Nitridation of niobium films by rapid thermal processing: different behaviour of films on oxydized silicon and monocrystalline sapphire substrates

By electron beam evaporation and RF magnetron sputtering 500 nm thick niobium films were deposited on thermally oxidized Si-(100)-wafers and by RF magnetron sputtering on monocrystalline sapphire-(1-102)-wafers. Investigations by scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed differences of the film morphology depending on the substrate used: films deposited on SiO₂ exhibited an even surface with small crystallites, films on sapphire showed parallel surface structures with relatively large and well-shaped crystallites pointing at regular crystal growth influenced by the substrate. These differences in film morphology were also reflected in different reflection intensities of the films in XRD patterns, indicating that the films deposited on sapphire were strongly textured. In a first set of experiments nitridation in molecular nitrogen and ammonia was investigated. In a second set of experiments, it was tried to form oxynitrides of niobium by annealing the nitrided films in molecular oxygen. Particularly by X-ray-diffraction the formation of different nitride and oxide phases in dependence of the reaction temperature was examined. Further, elemental depth profiles were recorded by secondary ion mass spectrometry (SIMS) to track the position of the phases formed in the film. The different substrates led to disparate film reactivities, resulting in different nitridation grades of the films at similar reaction temperatures. In general, larger crystallite sizes resulted in less chemical reactivity of the films: even after nitridation at 1000 °C metallic niobium was still present in films deposited on sapphire. However, no evidence was obtained for the formation of oxynitrides by the process sequence observed.     

Ellipsometric characterization of inhomogeneous non‐stoichiometric silicon nitride films

Variable‐angle spectroscopic ellipsometry is employed for the optical characterization of non‐stoichiometric silicon nitride thin films exhibiting inhomogeneity formed by refractive index and extinction index changes through the film thickness. For all the film samples, the best fit of the experimental data is achieved if, in addition to the inhomogeneity, an overlayer or roughness of the upper boundary is included. However, distinguishing of these two defects is found not to be possible. The influence of working gas ratio, deposition temperature and on/off time on the film properties is studied. The refractive index and extinction coefficient is found to increase with increasing working gas ratio and less significantly with decreasing deposition temperature. It is also found that the inhomogeneity increases with decreasing deposition temperature, and the deposition rate of the films decreases with increasing working gas ratio. The influence of the on/off time on the film properties is practically unimportant. Copyright © 2013 John Wiley & Sons, Ltd.     

From cyclotetrasilazane [(CH3)2SiNH]4 via crystalline silicon nitride imide Si2N2NH to α-Si3N4

α-Si₃N₄ is synthesized by an ammonia thermal synthesis using a cyclic oligosilazane, [(CH₃)₂SiNH]₄, as the starting material. [(CH₃)₂SiNH]₄ reacts in the presence of ammonia at 900°C and 80 MPa pressure to give silicon nitride imide (Si₂N₂NH). Subsequently, Si₂N₂NH is converted into α-Si₃N₄ by thermal decomposition at 1500°C and 0.1 MPa nitrogen with the simultaneous loss of NH₃.     

Surface spectroscopic characterization of advanced polymer materials

The potential of a complementary use of X-ray photoelectron spectroscopy and static ToF-SIMS has been exploited with reference to the characterization of electron conducting polymers (polybithiophene) electrochemically synthetized. Particular attention has been focused on the problem of material stability under electrochemical switching.A coherent picture could be drawn showing that irreversible modifications of the surface chemistry occur, strongly dependent on the dryness of the solvent; moreover, the pathway of doping-undoping process can vary noticeably in dependence on the experimental conditions.     

Time‐of‐flight secondary ion mass spectroscopic characterization of the nitrogen profile of shallow gate oxynitride thermally grown on a silicon substrate

Silicon oxynitride has been used as a shallow gate oxide material for microelectronics and its thickness has been reduced over the years to only a few tens of angstroms due to device size scaling. The nitride distribution and density characteristic in the gate oxide thus becomes imperative for the devices. The shallow depth profiling capability using time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) has huge potential for the nitrogen characterization of the shallow gate oxide film. In this article, both positive and negative spectra of TOF‐SIMS on silicon oxynitride have been extensively studied and it was found that the silicon nitride clusters Si_xN^? (x = 1–4) are able to represent the nitrogen profiles because their ion yields are high enough, especially for the low‐level nitride doping in the oxide, which is formed by the annealing of nitric oxide on SiO₂/Si. The gate oxide thickness measured by the TOF‐SIMS profiling method using ¹⁸O or CsO profile calibration was found to correlate very well with transmission electron microscope measurement. The nitrogen concentration in the gate oxide measured using the TOF‐SIMS method was consistent with the results obtained using the dynamic SIMS method, which is currently applied to relatively thicker oxynitride films. Copyright © 2012 John Wiley & Sons, Ltd.     

Effective attenuation lengths for photoelectrons in thin films of silicon oxynitride and hafnium oxynitride on silicon

We have used the National Institute of Standards and Technology Database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to simulate photoelectron intensities for thin films of SiO_1.6N_0.4 and HfO_1.9N_0.1 on silicon with excitation by Al Kα X‐rays. We considered Si 2p_3/2 photoelectrons from SiO_1.6N_0.4 and the substrate and Hf 4f_7/2 photoelectrons from HfO_1.9N_0.1. The simulations were performed for ranges of film thicknesses and photoelectron emission angles and for two common configurations for X‐ray photoelectron spectroscopy (XPS), the sample‐tilting configuration and the Theta Probe configuration. We determined photoelectron effective attenuation lengths (EALs) by two methods, one by analyzing photoelectron intensities as a function of film thickness for each emission angle (Method 1) and the other by analyzing photoelectron intensities as a function of emission angle for each film thickness (Method 2). Our analyses were made with simple expressions that had been derived with the assumption that elastic‐scattering effects were negligible. We found that EALs from both methods were systematically larger for the Theta Probe configuration, by amounts varying between 1% and 5%, than those for the sample‐tilting configuration. These differences were attributed to anisotropy effects in the photoionization cross section that are expected to occur in the former configuration. Generally, similar EALs were found by each method for each film material although larger EALs were found from Method 2 for film thicknesses less than 1.5 nm. SESSA is a useful tool for showing how elastic scattering of photoelectrons modifies EALs for particular materials, film thicknesses, and XPS configurations. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural,compositional and hardness properties of hydrogenated amorphous carbon nitride thin films synthesized by dense plasma focus device

The hydrogenated amorphous carbon nitride (a‐CN_x:H) thin films were synthesized on the SS‐304 substrates using a dense plasma focus device. The a‐CN_x:H thin films were synthesized using CH₄/N₂ admixture gas and 20 focus deposition shots on substrates placed at different distances from the anode top. X‐ray photoelectron spectroscopy and Raman analysis confirmed different C–N bonding in the a‐CN_x:H thin films. A decrease in the N/C ratio as well as the sp³/sp² ratio with an increase in the substrate distance has been observed. The higher amount of C–N formation for the film synthesized at 10 cm is observed which decreases with increasing distance. The X‐ray photoelectron spectroscopy and Raman analysis affirmed the C ≡ N presence in all the thin films synthesized at different distances. The morphology of the synthesized a‐CN_x:H thin films showed nanoparticles and nanoparticle clusters formation at the surface. The hardness results showed comparatively lower hardness of the a‐CN_x:H thin films due to the presence of C ≡ N. The C–N formation with lower amount of C ≡ N and a higher N/C ratio as well as a higher sp³/sp² ratio for the films synthesized at 10 cm show reasonably higher hardness. Copyright © 2016 John Wiley & Sons, Ltd.     

Deposition of silicon nitride thin films by reaction of SiH4 in a nitrogen post-discharge

Silicon nitride thin films are deposited on silicon wafers at room temperature when silane gas is injected in a nitrogen flowing post-discharge. Reactive processes involving siane molecules and long-lifetime nitrogen species are studied, pointing out the nonreactivity of the N₂(A³ _u ⁺ ) metastable state, the low contribution of the vibrationally excited nitrogen ground-state molecules, and the high reactivity of N(⁴S) atoms. Spectroscopic observations performed in the reaction region are correlated with thin-film characteristics.     

XPS and AFM characterization of aminosilanes with different numbers of bonding sites on a silicon wafer

The aim of this work was the preparation and characterization of a silicon surface modified by different self‐assembled aminopropylsilanes with the purpose of using them in sensor applications. Single‐crystal silicon wafers (111) were modified with aminosilanes that have different numbers of bonding sites: 3‐aminopropyltrimethoxysilane (APTMS), 3‐aminopropyldiethoxymethylsilane (APRDMS) and 3‐aminopropylethoxydimethylsilane (APREMS). We deposited the self‐assembled layers from a solution of aminosilanes in toluene under various reaction conditions. The surface composition and the chemical bonding were determined using X‐ray photoelectron spectroscopy. Furthermore, the surface morphology was investigated using atomic force microscopy. Our results show that the reactivity with the Si‐oxide layer and the polymerization of aminosilanes depend on the number of possible bonding sites. The APTMS reacted the most intensively with the Si‐oxide layer; a less intensive reaction was observed for the APRDMS; and the least intensive reaction was observed for the APREMS. Copyright © 2013 John Wiley & Sons, Ltd.     

Use of the Richardson extrapolation in optics of inhomogeneous layers: Application to optical characterization

A new approach to calculation of optical quantities of inhomogeneous layers is presented. In this approach, the Richardson extrapolation is used to improve the accuracy of the method, in which the inhomogeneous layer is approximated by a stack of thin homogeneous layers. The results presented in this paper are based on the assumption that the media are isotropic and the inhomogeneity is along the axis normal to the boundary. The results obtained by the new method are compared with those obtained without the Richardson extrapolation. The Richardson extrapolation brings significant improvement in accuracy, especially if the number of approximating layers is large. Moreover, the method using the Richardson extrapolation proceeds in steps with an error estimate available in each step; thus, the calculation can be stopped when the desired accuracy is reached. The use of the method is illustrated by means of the optical characterization of strongly inhomogeneous film of non‐stoichiometric silicon nitride.     

Synthesis of BN coatings on carbon fiber by dip coating

BN coatings were deposited on carbon fibers by dip coating method. The deposited coatings were characterized by scanning electron microscopy, Fourier‐transformed infrared spectroscopy, X‐ray photoelectron spectroscopy and X‐ray diffraction. The influence of temperature on composition and structure of the coatings was investigated. Composition and structure examinations revealed that the crystallinity of the coatings increased with the increasing temperature, and the coating is a mixture of little oxides, turbostratic boron nitride and hexagonal boron nitride. Furthermore, experiments were also conducted in order to describe the growth mechanism, thus forming the basis of future growth of BN coating on fibers by dip coating. Copyright © 2016 John Wiley & Sons, Ltd.     

Growth and characterization of ultrathin carbon films on electrodeposited Cu and Ni

Ultrathin carbon films were grown on different types of metallic substrates. Free‐standing foils of Cu and Ni were prepared by electroforming, and a pure Ni film was obtained by galvanic displacement on a Si wafer. Commercial foil of Ni 99.95% was used as a reference substrate. Carbon films were grown on these substrates by chemical vapour deposition in a CH₄‐H₂ atmosphere. Obtained films were characterized by Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and ultraviolet photoemission spectroscopy. The XPS at grazing collection angle was used to determine the thickness of carbon films. Depending on the deposition parameters, the films of graphene or graphite were obtained on the different substrates. The uniformity of graphene and its distribution over the sample area were investigated from Raman data, optical images, and XPS chemical maps. The presence of graphene or graphite in the films was determined from the Raman spectra and Auger peak of C KVV. For this purpose, the D parameter, which is a fingerprint of carbon allotropes, was determined from C KVV spectra acquired by using X‐rays and electron beam. A formation of an intermediate layer of metal hydroxide was revealed in the samples with graphene overlayer.     

Ion bombardment-induced mechanical stress in plasma-enhanced deposited silicon nitride and silicon oxynitride films

We have studied the influence of different deposition conditions on the mechanical stress of silicon nitride and silicon oxynitride layers formed by plasma-enhanced deposition onto silicon substrates. It appears that the mechanical stress of the as-deposited silicon (oxy)nitride layer is a combined effect of the extent of ion bombardment and the deposition temperature on the hydrogen desorption rate. Deposited films show a tensile stress character when the hydrogen desorption rate is thermally controlled, whereas in the case of an ion-bombardement-controlled hydrogen desorption rate the deposited films have a compressive stress. It is also shown that due to annealing at temperatures above the deposition temperature the films are densified as a result of hydrogen desorption and cross-linking.     

Synthesis and characterization of aluminum–polyaniline thin films and membranes

Polyaniline (PAni) films of different intrinsic oxidation states, including emeraldine salt, emeraldine base and leucoemeraldine base, were synthesized. Free‐standing membranes and thin film bilayers of aluminum–polyaniline were fabricated by magnetron sputter deposition of aluminum onto polyaniline films. Aluminum–polyaniline samples were analyzed by transmission electron microscopy (TEM) to investigate the microstructures of specimens, including cross‐sectional TEM micrographs of the metal‐polyaniline interfacial structure not previously reported in the literature. Auger electron spectroscopy (AES) and X‐ray photoelectron spectroscopy (XPS) were employed to study the chemical bonding and interaction between deposited aluminum and polyaniline at the interface. Results indicated that the intrinsic oxidation state of the polyaniline influenced the chemistry of the aluminum–polyaniline interface. Distinct interaction between aluminum and polyaniline in the emeraldine salt‐form was observed. However, there was no evidence of direct interactions of the aluminum with emeraldine base and leucoemeraldine base polyaniline. Copyright © 2005 John Wiley & Sons, Ltd.     

Charge referencing issues in XPS of insulators as evidenced in the case of Al‐Si‐N thin films

Accurate charge referencing in XPS of insulating specimens is a delicate issue. This difficulty is illustrated in the case of Al‐Si‐N composite thin films deposited by reactive magnetron sputtering with variable composition from pure aluminum nitride to pure silicon nitride. The samples were mounted with Au‐coated metallic clamps. Argon sputter cleaning was required to remove a surface native oxide before analysis. For charge referencing implanted argon atoms from the sputter gas and a small amount of gold re‐deposited from the metallic clamps onto the specimen surface during sputter cleaning were evaluated. For the argon atoms, a surprisingly large chemical shift (～1 eV) and a significant peak broadening (0.6 eV) of the Ar 2p_3/2 photoelectron line were found with varying the Si content of the films. This could be related to chemical and structural changes of the Al‐Si‐N films. Hence implanted argon could not be used for charge referencing of Al‐Si‐N samples. In contrast to the implanted argon, the Au 4f_7/2 line width of the gold re‐deposited onto the sample surface did not depend on the Si content of Al‐Si‐N films. A constant energy shift (～1.2 eV) of the Au 4f_7/2 line as compared with bulk gold was, however, found, which was related to the size of gold particles formed on the insulating films. Therefore gold could be reliably used to study chemical shifts of sample‐relevant species in Al‐Si‐N films, but the absolute binding energies of Al 2p, Si 2p and N 1s photoelectrons could not be determined. Copyright © 2011 John Wiley & Sons, Ltd.     

Multi-element characterization of silicon nitride powders by atomic and mass spectrometric solution methods

A sample pretreatment technique for silicon nitride involving digestion and matrix/traces separation was developed by means of radiotracers and applied to analysis of this material by inductively coupled plasma atomic emission spectrometry, inductively coupled plasma mass spectrometry and graphite furnace atomic absorption spectrometry. The results obtained for a high purity silicon nitride material by these methods are compared each with the other and with those obtained by neutron activation analysis. The limits of detection and the capabilities of the methods are compared and discussed.     

Synthesis,analytical characterization and bioactivity of Ag and Cu nanoparticles embedded in poly-vinyl-methyl-ketone films

The electrosynthesis of copper and silver core-shell nanoparticles (NPs) by the sacrificial anode technique, employing tetraoctylammonium (TOA) salts as base electrolyte for the first time, is described. These surfactants were selected because they combine high NP stabilizing power with useful disinfecting properties. The resulting colloids were mixed with a solution of an inert dispersing polymer and used to prepare nanostructured composite thin films. The morphologies and chemical compositions of the nanomaterials were characterized by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The TEM reveals that the average core diameter of the metal NPs ranges between 1.7 and 6.3 nm, as a function of the nature of the metal and of the electrosynthesis conditions, and does not change significantly upon inclusion in the polymer matrix. An appreciable concentration of the metal is detected on the nanoparticle surface by XPS. High-resolution XP spectra indicate that both copper and silver are present at zero oxidation state in all of the materials (colloids and composite films). This demonstrates the high efficiency of the surfactant at controlling the morphology and the chemical composition of the nanodispersed metal in both the as-synthesized colloid and in the polymeric dispersion. The nanocoatings are shown to exert a marked inhibitory effect on the growth of eukaryote and prokaryote target microrganisms, and experimental evidence of a synergic disinfecting effect due to the surfactant and the nanodispersed metal is provided. On the basis of these stability and bioactivity results, it is clear that Cu-NPs and Ag-NPs are suitable for application in disinfecting or antifouling paint and coating formulations.Electronic Supplementary Material Supplementary material is available for this article at Dedicated to the memory of Wilhelm Fresenius     

Microfabrication and imaging XPS analysis of ITO thin films

In this paper the microfabrication of ITO (tin‐doped indium oxide) films by the sol–gel process combined with chemical modification is presented. The microfabricated ITO thin film could be obtained through a one‐step process that combines film patterning with film leaching. The morphology and chemical components of the patterned ITO thin films were assessed by microscopy and XPS, respectively. Imaging XPS analysis is an effective way to evaluate the quality of the fine patterning. Copyright © 2007 John Wiley & Sons, Ltd.     

Characterization of silver selenide thin films grown on Cr‐covered Si substrates

Thermal stability of silver selenide thin films formed from the solid‐state reaction of Ag‐Se diffusion couples on Si substrates covered with a thin Cr film, is investigated. Glancing angle X‐ray diffraction (GXRD), XPS, atomic force microscopy (AFM) and Rutherford backscattering spectrometry (RBS) are used to characterize the as‐deposited films and those annealed at 100, 200, 300, and 400 °C. The results reveal the formation of polycrystalline orthorhombic silver selenide films that remain stable without compositional change upon thermal annealing, in marked contrast to the agglomeration exhibited by silver selenide films deposited on Si without Cr film. The improvement in the thermal stability is attributed to compressive stress relief by a grainy morphology with large surface area, the formation of which is promoted by partially oxidized Cr adhesion film. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface characterization and radical decay studies of oxygen plasma‐treated PMMA films

Polymethylmethacrylate (PMMA) films were modified by RF oxygen plasma with various powers applied for different periods, and the effects of these parameters on the surface properties such as hydrophilicity, surface free energy (SFE), chemistry, and topography were investigated by water contact angle, goniometer, X‐ray photoelectron spectroscopy (XPS), and atomic force microscopy, and the types of the created free radicals and their decay were detected by electron spin resonance spectroscopy (ESR). SFE and contact angle results varied depending on the plasma parameters. Oxygen plasma treatment (100 W–30 min) enhanced the hydrophilicity of PMMA surface as shown by decreasing the water contact angle from 70° to 26°. XPS analysis showed the change in the amounts of the present functionalities as well as formation of new groups as free carbonyl and carbonate groups. The roughness of the surface increased considerably from ~2 nm to ~75 nm after 100 W–30 min oxygen plasma treatment. ESR analysis indicated the introduction of peroxy radicals by oxygen plasma treatment, and the intensity of the radicals increased with increasing the applied power. Significant decrease in radical concentration was observed especially for the samples treated with higher powers when the samples were kept under the atmospheric conditions. As a conclusion, RF plasma, causes changes in the chemical and physical properties of the materials depending on the applied parameters, and can be used for the creation of specific groups or radicals to link or immobilize active molecules onto the surface of a material. Copyright © 2012 John Wiley & Sons, Ltd.