Two-Dimensional Quantum Dynamics of O2_2 Dissociative Adsorption on Ag(111)

We have investigated the quantum dynamics of O2 dissociative adsorption on a Ag(111) surface. We performed the calculations with a Hamiltonian where the O2 translational motion is perpendicular to the surface and for O2 vibrational energy. We found that dissociative adsorption occurs with an incident translational energy below the expected activation barrier, while the translational-energy dependence for adsorption probabilities is a smooth sigmoid. Thus, there are non-negligible tunneling effects in the dissociative adsorption that are affected by the activation barrier width. Moreover, the incident translational energies at the inflection points of the adsorption probabilities shift lower with increasing in vibrational quantum numbers of the incident O2. Thus, there is significant energy transfer and coupling from vibration to translational motion. The vibrational energy assists the O2 dissociative adsorption via a vibrationally assisted sticking effect.Comment: 15 pages, 5 figure

Estimating the dopant distribution in Ca-doped alpha-SiAlON: statistical HAADF-STEM analysis and large-scale atomic modeling

We investigated the dopant distribution in Ca-doped alpha-SiAlON by using high-angle annular dark-field scanning transmission electron microscopy and a multi-slice image simulation. Our results showed that the electron wave propagated by hopping to adjacent Si(Al) and N(O) columns. The image intensities of the Ca columns had wider dispersions than other columns. To estimate the Ca distribution in the bulk material, we performed a Monte Carlo atomic simulation of the alpha-SiAlON with Ca dopants. A model including a short-range Coulomb-like repulsive force between adjacent Ca atoms reproduced the dispersion of the intensity distribution of the Ca column in the experimental image

Co-appearance of superconductivity and ferromagnetism in a Ca2_2RuO4_4 nanofilm crystal

By tuning the physical and chemical pressures of layered perovskite materials we can realize the quantum states of both superconductors and insulators. By reducing the thickness of a layered crystal to a nanometer level, a nanofilm crystal can provide novel quantum states that have not previously been found in bulk crystals. Here we report the realization of high-temperature superconductivity in Ca$_2$RuO$_4$ nanofilm single crystals. Ca$_2$RuO$_4$ thin film with the highest transition temperature $T_c$ (midpoint) of 64~K exhibits zero resistance in electric transport measurements. The superconducting critical current exhibited a logarithmic dependence on temperature and was enhanced by an external magnetic field. Magnetic measurements revealed a ferromagnetic transition at 180~K and diamagnetic magnetization due to superconductivity. Our results suggest the co-appearance of superconductivity and ferromagnetism in Ca$_2$RuO$_4$ nanofilm crystals. We also found that the induced bias current and the tuned film thickness caused a superconductor-insulator transition. The fabrication of micro-nanocrystals made of layered material enables us to discuss rich superconducting phenomena in ruthenates

Improving the measurement of dielectric function by TEM-EELS: avoiding the retardation effect

We investigated an improved Kramers-Kronig analysis (KKA) routine for measuring the dielectric function of alpha-Al2O3, avoiding the retardation effect arising in electron energy-loss spectroscopy (EELS). The EELS data differed from the optical data in the energy range of 10-20 eV due to the retardation effect, even though Cerenkov loss was thoroughly suppressed. The calculated differential cross-section indicates that the influence of the retardation appears at scattering angles less than 0.2 mrad in the loss energy range of 10-15 eV. Using the improved KKA routine, we obtained the correct dielectric function that agreed with the optical data. The present technique is especially useful in measuring the dielectric function by EELS with a small collection semi-angle

Adsorption and Diffusion Properties of a Single Iron Atom on Light-Element-Doped Graphene

In this study, we calculated the diffusion of an Fe atom on graphene and various light-element (B, N, O, Si, P, and S)-doped graphene supports, using first-principles calculations based on density functional theory. We focused on dopants that could suppress the detachment and diffusion of an Fe atom. Such doped graphene supports would have strong potential in high-durability fuel cell catalysts and hydrogen storage materials. The Fe atom adsorbs on pristine graphene via ionic bonding. The bonding between the Fe atom and pristine graphene is very weak, and it has a low adsorption energy of −0.61 eV. Doped graphene contains unoccupied localized orbitals. B-, O-, Si-, and P-doped graphene show high adsorption energies of −1.70 eV, −2.70 eV, −1.46 eV, and −1.38 eV, respectively. Thus, these graphene supports could suppress the detachment of Fe nanoclusters and nanoparticles. We demonstrate that these doped graphene supports with high adsorption energies also have high diffusion barriers, which suppresses the agglomeration of Fe nanoclusters and nanoparticles. We conclude that B-, O-, Si-, and P-doped graphene are promising supports for enhancing the adsorption lifetime of Fe nanoclusters and nanoparticles. [DOI: 10.1380/ejssnt.2018.193

Hydrogen Isotope Absorption in Unary Oxides and Nitrides with Anion Vacancies and Substitution

The absorption states of hydrogen isotopes in various ceramic materials were investigated by density functional theory. For pristine ceramic materials, main-group oxides do not form any bond with a hydrogen atom. However, transition metal oxides form hydroxyl groups and absorb hydrogen atoms. Main-group and transition metal nitrides form ionic bonds between a hydrogen atom and the surrounded cation. For anion-deficient ceramic materials, hydrogen atoms are negatively charged because of excess electrons induced by anion vacancies, and ionic bonds form with the surrounded cation, which stabilizes the hydrogen absorption state. N substitutional doping into oxides introduces an electron hole, while O substitutional doping into the nitrides introduces an excess of electrons. Therefore, hydrogen isotopes form covalent bonds in N-substituted oxides, and form hydride ions in O-substituted nitrides. Thus, Al2O3, SiO2, CrN, and TiN are promising materials as hydrogen permeation barriers

Combustion synthesis of Ca-alpha-SiAlON:Eu2+ phosphors with different Ca concentrations and diluent ratios

Yellow Ca-alpha-SiAlON:Eu2+ phosphors for white light-emitting diodes (LEDs) were synthesized by a facile combustion synthesis method using CaO, Eu2O3, alpha-Si3N4, Si, and Al as raw materials. Ca concentrations and diluent ratios were optimized to improve their luminescence properties. The lattice constant and luminescence properties improved as x increased from 0.4 to 1.2 in Ca(x)Si(12-(m+n))Al(m+n)OnN(16-n):En(0.06). The optimum value was x = 1.2. Scanning transmission electron microscopy combined with energy dispersive X-ray analysis detected segregation of Ca and Eu at grain boundaries, which decreased luminescence behavior in the x = 1.4 sample. The influence of Si and Si3N4 diluents was investigated by varying the diluent ratio phi = (CaO + Eu2O3 + alpha-Si3N4)/(CaO + Eu2O3 + a-Si3N4 + Al + Si). Changes in temperature and flame propagation speed were measured during combustion synthesis using two thermocouples. When phi, was less than 0.5, the combustion temperature exceeded 1600 degrees C and the synthesized material contained an amount of the high-temperature beta-SiAlON phase. At phi > 0.7, the reaction temperature fell below 1200 degrees C, and unreacted raw materials remained. The optimum value of phi was 0.6. The internal quantum efficiency of the product synthesized at x = 1.2 and (I, = 0.6 was approximately 35% under 450-nm excitation. According to electron probe X-ray microanalysis, composition varied within individual synthesized particles, which may explain the decrease in emission behavior relative to a commercial product

Sr substitution effects on atomic and local electronic structure of Ca2AlMnO5+δ

We performed the first-principle calculations based on spin-polarized density functional theory to investigate the Sr substitution effects on the atomic and local electronic structure of Ca2AlMnO5+delta. The ionic radius of Sr2+ is larger than that of Ca2+; thus, the lattice expansion occurs with Sr substitution. From the total energy calculations, we found that Sr substitution makes the oxygen-absorbed phase unstable and realizes the lower operation temperature. From the point of atomic structure, Sr substitution lengthens the bond length between Mn and O atoms connecting Mn and Al atoms in Al tetrahedral (OMn-Alt) in oxygen-absorbed phase, because the large Sr2+ prevents the release of the Jahn-Teller distortion. We also found that the covalent bonding between Mn and OMn-Alt atoms weaken with Sr substitution by the local electronic structure analysis, which results in the unstable oxygen-absorbed phase and weak prepeak and main peak intensity near the onset of O-K edge ELNES of OMn-Alt atoms

Twin formation in hematite during dehydration of goethite

Twin formation in hematite during dehydration was investigated using X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy (TEM). When synthetic goethite was heated at different temperatures between 100 and 800 degrees C, a phase transformation occurred at temperatures above 250 degrees C. The electron diffraction patterns showed that the single-crystalline goethite with a growth direction of [001](G) was transformed into hematite with a growth direction of [100](H). Two non-equivalent structures emerged in hematite after dehydration, with twin boundaries at the interface between the two variants. As the temperature was increased, crystal growth occurred. At 800 degrees C, the majority of the twin boundaries disappeared; however, some hematite particles remained in the twinned variant. The electron diffraction patterns and high-resolution TEM observations indicated that the twin boundaries consisted of crystallographically equivalent prismatic (100) (010), and (10) planes. According to the total energy calculations based on spin-polarized density functional theory, the twin boundary of prismatic (100) screw had small interfacial energy (0.24 J/m(2)). Owing to this low interfacial energy, the prismatic (100) screw interface remained after higher-temperature treatment at 800 degrees C