the spin coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), spectroscopic ellipsometry and fluorescence spectroscopy. The ellipsometric analysis of thin materials obtained by thermal vapor deposition showed that the band-gap energy was 3.45 ± 0.02 eV (359 ± 2 nm) and 3.29 ± 0.02 eV (377 ± 2 nm) for L1/Si and L2/Si samples, respectively. Furthermore, the materials of the L1/Si and L2/Si exhibited broad emission. This feature can allow for using these compounds in LED diodes.

Influence of Heat Treatment on Surface, Structural and Optical Properties of Nickel and Copper Phthalocyanines Thin Films.

The work presents the effect of annealing on the change of polycrystalline α and ß phases of copper and nickel phthalocyanines. We have found that this process has a great influence on the optical properties of the vapor-deposited layers. The performed measurements showed that for various forms of MPc, the values of the refractive index and the extinction coefficient increased, and consequently, so did the absorption coefficient. The AFM images taken showed that the values before and after heating are morphologically different. Raman measurements showed that the band at about 1526 cm-1 (B1g symmetry) has higher intensity for the α form than for the ß form. The intensity of this band is related to changing the form of phthalocyanine from α to ß. Our measurements have shown that by changing the annealing temperature of the layers, we change their optical properties. As a consequence, we change their optoelectronic parameters, adjusting them to the requirements of new optoelectronic devices, such as solar cells, sensors, displays and OLEDs.

Influence of the Microstructure and Optical Constants on Plasmonic Properties of Copper Nanolayers.

Copper layers with thicknesses of 12, 25, and 35 nm were thermally evaporated on silicon substrates (Si(100)) with two different deposition rates 0.5 and 5.0 Å/s. The microstructure of produced coatings was studied using atomic force microscopy (AFM) and powder X-ray diffractometer (XRD). Ellipsometric measurements were used to determine the effective dielectric functions <ε˜> as well as the quality indicators of the localized surface plasmon (LSP) and the surface plasmon polariton (SPP). The composition and purity of the produced films were analysed using X-ray photoelectron spectroscopy (XPS).

The Influence of Annealing on the Optical Properties and Microstructure Recrystallization of the TiO2 Layers Produced by Means of the E-BEAM Technique.

Titanium dioxide films, about 200 nm in thickness, were deposited using the e-BEAM technique at room temperature and at 227 °C (500K) and then annealed in UHV conditions (as well as in the presence of oxygen (at 850 °C). The fabricated dielectric films were examined using X-ray powder diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, transmission electron microscopy, and spectroscopic ellipsometry. The applied experimental techniques allowed us to characterize the phase composition and the phase transformation of the fabricated TiO2 coatings. The films produced at room temperature are amorphous but after annealing consist of anatase crystallites. The layers fabricated at 227 °C contain both anatase and rutile phases. In this case the anatase crystallites are accumulated near the substrate interface whilst the rutile crystallites were formed closer to the surface of the TiO2 film. It should be emphasized that these two phases of TiO2 are distinctly separated from each other.

Distance Effects of Phenylpiperazine-Containing Methacrylic Polymers on Optical and Structural Properties.

New materials based on methacrylic polymers modified with 1-(4-nitrophenyl)piperazine side chains, differing in the distance of the chromophore from the polymer main chain and/or the separation between the chromophoric units in the chain, are obtained and characterized in terms of their potential applications in optoelectronic devices. The surface, structural, and optical properties of the investigated materials are determined using atomic force microscopy, spectroscopic ellipsometry combined with transmission measurements, Raman and Fourier transform infrared spectroscopy, as well as cyclic voltammetry. The relevant model systems are additionally analyzed with quantum chemical density functional theory calculations in order to enable the generalization of the structure-photophysical property relationships for the optimization of the material features. It is found that the structural modification of the material, relying on the transit of the piperazine moiety away from the main polymer chain, leads to the hypsochromic shift of the absorption spectrum. Moreover, the lowest refractive index values are obtained for the polymer with a distant ethylene group in the side-chains and increased separation between the piperazine units. It was shown that the optical energy band gaps of the investigated piperazine-containing polymers are in the range from 2.73 to 2.81 eV, which reveals their promising potential for the advances in photovoltaics, field effect transistors, or electrochromic devices as an alternative for other widely applied polymer materials.

Properties of poly (vinyl chloride) membranes containing cadmium pigments, irradiated with UV radiation.

The cadmium pigments were yellow, orange and red pigments. They consisted of cadmium sulphide and cadmium sulphide with zinc sulphide as well as cadmium sulphide with cadmium selenide. Their quantitative composition and specific surface area were examined. The pigments were used to color the poly (vinyl chloride) plastisol films, which were then exposed to UV radiation. The surfaces of the coloured membranes were examined by infrared spectroscopy before and after irradiation with UV. The changes occurred in the PVC membrane were investigated by thermogravimetric analysis. The degree of crystallinity of the pigments and the membrane was determined by X-ray diffraction. The color change of the membranes was determined from the spectra obtained by reflection spectroscopy, and the components of colour L*, a* and b* were calculated. Base of them, the tolerance of colour deviations (ΔE*) was determined. The calculations allowed for the determination of the effect of UV irradiation on the change of the colour of the membranes and confirmation of the degradation of the pigments and polymer membrane.

Microstructure and Optical Properties of Nanostructural Thin Films Fabricated through Oxidation of Au-Sn Intermetallic Compounds.

AuSn and AuSn2 thin films (5 nm) were used as precursors during the formation of semiconducting metal oxide nanostructures on a silicon substrate. The nanoparticles were produced in the processes of annealing and oxidation of gold-tin intermetallic compounds under ultra-high vacuum conditions. The formation process and morphology of a mixture of SnO2 and Au@SnOx (the core-shell structure) nanoparticles or Au nanocrystalites were carefully examined by means of spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy (EDX). The annealing and oxidation of the thin film of the AuSn intermetallic compound led to the formation of uniformly distributed structures with a size of ∼20-30 nm. All of the synthesized nanoparticles exhibited a strong absorption band at 520-530 nm, which is typical for pure metallic or metal oxide systems.

Synthesis of Copper Nitride Layers by the Pulsed Magnetron Sputtering Method Carried out under Various Operating Conditions.

Copper nitride shows various properties that depend on the structure of the material and is influenced by the change in technical parameters. In the present work, Cu-N layers were synthesized using the pulsed magnetron sputtering method. The synthesis was performed under different operating conditions: direct current (DC) or alternating current (AC) power supply, and various atmospheres: pure Ar and a mixture of Ar + N2. The structural properties of the deposited layers were characterized by X-ray diffraction measurements, and Raman spectroscopy and scanning electron microscopy have been performed. Optical properties were also evaluated. The obtained layers showed tightly packed columnar grain features. The kinetics of the layer growth in the AC mode was lower than that observed in the DC mode, and the layers were thinner and more fine-grained. The copper nitride layers were characterized by the one-phase and two-phase polycrystalline structure of the Cu3N phase with the preferred growth orientation (100). The lattice constant oscillates between 3.808 and 3.815 Å for one-phase and has a value of 3.828 Å for a two-phase structure. Phase composition results were correlated with Raman spectroscopy measurements. Raman spectra exhibited a broad, diffused, and intense signal of Cu3N phase, with Raman shift located at 628-635 cm-1. Studies on optical properties showed that the energy gap ranged from 2.17 to 2.47 eV. The results showed that controlling technical parameters gives a possibility to optimize the structure and phase composition of deposited layers. The reported changes were discussed and attributed to the properties of the material layers and technology method.

Copper Nitride Nanowire Arrays-Comparison of Synthetic Approaches.

Copper nitride nanowire arrays were synthesized by an ammonolysis reaction of copper oxide precursors grown on copper surfaces in an ammonia solution. The starting Cu films were deposited on a silicon substrate using two different methods: thermal evaporation (30 nm thickness) and electroplating (2 µm thickness). The grown CuO or CuO/Cu(OH)2 architectures were studied in regard to morphology and size, using electron microscopy methods (SEM, TEM). The final shape and composition of the structures were mostly affected by the concentration of the ammonia solution and time of the immersion. Needle-shaped 2-3 µm long nanostructures were formed from the electrodeposited copper films placed in a 0.033 M NH3 solution for 48 h, whereas for the copper films obtained by physical vapor deposition (PVD), well-aligned nano-needles were obtained after 3 h. The phase composition of the films was studied by X-ray diffraction (XRD) and selected area electron diffraction (SAED) analysis, indicating a presence of CuO and Cu(OH)2, as well as Cu residues. Therefore, in order to obtain a pure oxide film, the samples were thermally treated at 120-180 °C, after which the morphology of the structures remained unchanged. In the final stage of this study, Cu3N nanostructures were obtained by an ammonolysis reaction at 310 °C and studied by SEM, TEM, XRD, and spectroscopic methods. The fabricated PVD-derived coatings were also analyzed using a spectroscopic ellipsometry method, in order to calculate dielectric function, band gap and film thickness.

Microstructure and Optical Properties of E-Beam Evaporated Zinc Oxide Films-Effects of Decomposition and Surface Desorption.

Zinc oxide films have been fabricated by the electron beam physical vapour deposition (PVD) technique. The effect of substrate temperature during fabrication and annealing temperature (carried out in ultra high vacuum conditions) has been investigated by means of atomic force microscopy, scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy and spectroscopic ellipsometry. It was found that the layer deposited at room temperature is composed of Zn and ZnO crystallites with a number of orientations, whereas those grown at 100 and 200 ∘C consist of ZnO grains and exhibit privileged growth direction. Presented results clearly show the influence of ZnO decomposition and segregation of Zn atoms during evaporation and post-deposition annealing on microstructure and optical properties of zinc oxide films.

Physico-Chemical and Light-Induced Properties of Quinoline Azo-dyes Polymers.

We present investigation of optical and photochromic properties as well as of surface quality of thin films of novel methacrylic polymers with 8-hydroxyquinoline azo-dyes in side-chain. Additionally, thermal stability of polymer powders was examined and their glass transition temperature was determined. Optical properties (extinction coefficient and refractive index) were determined by spectroscopic ellipsometry (SE) combined with absorbance measurements. Photoresponsive behavior was investigated by determination of photoisomerization rates under irradiation with unpolarized 365 nm light, as well as by conduction of holographic grating inscription experiment. Thin film quality was determined by atomic force microscopy (AFM) measurements. Thermal analysis was performed by thermogravimetric (TG), derivative thermogravimetric (DTG) and differential scanning calorimetry (DSC) measurements. We found that optical properties as well as photoisomerization rates of investigated polymers are dependent on the substituent in the para position of the phenyl ring. Surface relief grating inscription was successfully generated only for materials with chromophores containing dimethylamino (N(CH3)2) and methyl (CH3) substituents, but all materials exhibited birefringence grating in the bulk. Surface of most thin films was very smooth, but its quality was impaired by neutral (H) as well as carboxyl (COOH) substituent. Thermal stability of copolymers with side-chain chromophores was improved compared to pure poly(methyl methacrylate) (PMMA).

Synthesis, Optical, and Morphological Studies of ZnO Powders and Thin Films Fabricated by Wet Chemical Methods.

Zinc oxide nanoparticles were prepared from Zn5(CO3)2(OH)6 precursor, capped with poly(vinylpyrrolidone) (PVP), and annealed at 600 °C. The obtained powders were characterized by a powder X-ray diffraction (PXD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-visible spectroscopy (UV-vis), Raman spectroscopy, infrared spectroscopy (IR), thermal analysis (TGA/DTA), and third-order nonlinear (NL) optical measurement. Morphological evaluation by TEM and SEM measurements indicated that the precursor micro-particles are ball-shaped structures composed of plates with a thickness of approximately 10 nm. ZnO thin films, as well as ZnO/polymer multilayer layouts, were obtained by wet chemical methods (spin- and dip-coating). Surface topography and morphology of the obtained films were studied by SEM and AFM microscopy. Films with uniformly distributed ZnO plates, due to the erosion of primary micro-particles were formed. The fabricated specimens were also analyzed using a spectroscopic ellipsometry in order to calculate dielectric function and film thickness.

Structural and Micromechanical Properties of Nd:YAG Laser Marking Stainless Steel (AISI 304 and AISI 316).

The purpose of this study is to examine the microstructure and micromechanical properties of pulsed-laser irradiated stainless steel. The laser marking was conducted for AISI 304 and AISI 316 stainless steel samples through a Nd:YAG (1064 nm) laser. The influence of process parameters such as the pulse repetition rate and scanning speed have been considered. The microstructures of obtained samples were analyzed using confocal optical microscopy (COM). The continuous stiffness measurements (CSM) technique was applied for nanoindentional hardness and elastic modulus determination. The phase compositions of obtained specimens were characterized by X-ray diffraction (XRD) and confirmed by Raman spectroscopy. The results revealed that surface roughness is directly related to overlapping distance and the energy provided by a single pulse. The hardness of irradiated samples changes significantly with the indentation depth. The instrumental hardness HIT and elastic modulus EIT drop sharply with the rise of the indentation depth. Thus, the hardness enhancement can be observed as the indentation depth varies between 100-1000 nm for all exanimated samples. The maximum values of HIT and EIT were evaluated for the region of small depths (100-200 nm). The XRD results reveal the presence of iron and chromium oxides due to irradiation, which indicates a surface hardening effect.

Optical Properties of Titanium in the Regime of the Limited Light Penetration.

In this study, the titanium layers from 12 to 1470 nm thick were fabricated by using the method involving dynamically changed working gas pressure (gas injection magnetron sputtering). The influence of the deposition time on the optical and electrical properties of Ti films, as well as on their microstructure, are considered. The samples are investigated by means of spectroscopic ellipsometry, atomic force microscopy, X-ray diffraction, and confocal optical microscopy. Additionally, for the Ti layers, the sheet resistance was determined. The produced coatings exhibit privileged direction of growth (002). The obtained results show a gradual increase in the mean relaxation time of free-carriers with the increase in the thickness of titanium film. However, the plasma energy exhibits maximum for the coating with the thickness of 93 nm. For such thickness, the lowest value of optical resistivity (about 200 µ Ω cm) was observed. It was found that the dc- and optical resistivity exhibit similar values for titanium films with thickness up to 93 nm. For thicker Ti layers, significant differences in resistivities (dc- and optical) were noticed. The behavior of the Drude parameter (the plasma energy), calculated optical resistivity, and discrepancies between values of optical and dc-resistivities for thicker Ti coatings can be explained as a result of the limited light penetration.

Interaction of Te and Se interlayers with Ag or Au nanofilms in sandwich structures.

Noble metal nanolayers on flat substrates are often deposited with the use of semiconductor interlayers, which may strongly interact with the noble metal overlayer. We investigated the crystallinity, atomic concentration profile and optical parameters of ≈35 nm-thick silver and gold layers deposited on glass substrates with 2 nm-thick tellurium or selenium interlayers. Our study, based on X-ray reflectometry (XRR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and ellipsometric measurements, showed that using either of these interlayers introduces strain in nanocrystals of both plasmonic films. This, in turn, influences the migration of Se and Te into the metal layers. Selenium atoms migrate both in the silver and gold nanolayers, while tellurium atoms migrate only in silver. The Te concentration curve clearly suggests that this migration is an effect of the segregation of Te atoms in the silver structure. The differences in crystallinity, as well as the migration process, strongly influence the optical parameters of Ag and Au. In the permittivity of Ag deposited on either Te or Se, additional plasmonic bands originating from grain boundary segregation or diffusion occur, while for the Au layer, such resonances were not pronounced. In the permittivity of both materials, the intensity of the interband transition peaks is strongly altered, possibly due to the nano-alloy formation, but more likely due to the microstrain on metal grains.

Growth model and structure evolution of Ag layers deposited on Ge films.

We investigated the crystallinity and optical parameters of silver layers of 10-35 nm thickness as a function 2-10 nm thick Ge wetting films deposited on SiO2 substrates. X-ray reflectometry (XRR) and X-ray diffraction (XRD) measurements proved that segregation of germanium into the surface of the silver film is a result of the gradient growth of silver crystals. The free energy of Ge atoms is reduced by their migration from boundaries of larger grains at the Ag/SiO2 interface to boundaries of smaller grains near the Ag surface. Annealing at different temperatures and various durations allowed for a controlled distribution of crystal dimensions, thus influencing the segregation rate. Furthermore, using ellipsometric and optical transmission measurements we determined the time-dependent evolution of the film structure. If stored under ambient conditions for the first week after deposition, the changes in the transmission spectra are smaller than the measurement accuracy. Over the course of the following three weeks, the segregation-induced effects result in considerably modified transmission spectra. Two months after deposition, the slope of the silver layer density profile derived from the XRR spectra was found to be inverted due to the completed segregation process, and the optical transmission spectra increased uniformly due to the roughened surfaces, corrosion of silver and ongoing recrystallization. The Raman spectra of the Ge wetted Ag films were measured immediately after deposition and ten days later and demonstrated that the Ge atoms at the Ag grain boundaries form clusters of a few atoms where the Ge-Ge bonds are still present.