XPS and ARXPS investigations of ultra thin TaN films deposited on SiO2 and Si

TaN films were deposited by reactive DC magnetron sputtering onto Si and SiO₂ with thicknesses of less than one monolayer up to 10 nm. After this, the samples were transferred into the analysis chamber without breaking the vacuum and analysed by means of X-ray photoelectron spectroscopy (XPS) and angular resolved XPS (ARXPS).XPS measurements as a sensitive method to characterise chemical states showed a silicon nitride formation at the interface at deposition on Si. On the SiO₂ no reaction was found at the interface.Based on these observations layer models for quantification of ARXPS measurements by means of model calculations were derived, so it was possible to obtain information on the in-depth element distribution in a non-destructive manner. For comparison to the ARXPS investigations analyses of the inelastic background of the Ta4d peak are shown and discussed.     

Tribological behavior of diamond-like carbon film with different tribo-pairs: A size effect study

A friction force microscope (FFM) with different probes and a ball-on-disk (BOD) tribo-meter were used to investigate the tribological properties of diamond-like carbon (DLC) films. DLC films were prepared by chemical vapor deposition (CVD) method by altering the deposition parameters, and their morphologies and structural information were examined with an atomic force microscope (AFM) and the Raman spectrum. The wear traces of the DLC films after frictional tests were analyzed by an optical microscope. It is found that surface roughness and adhesion play important roles in characterizing the tribological properties of DLC films using FFM. Moreover, the debris accumulation is another significant factor affecting the frictional behavior of DLC films, especially for the sharp tip. The difference in coefficients of friction (COFs) obtained by the BOD method among different DLC films under water lubrication is much smaller than the case without water lubrication. The variation trends in COF for the flat tip and the BOD test are similar in comparison with the result obtained with the sharp tip. The wear traces after frictional tests suggest that DLC films under water lubrication are prone to be damaged more readily.     

Determination of the hydrophilic character of membranes by pulsed force mode atomic force microscopy

Hydrophilic polysulphone (PSU) membranes were modified with hydrophilic polyethylene oxide (PEO) to obtain membranes less susceptible to fouling. Pulsed force atomic force microscopy was employed to determine the hydrophilic character of the different membranes and to acquire quantitative values that can be compared easily. This technique proved to be extremely valuable in the characterisation and quantification of membrane hydrophilicity.     

Photoelectron-spectroscopic and reactivity investigation of thin Pd-Sn films prepared by magnetron sputtering

We have studied Pd-Sn layers with different composition prepared by magnetron sputtering. Layers were sputtered onto Al₂O₃ and SiO₂ substrates and studied by X-ray photoelectron spectroscopy (XPS). Spectra confirmed that after vacuum annealing residual oxygen and carbon have been removed and bimetallic bonds have been created. The shift of Pd 3d_5/2 core level to higher binding energy followed by the peak narrowing in dependence on the composition was observed, accompanied by the shift of the Pd 4d in the valence band region, induced by hybridization of Pd-d and Sn-s,p states. Experiments carried out on a gas-flow reactor indicate increasing temperature of the CO oxidation with tin ratio in the alloy.     

The XPS and XAES spectra of Na0.88Mn0.56PS3

Na_0.88Mn_0.56PS₃compounds have been synthesized by starting from MnPS₃ polycrystalline powders by means of a two-step cation-exchange process at a higher intercalation time than the one used for producing the literature reported Na_0.62Mn_0.69PS₃ compounds. The obtained samples have been characterized by X-ray photoelectron spectroscopy (XPS). The resulting spectra of the so-synthesized compounds have been compared with those observed in Na_0.62Mn_0.69PS₃ in our previous paper and similar electronic properties have been noted. In particular by XPS it has been shown that greater sodium content affects neither the core-level binding energies of the host matrix elements nor the type of link between Na⁺ and (Mn_1−xPS₃)⁻.     

X-ray photoelectron spectroscopy characterization of the layered intercalated compound K2xMn1 − xPS3

Polycrystalline powders of the layered MnPS₃ compound have been intercalated with K⁺ ions by ion-exchange to yield the K_2xMn_1 − xPS₃ intercalate. X-ray photoelectron spectroscopy has been applied to learn about the electronic structure of this compound. In particular, we have studied the XPS spectra of the Mn 2p and 3p, P and S 2p, K 2p and 3p core levels and of the valence band region. The binding energies for various core levels of the elements present in this compound and their observed chemical shifts are analyzed. The data give evidence for the lack of non-equivalent atoms of K, Mn, P and S. Shake-up satellites are present at the Mn 2p and 3p core levels. The occurrence of such lines allows us to hypothesize that K_2xMn_1 − xPS₃ is a large-gap insulating Mn compound. Confirmation that only an ion transfer accompanies the intercalation process is given from both the strong observed similarity with the corresponding XPS spectra in MnPS₃ and the observed binding energy positions of the K 2p and 3p levels. As regards the valence band XPS spectrum, the observed analogies with the corresponding XPS spectra of the pure compound and of other K compounds have allowed us to single out two regions and their probable contributors.     

A method for the experimental determination of the net atomic charge via X-ray photoemission spectroscopy

A method for the experimental determination of the net charge distribution over the atoms in a large class of compounds is described. The method is based on X-ray photoemission spectroscopy and requires the determination of two core-level energies per constituting atomic species. Two special cases of large conceptual and practical interest are discussed: the silicon charge in CoSi₂, Si_1-xGe_x (0≤x≤0.3), SiC, Si₃N₄ and SiO₂, and the aluminum charge in aluminum-doped zeolites. Received: 20 March 2000 / Accepted: 28 March 2000 / Published online: 21 March 2001     

Determination of silicone coating Young's modulus using atomic force microscopy

The polymerisation degree of thin polymer coatings was checked by following the variation of their local mechanical properties. Atomic force microscope (AFM) was used in an indentation mode to investigate the mechanical characteristics of silicone coatings on polycarbonate substrates. The evolution of Young's modulus of the silicone coatings was determined as a function of the polymer annealing time. We have used a relative method to measure Young's moduli, which involves a calibration step with a set of reference polymers. No variation was observed for the modulus of silicone coatings annealed during more than 40 min at 130 °C. This result indicates that over-heating does not modify the mechanical properties of the coating.     

Quantification issues in the identification of nanoscale regions of homopolymers using modulus measurement via AFM nanoindentation

Since 1989, AFMs have been used to map the nanomechanical properties of surfaces using measurements such as force-distance curves. Quantification of the force and elastic parameters are critical to the nanomechanical analysis and positive identification of materials at the nanoscale, as well as for assessing behaviour at surfaces. In recent years, there have been AFM papers publishing “quantitative” values for the indentation modulus, however, many involved large uncertainties arising from the lack of calibration of key components, the use of manufacturers’ nominal values for these components or the use of incorrect models. This paper addresses the quantification issues in modulus measurement at surfaces for homogeneous materials using force-distance curves and how to do this with sufficient accuracy to identify materials at the nanoscale. We review the available theory and describe two routes to quantitative modulus measurement using both the AFM on its own and the AFM combined with a nanoindenter. The first involves the direct measurement of modulus using a fully calibrated instrument and allows depth analysis. The second uses indirect measurement through calibration by reference materials of known reduced modulus. For depth analysis by this second route, these reference moduli need to be known as a function of depth. We show that, using the second route, an unknown polymer may be analysed using the nanoindenter, its modulus determined and, providing the moduli of the polymers to be identified or distinguished differ by more than 20%, identified with 95% confidence. We recommend that users evaluate a set of reference samples using a traceable nanoindenter via the first route, and then use these to calibrate the AFM by the second route for identification of nano-regions using the AFM.     

Pulsed laser deposition of polyhydroxybutyrate biodegradable polymer thin films using ArF excimer laser

We demonstrated the pulsed laser deposition (PLD) of high quality films of a biodegradable polymer, the polyhydroxybutyrate (PHB). Thin films of PHB were deposited on KBr substrates and fused silica plates using an ArF (λ = 193 nm, FWHM = 30 ns) excimer laser with fluences between 0.05 and 1.5 J cm⁻². FTIR spectroscopic measurements proved that at the appropriate fluence (0.05, 0.09 and 0.12 J cm⁻²), the films exhibited similar functional groups with no significant laser-produced modifications present. Optical microscopic images showed that the layers were contiguous with embedded micrometer-sized grains. Ellipsometric results determined the wavelength dependence (λ ∼ 245-1000 nm) of the refractive index and absorption coefficient which were new information about the material and were not published in the scientific literature. We believe that our deposited PHB thin films would have more possible applications. For example to our supposal the thin layers would be applicable in laser induced forward transfer (LIFT) of biological materials using them as absorbing thin films.     

Characterization of a thin CeO2-ZrO2-Y2O3 films electrochemical deposited on stainless steel

In this paper, we report for the first time formation of a thin CeO₂-ZrO₂-Y₂O₃ films electrodeposited on a stainless steel substrate. The samples have been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The XRD and XPS data indicate formation of a solid solution and additional existence of Ce³⁺ states near the surface. After annealing, SEM examination has shown a microstructure formed by dispersed spherical agglomerates having a size between 20 and 60 nm.     

XPS study on silica-bismuthate glasses and glass ceramics

X-ray photoelectron spectroscopy (XPS) was used to evidence the effect of the Bi₂O₃ to SiO₂ ratio and of partial crystallisation on the electronic charge density around the atoms entering silica-bismuthate glasses of nominal composition 0.01Fe₂O₃⋅0.99[xSiO₂⋅(100−x)Bi₂O₃] with . The core level spectra show significant composition dependent changes in binding energy, and the full width at half maximum of photoelectron peaks both of cations and of oxygen atoms. The analysis reveals changes in electron density correlated with the ionic and covalent character of the samples. The shift in binding energy suggests charge transfer from silicon and oxygen atoms to bismuth atoms. Contrary to the expected behaviour in conventional silicate oxide systems, the results indicate an increase of ionicity for silicon and of covalency for bismuth atoms. The same evolution of ionicity/covalency is observed after partial crystallisation.     

Band gap energy and bowing parameter of In-rich InAlN films grown by magnetron sputtering

The crystal structure, band gap energy and bowing parameter of In-rich In_xAl_1−xN (0.7 < x < 1.0) films grown by magnetron sputtering were investigated. Band gap energies of In_xAl_1−xN films were obtained from absorption spectra. Band gap tailing due to compositional fluctuation in the films was observed. The band gap of the as-grown InN measured by optical absorption method is 1.34 eV, which is larger than the reported 0.7 eV for pure InN prepared by molecular beam epitaxy (MBE) method. This could be explained by the Burstein-Moss effect under carrier concentration of 10²⁰ cm⁻³ of our sputtered films. The bowing parameter of 3.68 eV is obtained for our In_xAl_1−xN film which is consistent with the previous experimental reports and theoretical calculations.     

Delineation of a p–n junction using dC/dX imagery produced by shear-mode scanning capacitance microscopy

Using a laterally oscillating all-metallic probe, a scanning capacitance microscope (SCM) has been used to yield an image of the spatial derivative of the local capacitance, dC/dX, where C and X are the local capacitance and the axis of the probe tip locus on the sample surface, respectively. Bias fields, except for the ultra-high-frequency fields used for sensing the capacitance, are not necessary to detect the dC/dX signal, which yields an image delineating clearly the depletion region due to the p–n junction. Simultaneously with the dC/dX image, the new SCM can give images of topography and dC/dV if an alternating field V is applied between the probe and sample. Received: 19 March 2001 / Accepted: 22 March 2001 / Published online: 27 June 2001     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.     

Annealing induced microstructural evolution of electrodeposited electrochromic tungsten oxide films

A significant influence of microstructure on the electrochromic and electrochemical performance characteristics of tungsten oxide (WO₃) films potentiostatically electrodeposited from a peroxopolytungstic acid (PPTA) sol has been evaluated as a function of annealing temperature. Powerful probes like X-ray diffractometry (XRD), transmission electron microscopy (TEM), UV-vis spectrophotometry, multiple step chronoamperometry and cyclic voltammetry have been employed for the thin film characterization. The as-deposited and the film annealed at 60 °C are composed of nanosized grains with a dominant amorphous phase, as well as open structure which ensues from a nanoporous matrix. This ensures a greater number of electroactive sites and a higher reaction area thereby manifesting in electrochromic responses superior to that of the films annealed at higher temperatures. The films annealed at temperatures ≥250 °C are characterized by a prominent triclinic crystalline structure and a hexagonal phase co-exists at temperatures ≥400 °C. The deleterious effect on the electrochromic properties of the film with annealing is ascribed to the loss of porosity, densification and the increasing crystallinity and grain size. Amongst all films under investigation, the film annealed at 60 °C exhibits a high transmission modulation (ΔT ∼ 68%) and coloration efficiency (η ∼ 77.6 cm² C⁻¹) at λ = 632.8 nm, charge storage capacity (Q_ins ∼ 21 mC cm⁻²), diffusion coefficient (6.08 × 10⁻¹⁰ cm² s⁻¹), fast color-bleach kinetics (t_c ∼ 275 s and t_b ∼ 12.5 s) and good electrochemical activity, as well as reversibility for the lithium insertion-extraction process upon cycling. The remarkable potential, which the film annealed at 60 °C has, for practical “smart window” applications has been demonstrated.     

Influence of aramid fiber moisture regain during atmospheric plasma treatment on aging of treatment effects on surface wettability and bonding strength to epoxy

One of the main differences between a low-pressure plasma treatment and an atmospheric pressure plasma treatment is that in atmosphere, the substrate material may absorb significant amount of water which may potentially influence the plasma treatment effects. This paper investigates how the moisture absorbed by aramid fibers during the atmospheric pressure plasma treatment influences the aging behavior of the modified surfaces. Kevlar 49 fibers with different moisture regains (MR) (0.5, 3.5 and 5.5%, respectively) are treated with atmospheric pressure plasma jet (APPJ) with helium as the carrier gas and oxygen as the treatment gas. Surface wettability and chemical compositions, and interfacial shear strengths (IFSS) to epoxy for the aramid fibers in all groups are determined using water contact angle measurements, X-ray photoelectron spectroscopy (XPS), and micro-bond pull out tests, respectively. Immediately after the plasma treatment, the treated fibers have substantially lower water contact angles, higher surface oxygen and nitrogen contents, and larger IFSS to epoxy than those of the control group. At the end of 30 day aging period, the fibers treated with 5.5% moisture regain had a lower water contact angle and more polar groups on the fiber surface, leading to 75% improvement of IFSS over the control fibers, while those for the 0.5 and 3.5% moisture regain groups were only 30%.     

Long-time stabilization of porous silicon photoluminescence by surface modification

We present results on the photoluminescence (PL) properties of porous silicon (PS) as a function of time. Stabilization of PL from PS has been achieved by replacing silicon-hydrogen bonds terminating the surface with more stable silicon-carbon bonds. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy at intervals of 1 month in ageing time up to 1 year. The position of the maximum PL peak wavelength oscillates between a blue-shift and a red-shift in the 615-660 nm range with time.     

Molecular dynamics simulation of AFM studies of a single polymer chain

Single polymer chain force-extension behavior measured by Atomic Force Microscopy (AFM) was interpreted by molecular dynamics (MD) simulation performed by applying a bead-spring (coarse-graining) model in which the bond potential function between adjacent beads is described by a worm-like chain (WLC) model. Simulation results indicate that caution should be applied when interpreting experimental AFM data, because the data vary depending on the point of AFM tip-polymer chain attachment. This approach offers an effective way for eventual analysis of the mechanical behavior of complex polymer networks.     

Effects of Substrate Hydrophobicity/Hydrophilicity on Height Measurement of Individual DNA Molecules

Effects of substrate hydrophobicity/hydrophilicity on height measurement of individual ds-DNA molecules are investigated with tapping mode atomic force microscopy （TMAFM） and vibrating mode scanning polarization force microscopy （VSPFM）. The measured heights of ds-DNA on hydrophobic highly oriented pyrolytic graphite （HOPG） are remarkably less than those on hydrophilic bare mica and Ni^2＋ treated mica in both TMAFM and VSPFM. By analysing the results, we propose that the hydrophobicity/hydrophilicity of substrate can greatly influence the height measurement of DNA molecules.