Praseodymium silicide formation at the Pr2O3/Si interface

The interface and layer structure of praseodymium (Pr) oxide layers grown on Si(0 0 1) from a high-temperature effusion cell are studied using grazing incidence X-ray diffraction. Due to the interdiffusion of praseodymium and silicon atoms, Pr silicide forms in the layers. We find that Pr silicide is the favorable structure under oxygen deficient growth conditions in the Pr oxide layer. To avoid the silicidation, additional oxygen must be supplied. The formation of Pr silicide is suppressed for layers grown with an oxygen partial pressure of 10⁻⁷ mbar at a substrate temperature of 700 °C.     

Polymeric sheets in Mg4C60

We present preliminary results on the preparation and structure of Mg₄C₆₀, a new fulleride polymer. A series of Mg_xC₆₀ compositions (0<x<6) were prepared by solid state reaction. While most samples were multiphase, a single phase material was obtained at the nominal composition Mg₄C₆₀. The X-ray diffraction pattern of Mg₄C₆₀ was successfully indexed and fitted to a rhombohedral structure based on two-dimensional polymeric sheets of C₆₀ ions. This result extends the family of fulleride polymers to the salts of multiply charged cations and thus opens a new direction in this field.     

Charge ordering in charge-compensated Na0.41CoO2 by oxonium ions

Charge ordering behavior is observed in the crystal prepared through the immersion of the Na_0.41CoO₂ crystal in distilled water. Discovery of the charge ordering in the crystal with Na content less than 0.5 indicates that the immersion in water brings about the reduction of the Na_0.41CoO₂. The formal valence of Co changes from +3.59 estimated from the Na content to +3.50, the same as that in Na_0.5CoO₂. The charge compensation is confirmed to arise from the intercalation of the oxonium ions as occurred in the superconducting sodium cobalt oxide bilayer-hydrate [K. Takada, et al. J. Mater. Chem. 14 (2004) 1448]. The charge ordering is the same as that observed in Na_0.5CoO₂. It suggests that the Co valence of +3.50 is necessary for the charge ordering.     

New features in the pressure dependence of photoluminescence spectra of C60 at room temperature

We present new results on the pressure dependence of the electronic band gap of molecular C₆₀ measured by photoluminescence spectroscopy up to 10 GPa at room temperature. In agreement with previous results, the energy gap decreases with increasing pressure up to about 6 GPa. For higher pressures, however, we observe an energy gap that is wider than that at 6 GPa.     

The application of RHEED intensity effects to interrupted growth and interface formation during MBE growth of GaAs/(Al,Ga)As structures

There is a diffraction-induced phase effect in the RHEED intensity oscillation technique used in MBE, whereby intensity maxima only correspond to monolayer completion for very restricted conditions. In particular, the angle of incidence of the primary beam is extremely critical. The effect occurs because the total intensity at the measured position of the specular beam is always derived from at least two different diffraction processes, which do not have the same phase relation to monolayer formation. It can be accomodated either by a systematic series of measurements to establish an empirical relationship between incidence angle and phase, or by Fourier transform techniques. Unless full account is taken of this purely diffraction-induced effect, very misleading results can be obtained for the time constants of the recovery period following cessation of growth and this is illustrated for GaAs. The effect also has important implications for the growth-interrupt technique. In addition, it is shown that for heterojunction formation in the GaAs/(Al, Ga)As system, adatom (Ga and Al) migration lengths are of greater importance than the position in the monolayer at which the composition is changed, and that RHEED can provide only limited information on the interface structure.     

Site selectivities of alkali ions in CsRb2C60 and Cs2RbC60 superconductors

The temperature-dependent site selectivities of Cs and Rb ions in CsRb₂C₆₀ and Cs₂RbC₆₀ superconductors are computed using the free energy obtained from the configuration entropy and the total energy calculated using the ab initio pseudopotential density-functional theory. It is found that in CsRb₂C₆₀ the smaller Rb ions can occupy a considerable number of large octahedral interstitial sites at high temperatures, however, the transition to random occupation never takes place. For Cs₂RbC₆₀ the Cs occupancy of the large octahedral interstitial sites is almost always 100%, and, interestingly, the two tetrahedral interstitial sites are randomly occupied by Cs and Rb ions even at very low temperatures.     

Growth of InN films on spinel substrates by pulsed laser deposition

We have grown InN films on MgAl₂O₄(111) substrates with atomically flat surfaces using pulsed laser deposition (PLD) and compared their structural properties with those grown on (Mn,Zn)Fe₂O₄(111) substrates. It has been revealed that InN(0001) films grow on MgAl₂O₄(111) with an in‐plane epitaxial relationship of InN[1 00] // MgAl₂O₄[1 0], achieving a lattice mismatch minimum. The InN films exhibited a clear sixfold rotational symmetry, without 30° rotational domains and with a full width at half maximum value of the InN 0002 rocking curve being 17.5 arcmin. Comparison between InN films grown on MgAl₂O₄ and those on (Mn,Zn)Fe₂O₄ led us to conclude that suppression of the interfacial reactions between the InN films and the substrate is inherently important to obtain high quality InN on substrates with a spinel structure. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microstructure of epitaxial SrRuO3 thin films on MgO substrates

SrRuO₃ thin films have been grown on singular (1 0 0) MgO substrates using pulsed laser deposition (PLD) in 30 Pa oxygen ambient and at a temperature of 400-700 °C. Ex situ reflection high-energy electron diffraction (RHEED) as well as X-ray diffraction (XRD) θ/2θ scan indicated that the films deposited above 650 °C were well crystallized though they had a rough surface as shown by atom force microscopy (AFM). XRD Φ scans revealed that these films were composed of all three different types of orientation domains, which was further confirmed by the RHEED patterns. The heteroepitaxial relationship between SrRuO₃ and MgO was found to be [1 1 0] SRO//[1 0 0] MgO and 45°-rotated cube-on-cube [0 0 1] SRO//[1 0 0] MgO. These domain structures and surface morphology are similar to that of ever-reported SrRuO₃ thin films deposited on the (0 0 1) LaAlO₃ substrates, and different from those deposited on (0 0 1) SrTiO₃ substrates that have an atomically flat surface and are composed of only the [1 1 0]-type domains. The reason for this difference was ascribed to the effect of lattice mismatch across the film/substrate interface. The room temperature resistivity of SrRuO₃ films fabricated at 700 °C was 300 μΩ cm. Therefore, epitaxial SrRuO₃ films on MgO substrate could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Mechanism of single-walled carbon nanotube growth on natural magnesite

Fe K-edge X-ray absorption fine structure (XAFS) measurements were performed in order to elucidate the formation mechanism of single-walled carbon nanotubes (SWCNTs) grown on natural magnesite by pyrolyzing methane gas. It was clearly shown by XAFS analyses that iron metal fine particles, which were reduced from iron oxides by methane gas, worked as a catalyst for SWCNT growth. Structural characteristics of the initial iron state in the natural magnesite were also discussed.     

Effect of microstructure of MgO buffer layer on BaTiO3 grown on silicon substrates

MgO ultrathin films were grown on Si(1 0 0) substrates as buffer layers for the growth of ferroelectric BaTiO₃ thin films by laser molecular beam epitaxy (L-MBE). The deposition process of MgO buffer layers grown on silicon was in situ monitored by reflection high-energy electron diffraction (RHEED). The structure of BaTiO₃ films fabricated on MgO buffers was investigated by X-ray diffraction. Biaxially textured MgO was obtained at high laser energy density, but when the laser energy was lowered, MgO buffer was transformed to the form of texture with angular dispersion with the increase of the film thickness. BaTiO₃ films grown on the former buffer were completely (0 0 1) textured, while those on the latter were (0 0 1) preferred orientated. Furthermore, the fabricated MgO buffers and BaTiO₃ films had atomically smooth surface and interface. All these can reveal that the quality of textured MgO buffer is a key factor for the growth of BaTiO₃ films on silicon.     

Isothermal equation of state for the skutterudites CoSb3 and LaFe3CoSb12

The thermoelectric materials CoSb₃ and LaFe₃CoSb₁₂ with skutterudite structure were subjected to high pressures using a diamond anvil high-pressure cell up to 20 GPa. Energy-dispersive X-ray diffraction was used to determine the dependence of the lattice parameter on pressure. No major change in the X-ray diffraction spectra was observed for both compounds, constituting evidence that both compounds are stable within this pressure range, despite their relatively open structures. Three distinct isothermal equations of state for solids under high pressure were fitted to the experimental data to determine the bulk modulus for both compounds. The filled skutterudite showed a greater compressibility than the unfilled one, this difference can be understood in terms of the larger lattice parameter of the former.     

Stress Analysis of ZnO Film with a GaN Buffer Layer on Sapphire Substrate

A 5.35-μm-thick ZnO film is grown by chemical vapour deposition technique on a sapphire （0001） substrate with a GaN buffer layer. The surface of the ZnO film is smooth and shows many hexagonal features. The full width at half maximum of ZnO （0002） u-rocking curve is 161 arcsec, corresponding to a high crystal quality of the ZnO film. From the result of x-ray diffraction 0 - 20 scanning, the stress status in ZnO film is tensile, which is supported by Raman scattering measurement. The reason of the tensile stress in the ZnO film is analysed in detail. The lattice mismatch and thermal mismatch are excluded and the reason is attributed to the coalescence of grains or islands during the growth of the ZnO film.     

Bi induced step-flow growth in the homoepitaxial growth of Au(1 1 1)

Homoepitaxial growth of Au on Bi-covered Au(1 1 1) was studied at room temperature using reflection high-energy electron diffraction (RHEED) and Auger electron spectroscopy (AES). From observations of RHEED it is found that the Au(1 1 1) (23 × 1) reconstruction structure changes to a (1 × 1) by about 0.16-0.5 ML deposition of Bi and to a (2√3 × 2√3)R30° by about 1.0 ML deposition of Bi, respectively. The surface morphology evolution by Bi deposition leads to a change of Au homoepitaxial growth behavior from layer-by-layer to step flow. This indicates that the surface diffusion distance of Au atoms on the Bi-precovered (1 × 1) and (2√3 × 2√3)R30° surfaces is longer than that on the Au(1 1 1) (23 × 1) clean surfaces. A strong surface segregation of Bi was found at top of surface. It is concluded that Bi atoms acted as an effective surfactant in the Au homoepitaxial growth by promoting Au intralayer mass transport.     

Conductance and EPR study of the endohedral fullerene Li@C60

Thin films and bulk samples of endohedral fullerenes Li@C₆₀ are studied using current-voltage (I-V) measurements and electron paramagnetic resonance (EPR). Electrical measurements show a linear behaviour for the I-V curves and give an average resistivity of ca. 1.5 kΩcm for thin Li@C₆₀ films deposited in vacuum, four orders of magnitude lower than C₆₀ samples. A drastic effect on the conductance, lowering it to the values typical for C₆₀, is observed when the Li@C₆₀ samples are exposed to ambient atmosphere. No additional paramagnetic centres (PCs) are found for the Li@C₆₀ compared to C₆₀ that can be related to the formation of dimers or trimers of the endohedral fullerene molecules. However, the presence of the Li atoms in the fullerene cages contributes to a change of the spin-spin and spin-lattice relaxation times. The spin-lattice relaxation time becomes four orders of magnitude longer compared to the spin-spin relaxation time.     

Effects of diffraction conditions and processes on rheed intensity oscillations during the MBE growth of GaAs

The RHEED intensity oscillation technique has received wide-spread attention for the study of MBE growth dynamics, but insufficient consideration has been given to the diffraction conditions and processes involved. We report here a systematic investigation of the intensity oscillation behaviour as a function of diffraction parameters (azimuth, incidence angle, specular and non-specular beams), with constant growth conditions for GaAs films on GaAs (001) substrates.We show that many reported anomalies attributed to growth effects, such as phase differences and periodicity variations, can be accounted for entirely by diffraction events, provided it is realised that multiple scattering processes are the dominant cause of RHEED intensity variations during growth.The technique can provide valuable information on growth behaviour, but only if diffraction-dependent effects are first eliminated.     

InGaP/GaAs heterojunction bipolar transistor grown by solid-source molecular beam epitaxy with a GaP decomposition source

Lattice-matched InGaP epilayers on GaAs (001) and InGaP/GaAs heterojunction bipolar transistors (HBTs) were successfully grown by solid-source molecular beam epitaxy (SSMBE) with a GaP decomposition source. A 3 μm thick InGaP epilayer shows that low temperature photoluminescence (PL) peak energy is as large as 1.998 eV, full width at half maximum (FWHM) is 5.26 meV, which is the smallest ever reported, and X-ray diffraction (XRD) rocking curve linewidth is as narrow as that of GaAs substrate. The electron mobilities at room temperature of nominally undoped InGaP layers obtained by Hall measurements are comparable to similar InGaP epilayer grown by solid-source molecular beam epitaxy (SSMBE) with other sources or other growth techniques. The large area InGaP/GaAs HBTs show very good Dc characteristics.     

Photocatalytic property of TiO2 thin films sputtered-deposited on unheated substrates

TiO₂ films deposited on unheated substrates of alumina silicate glass by rf. (13.56 MHz) magnetron sputtering in the mixture of O₂ and Ar gases have been studied with X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and optical spectroscopy. Structural and optical properties of TiO₂ films deposited at different O₂ concentrations and total pressures have been analyzed. Photocatalytic properties of TiO₂ films were characterized by following the degradation of methylene blue molecules under UV irradiation. It was found that the rate of methylene blue decomposition strongly depends on morphology and crystallinity of the deposited films, namely on the content of the anatase phase and on the size of the anatase grains. The best photocatalytic activity was found on TiO₂ films consisting of pure anatase phase with the size of grains of about 450 Å. With the help of those films a thin film reactor for water purification has been designed and tested.     

STM study of the initial stages of C60 adsorption on the Pt(1 1 0)-(1 × 2) surface

We have studied the initial stages of adsorption of C₆₀ on the Pt (1 1 0)-(1 × 2) surface by means of STM. At room temperature, fullerene molecules adsorb in the troughs between two adjacent Pt rows of the missing row reconstruction. Mobility over the terraces is negligible, denoting strong bonding with the surface, also testified by a well-defined orientation of fullerene monomers with respect to the substrate. Upon annealing at 750 K, molecular migration towards kinks and step edges occurs, where small islands nucleation begins. A commensurate registry with the substrate is maintained by small (5-10 molecules) C₆₀ aggregates, leading to expanded nearest-neighbour distances with respect to those found in hexagonal close packed fullerene ad-islands grown on other metallic substrates.     

Extended X-ray absorption fine-structure (EXAFS) of a complex oxide structure: a full multiple scattering analysis of the Au L3-edge EXAFS of Au2O3

Crystalline Au₂O₃ was obtained by hydrothermal synthesis at 3000 atm and its extended X-ray absorption fine-structure (EXAFS) at the Au L₃-edge was measured at room temperature. A detailed full multiple scattering (MS) analysis using FEFF8 theory shows that only a small number of scattering paths contribute significantly to the EXAFS of Au₂O₃. Because of the complex unit cell (low local symmetry) of the Au₂O₃ structure, contributions of MS paths are almost negligible. The results indicate that FEFF8 theory provides a good reference for the analysis of Au-O phases.