Oxygen on Fe(1 1 0): magnetic properties of the adsorbate system

Investigations concerning the electronic and magnetic properties of oxygen adsorbed on magnetized iron films were carried out by means of angle and spin resolving photoelectron spectroscopy. Iron(1 1 0), epitaxially grown on a W(1 1 0) crystal, served as the ferromagnetic substrate. Exchange splittings of the O 2p_x derived level were detected demonstrating a magnetic coupling between the chemisorbate and the iron layer. This observation indicates the presence of an induced magnetic moment within the adsorbate overlayer. Variations of the exchange splitting occurred as a function of the oxygen coverage, energy of the exciting radiation, and detection angle of the emitted photoelectrons pointing to a k₆-dependent exchange splitting. High oxygen exposures lead to a FeO overlayer at the surface, showing vanishing peak separations due to the antiferromagnetic behavior of iron oxide.     

Image quality of microns-thick specimens in the ultra-high voltage electron microscope

Image quality of MeV transmission electrons is an important factor for both observation and electron tomography of microns-thick specimens with the high voltage electron microscope (HVEM) and the ultra-HVEM. In this work, we have investigated image quality of a tilted thick specimen by experiment and analysis. In a 3 MV ultra-HVEM, we obtained transmission electron images in amplitude contrast of 100 nm gold particles on the top surface of a tilted 5 μm thick amorphous epoxy-resin film. From line profiles of the images, we then measured and evaluated image blurring, contrast, and the signal-to-noise ratio (SNR) under different effective thicknesses of the tilted specimen and accelerating voltages of electrons. The variation of imaging blurring was consistent with the analysis based on multiple elastic scattering. When the effective thickness almost tripled, image blurring increased from ～3 to ～20 nm at the accelerating voltage of 3 MV. For the increase of accelerating voltage from 1 to 3 MV in the condition of the 14.6 μm effective thickness, due to the reduction of multiple scattering effects, image blurring decreased from ～54 to ～20 nm, and image contrast and SNR were both obviously enhanced by a factor of ～3 to preferable values. The specimen thickness was shown to influence image quality more than the accelerating voltage. Moreover, improvement on image quality of thick specimens due to increasing the accelerating voltage would become less when it was further increased from 2 to 3 MV in this work.     

Stress and morphological development of CdS and ZnS thin films during the SILAR growth on (1 0 0)GaAs

Cadmium sulfide and zinc sulfide films were grown on (1 0 0)GaAs substrate by successive ionic layer adsorption and reaction (SILAR) technique from aqueous precursor solutions at room temperature and normal pressure. The stress development of the thin films was characterized by laser interferometry as a function of the thickness of the films. The morphology and roughness of the films were monitored by atomic force microscopy. Additionally the crystallinity and crystallite size were analyzed by X-ray diffraction and composition by electron spectroscopy for chemical analysis. The CdS thin films had significantly higher stress level and also better crystallinity compared with ZnS thin films. Both films were polycrystalline and cubic, but the CdS thin films followed the substrate (1 0 0) orientation, whereas the ZnS films were (1 1 1) orientated. The roughness vs. film thickness curves of both films followed each other in shape, but the CdS films consisted of smaller particles.     

Oxidation of ultra-thin zinc films on Rh(100) surface

The oxidation of submonolayer zinc films on Rh(100) surface by O₂ gas has been studied using low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), and scanning tunneling microscopy (STM). With a zinc coverage of 0.8 ML, an atomically flat ultra-thin zinc oxide film formed at an oxygen partial pressure of 2 × 10^? 8 mbar and a temperature of 150 °C. The zinc oxide film showed a c(16 × 2) LEED pattern. The high resolution STM image of the zinc oxide film showed single dotted spots and double dotted spots arranged linearly and periodically along the [01¯1] direction. We propose an atomic arrangement model of the film accounting for the LEED pattern, the STM image, and the atomic arrangement of the bulk ZnO(0001) surface.     

Optical properties of Cr/Fe(t)/MgO (0 0 1) thin films

In this work we report on the optical properties of single-crystalline iron thin films. For this, Cr-capped Fe films with thickness, t, in the range 30–300 Å were prepared on MgO (0 0 1) by DC magnetron sputtering, and then studied by optical absorption technique within the range from 1.0 to 3.6 eV. All measurements were carried out at room temperature using a fiber optics spectrophotometer. The intensity of the transmitted light decreases with increasing film thickness. The optical constants of the films are deduced from a model that considers the transmission of light by two absorbing films on an absorbing substrate. The absorption coefficient of the Fe films is also calculated from the transmission data. The absorption spectra show the following characteristics: (i) two large absorption peaks centered at about 1.20 and 2.65 eV; and (ii) a sharp step near 1.40 eV. These structures are associated with conventional interband transitions of the iron film.     

The effect of spacer layer thickness on vertical alignment of InGaAs/GaNAs quantum dots grown on GaAs(3 1 1)B substrate

We fabricated multiple stacked self-organized InGaAs quantum dots (QDs) on GaAs (3 1 1)B substrate by atomic hydrogen-assisted molecular beam epitaxy (H-MBE) to realize an ordered three-dimensional QD array. High quality stacked QDs with good size uniformity were achieved by using strain-compensation growth technique, in which each In_0.35Ga_0.65As QD layer was embedded by GaNAs strain-compensation layer (SCL). In order to investigate the effect of spacer layer thickness on vertical alignment of InGaAs/GaNAs QDs, the thickness of GaNAs SCL was varied from 40 to 20 nm. We observed that QDs were vertically aligned in [3 1 1] direction when viewed along [0 1 −1], while the alignment was inclined when viewed along [−2 3 3] for all samples with different SCL thickness. This is due to their asymmetric shape along [−2 3 3] with two different dominant facets thereby the local strain field around QD extends further outward from the lower-angle facet. Furthermore, the inclination angle of vertical alignment QDs became monotonously smaller from 22° to 2° with decreasing SCL thickness from 40 to 20 nm. These results suggest that the strain field extends asymmetrically resulting in vertically tilted alignment of QDs for samples with thick SCLs, while the propagated local strain field is strong enough to generate the nucleation site of QD formation just above lower QD in the sample with thinner SCLs.     

Influence of growth temperature and deposition duration on the structure,surface morphology and optical properties of InN/YSZ (1 0 0)

InN films with the wurtzite structure have been grown directly on YSZ (1 0 0) substrate by the RF-magnetron sputtering technique. Strongly (0 0 2) oriented films with smooth surfaces (0.7–2.9 nm surface roughness depending on substrate temperature), were grown within 30 min. Films deposited for 60 min developed three-dimensional (3D) pyramidal islands on top of their surfaces, which diminished the residual elastic strain. The optical absorption edge and PL peak energy around 1.7 eV were found to redshift with increasing film thickness and substrate temperature.     

Experimental study of annular bright field (ABF) imaging using aberration-corrected scanning transmission electron microscopy (STEM)

Experimental parameters used in the annular bright field (ABF) imaging method were tested using images simulated with the multislice method. Images simulated under identical conditions were found to agree well with experimental images. The ABF technique was shown to be relatively insensitive to the sample thickness and the defocus. In experimental ABF images, atomic columns exhibited dark contrast over a wide range of specimen thickness and defocus values, from 10 to 70 nm and ?20 to +20 nm, respectively. A series of diffraction patterns at atomic columns, obtained using the diffraction imaging method, exhibited higher intensities in their central regions (0–11 mrad) for light elements and in their peripheral regions (11–22 mrad) for heavy elements. The results indicated that the contrast of light elements is enhanced by subtraction of the central region of the transmitted beam, since this is blocked by a circular mask in the ABF-STEM technique. Thus, the overall contrast of light elements is greatly improved, allowing them to be clearly visualized.     

Coverage-dependent molecular tilt of carbon monoxide chemisorbed on Pt{110}: A combined LEED and DFT structural analysis

The adsorption of carbon monoxide on the Pt{110} surface at coverages of 0.5 ML and 1.0 ML was investigated using quantitative low-energy electron diffraction (LEED IV) and density-functional theory (DFT). At 0.5 ML CO lifts the reconstruction of the clean surface but does not form an ordered overlayer. At the saturation coverage, 1.0 ML, a well-ordered p(2 × 1) superstructure with glide line symmetry is formed. It was confirmed that the CO molecules adsorb on top of the Pt atoms in the top-most substrate layer with the molecular axes tilted by ± 22° with respect to the surface normal in alternating directions away from the close packed rows of Pt atoms. This is accompanied by significant lateral shifts of 0.55 Å away from the atop sites in the same direction as the tilt. The top-most substrate layer relaxes inwards by ? 4% with respect to the bulk-terminated atom positions, while the consecutive layers only show minor relaxations. Despite the lack of long-range order in the 0.5 ML CO layer it was possible to determine key structural parameters by LEED IV using only the intensities of the integer-order spots. At this coverage CO also adsorbs on atop sites with the molecular axis closer to the surface normal (< 10°). The average substrate relaxations in each layer are similar for both coverages and consistent with DFT calculations performed for a variety of ordered structures with coverages of 1.0 ML and 0.5 ML.     

Identification of iron oxide phases in thin films grown on Al2O3(0 0 0 1) by Raman spectroscopy and X-ray diffraction

We report on the identification of Fe₃O₄ (magnetite) and α-Fe₂O₃ (hematite) in iron oxide thin films grown on α-Al₂O₃(0 0 0 1) by evaporation of Fe in an O₂-atmosphere with a thickness of a few unit cells. The phases were observed by Raman spectroscopy and confirmed by X-ray diffraction (XRD). Magnetite appeared independently from the substrate temperature and could not be completely removed by post-annealing in an oxygen atmosphere as observed by X-ray diffraction. In the temperature range between 400 °C and 500 °C the X-ray diffraction shows that predominantly hematite is formed, the Raman spectrum shows a mixture of magnetite and hematite. At both lower and higher substrate temperatures (300 °C and 600 °C) only magnetite was observed. After post-annealing in an O₂-atmosphere of 5 × 10^?5 mbar only hematite was detectable in the Raman spectrum.     

Influence of argon ambience on the structural,morphological and optical properties of pulsed laser ablated zinc sulfide thin films

Nanostructured zinc suplhide thin films are successfully deposited on quartz substrates using pulsed laser deposition (PLD) under different argon pressures (0, 5, 10, 15 and 20 Pa). The influence of argon ambience on the microstructural, optical and luminescence properties of zinc sulfide (ZnS) thin films is systematically investigated. The GIXRD data suggests rhombohedral structure for ZnS films prepared under different argon ambience. Self-assembly of grains into well-defined patterns along the y direction is observed in the AFM image of the film deposited under argon pressure 20 Pa. All the films show a blue shift in optical band gap. This can be due to the quantum confinement effect and less widening of conduction and valence band for the films with less thickness and smaller grain size. The PL spectra of the different films are recorded at excitation wavelengths 250 nm and 325 nm and the spectra are interpreted. The PL spectra of the films recorded at excitation wavelength 325 nm show intense yellow emission. The film deposited under an argon pressure of 15 Pa shows the highest PL intensity for excitation wavelength 325 nm. For the PL spectra (excitation at 250 nm), the highest PL intensity is observed for the film prepared under argon free ambience. In our study, 15 Pa is the optimum argon pressure for better crystallinity and intense yellow emission when excited at 325 nm.     

Attenuation lengths of high energy photoelectrons in compact and mesoporous SiO2 films

We have experimentally evaluated attenuation lengths (AL) of photoelectrons traveling in compact and micro and mesoporous (~ 45% voids) SiO₂ thin films with high (8.2–13.2 keV) kinetic energies. The films were grown on polished Si(100) wafers. ALs were deduced from the intensity ratio of the Si 1s signal from the SiO₂ film and Si substrate using the two-peaks overlayer method. We obtain ALs of 15–22 nm and 23–32 nm for the compact and porous SiO₂ films for the range of kinetic energies considered. The observed AL values follow a power law dependence on the kinetic energy of the electrons where the exponent takes the values 0.81 ± 0.13 and 0.72 ± 0.12 for compact and porous materials, respectively.     

Hard antireflective films of SiAlON for zinc sulfide in 3–5 μm regions

SiAlON films with antireflective and protective functionality for zinc sulfide were prepared by an ion beam sputtering method. A great transmittance improvement (at 3.8 μm) of 25.1% has been realized for zinc sulfide substrate. At the same time, the in situ high temperature transmittance was also recorded and it was proven that the SiAlON films on zinc sulfide window materials can keep thermal stability well at temperature as high as 250 °C in the region of 3–5 μm. The micro hardness of the zinc sulfide was improved by 75% in average after being coated with SiAlON films, and the SiAlON films possess good behaviors in harsh environmental tests including adhesion, abrasion, moisture, and thermal shock circle.     

Preparation of cadmium stannate films by spray pyrolysis technique

Cadmium stannate thin films were prepared by spray pyrolysis technique using cadmium acetate and tin(II) chloride precursors at substrate temperatures 450 °C and 500 °C. XRD pattern confirms the formation of orthorhombic (1 1 1) cadmium stannate phase for the film prepared at substrate temperature of 500 °C, whereas, films prepared at 450 °C are amorphous. Film formation does not occur at substrate temperature from 300 to 375 °C. SEM images reveal that the surface of the prepared Cd₂SnO₄ film is smooth. The average optical transmittance of ∼86% is obtained for the film prepared at substrate temperature of 500 °C with the film thickness of 400 nm. The optical band gap value of the films varies from 2.7 to 2.94 eV. The film prepared at 500 °C shows a minimum resistivity of 35.6 × 10⁻⁴ Ω cm.     

Shell thickness determination of polymer-shelled microbubbles using transmission electron microscopy

Intravenously injected microbubbles (MBs) can be utilized as ultrasound contrast agent (CA) resulting in enhanced image quality. A novel CA, consisting of air filled MBs stabilized with a shell of polyvinyl alcohol (PVA) has been developed. These spherical MBs have been decorated with superparamagnetic iron oxide nanoparticles (SPIONs) in order to serve as both ultrasound and magnetic resonance imaging (MRI) CA. In this study, a mathematical model was introduced that determined the shell thickness of two types of SPIONs decorated MBs (Type A and Type B). The shell thickness of MBs is important to determine, as it affects the acoustical properties. In order to investigate the shell thickness, thin sections of plastic embedded MBs were prepared and imaged using transmission electron microscopy (TEM). However, the sections were cut at random distances from the MB center, which affected the observed shell thickness. Hence, the model determined the average shell thickness of the MBs from corrected mean values of the outer and inner radii observed in the TEM sections. The model was validated using simulated slices of MBs with known shell thickness and radius. The average shell thickness of Type A and Type B MBs were 651 nm and 637 nm, respectively.     

ZnO nanocubes with (1 0 1) basal plane photocatalyst prepared via a low-frequency ultrasonic assisted hydrolysis process

The crystallographic plane of the ZnO nanocrystals photocatalyst is considered as a key parameter for an effective photocatalysis, photoelectrochemical reaction and photosensitivity. In this paper, we report a simple method for the synthesis of a new (1 0 1) high-energy plane bounded ZnO nanocubes photocatalyst directly on the FTO surface, using a seed-mediated ultrasonic assisted hydrolysis process. In the typical procedure, high-density nanocubes and quasi-nanocubes can be grown on the substrate surface from a solution containing equimolar (0.04 M) zinc nitrate hydrate and hexamine. ZnO nanocubes, with average edge-length of ca. 50 nm, can be obtained on the surface in as quickly as 10 min. The heterogeneous photocatalytic property of the sample has been examined in the photodegradation of methyl orange (MO) by UV light irradiation. It was found that the ZnO nanocubes exhibit excellent catalytic and photocatalytic properties and demonstrate the photodegradation efficiency as high as 5.7 percent/μg mW. This is 200 times higher than those reported results using a relatively low-powered polychromatic UV light source (4 mW). The mechanism of ZnO nanocube formation using the present approach is discussed. The new-synthesized ZnO nanocubes with a unique (1 0 1) basal plane also find potential application in photoelectrochemical devices and sensing.     

Proton transfer in water–hydroxyl mixed overlayers on Pt(1 1 1): Combined approach of laser desorption and spatially-resolved X-ray photoelectron spectroscopy

Proton transfer in water–hydroxyl mixed overlayers on a Pt(1 1 1) surface was studied by a combination of laser induced thermal desorption (LITD) method and spatially-resolved X-ray photoelectron spectroscopy (micro-XPS). The modulated pattern OH + H₂O/H₂O/OH + H₂O was initially prepared by the LITD method; vacant area with a 400 μm width was first formed in the mixed OH + H₂O overlayer by irradiation of focused laser pulses, and followed by refilling the vacant area with pure H₂O. Spatial distribution changes of OH and H₂O were measured as a function of time with the micro-XPS technique, which indicated that H₂O molecules in the central region flow into the OH + H₂O region. From quantitative analyses using a diffusion equation, we found that the proton transfer in the mixed overlayer consists of at least two pathways: direct proton transfer from H₂O to OH in the nearest site and the proton transfer to the next-nearest site via H₃O⁺ formation. The time scale of first and second path was estimated to be 5.2 ± 0.9 ns and 48 ± 12 ns at 140 K, respectively. In the presence of water capping layer, however, the rate of proton transfer is reduced by an order of magnitude, which would be explained by peripatetic behavior of proton into H₂O capping layer.     

Microstructure and characterization of Al-doped ZnO films prepared by RF power sputtering on Al and ZnO targets

Al-doped zinc oxide (AZO) transparent conductive films were prepared on a glass substrate using a magnetron sputtering system with a pure zinc oxide (ZnO) target and a pure Al target sputtered using radio frequency (RF) power. The RF power was set at 100 W for the ZnO target and varied from 20 to 150 W for the Al target. The morphology of the thin films was examined by field-emission scanning electron microscope (FE-SEM), and their composition was analyzed by the equipped energy-dispersive X-ray spectroscopy (EDS). The cross section of the films determined through FE-SEM indicated that their thickness was around 650 nm. EDS analysis revealed that the Al-dopant concentration of the AZO films increased in the following order: 0.85 at.% (20 W) < 1.60 at.% (40 W) < 3.52 at.% (100 W) < 4.34 at.% (150 W). Analysis of the films using X-ray diffractometer (XRD) indicated that all films had a wurtzite structure with a texture of (0 0 2). High-resolution transmission electron microscopy (HRTEM) revealed a number of defects in the films, such as stacking faults and dislocations. Ultraviolet photoelectron spectroscopy (UPS) was used to estimate the optical energy gap (E_g) for the AZO thin films. The energy gap increases from 3.39 to 3.58 eV as the RF power applied to the Al target increase. The electrical resistivity of the films decreased from 3.43 × 10^?2 Ω cm to 3.29 × 10^?3 Ω cm as the RF power increased from 20 to 150 W when a four-point probe was used to investigate. Atomic force microscope (AFM) revealed that the surface roughness of the films increased with increasing RF power. The average optical transmittance of the films was determined by UV–visible spectrometer. The films are suitable for use as transparent conductive oxide films in the optoelectronic industry. A decrease in the electrical resistivity of the film with increasing Al-dopant concentration was ascribed to an increase in the carrier concentration and density of stacking faults in the films.     

Scanning tunneling microscope study of nanosized metal–semiconductor contacts between ErSi2 nanoislands and Si(0 0 1) substrate

The current–voltage (I–V) characteristics of the nanosized metal–semiconductor contacts formed between the epitaxially grown ErSi₂ islands and p-Si(0 0 1) substrate are measured in situ by the scanning tunneling microscope. Experimental results show that the current densities passing through the nanocontacts are five orders of magnitude larger than that of the macroscopic ones and have an obvious dependence on the contact area. Especially, it is found that I–V characteristics of the contacts are sensitive to the sample surface adsorption. Our investigations indicate that surface conduction plays an important role in the electrical transport process from ErSi₂ islands to the Si(0 0 1) substrate. Furthermore, for the nanocontacts with surface currents suppressed effectively, the ideality factor and the effective Schottky barrier height are estimated by using the standard thermionic emission model. Our analysis suggests that the current through the interface between ErSi₂ nanoislands and the p-Si(0 0 1) substrate is enhanced due to the effects of tunneling and image force lowering.     

Effect of film thickness on the transport properties of MgB2 synthesized by spray pyrolysis

Polycrystalline MgB₂ films of different thickness have been prepared by employing spray pyrolysis technique on MgO (1 0 0) substrate. The MgB₂ and other phases have been confirmed using X-ray diffraction technique and no trace of impurities phases have been found. The resistivity behavior shows that the superconducting transition temperature lies in the range of 37–39 K with narrow transition width. The transport critical current density vary with films thickness and achieved highest value ～1.2 × 10⁶ A/cm² at 20 K for 2.0 μm thick film and its values increase as thickness increases.