377 research outputs found
Surface Structure Determination of Black Phosphorus Using Photoelectron Diffraction
Atomic structure of single-crystalline black phosphorus was studied by high
resolution synchrotron-based photoelectron diffraction (XPD). The results show
that the topmost phosphorene layer in the black phosphorus is slightly
displaced compared to the bulk structure and presents a small contraction in
the direction perpendicular to the surface. Furthermore, the XPD results show
the presence of a small buckling among the surface atoms, in agreement with
previously reported scanning tunneling microscopy results. The contraction of
the surface layer added to the presence of the buckling indicates an uniformity
in the size of the sp3 bonds between P atoms at the surface
Determinação estrutural de ligas metálicas de superfície via difração de fotoelétrons
Orientadores: Richard Landers, George G. KleimanTese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb WataghinResumo: As propriedades físico-químicas de um material, como uma liga metálica, podem ser entendidas como uma função da sua estrutura eletrônica e das posições relativas entre os átomos. A superfície representa um caso particular, e a quebra da periodicidade em uma direção pode provocar mudanças estruturais e eletrônicas importantes que afetam as propriedades do material. É particularmente importante conhecer a posição dos átomos na rede cristalina. No volume de um material isto pode ser feito através de técnicas consagradas como difração de raios-x; contudo, para a superfície esta tarefa é muito mais complicada. No caso de ligas de superfície estas apresentam-se como novos materiais e desenvolvem um grande interesse do ponto de vista acadêmico e aplicado. Este trabalho apresenta uma investigação da estrutura eletrônica e cristalográfica de ligas de superfície a partir de filmes finos crescidos por MBE sobre superfícies monocristalinas bem caracterizadas. A caracterização da dinâmica de crescimento dos filmes foi feita por XPS e RHEED; e na determinação estrutural das ligas utilizou-se LEED (qualitativo) e Difração de Fotoelétrons. Para o caso de liga ordenada de superfície também é apresentado a determinação estrutural por cálculos de primeiros princípios usando a Teoria do Funcional-Densidade. Nesta dissertação são apresentados os casos de Pd sobre Cu(111), Cu sobrePd(111) e Sb sobre Pd(111)Abstract: The physico-chemical properties of a material, such as a metallic alloy, can be understood as a function of its electronic structure and the relative positions between its atoms. The surface is a particular case in the material, due to the break of periodicity in the direction perpendicular to the surface this can affect the structural and electronic properties of the material. It is particularly important to know the position of the atoms in the crystalline lattice. In the bulk of a material this can be measured using techniques such as rays-x diffraction. For the surface this task is much more complicated. Surface alloys represent new materials and their development is of great interest both from the academic and technological point of view. The present body of work presents a study of the electronic and geometric structure of surface alloys; grown by MBE on well-characterized monocrystalline surfaces. XPS and RHEED were used to characterize the dynamics of growth, and LEED (qualitative) and Photoelectron Diffraction did the structural determination of surface alloys. For the particular case of ordered surface alloys we also present a theoretical first principles structural determination using Density Functional-Theory. This dissertation shows three systems: Pd on Cu(111), Cu on Pd(111) and Sb on Pd(111)DoutoradoFísicaDoutor em Ciência
High-energy Auger line shapes of Pd and Rh: experiment and theory
FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFINEP - FINANCIADORA DE ESTUDOS E PROJETOSWe compare nonrelativistic atomic multiplet calculations of the L1,2,3M4,5M4,5 spectra of Rh and Pd in the jj intermediate-coupling scheme with high-resolution experimental spectra excited with a Ti anode, indicating general, good agreement even for these open valence shell metals: the simplicity of the calculations indicates their suitability for experimental analyses. Comparison with relativistic calculations, including configuration interaction, for Rh indicates that the nonrelativistic spectra appear to agree better with the experimental data than do the relativistic ones. The influence of relativistic and correlation effects on the intensities does not seem to be important. The major influence on the forms of the spectra is that of the relative positions of the multiplet components. Satellites of all three spectra would seem to be produced by shake-up, rather than Coster-Kronig processes. The positions and forms of these satellites are consistent with a model in which spectator vacancies in the 4d band exist in both the initial and final states of the Auger transitionWe compare nonrelativistic atomic multiplet calculations of the L1,2,3M4,5M4,5 spectra of Rh and Pd in the ii intermediate-coupling scheme with high-resolution experimental spectra excited with a Ti anode, indicating general, good agreement even for these open valence shell metals: the simplicity of the calculations indicates their suitability for experimental analyses. Comparison with relativistic calculations, including configuration interaction, for Rh indicates that the nonrelativistic spectra appear to agree better with the experimental data than do the relativistic ones. The influence of relativistic and correlation effects on the intensities does not seem to be important. The major influence on the forms of the spectra is that of the relative positions of the multiplet components. Satellites of all three spectra would seem to be produced by shake-up, rather than Coster-Kronig processes. The positions and forms of these satellites are consistent with a model in which spectator vacancies in the 4d band exist in both the initial and final states of the Auger transition. [S0163-1829(98)02548-X].58241610316109FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFINEP - FINANCIADORA DE ESTUDOS E PROJETOSFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFINEP - FINANCIADORA DE ESTUDOS E PROJETOSSem informaçãoSem informaçãoSem informaçã
Electronic and structural study of Pt-modified Au vicinal surfaces: a model system for Pt–Au catalysts
FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOTwo single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (θPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on θPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings. © 2014 The Owner Societies.Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (yPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on yPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings.Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (yPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on yPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings.16261332913339FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO07/54829-5; 2011/12.566-3; 2012/16860-6160172/2011-0Greeley, J., Stephens, I.E.L., Bondarenko, A.S., Johansson, T.P., Hansen, H.A., Jaramillo, T.F., Rossmeisl, J., Nørskov, J.K., (2009) Nat. Chem., 1, pp. 552-556Wu, G., More, K.L., Johnston, C.M., Zelenay, P., (2011) Science, 332, pp. 443-447Chu, Y.H., Shul, Y.G., (2010) Int. J. Hydrogen Energy, 35, pp. 11261-11270Kowal, A., Li, M., Shao, M., Sasaki, K., Vukmirovic, M.B., Zhang, J., Marinkovic, N.S., Adzic, R.R., (2009) Nat. 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Chem., 607, pp. 47-53Kobiela, T., Moors, M., Linhart, W., Cebula, I., Krupski, A., Becker, C., Wandelt, K., (2010) Thin Solid Films, 518, pp. 3650-3657Petkov, V., Wanjala, B.N., Loukrakpam, R., Luo, J., Yang, L., Zhong, C.-J., Shastri, S., (2012) Nano Lett., 12, pp. 4289-4299Authors thank Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP-07/54829-5) and Conselho Nacional de Pesquisa (CNPq) for financial support. Specially thank to L. H. Lima for experimental assistance with STM measurements and Prof. G. Tremiliosi-Filho for lending the Au(332) crystal. MJP, SF and EAC thank FAPESP and CNPq for the fellowships granted (Procs. FAPESP 2011/12.566-3 and 2012/16860-6; Proc. CNPq 160172/2011-0)
A new ultra-high-vacuum variable temperature and high-magnetic-field X-ray magnetic circular dichroism facility at LNLS
FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOX-ray magnetic circular dichroism (XMCD) is one of the most powerful tools for investigating the magnetic properties of different types of materials that display ferromagnetic behavior. Compared with other magnetic-sensitive techniques, XMCD has the advantage of being element specific and is capable of separating the spin and magnetic moment contributions associated with each element in the sample. In samples involving, for example, buried atoms, clusters on surfaces or at interfaces, ultrathin films, nanoparticles and nanostructures, three experimental conditions must be present to perform state-of-the-art XMCD measurements: high magnetic fields, low temperatures and an ultra-high-vacuum environment. This paper describes a new apparatus that can be easily installed at different X-ray and UV beamlines at the Brazilian Synchrotron Light Laboratory (LNLS). The apparatus combines the three characteristics described above and different methods to measure the absorption signal. It also permits in situ sample preparation and transfer to another chamber for measurement by conventional surface science techniques such as low-energy electron diffraction (LEED), reflection high-energy electron diffraction (RHEED), X-ray photoelectron spectroscopy (XPS) and X-ray photoelectron diffraction (XPD). Examples are given of XMCD measurements performed with this set-up on different materials.X-ray magnetic circular dichroism (XMCD) is one of the most powerful tools for investigating the magnetic properties of different types of materials that display ferromagnetic behavior. Compared with other magnetic-sensitive techniques, XMCD has the advantage of being element specific and is capable of separating the spin and magnetic moment contributions associated with each element in the sample. In samples involving, for example, buried atoms, clusters on surfaces or at interfaces, ultrathin films, nanoparticles and nanostructures, three experimental conditions must be present to perform state-of-the-art XMCD measurements: high magnetic fields, low temperatures and an ultra-high-vacuum environment. This paper describes a new apparatus that can be easily installed at different X-ray and UV beamlines at the Brazilian Synchrotron Light Laboratory (LNLS). The apparatus combines the three characteristics described above and different methods to measure the absorption signal. It also permits in situ sample preparation and transfer to another chamber for measurement by conventional surface science techniques such as low-energy electron diffraction (LEED), reflection high-energy electron diffraction (RHEED), X-ray photoelectron spectroscopy (XPS) and X-ray photoelectron diffraction (XPD). Examples are given of XMCD measurements performed with this set-up on different materials.163346351FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP [2007/08244-5]2007/08244-5Sem informaçãoThe authors would like to thank the LNLS staff, particularly the magnets, project and vacuum groups for their help during the construction of the XMCD UHV chamber. P. T. Fonseca and Dr F. Vicentin are acknowledged for their excellent technical support at the SGM and SXS beamlines. Furthermore, the authors would like to thank Dr A. Gobbi and M. M. Soares for their help in the preparation of the multilayer samples. JJSF would like to thank FAPESP for the studentship support. This project was supported financially by FAPESP (grant No. 2007/08244-5), CNPq and LNLS of Brazil
Spin orientation in an ultrathin CoO/PtFe double-layer with perpendicular exchange coupling
International audienceWe studied by soft x-ray absorption spectroscopy the magnetization axis in an 4nm thin CoO (111) layer exchange-coupled to an ultra thin L1 0 PtFe layer with perpendicular magnetic anisotropy. The angular dependence of the linear magnetic dichroism at 10K and the relative variations of the spectral features provide a full description of the spin orientation in this antiferromagnetic layer. The spins are found in the film plane, pointing along the 110 direction. This results is discussed in relation to the film strain and preferential occupation of t 2g orbitals.The strong orthogonal coupling between Co and Fe spins should be at the origin of the robustness of the exchange bias effect foun in this bilayer system
Theoretical study of the heteroepitaxial growth of Pd on Cu(111), Pd on Ni(111), Ni on Pd(111), and Cu on Pd(111) using a semiempirical method
CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPEMIG - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE MINAS GERAISHeteroepitaxy has been widely studied by many different theoretical and experimental techniques. Each technique focuses on some features of the growth process, and only by combining the information each provides a full characterization can be given. In this work, the growth of Pd on Ni (111), Pd on Cu (111),Cu on Pd (111), and Ni on Pd (111) is studied with a purely energetic approach which consists of determining a unit cell with a size that depends on the relation between the lateral misfit of the deposited film and the substrate. The energetic is evaluated using a semiempirical coupled with a genetic algorithm global search method to determine with accuracy the relaxation magnitudes of the system. With this approach, features such as interlayer spacings, variation in the film's lattice parameter with coverage, and diffusion influence in the growth process are studied qualitative and quantitatively. The results obtained are directly compared with experimental findings from literature and also presented in this work. The theory-experiment comparison shows that the methodology used is successful in describing qualitatively most features of all four systems. However, for the Pd on Cu (111) case, poor agreement is found, and the analysis of the influence of diffusion and temperature suggests that a somewhat complex alloy formation in the interface is expected for this particular system.Heteroepitaxy has been widely studied by many different theoretical and experimental techniques. Each technique focuses on some features of the growth process, and only by combining the information each provides a full characterization can be given. In this work, the growth of Pd on Ni (111), Pd on Cu (111),Cu on Pd (111), and Ni on Pd (111) is studied with a purely energetic approach which consists of determining a unit cell with a size that depends on the relation between the lateral misfit of the deposited film and the substrate. The energetic is evaluated using a semiempirical coupled with a genetic algorithm global search method to determine with accuracy the relaxation magnitudes of the system. With this approach, features such as interlayer spacings, variation in the film's lattice parameter with coverage, and diffusion influence in the growth process are studied qualitative and quantitatively. The results obtained are directly compared with experimental findings from literature and also presented in this work. The theory-experiment comparison shows that the methodology used is successful in describing qualitatively most features of all four systems. However, for the Pd on Cu (111) case, poor agreement is found, and the analysis of the influence of diffusion and temperature suggests that a somewhat complex alloy formation in the interface is expected for this particular system.818114CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPEMIG - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE MINAS GERAISCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPEMIG - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE MINAS GERAISSem informaçãoSem informaçã
Costituzione Concilio Contestazione. Democrazia e sinodalità nel cattolicesimo italiano del Novecento
Robust perpendicular exchange coupling in an ultrathin CoO/PtFe double layer: Strain and spin orientation
5 pagesInternational audienceWe report on the exchange coupling and magnetic properties of a strained ultrathin CoO/PtFe double layer with perpendicular magnetic anisotropy. The cobalt oxide growth by reactive molecular beam epitaxy on a Pt-terminated PtFe/Pt(001) surface gives rise to a hexagonal surface and a monoclinic distorted CoO 3 nm film at room temperature. This distorted ultrathin CoO layer couples with the PtFe(001) layer establishing a robust perpendicular exchange bias shift. Soft x-ray absorption spectroscopy provides a full description of the spin orientations in the CoO/PtFe double layer. The exchange bias shift is preserved up to the N'eel antiferromagnetic ordering temperature of TN = 293 K. This unique example of selfsame value for blocking and ordering temperatures, yet identical to the bulk ordering temperature, is likely related to the original strain-induced distortion and strengthened interaction between the two well-ordered spin layers
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