LEED and STM studies of the stability of the MoO2(100) surface

Atomic scale images and low energy electron diffraction pattern of a MoO₂(100) single crystal surface are presented, which show different structural modifications depending on surface preparation. A short in-situ heat treatment of the as-grown single crystal results in an atomically ordered surface whose diffraction pattern and STM images are consistent with those expected from the bulk structure. The symmetry of the STM images suggests an oxygen termination of the surface. A significantly longer heat treatment causes a thermodynamically stable (4 × 1) reconstruction which is interpreted to be due to a loss of oxygen chains. The (4 × 1) reconstruction vanishes after Ar-ion-sputtering and subsequent annealing. Additional long sputtering cycles result in a (2 × 1) reconstruction. The observed surface reconstructions can be transformed into each other by heating or sputtering cycles.     

Oxygen-rich Ti1−xO2 pillar growth at a gold nanoparticle–TiO2 contact by O2 exposure

In-situ gas-injection transmission electron microscopy revealed that a pillar grew at the edge of the interface of a gold nanoparticle and a TiO₂ substrate during exposure to O₂ gas at 100 Pa. The pillar was found to have a titanium-deficient chemical composition of Ti_1 ? xO₂ (x > 0) by electron energy loss spectroscopy (EELS). The spectra showed a chemical shift of oxygen and titanium ions to have ionic states of Ti³⁺ and O^y? (y < 3/2). The formation of the Ti_1 ? xO₂ at the contact edge of gold–Ti_1 ? xO₂ interface is discussed from the perspective of an O₂ affinity, which plays an important role in CO oxidation process of supported gold particle.     

Inversion recovery ultrashort echo time magnetic resonance imaging: A method for simultaneous direct detection of myelin and high signal demonstration of iron deposition in the brain – A feasibility study

Multiple sclerosis (MS) causes demyelinating lesions in the white matter and increased iron deposition in the subcortical gray matter. Myelin protons have an extremely short T2* (< 1 ms) and are not directly detected with conventional clinical magnetic resonance (MR) imaging sequences. Iron deposition also reduces T2*, leading to reduced signal on clinical sequences. In this study we tested the hypothesis that the inversion recovery ultrashort echo time (IR-UTE) pulse sequence can directly and simultaneously image myelin and iron deposition using a clinical 3 T scanner. The technique was first validated on a synthetic myelin phantom (myelin powder in D₂O) and a Feridex iron phantom. This was followed by studies of cadaveric MS specimens, healthy volunteers and MS patients. UTE imaging of the synthetic myelin phantom showed an excellent bi-component signal decay with two populations of protons, one with a T2* of 1.2 ms (residual water protons) and the other with a T2* of 290 μs (myelin protons). IR-UTE imaging shows sensitivity to a wide range of iron concentrations from 0.5 to ~ 30 mM. The IR-UTE signal from white matter of the brain of healthy volunteers shows a rapid signal decay with a short T2* of ~ 300 μs, consistent with the T2* values of myelin protons in the synthetic myelin phantom. IR-UTE imaging in MS brain specimens and patients showed multiple white matter lesions as well as areas of high signal in subcortical gray matter. This in specimens corresponded in position to Perl's diaminobenzide staining results, consistent with increased iron deposition. IR-UTE imaging simultaneously detects lesions with myelin loss in the white matter and iron deposition in the gray matter.     

Electron penetration depth in amorphous AlN exploiting the luminescence of AlN:Tm/AlN:Ho bilayers

The penetration depth of electron in amorphous aluminum nitride (AlN) is determined in terms of energy loss per unit length using electron beam in a cathodoluminescence (CL) apparatus. Thin films bilayers of holmium doped aluminum nitride (AlN:Ho) and thulium doped aluminum nitride (AlN:Tm) are deposited on silicon substrates by rf magnetron sputtering method at liquid nitrogen temperatures. The bilayers structure consisted of a 37.8 nm thick AlN:Tm film on the top of a 15.3 nm thick AlN:Ho film. Electron beam of different energies are allowed to penetrate the AlN:Tm/AlN:Ho bilayers film. The spectroscopic properties of AlN:Ho and AlN:Tm, the thickness of the film and the energies of electron beam are used to calculate the penetration depth of electron in amorphous AlN. Electron beam of 2.5 keV energy was able to pass through the 37.8 nm thick AlN:Tm film. The electron penetration depth for AlN is found to be 661.4 MeV/cm.     

Phase transition of Sr on Si (0 0 1): First principles prediction and experiment

The ability to understand and predict the phase diagrams of surface phases from first principles can be valuable for developing processes for growth of epitaxial structures. In the growth of epitaxial oxides on Si (0 0 1), a submonolayer phase of Sr plays a key role. The physical structure for this phase, which has 2 × 3 symmetry and occurs at 1/6 monolayer Sr coverage, was recently elucidated using both first principles theory and diffraction experiments [J.W. Reiner, K.F. Garrity, F.J. Walker, S. Ismail-Beigi, C.H. Ahn, Role of strontium in oxide epitaxy on silicon (0 0 1), Phys. Rev. Lett. 101 (10) (2008) 105503.]. Our approach to understanding the broader Sr/Si phase diagram combines density functional theory with a thermodynamic analysis of the phase equilibrium between a Sr lattice gas and the 2 × 3 structure. We use reflection high energy electron diffraction (RHEED) to experimentally determine the phase diagram, finding good agreement with theoretical predictions.     

Ultrasonic treatment of glassy carbon for nanoparticle preparation

Glassy carbon particles (millimetric or micrometric sizes) dispersions in water were treated by ultrasound at 20 kHz, either in a cylindrical reactor, or in a “Rosette” type reactor, for various time lengths ranging from 3 h to 10 h. Further separations sedimentation allowed obtaining few nanoparticles of glassy carbon in the supernatant (diameter <200 nm). Thought the yield of nanoparticle increased together with the sonication time at high power, it tended to be nil after sonication in the cylindrical reactor. The sonication of glassy carbon micrometric particles in water using “Rosette” instead of cylindrical reactor, allowed preparing at highest yield (1–2 wt%), stable suspensions of carbon nanoparticles, easily separated from the sedimented particles. Both sediment and supernatant separated by decantation of the sonicated dispersions were characterized by laser granulometry, scanning electron microscopy, X-ray microanalysis, and Raman and infrared spectroscopies. Their multiscale organization was investigated by transmission electron microscopy as a function of the sonication time. For sonication longer than 10 h, these nanoparticles from supernatant (diameter <50 nm) are aggregated. Their structures are more disordered than the sediment particles showing typical nanometer-sized aromatic layer arrangement of glassy carbon, with closed mesopores (diameter ∼3 nm). Sonication time longer than 5 h has induced not only a strong amorphization (subnanometric and disoriented aromatic layer) but also a loss of the mesoporous network nanostructure. These multi-scale organizational changes took place because of both cavitation and shocks between particles, mainly at the particle surface. The sonication in water has induced also chemical effects, leading to an increase in the oxygen content of the irradiated material together with the sonication time.     

Common fingerprint of hydroxylated non-polar steps on MgO smoke and MgO films

The infrared spectra of MgO smoke exposed to water are compared to high-resolution electron energy loss spectra (HREELS) of hydroxylated ultrathin MgO(1 0 0)/Ag(1 0 0) films. Very similar bands are observed at 3458–3480 cm^?1 and 3710–3714 cm^?1. On the basis of first principle calculations, these bands are interpreted as the stretching modes of the two distinct OH groups that are formed at monatomic steps parallel to 〈1 0 0〉 crystallographic directions. The lower frequency band is due to H adsorbed on O at the step edge, while the higher frequency one originates from OH groups that are twofold coordinated with Mg. Consistently, scanning tunnelling microscopy images of MgO films, prepared in similar conditions as during the HREELS experiments, show that the MgO/Ag(1 0 0) island edges are mainly non-polar, i.e. oriented along the 〈1 0 0〉 direction. In spite of that, a minor contribution to the OH-stretch intensity from hydroxylated polar 〈1 1 0〉 steps cannot be excluded; for such geometry density functional theory predicts indeed a single OH species with a vibrational frequency very close to the high-frequency band of OH adsorbed at 〈1 0 0〉 steps.     

Verifying the presence of low levels of neptunium in a uranium matrix with electron energy-loss spectroscopy

This paper examines the problems associated with analysis of low levels of neptunium in a uranium matrix with electron energy-loss spectroscopy (EELS) on the transmission electron microscope (TEM). The detection of neptunium in a matrix of uranium can be impeded by the occurrence of a plural scattering event from uranium (U-M₅ + U-O_4,5) that results in severe overlap on the Np-M₅ edge at 3665 eV. Low levels of Np (1600–6300 ppm) can be detected in a uranium solid, uranophane [Ca(UO₂)₂(SiO₃OH)₂(H₂O)₅], by confirming that the energy gap between the Np-M₅ and Np-M₄ edges is at 184 eV and showing that the M₄/M₅ ratio for the neptunium is smaller than that for uranium. The Richardson–Lucy deconvolution method was applied to energy-loss spectral images and was shown to increase the signal to noise ratio.     

Aggregation kinetics of single walled carbon nanotubes influenced by the frequency of ultrasound irradiation in the aquatic environment

The colloidal stability of single-walled carbon nanotubes (SWNTs) sonicated at three different ultrasonication (US) frequencies (28, 580, and 1000 kHz) were investigated under environmentally relevant conditions. In particular, correlations between surface chemistry, electrokinetic potential, interaction energy, and the aggregation kinetics of the aqueous SWNTs were studied. We observed that H₂O₂ production is negatively correlated with the yield of hydroxylation and carboxylation of SWNTs, which was dependent on the generation of ultrasonic energy by cavity collapse during US process. The SWNTs sonicated at relatively high US frequencies (580 and 1000 kHz) aggregated rapidly in synthetic surface water, whereas alkalinity affected the stability of SWNTs insignificantly. This was because the SWNTs became less negatively charged under such conditions and were captured in deep primary energy wells, according to the Derjaguin-Landau-Verwey-Overbeek theory. Critical coagulation concentration values for the ultrasonicated SWNTs were determined to be 102 mM NaCl for 28 kHz, 22 mM NaCl for 580 kHz, and 43 mM NaCl for 1000 kHz. Suwannee River humic acid decreased the aggregation rate of SWNTs due to the steric hindrance, because of adsorbed macromolecules. Our findings show that the aggregate stability of SWNTs is controlled largely by a complex interplay between the evolution of surface functional groups on the SWNTs during US and solution chemistry.     

The effect of heating on InGaAs/InP(1 0 0) and InPO4/InP(1 0 0)

We have used Auger and electron energy loss spectroscopy to study the effect of temperature on InGaAs and InPO₄ grown on InP. The thickness of InPO₄ is of about 10 Å whereas that of InGaAs is of about 800 Å. InPO₄ is of great interest because it protects InP from loss of stoichiometry when heated to 450 °C. The InGaAs system heated at 450 °C seems to be unstable; metallic indium appears on the surface in conjunction with formation of GaAs.     

Sr and Ga substituted Ba2In2O5: Linking ionic conductivity and the potential energy surface

We study in detail the potential energy surface of Ga and Sr substituted Ba₂In₂O₅ by considering the changes in the relative energies of the local structures of Ba₂In₂O₅ when replacing 1 / 8th of the indium atoms with gallium or 1 / 8th of the barium atoms with strontium. The calculations are subsequently used to interpret the increase in ionic conductivity of cubic Ba₂In₂O₅ when strontium is substituted for barium and the decrease in ionic conductivity when gallium is substituted for indium. The effects of replacing 1 / 8th of the indium atoms with gallium or 1 / 8th of the barium atoms with strontium are significant and affect considerably the relative stability of the different low energy local structures present for Ba₂In₂O₅. While a higher density of low energy structures is observed for Ba_1.75Sr_0.25In₂O₅ than for Ba₂In₂O₅, the opposite occurs for Ba₂In_1.75Ga_0.25O₅. This observation supports our main hypothesis: a high density of low energy local structures is a prerequisite for high ionic conductivity.     

Selective resonance population in high resolution electron energy loss spectroscopy of 4-ethylbenzenethiol self-assembled monolayers on Au(1 1 1)

We have investigated the vibrational frequencies and excitation cross-section of self-assembled monolayers (SAMs) of 4-ethylbenzenethiol (CH₃CH₂(C₆H₄)SH) on Au(1 1 1) by high resolution electron energy loss spectroscopy (HREELS). Negative ion resonances were observed in the energy loss intensities as a function of the incident electron energy. Analysis of the C–H stretching modes indicates resonances of different energies are localised in both the ethyl and phenyl functional groups of the SAM molecules, which regulate the observed vibrational lineshape.     

The oxidation of Fe(111)

The oxidation of Fe(111) was studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ion scattering spectroscopy (ISS) and scanning tunnelling microscopy (STM). Oxidation of the crystal was found to be a very fast process, even at 200 K, and the Auger O signal saturation level is reached within ~ 50 × 10^? 6 mbar s. Annealing the oxidised surface at 773 K causes a significant decline in apparent surface oxygen concentration and produces a clear (6 × 6) LEED pattern, whereas after oxidation at ambient temperature no pattern was observed. STM results indicate that the oxygen signal was reduced due to the nucleation of large, but sparsely distributed oxide islands, leaving mainly the smooth (6 × 6) structure between the islands. The reactivity of the (6 × 6) layer towards methanol was investigated using temperature programmed desorption (TPD), which showed mainly decomposition to CO and CO₂, due to the production of formate intermediates on the surface. Interestingly, this removes the (6 × 6) structure by reduction, but it can be reformed from the sink of oxygen present in the large oxide islands simply by annealing at 773 K for a few minutes. The (6 × 6) appears to be a relatively stable, pseudo-oxide phase, that may be useful as a model oxide surface.     

High-energy ion induced physical and surface modifications in antimony sulphide thin films

Sb₂S₃ thin films prepared by electrodeposition on indium tin oxide coated glass substrate were irradiated with 150 MeV Ni¹¹⁺ ions for various fluence in the range of 10¹¹–10¹³ ions/cm². The modifications in the structure, surface morphology and optical properties have been studied as a function of ion fluence. X-ray diffraction (XRD) analysis indicates a shift in the (2 4 0) peak position towards lower diffraction angle and a decrease in grain size with increase in ion fluence. Presence of microcracks due to irradiation induced grain splitting effect has been observed from the SEM micrograph at higher ion fluence. The optical absorbance spectrum revealed a shift in the fundamental absorption edge and the band gap energy increased from a value of 1.63 eV for as-deposited films to 1.80 eV for the films irradiated with 10¹³ ions/cm².     

The 2-D growth of gold on single-layer graphene/Ru(0001): Enhancement of CO adsorption

The growth and morphology of two-dimensional (2-D) gold islands on a single-layer graphene supported on Ru(0001) have been studied by scanning tunneling microscopy (STM). Our findings show that gold exhibits 2-D structures up to a gold dosage of 0.75 equivalent monolayers, and that these 2-D gold islands are thermally stable at room temperature. Parallel polarization modulation infrared reflection absorption spectroscopic (PM-IRAS) and high resolution electron energy loss spectroscopic (HREELS) studies indicate that carbon monoxide (CO) adsorbs on these 2-D gold islands at 85 K, showing a characteristic CO stretching feature at 2095 cm^? 1 for a saturation coverage of CO. The red shift of the CO stretching frequency compared to that on charge neutral gold is consistent with electron transfer from graphene to gold, i.e., an electron-rich gold overlayer. Preliminary data obtained by dosing molecular oxygen onto this CO pre-covered surface suggest that the 2-D gold islands catalyze the oxidation of CO.     

Quintuple-period Si atomic wires with alternative double and triple modulations by metal: Mg/Si(557)

The formation of Mg-induced quasi-one-dimensional atomic wires on a Si(557) surface was studied by low energy electron diffraction (LEED), scanning tunneling microscopy (STM), and first-principles calculations. The atomic wires were produced on the Si(557) surface without faceting when heated to 330 ?C. The atomic wires had a × 5 period along the wires, as observed by LEED. STM images showed the existence of three kinds of atomic wires in a unit cell: an atomic wire located at the step edge and the others on the terrace. Interestingly, alternative double and triple modulations resulting in the × 5 period was observed at the atomic wire located at the step edge. Among the variety of atomic structure models available, the one based on a honeycomb-chain-channel model, which is that of a metal/Si(111)-(3 × 1) surface, reproduced the STM images well and was relatively stable energetically.     

Geometric and electronic structures of sulfur-edge-terminated zigzag edge graphene nanoribbons

The stable geometric and electronic structures of the fully and half sulfur-edge-functionalized ZGNRs at their widths of four zigzag carbon chains (S-4-ZGNRs) have been studied by using the ab initio density-functional method. It is found from our calculations that (1) under the periodic boundary condition, the two-dimensional plane structures are the most stable ground states in all the possible isomers of the S-4-ZGNRs at both 100% and 50% terminations, which are all metallic. (2) A much delocalized characteristic S-px lone-pair electron's band crossing its Fermi level appears in the case of fully S-edge-termination, which is more extended in a large energy range of over 8.0 eV, in contrast to the corresponding oxygen-px (O-px) band of the O-4-ZGNR, covering only a small energy range of 3.2 eV. In the case of half S-edge-termination, however, the S-px band is found to be much more localized, which forms two almost flat bands at about+3.0 eV above its Fermi level. (3) More interestingly, at 50% S-edge-termination, a flat portion of the π-electron edge states is found to lie a little bit below its Fermi level, making its unpolarized ground state unstable. And thus the spin-polarized antiferromagnetic (AFM) state is found to be the real ground state of the half S-4-ZGNR, which is a semiconductor with an indirect energy gap of about 0.16 eV. In the AFM ground state, there exists magnetic moments of about 0.2μ_B on each edge carbon atom, which is FM coupling along the same edge, but AFM coupling between its two edges.     

Compositional modification of Se-Ge-Sb chalcogenide glasses by addition of arsenic element

The modification of structural, thermal and optical properties of Se-Ge-Sb glasses by addition of arsenic element was the goal of this study. In this regards, six different glasses of Se₆₀Ge_40-xSb₅As_x (0 ≤ x ≤ 15) were prepared by conventional melt quenching technique in quartz ampoule. The produced samples were characterized using X-ray diffraction (XRD), differential scanning calorimetry (DSC), UV–Vis–NIR spectrophotometer, Fourier transform infrared (FTIR) and Raman spectroscopy. The fundamental absorption edge for of the glasses was analyzed in terms of the theory proposed by Davis and Mott. Based on the obtained results, the glass transition temperature, optical energy gap and Urbach energy of prepared glasses in this alloying system were in the range of 325–380 °C, 1.43–1.64 eV and 0.03–0.3547 eV, respectively. The as prepared glasses show anomalous behavior at 5–7.5 mole% of arsenic for the glass transition temperature, transmittance, absorption edge, optical energy gap and Urbach energy. Based on the Raman spectra, the structural analysis indicates that, increasing the network connectivity upon increasing the arsenic content up to 7.5 mole% is the main reason of anomalous behavior in Se₆₀Ge_40-xSb₅As_x (0 ≤ x ≤ 15) system.     

Competing nucleation mechanisms and growth of InAsSbP quantum dots and nano-pits on the InAs(100) surface

InAsSbP quantum dots (QDs) and nano-pits (NPs) are grown on a InAs(100) surface by liquid phase epitaxy (LPE). Their morphology, dimensions and distribution density are investigated by high resolution scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and total energy calculations. QDs average density ranges from 5 to 7 × 10⁹ cm^?2, with heights and widths having a Gaussian distribution with sizes from 5 nm to 15 nm and 10 nm to 40 nm respectively. The average pits density is (2–6) × 10¹⁰ cm^?2 with dimensions ranging from 5–30 nm in width and depth. We also find a shift in the absorption edge towards the longer wavelengths together with broadening towards shorter wavelengths indicating that these QDs and lateral overgrown nano-pits are grown at the n-InAs/p-InAsSbP heterojunction interface. Together with total energy calculations, the results indicate that lattice mismatch ratio plays a central role in the growth of these strain-induced nano-objects.     

Microwave irradiation on carbon black: Studies on the transformation of particles into nano-balls,nano-sticks and nano-onion like structures

The solid-state transformation behavior of carbon black (CB) nanoparticles after irradiated with microwave energy was studied with and without influence of a metal catalyst. The CB sample was exposed to microwave radiation at power of 900 W from the oven and collected after 15 min and after 30 min and 45 min of irradiation. The samples were characterized using X-ray diffraction measurements, Raman spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM) and thermogravimetric analysis. Characterization of the samples prepared without catalyst shows that microwave irradiation can transform CB nanoparticles into nano–balls and nano–stick like structures. While nanoballs of almost 300–500 nm diameter are visible in all the samples irrespective of microwave irradiation time, amorphous nano-stick like structure are present only in the sample collected after 30 min of microwave irradiation. CB irradiated together with a metal catalyst resulted in metal-encapsulated onion like structures with perfectly arranged graphene layers.