Comparative XPS study of surface reduction for nanocrystalline and microcrystalline ceria powder

Nanoscale materials have attracted great interest because of their distinct properties. By means of XPS, the present work investigated the difference of reduction behavior between nanocrystalline and microcrystalline ceria on condition of Ar⁺ bombardment or X-ray irradiation. For the first time, the results indicate that the reduction level of Ce⁴⁺ to Ce³⁺ is lower for nanocrystalline ceria than for microcrystalline ceria although the experimental conditions are identical. These differences have been attributed to the differences in the concentration of oxygen vacancies in the bulk and the diffusion ability of oxygen atoms between them. Besides, the key factor for the reduction of ceria produced by X-ray exposure is discussed.     

Quantitative analysis of surface amine groups on plasma-polymerized ethylenediamine films using UV-visible spectroscopy compared to chemical derivatization with FT-IR spectroscopy, XPS and TOF-SIMS

A quantitative analysis of the surface density of amine groups on a plasma-polymerized ethylenediamine thin film deposited on a platinum surface using inductively coupled plasma chemical vapor deposition method is described. UV-visible spectroscopy together with a chemical derivatization technique using Fourier transform infrared (FT-IR) spectroscopy was used to obtain the quantitative information. Chemical tags of pentafluorobenzaldehyde were hybridized with the surface amine groups and were easily detected due to the characteristic absorption bands of C-F stretching, aromatic ring and CN stretching vibrations in the reflection-absorption FT-IR spectra. The surface amine density was reproducibly controlled as a function of deposition plasma power and quantified using UV-visible spectroscopy. A good linear correlation was observed between the FT-IR intensities of the characteristic absorption bands and the surface amine densities, suggesting the possibility of using this chemical derivatization technique to quantify the surface densities of specific functional groups on an organic surface. Chemical derivatization was also used with X-ray photoelectron spectroscopy on the same samples, and the results were compared with those obtained from FT-IR and time-of-flight secondary ion mass spectrometry. Although each analysis technique has different probing depths from the surface, the three different data sets obtained from the chemical tags correlated well with each other since each analysis technique measured the chemical tags on the sample surface.     

Study of optical band gap, carbonaceous clusters and structuring in CR-39 and PET polymers irradiated by 100 MeV O ions

Commercially purchased CR-39 and PET polymers were irradiated by 100 MeV O⁷⁺ ions of varying fluences, ranging from 1×10¹¹ to 1×10¹³ ions/cm². The effects of swift heavy ions (SHI) on the structural, optical and chemical properties of CR-39 and PET polymers were studied using X-ray diffraction (XRD), UV-visible spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The XRD patterns of CR-39 show that the intensity of the peak decreases with increasing ion fluence, which indicates that the semicrystalline structure of polymer changes to amorphous with increasing fluences. The XRD patterns of PET show a slight increase in the intensity of the peaks, indicating an increase in the crystallinity. The UV-visible spectra show the shift in the absorbance edge towards the higher wavelength, indicating the change in band gap. Band gap in PET and CR-39 found to be decrease from 3.87 to 2.91 and 5.3-3.5 eV, respectively. The cluster size also shows a variation in the carbon atoms per cluster that varies from 42 to 96 in CR-39 and from 78 to 139 in PET. The FTIR spectra show an overall reduction in intensity of the typical bands, indicating the degradation of polymers after irradiation.     

Thickness dependence of X-ray absorption and photoemission in Fe thin films on Si(0 0 1)

To investigate the initial growth of Fe films on Si(0 0 1) and the Fe/Si interface, Fe films at various thicknesses have been systematically studied by soft X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS). The Fe L edge XAS spectrum shows a strong thickness dependence with broader line-width for thinner films. Detailed analysis of the Fe absorption signal as a function of the thickness shows that the broad linewidth of Fe L edge XAS spectra is mostly contributed by the first Fe layer at the Fe/Si interface. In contrast to XAS, Fe 2p photoemission spectra for these films are identical. However, valence band photoemission also shows a strong thickness dependence. Comparing the valence band photoemission spectra of the thin Fe/Si(0 0 1) films with that of pure Si and the thickest Fe film, the difference spectra at all thicknesses show almost identical shape indicating the same origin: the Fe/Si interface. Thus, it is mainly the first Fe layer at Fe/Si layer that is reactive with the Si substrate changing its electronic structure.     

La1−xCaxCoO3 perovskite-type oxides: Identification of the surface oxygen species by XPS

A detailed study of the La_1−xCa_xCoO₃ perovskites surface by XPS was carried out since this is a potentially useful tool to identify the oxygen species involved in the catalytic reaction and discriminate them. Mainly, the concentration of surface oxygen vacancies (λ′) can be estimated from the XPS atomic ratio.     

Nitrogen incorporation in amorphous SiCN layers prepared from electron cyclotron resonance plasmas

Electron cyclotron resonance plasma chemical vapor deposition with nitrogen, methane, and argon-diluted silane as precursors has been used to prepare SiCN thin films. Optical emission from CN species in the plasma has been observed. Infrared measurements show that most of the nitrogen is incorporated to the thin solid films in the form of Si-N, C=N and C≡N bonds suggesting a basic structure of incomplete SiN tetrahedra with C=N and C≡N bridging bonds. The deposited films are nearly transparent in the visible range with a weak absorption threshold between 2.2 and 3.5 eV. Received: 3 April 1998 / Accepted: 5 January 1999 / Published online: 31 March 1999     

Surface XPS characterization of NiTi shape memory alloy after advanced oxidation processes in UV/H2O2 photocatalytic system

Surface structure of NiTi shape memory alloy (SMA) was modified by advanced oxidation processes (AOP) in an ultraviolet (UV)/H₂O₂ photocatalytic system, and then systematically characterized with x-ray photoelectron spectroscopy (XPS). It is found that the AOP in UV/H₂O₂ photocatalytic system leads to formation of titanium oxides film on NiTi substrate. Depth profiles of O, Ni and Ti show such a film possesses a graded interface structure to NiTi substrate and there is no intermediate Ni-rich layer like that produced in conventional high temperature oxidation. Except TiO₂ phase, some titanium suboxides (TiO, Ti₂O₃) may also exist in the titanium oxides film. Oxygen mainly presents in metal oxides and some chemisorbed water and OH⁻ are found in titanium oxides film. Ni nearly reaches zero on the upper surface and relatively depleted in the whole titanium oxides film. The work indicates the AOP in UV/H₂O₂ photocatalytic system is a promising way to favor the widespread application of biomedical NiTi SMA by improving its biocompatibility.     

Plasma-electrolytic formation, composition and catalytic activity of manganese oxide containing structures on titanium

In the present work, we report the data about formation of TiO₂-rutile or TiO₂ and Mn₂O₃, Mn₃O₄ containing oxide structures on titanium in aqueous electrolytes by means of plasma-electrolytic deposition. The layers formed are characterized by X-ray diffraction, electron probe microanalysis and scanning electron microscopy methods. The PEO coatings on titanium formed in sodium tetraborate solution contain the TiO₂ stabile rutile modification that is important when utilizing such a structure as a catalyst carrier. Manganese acetate adding into the electrolyte leads to formation of layers that contain Mn₂O₃, Mn₃O₄ and TiO₂-rutile in outer region. The manganese content in the surface layer depends on the formation conditions as well as on manganese acetate concentration in the electrolyte. Catalytic activity of the layers in CO → CO₂ reaction is studied in the static and flow conditions. The manganese-containing layers obtained possess the catalytic activity in CO → CO₂ oxidation reaction at the temperature range of 250-350 °C. The catalytic activity depends on the concentration and surface distribution of manganese as well as on the layers morphology.     

New method to calibrate binding energy using Au nanocolloids in X-ray photoelectron analysis of diamondlike carbon films with different electrical resistivities

A new method to calibrate the binding energy (E_B) using Au nanocolloids as a calibrant in XPS analysis of diamondlike carbon (DLC) is proposed by considering the DLC films with different electrical resistivities. A few microliters of a dilute aqueous solution containing Au nanocolloids were dropped onto a small local surface area of the DLC film, which became a stain before XPS measurements by gradually drying in vacuo. The observed peak E_B of the C 1s spectrum at another native surface (an area without Au nanocolloids) of the DLC film was calibrated by setting that of the Au 4f_7/2 spectrum of the Au nanocolloids to 84.0 (83.98 ± 0.02) eV. The adequacy of this method was investigated by considering the correlation among the full width at half maximums (FWHMs) of the Au 4f_7/2 spectra of the Au nanocolloids on the DLC surfaces and that of a Au plate as a reference. Consequently, the FWHM of the Au 4f_7/2 spectrum of the Au nanocolloids on the DLC surface is a candidate to investigate the differential charging effect of the DLC surface, and the calibration method is reliable if the FWHM agrees with that of the Au plate.     

Semiconducting P3HT microstructures: fibres and tubes obtained from macroporous silicon template

Microtubes and microfibres composed of poly(3‐hexylthiophene) (P3HT) were fabricated by melt‐assisted templates using ordered macroporous silicon. We have studied the influence of the pore depth and the template type on the microstructure fabrication, where the templates were membranes or structures opened only at one end. Current– voltage (I–V) measurements demostrated that the resistivity of these P3HT microstructures was in the same order as that of homogeneous films, which allows them to be used in electronic devices. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and electronic properties of gold adsorbed on Ti(0 0 0 1)

The Au/Ti(0 0 0 1) adsorption system was studied by low energy electron diffraction (LEED) and photoemission spectroscopy with synchrotron radiation after step-wise Au evaporation onto the Ti(0 0 0 1) surface. For adsorption of Au at 300 K, no additional superstructures were observed and the (1 × 1) pattern of the clean surface simply became diffuse. Annealing of gold layers more than 1 ML thick resulted in the formation of an ordered Au-Ti surface alloy. Depending on the temperature and annealing time, three surface reconstructions were observed by LEED: (√3 × √3) R30°, (2 × 2) and a one-dimensional incommensurate (√3 × √3) rectangular pattern. The Au 4f core level and valence band photoemission spectra provided evidence of a strong chemical interaction between gold and titanium. The data indicated formation of an intermetallic interface and associated valence orbital hybridization, together with diffusion of gold into the bulk. Au core-level shifts were found to be dependent on the surface alloy stoichiometry.     

The growth of Au/Pd/alumina/Cu-Al system studied by SRPES

An ultra-thin alumina layer grown on Cu-9at.%Al (1 1 1) surface was studied using synchrotron radiation photoelectron spectroscopy (SRPES), X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). By deconvolving SRPES spectra of the Al 2p doublet, four components belonging to metallic as well as oxide phases were recognized. Pd-Au alloy formation was confirmed by SRPES measurement during Pd and Au deposition. The study of the system's thermal stability reveals diffusion of Pd and Au atoms through the alumina layer. While Au atoms start to diffuse under the alumina layer at 670 K, Pd atoms are forming Pd-Al surface alloy at this temperature. The diffusion of Pd atoms through alumina occurs when sample was heated over 770 K. Alumina layer was stable even after heating the sample at 870 K, but its structure was corrupted probably due to the diffusion of metal atoms.     

Growth of thin Si oxide in a cyclic oxygen plasma environment below 200 °C

The growth of Si oxide by means of a cyclic radio-frequency (rf) plasma oxidation process has been explored in a low temperature range of 100-200 °C. The growth mechanism exhibits Cabrera-Mott (CM) oxidation, that is, the transport of mobile ionic species is assisted by an electric field. The low activation energy of 0.3 eV is attributed to the small size of O⁻ and the assistance of the electric field. The oxide becomes off-stoichiometric as one approaches to the exterior surface of the oxide layer.     

Desorption and photopolymerization behavior of mixed and multilayered styrene-pyrrole nanofilms

The molecular arrangement and polymerization of adsorbed styrene-pyrrole films were explored using two different dosing schemes: simultaneous dosing to form an intimately mixed film of the two monomers and sequential dosing to form films with distinct layers of styrene and pyrrole. It was found that the desorption of pyrrole was delayed until 175 K when either simultaneously dosed with styrene or in the presence of an overlying styrene layer, whereas it normally desorbs at 165 K when dosed alone. No such effects were observed with styrene in any dosing configuration. The polymerization rate of pyrrole was unaffected in the films when present as the top layer and was observed to decrease by 50% when beneath a styrene layer. Moreover, the rate of polymerization increased by two orders of magnitude in the case of the intimately mixed film. The rate of styrene polymerization was not found to change in any of the explored geometries. These effects are explained by considering the proximity of the components and the potential for screening UV radiation based on their molecular structure.     

Electron transport with mobility above 10–3 cm2/Vs in amorphous film of co‐planar bipyridyl‐substituted oxadiazole

We demonstrate that a bipyridyl substituted oxadiazole (Bpy‐OXD) shows high electron mobility that reached above 10^–3 cm²/Vs. We believe that the high mobility results from both the hybrid molecular structure of the two electron‐accepting units: bipyridyl and oxadiazole, and the planar molecular structure based on its lack of sterically hindered bulky substituent. The computational analysis elucidates that the amorphous nature of Bpy‐OXD in thin‐film state probably results from the polymorphic effect in isolated state and the volume effect in solid state. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nonlinear optics of chiral surface systems

Differential SHG signals from chiral surfaces are recorded using right and left circularly polarized incident light. We show that chiral information from the surface is conveyed through this SHG process. This study focuses on the model protein system, cytochrome c, adsorbed on various self-assembled mono- and bi-layers at the solid/liquid interface. SHG-CD signals are shown to be related to the oxidation state of the protein and are utilized to observe changes in this feature of the protein in situ at surfaces of varying chemical properties. Received: 20 September 1998 / Revised version: 9 December 1998     

Characterization of soft-X-ray detectors fabricated with high-quality CVD diamond thin films

We have characterized the performance of soft-X-ray detectors fabricated with undoped and B-doped homoepitaxial diamond layers of high quality which were grown on a commercially available type Ib (1 0 0) substrate by means of a high-power microwave-plasma chemical-vapor-deposition (CVD) method. The signal currents of the diamond-based detectors with thin TiN electrodes formed vertically (along the homoepitaxial growth direction) were measured at room temperature as a function of the applied voltage, V_a, for irradiations of 500-1200 eV soft-X-ray beams ranging from ≈6 × 10⁹ to ≈1 × 10¹¹ photons/s. The deduced apparent quantum efficiencies increased with the increasing V_a and reached to 2.5 × 10³ at V_a = 60 V. As expected from the device structure, the detector performance depended only very slightly on the applied magnetic field up to 10 T. The excellently high sensitivities attained for soft-X-ray photons are discussed in relation to carrier amplification mechanisms which invested the above diamond detectors.     

Interface characterization and current conduction in HfO2-gated MOS capacitors

Metal-oxide-semiconductor (MOS) capacitors incorporating hafnium dioxide (HfO₂) dielectrics were fabricated and investigated. In this work, the electrical and interfacial properties were characterized based on capacitance-voltage (C-V) and current-voltage (I-V) measurements. Thereafter the current conduction mechanism, electron effective mass (m*), mean density of interface traps per unit area and energy (), energy distribution of interface traps density and near-interface oxide traps density (N_NIOT) were studied in details. The characterization reveals that the dominant conduction mechanism in the region of high temperature and high field is Schottky emission. The mean density of interface traps per unit area and energy is about 6.3 × 10¹² cm⁻² eV⁻¹ by using high-low frequency capacitance method. The maximum D_it is about 7.76 × 10¹² cm⁻² eV⁻¹ located at 0.27 eV above the valence band.     

Catalysed growth of novel aluminium oxide nanorods

Micron-scale coral-like aluminium oxide structures have been generated by heating a mixture of AlB₂ and Co powders in a quartz boat at ca. 1050 °C under N₂. Upon sonication in acetone, the structures break down into elongated single-crystal aluminium oxide nanorods ranging from 20 to 200 nm in diameter and up to 5 μm in length. Single Co particles are often found attached to nanorod tips. A vapour–liquid–solid (V–L–S) mechanism appears to be responsible for the aluminium oxide nanorod growth. Received: 21 January 2003 / Accepted: 22 January 2003 / Published online: 28 March 2003 RID="*" ID="*"Corresponding author. E-mail: d.walton@sussex.ac.uk