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

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. Mater., 8, pp. 325-330Xu, C.W., Su, Y.Z., Tan, L.L., Liu, Z.L., Zhang, J.H., Chen, S.A., Jiang, S.P., (2009) Electrochim. Acta, 54, pp. 6322-6326Colmati, F., Antolini, E., Gonzalez, E.R., (2008) J. Alloys Compd., 456, pp. 264-270Antolini, E., (2007) J. Power Sources, 170, pp. 1-12Colmati, F., Antolini, E., Gonzalez, E.R., (2006) J. Power Sources, 157, pp. 98-103Stamenkovic, V.R., Mun, B.S., Mayrhofer, K.J.J., Ross, P.N., Markovic, N.M., (2006) J. Am. Chem. Soc., 128, pp. 8813-8819Freund, H.-J., Pacchioni, G., (2008) Chem. Soc. Rev., 37, pp. 2224-2242Kim, Y., Kim, H.J., Kim, Y.S., Choi, S.M., Seo, M.H., Kim, W.B., (2012) J. Phys. Chem. C, 116, pp. 18093-18100Kwon, Y., Birdja, Y., Spanos, I., Rodriguez, P., Koper, M.T.M., (2012) ACS Catal., 2, pp. 759-764Freitas, R.G., Pereira, E.C., (2010) Electrochim. Acta, 55, pp. 7622-7627Colmati, F., Tremiliosi, G., Gonzalez, E.R., Berna, A., Herrero, E., Feliu, J.M., (2009) Phys. Chem. Chem. Phys., 11, pp. 9114-9123Repain, V., Baudot, G., Ellmer, H., Rousset, S., (2002) Europhys. Lett., 58, p. 730Repain, V., Berroir, J.M., Rousset, S., Lecoeur, J., (1999) Europhys. Lett., 47, p. 435Nahas, Y., Repain, V., Chacon, C., Girard, Y., Rousset, S., (2010) Surf. Sci., 604, pp. 829-833Rohart, S., Girard, Y., Nahas, Y., Repain, V., Rodary, G., Tejeda, A., Rousset, S., (2008) Surf. Sci., 602, pp. 28-36Rohart, S., Baudot, G., Repain, V., Girard, Y., Rousset, S., Bulou, H., Goyhenex, C., Proville, L., (2004) Surf. Sci., 559, pp. 47-62Axel, G., (2009) J. Phys.: Condens. Matter, 21, p. 084205Rodriguez, J., (1996) Surf. Sci. Rep., 24, pp. 223-287Eyrich, M., Diemant, T., Hartmann, H., Bansmann, J., Behm, R.J., (2012) J. Phys. Chem. C, 116, pp. 11154-11165Bowker, M., (1995) Chem. Vap. Deposition, 1, p. 90Xu, J.B., Zhao, T.S., Yang, W.W., Shen, S.Y., (2010) Int. J. Hydrogen Energy, 35, pp. 8699-8706Wang, J., Yin, G., Wang, G., Wang, Z., Gao, Y., (2008) Electrochem. Commun., 10, pp. 831-834Horcas, I., Fernandez, R., Gomez-Rodriguez, J.M., Colchero, J., Gomez-Herrero, J., Baro, A.M., (2007) Rev. Sci. Instrum., 78, pp. 013705-013708Doniach, S., Sunjic, M., (1970) J. Phys. C: Solid State Phys., 3, p. 285Hörnström, S.E., Johansson, L., Flodström, A., Nyholm, R., Schmidt-May, J., (1985) Surf. Sci., 160, pp. 561-570Shevchik, N.J., (1974) Phys. Rev. Lett., 33, p. 1336Powell, C.J., (2012) J. Electron Spectrosc. Relat. Phenom., 185, pp. 1-3Rousset, S., Repain, V., Baudot, G., Garreau, Y., Lecoeur, J., (2003) J. Phys.: Condens. Matter, 15, p. 3363Prévot, G., Girard, Y., Repain, V., Rousset, S., Coati, A., Garreau, Y., Paul, J., Narasimhan, S., (2010) Phys. Rev. B: Condens. Matter Mater. Phys., 81, p. 075415Repain, V., Rohart, S., Girard, Y., Tejeda, A., Rousset, S., (2006) J. Phys.: Condens. Matter, 18, p. 17Repain, V., Baudot, G., Ellmer, H., Rousset, S., (2002) Mater. Sci. Eng., B, 96, pp. 178-187Repain, V., Berroir, J.M., Rousset, S., Lecoeur, J., (2000) Surf. Sci., 447, pp. 152-L156Campiglio, P., Repain, V., Chacon, C., Fruchart, O., Lagoute, J., Girard, Y., Rousset, S., (2011) Surf. Sci., 605, pp. 1165-1169Prieto, M.J., Carbonio, E.A., Landers, R., De Siervo, A., (2013) Surf. Sci., 617, pp. 87-93Antczak, G., Ehrlich, G., (2010) Surface Diffusion: Metals, Metal Atoms, and Clusters, , Cambridge Univesrity Press, New YorkKim, S.Y., Lee, I.-H., Jun, S., (2007) Phys. Rev. B: Condens. Matter Mater. Phys., 76, p. 245407Liu, Y.B., Sun, D.Y., Gong, X.G., (2002) Surf. Sci., 498, pp. 337-342Prévot, G., Barbier, L., Steadman, P., (2010) Surf. Sci., 604, pp. 1265-1272Pedersen M.Ø, Helveg, S., Ruban, A., Stensgaard, I., Lægsgaard, E., Nørskov, J.K., Besenbacher, F., (1999) Surf. Sci., 426, pp. 395-409Gohda, Y., Groß, A., (2007) Surf. Sci., 601, pp. 3702-3706Pastor, E., Rodriguez, J.L., Iwasita, T., (2002) Electrochem. Commun., 4, pp. 959-962Keister, J.K., Rowe, J.E., Kolodziej, J.J., Madey, T.E., (2000) J. Vac. Sci. Tech. B, 18, pp. 2174-2178. , 10.1116/1.1305872Martin, R., Gardner, P., Bradshaw, A.M., (1995) Surf. Sci., 342, pp. 69-84Bare, S.R., Hofmann, P., King, D.A., (1984) Surf. Sci., 144, pp. 347-369Yamagishi, S., Fujimoto, T., Inada, Y., Orita, H., (2005) J. Phys. Chem. B, 109, pp. 8899-8908Watanabe, S., Inukai, J., Ito, M., (1993) Surf. Sci., 293, pp. 1-9Sarkar, A., Kerr, J.B., Cairns, E.J., (2013) ChemPhysChem, 14, pp. 2132-2142Du, B., Zaluzhna, O., Tong, Y.J., (2011) Phys. Chem. Chem. Phys., 13, pp. 11568-11574Auten, B.J., Lang, H., Chandler, B.D., (2008) Appl. Catal., B, 81, pp. 225-235Gohda, Y., Groß, A., (2007) J. Electroanal. 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)

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

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

Self-assembly Of Nitpp On Cu(111): A Transition From Disordered 1d Wires To 2d Chiral Domains.

The growth and self-assembling properties of nickel-tetraphenyl porphyrins (NiTPP) on the Cu(111) surface are analysed via scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). For low coverage, STM results show that NiTPP molecules diffuse on the terrace until they reach the step edge of the copper surface forming a 1D system with disordered orientation along the step edges. The nucleation process into a 2D superstructure was observed to occur via the interaction of molecules attached to the already nucleated 1D structure, reorienting molecules. For monolayer range coverage a 2D nearly squared self-assembled array with the emergence of chiral domains was observed. The XPS results of the Ni 2p(3/2) core levels exhibit a 2.6 eV chemical shift between the mono- and multilayer configuration of NiTPP. DFT calculations show that the observed chemical shifts of Ni 2p(3/2) occur due to the interaction of 3d orbitals of Ni with the Cu(111) substrate.1718344-1835

Robust perpendicular exchange coupling in an ultrathin CoO/PtFe double layer: strain and spin orientation

Sem informaçãoWe 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 Néel 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.We 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 Néel 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.881415Sem informaçãoSem informaçãoSem informaçã