Lifshitz analysis of dispersion forces based on quantitative reflection electron energy loss spectroscopy.

HYPOTHESIS: The energy loss experienced by an electron while moving through a solid is determined by the optical properties of the surrounding. Hence, quantitative Reflection Electron Energy Loss Spectroscopy (REELS) should allow the determination of optical data required for the calculation of Hamaker coefficients using Lifshitz theory. This approach might improve the accuracy of calculated Hamaker coefficients and should also enable to harness the unique capabilities of REELS to analyse nanostructured surfaces and thin-films with great spatial resolution and surface sensitivity. EXPERIMENTS: REELS spectra of a survey of insulating polymers and of metal-like Ti0.23Al0.32N0.44 (TiAlN) were measured, the complex dielectric functions determined and the corresponding Hamaker coefficients across vacuum and water calculated. The sensitivity of the quantification procedure towards typical systematic errors was investigated. For polystyrene the results were comparatively analysed using vacuum ultraviolet spectroscopy (VUV). FINDINGS: The accuracy especially of the non-retarded vacuum Hamaker constants of the polymers was increased when compared to VUV reflectance spectroscopy due to the higher spectral range of REELS. Furthermore, a new correction procedure for the intricate case of unresolved inelastic losses in the REELS spectrum, such as encountered in the case of TiAlN, could be developed using spectroscopic ellipsometry as a complementary mean.

Analysis of dispersive interactions at polymer/TiAlN interfaces by means of dynamic force spectroscopy.

The structural and electronic origins of the interactions between polycarbonate and sputter deposited TiAlN were analysed using a combined electron and force spectroscopic approach. Interaction forces were measured by means of dynamic force spectroscopy and the surface polarizability was analysed by X-ray photoelectron valence band spectroscopy. It could be shown that the adhesive interactions between polycarbonate and TiAlN are governed by van der Waals forces. Different surface cleansing and oxidizing treatments were investigated and the effect of the surface chemistry on the force interactions was analysed. Intense surface oxidation resulted in a decreased adhesion force by a factor of two due to the formation of a 2 nm thick Ti0.21Al0.45O surface oxide layer. The origin of the residual adhesion forces caused by the mixed Ti0.21Al0.45O surface oxide was clarified by considering the non-retarded Hamaker coefficients as calculated by Lifshitz theory, based on optical data from Reflection Electron Energy Loss Spectroscopy. This disclosed increased dispersion forces of Ti0.21Al0.45O due to the presence of Ti(iv) ions and related Ti 3d band optical transitions.

New amidinate complexes of indium(iii): promising CVD precursors for transparent and conductive In2O3 thin films.

For the first time, synthesis of two new amidinate-ligand comprising heteroleptic indium complexes, namely [InCl(amd)2] (1) and [InMe(amd)2] (2), via salt-metathesis and their detailed characterization is reported. For comparison, the earlier reported homoleptic tris-amidinate [In(amd)3] (3) was also synthesized and analyzed in detail especially with respect to the thermal properties and molecular crystal structure analysis which are reported here for the first time. From nuclear magnetic resonance spectroscopy (NMR) and single-crystal X-ray diffraction (XRD), all three compounds were found to be monomeric with C2 (compound 1 and 2) and C3 symmetry (compound 3). Both halide-free compounds 2 and 3 were evaluated regarding their thermal properties using temperature-dependent 1H-NMR, thermogravimetric analysis (TGA) and iso-TGA, revealing suitable volatility and thermal stability for their application as potential precursors for chemical vapor phase thin film deposition methods. Indeed, metalorganic chemical vapor deposition (MOCVD) experiments over a broad temperature range (400 °C-700 °C) revealed the suitability of these two compounds to fabricate In2O3 thin films in the presence of oxygen on Si, thermally grown SiO2 and fused silica substrates. The as-deposited thin films were characterized in terms of their crystallinity via X-ray diffraction (XRD), morphology by scanning electron microscopy (SEM) and composition through complementary techniques such as Rutherford-backscattering spectrometry (RBS) in combination with nuclear reaction analysis (NRA) and X-ray photoelectron spectroscopy (XPS). From UV/Vis spectroscopy, the deposited In2O3 thin films on fused silica substrates were found to be highly transparent (T > 95% at 560 nm, compound 3). In addition, Hall measurements revealed high charge carrier densities of 1.8 × 1020 cm-3 (2) and 6.5 × 1019 cm-3 (3) with a Hall-mobility of 48 cm2 V-1 s-1 (2) and 74 cm2 V-1 s-1 (3) for the respective thin films, rendering the obtained thin films applicable as a transparent conducting oxide that could be suitable for optoelectronic applications.

Study of water adsorption and capillary bridge formation for SiO(2) nanoparticle layers by means of a combined in situ FT-IR reflection spectroscopy and QCM-D set-up.

Water adsorption and capillary bridge formation within a layer of SiO2-nanoparticles were studied in situ by means of a combination of quartz crystal microbalance (QCM-D) with dissipation analysis and Fourier transformation infrared reflection absorption spectroscopy (FT-IRRAS). FT-IR data were employed to distinguish the "ice-like" and "liquid-like" contributions and to support the analysis of the QCM-D data concerning mass change and dissipation. Combined measurements show that for SiO2-nanoparticles with a diameter of about 250 nm, the formation of two adsorbed monolayers of water as well as bulk water leads to a rather linear increase in the dissipation for relative humidity values of up to 60% which is followed by a strong increase in dissipation during the actual liquid bridge formation. Subsequently, the dissipation drops again when the relative humidity is further increased to values >90%.

All-optical tunability of microdisk lasers via photo-adressable polyelectrolyte functionalization.

Photoactive materials are highly promising candidates for novel applications as they enable all-optical control of photonic devices. Photochromic molecules exhibit a reversible change of their dielectric function upon irradiation with light of proper wavelength. The trans- and cis-isomers of azobenzene exhibit different absorption properties due to the effect of the configuration on the polarizability of the molecule. Here, we introduce a novel molecular/semiconductor hybrid device which is fully tunable by all-optical means via the integration of a semiconductor microdisk into a photo-adressable polyelectrolyte material. We demonstrate that such polyelectrolyte superlattices can be used to tune semiconductor photonic resonators with high precision and without any significant degeneration of device performance. Moreover, we demonstrate an all-optically tunable laser based on this hybrid concept.

Defect formation in thin polyelectrolyte films on polycrystalline NiTi substrates.

This paper reports on the mechanical properties of ultrathin PAA/PAH (polyacrylic acid/polyallylamine hydrochloride) polyelectrolyte films deposited by a layer-by-layer technique on a polycrystalline Nickel-Titanium (NiTi) substrate. Since thin polyelectrolyte films are potentially suitable coatings to reduce the Ni release in biomedical applications, the mechanical properties of the thin films were determined by applying monotonic and cyclic tensile strains of 5% and 3%, respectively. While single tensile strains up to 5% revealed the amazing strain to failure of the applied coating, cyclic strains resulted in defect formation within the polyelectrolytes. To provide a better understanding of the mechanisms that are determining the defect formation, macroscopic and microscopic defect localizations were determined by digital image correlation-and EBSD (electron back-scattered diffraction)-techniques. Defects emerged particularly within areas of elevated local strain differences and were predominantly observed in the vicinity of grain boundaries. To relate these findings to the transformation behavior of polycrystalline NiTi considering strain localizations and intergranular constraints, crystallographic data obtained from the EBSD measurements were correlated with the defect distribution. EBSD data revealed a distinct dependence of defect formation on misorientation of neighboring grains.

Adsorption kinetics of organophosphonic acids on plasma-modified oxide-covered aluminum surfaces.

Tailoring of oxide chemistry on aluminum by means of low-pressure water and argon plasma surface modification was performed to influence the kinetics of the self-assembly process of octadecylphosphonic acid monolayers. The plasma-induced surface chemistry was studied by in situ FTIR reflection-absorption spectroscopy (IRRAS). Ex situ IRRAS and X-ray photoelectron spectroscopy were applied for the analysis of the adsorbed self-assembled monolayers. The plasma-induced variation of the hydroxide to oxide ratio led to different adsorption kinetics of the phosphonic acid from dilute ethanol solutions as measured by means of a quartz crystal microbalance. Water plasma treatment caused a significant increase in the density of surface hydroxyl groups in comparison to that of the argon-plasma-treated surface. The hydroxyl-rich surface led to significantly accelerated adsorption kinetics of the phosphonic acid with a time of monolayer formation of less than 1 min. On the contrary, decreasing the surface hydroxyl density slowed the adsorption kinetics.