Abstract
Decomposition of the XPS profiles into components of sublayers derives information on the local bond length, bond energy, atomic cohesive energy, binding energy density, and the energy levels Eν(0) of an isolated atom and its shift with the coordination environment. The Eν(0) and Eν(12) remain constant and the atomic CN varies only with the layer order and surface registry, regardless of the skin chemical constituent. Atomic undercoordination induced bond contraction drives relaxation and reconstruction of the surface of a crystal.
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References
B.S. Fang, W.S. Lo, T.S. Chien, T.C. Leung, C.Y. Lue, C.T. Chan, K.M. Ho, Surface band structures on Nb(001). Phys. Rev. B 50(15), 11093–11101 (1994)
M. Alden, H.L. Skriver, B. Johansson, Ab-initio surface core-level shifts and surface segregation energies. Phys. Rev. Lett. 71(15), 2449–2452 (1993)
T. Balasubramanian, J.N. Andersen, L. Wallden, Surface-bulk core-level splitting in graphite. Phys. Rev. B 64, 205420 (2001)
E. Navas, K. Starke, C. Laubschat, E. Weschke, G. Kaindl, Surface core-level shift of 4f states for Tb(0001). Phys. Rev. B 48(19), 14753 (1993)
R.A. Bartynski, D. Heskett, K. Garrison, G. Watson, D.M. Zehner, W.N. Mei, S.Y. Tong, X. Pan, The 1st interlayer spacing of Ta(100) determined by photoelectron diffraction. J. Vac. Sci. Technol., A 7(3), 1931–1936 (1989)
D.M. Riffe, G.K. Wertheim, Ta(110) surface and subsurface core-level shifts and 4f7/2 line shapes. Phys. Rev. B 47(11), 6672–6679 (1993)
J.H. Cho, K.S. Kim, S.H. Lee, M.H. Kang, Z.Y. Zhang, Origin of contrasting surface core-level shifts at the Be(10-10) and Mg(10-10) surfaces. Phys. Rev. B 61(15), 9975–9978 (2000)
A.V. Fedorov, E. Arenholz, K. Starke, E. Navas, L. Baumgarten, C. Laubschat, G. Kaindl, Surface shifts of 4f electron-addition and electron-removal states on Gd(0001). Phys. Rev. Lett. 73(4), 601–604 (1994)
L.I. Johansson, H.I.P. Johansson, J.N. Andersen, E. Lundgren, R. Nyholm, Surface-shifted core levels on Be(0001). Phys. Rev. Lett. 71(15), 2453–2456 (1993)
S. Lizzit, K. Pohl, A. Baraldi, G. Comelli, V. Fritzsche, E.W. Plummer, R. Stumpf, P. Hofmann, Physics of the Be(10-10) surface core level spectrum. Phys. Rev. Lett. 81(15), 3271–3274 (1998)
H.I.P. Johansson, L.I. Johansson, E. Lundgren, J.N. Andersen, R. Nyholm, Core-level shifts on Be(10-10). Phys. Rev. B 49(24), 17460–17463 (1994)
A. Baraldi, S. Lizzit, G. Comelli, A. Goldoni, P. Hofmann, G. Paolucci, Core-level subsurface shifted component in a 4d transition metal: Ru(10(1)over-bar-0). Phys. Rev. B 61(7), 4534–4537 (2000)
E. Lundgren, U. Johansson, R. Nyholm, J.N. Andersen, Surface core-level shift of the Mo(110) surface. Phys. Rev. B 48(8), 5525–5529 (1993)
R. Nyholm, J.N. Andersen, J.F. Vanacker, M. Qvarford, Surface core-level shifts of the Al(100) and Al(111) surfaces. Phys. Rev. B 44(19), 10987–10990 (1991)
D.M. Riffe, B. Kim, J.L. Erskine, Surface core-level shifts and atomic coordination at a stepped W(110) surface. Phys. Rev. B 50(19), 14481–14488 (1994)
J.H. Cho, D.H. Oh, L. Kleinman, Core-level shifts of low coordination atoms at the W(320) stepped surface. Phys. Rev. B 64(11), 115404 (2001)
J.N. Andersen, D. Hennig, E. Lundgren, M. Methfessel, R. Nyholm, M. Scheffler, Surface core-level shifts of some 4d-metal single-crystal surfaces: Experiments and ab initio calculations. Phys. Rev. B 50(23), 17525–17533 (1994)
G.A. Slack, S.F. Bartram, Thermal expansion of some diamondlike crystals. J. Appl. Phys. 46(1), 89–98 (1975)
T.R. Hart, R.L. Aggarwal, B. Lax, Temperature dependence of Raman scattering in silicon. Phys. Rev. B 1(2), 638–642 (1970)
M.S. Liu, L.A. Bursill, S. Prawer, R. Beserman, Temperature dependence of the first-order Raman phonon lime of diamond. Phys. Rev. B 61(5), 3391–3395 (2000)
M. Kuzmin, M.J.P. Punkkinen, P. Laukkanen, J.J.K. Lång, J. Dahl, V. Tuominen, M. Tuominen, R.E. Perälä, T. Balasubramanian, J. Adell, B. Johansson, L. Vitos, K. Kokko, I.J. Väyrynen, Surface core-level shifts on Ge(111)c(2×8): experiment and theory. Phys. Rev. B 83(24), 245319 (2011)
S. Lizzit, A. Baraldi, A. Groso, K. Reuter, M.V. Ganduglia-Pirovano, C. Stampl, M. Scheffler, M. Stichler, C. Keller, W. Wurth, D. Menzel, Surface core-level shifts of clean and oxygen-covered Ru(0001). Phys. Rev. B 63(20), 205419 (2001)
J.B. Cui, K. Amtmann, J. Ristein, L. Ley, Noncontact temperature measurements of diamond by Raman scattering spectroscopy. J. Appl. Phys. 83(12), 7929–7933 (1998)
Y. Wang, Y.G. Nie, J.S. Pan, L.K. Pan, Z. Sun, L.L. Wang, C.Q. Sun, Orientation-resolved 3d(5/2) binding energy shift of Rh and Pd surfaces: anisotropy of the skin-depth lattice strain and quantum trapping. Phys. Chem. Chem. Phys. 12(9), 2177–2182 (2010)
G. Wertheim, D.M. Riffe, N. Smith, P. Citrin, Electron mean free paths in the alkali metals. Phys. Rev. B 46(4), 1955 (1992)
L.K. Pan, Y.K. Ee, C.Q. Sun, G.Q. Yu, Q.Y. Zhang, B.K. Tay, Band-gap expansion, core-level shift, and dielectric suppression of porous silicon passivated by plasma fluorination. J. Vac. Sci. Technol., B 22(2), 583–587 (2004)
C.J. Powell, A. Jablonski, Progress in quantitative surface analysis by X-ray photoelectron spectroscopy: current status and perspectives. J. Electron Spectrosc. Relat. Phenom. 178–179, 331–346 (2010)
J. Chawla, X. Zhang, D. Gall, Effective electron mean free path in TiN (001). J. Appl. Phys. 113(6), 063704 (2013)
Y.G. Nie, J.S. Pan, W.T. Zheng, J. Zhou, C.Q. Sun, Atomic scale purification of Re surface kink states with and without oxygen chemisorption. J. Phys. Chem. C 115(15), 7450–7455 (2011)
Y. Wang, Y.G. Nie, L.L. Wang, C.Q. Sun, Atomic-layer- and crystal-orientation-resolved 3d5/2 binding energy shift of Ru(0001) and Ru(1010) surfaces. J. Phys. Chem. C 114(2), 1226–1230 (2010)
C.Q. Sun, Relaxation of the Chemical Bond (Springer Ser. Chem. Phys.), vol 108 (Springer, Heidelberg, 2014) 807 pp
W.J. Huang, R. Sun, J. Tao, L.D. Menard, R.G. Nuzzo, J.M. Zuo, Coordination-dependent surface atomic contraction in nanocrystals revealed by coherent diffraction. Nat. Mater. 7(4), 308–313 (2008)
W.H. Qi, B.Y. Huang, M.P. Wang, Bond-length and -energy variation of small Gold nanoparticles. J. Comput. Theor. Nanosci. 6(3), 635–639 (2009)
A. Baraldi, L. Bianchettin, E. Vesselli, S. de Gironcoli, S. Lizzit, L. Petaccia, G. Zampieri, G. Comelli, R. Rosei, Highly under-coordinated atoms at Rh surfaces: interplay of strain and coordination effects on core level shift. New J. Phys. 9, 143 (2007)
F. Matsui, T. Matsushita, Y. Kato, M. Hashimoto, K. Inaji, F.Z. Guo, H. Daimon, Atomic-layer resolved magnetic and electronic structure analysis of Ni thin film on a Cu(001) surface by diffraction spectroscopy. Phys. Rev. Lett. 100(20), 207201 (2008)
P. Heimann, J.F. van der Veen, D.E. Eastman, Structure-dependent surface core level shifts for the Au(111), (100), and (110) surfaces. Solid State Commun. 38(7), 595–598 (1981)
A.Y. Klyushin, T.C.R. Rocha, M. Havecker, A. Knop-Gericke, R. Schlogl, A near ambient pressure XPS study of Au oxidation. Phys. Chem. Chem. Phys. 16, 7881–7886 (2014)
C.Q. Sun, Oxidation electronics: bond-band-barrier correlation and its applications. Prog. Mater Sci. 48(6), 521–685 (2003)
M. Bianchi, D. Cassese, A. Cavallin, R. Comin, F. Orlando, L. Postregna, E. Golfetto, S. Lizzit, A. Baraldi, Surface core level shifts of clean and oxygen covered Ir(111). New J. Phys. 11, 063002 (2009)
N. Barrett, C. Guillot, B. Villette, G. Treglia, B. Legrand, Inversion of the core level shift between surface and subsurface atoms of the iridium (100)(1×1) and (100)(5×1) surfaces. Surf. Sci. 251, 717–721 (1991)
M.J. Gladys, I. Ermanoski, G. Jackson, J.S. Quinton, J.E. Rowe, T.E. Madey, A high resolution photoemission study of surface core-level shifts in clean and oxygen-covered Ir(2 1 0) surfaces. J. Electron Spectrosc. Relat. Phenom. 135(2–3), 105–112 (2004)
M. Borg, M. Birgersson, M. Smedh, A. Mikkelsen, D.L. Adams, R. Nyholm, C.-O. Almbladh, J.N. Andersen, Experimental and theoretical surface core-level shifts of aluminum (100) and (111). Phys. Rev. B 69(23), 235418 (2004)
M. Bo, Y. Wang, Y. Huang, X. Yang, Y. Yang, C. Li, C.Q. Sun, Coordination-resolved local bond relaxation, electron binding-energy shift, and Debye temperature of Ir solid skins. Appl. Surf. Sci. 320, 509–513 (2014)
W. Qin, Y. Wang, Y.L. Huang, Z.F. Zhou, C. Yang, C.Q. Sun, Bond order resolved 3d(5/2) and valence band chemical shifts of Ag surfaces and nanoclusters. J. Phys. Chem. A 116(30), 7892–7897 (2012)
W. Yu, M. Bo, Y. Huang, Y. Wang, C. Li, C.Q. Sun, Coordination-resolved bond and electron spectrometrics of Au atomic clusters, solid skins, and oxidized foils. Chem. Phys. Chem. 16, 2159–2164 (2015)
M. Rocca, L. Savio, L. Vattuone, U. Burghaus, V. Palomba, N. Novelli, F.B. de Mongeot, U. Valbusa, R. Gunnella, G. Comelli, A. Baraldi, S. Lizzit, G. Paolucci, Phase transition of dissociatively adsorbed oxygen on Ag(001). Phys. Rev. B 61(1), 213–227 (2000)
Y. Zhu, Q. Qin, F. Xu, F. Fan, Y. Ding, T. Zhang, B.J. Wiley, Z.L. Wang, Size effects on elasticity, yielding, and fracture of silver nanowires: In situ experiments. Phys. Rev. B 85(4), 045443 (2012)
J. Jupille, K.G. Purcell, D.A. King, W(100) clean surface phase transition studied by core-level-shift spectroscopy: order-order or order-disorder transition. Phys. Rev. B 39(10), 6871–6879 (1989)
K.G. Purcell, J. Jupille, G.P. Derby, D.A. King, Identification of underlayer components in the surface core-level spectra of W(111). Phys. Rev. B 36(2), 1288–1291 (1987)
E. Minni, F. Werfel, Oxygen interaction with Mo (100) studied by XPS, AES and EELS. Surf. Interface Anal. 12(7), 385–390 (1988)
X.B. Zhou, J.L. Erskine, Surface core-level shifts at vicinal tungsten surfaces. Phys. Rev. B 79(15), 155422 (2009)
J. Van der Veen, F. Himpsel, D. Eastman, Chemisorption-induced 4 f-core-electron binding-energy shifts for surface atoms of W (111), W (100), and Ta (111). Phys. Rev. B 25(12), 7388 (1982)
Y.G. Nie, X. Zhang, S.Z. Ma, Y. Wang, J.S. Pan, C.Q. Sun, XPS revelation of tungsten edges as a potential donor-type catalyst. Phys. Chem. Chem. Phys. 13(27), 12640–12645 (2011)
W. Zhou, M. Bo, Y. Wang, Y. Huang, C. Li, C.Q. Sun, Local bond-electron-energy relaxation of Mo atomic clusters and solid skins RSC. Advances 5, 29663–29668 (2015)
D.M. Riffe, W. Hale, B. Kim, J. Erskine, Conduction-electron screening in the bulk and at low-index surfaces of Ta metal. Phys. Rev. B 51(16), 11012 (1995)
Y. Wang, X. Zhang, Y.G. Nie, C.Q. Sun, Under-coordinated atoms induced local strain, quantum trap depression and valence charge polarization at W stepped surfaces. Phys. B-Condens. Matter 407(1), 49–53 (2012)
F. Himpsel, P. Heimann, T. Chiang, D. Eastman, Geometry-dependent Si(2p) surface core-level excitations for Si(111) and Si(100) surfaces. Phys. Rev. Lett. 45(13), 1112–1115 (1980)
F. Himpsel, G. Hollinger, R. Pollak, Determination of the Fermi-level pinning position at Si(111) surfaces. Phys. Rev. B 28(12), 7014–7018 (1983)
R. Niikura, K. Nakatsuji, F. Komori, Local atomic and electronic structure of Au-adsorbed Ge (001) surfaces: scanning tunneling microscopy and x-ray photoemission spectroscopy. Phys. Rev. B 83(3), 035311 (2011)
L. Pan, S. Xu, X. Liu, W. Qin, Z. Sun, W. Zheng, C.Q. Sun, Skin dominance of the dielectric electronic-phononic-photonic attribute of nanoscaled silicon. Surf. Sci. Rep. 68(3–4), 418–445 (2013)
L. Wu, M. Bo, Y. Guo, Y. Wang, C. Li, Y. Huang, C.Q. Sun, Skin bond electron relaxation dynamics of germanium manipulated by interactions with H2, O2, H2O, H2O2, HF, and Au. ChemPhysChem 17(2), 310–316 (2016)
M. Bo, Y. Wang, Y. Huang, X. Zhang, T. Zhang, C. Li, C.Q. Sun, Coordination-resolved local bond contraction and electron binding-energy entrapment of Si atomic clusters and solid skins. J. Appl. Phys. 115(14), 4871399 (2014)
L.I. Johansson, P.A. Glans, T. Balasubramanian, Fourth-layer surface core-level shift on Be(0001). Phys. Rev. B 58(7), 3621–3624 (1998)
L.I. Johansson, H.I.P. Johansson, Unusual behavior of surface shifted core levels on Be (0001) and Be(10-10). Nucl. Instrum. Methods Phys. Res. B 97, 430–435 (1995)
A. Baraldi, S. Lizzit, G. Comelli, G. Paolucci, Oxygen adsorption and ordering on Ru(10(1)over-bar-0). Phys. Rev. B 63(11), 115410 (2001)
N. Martensson, H.B. Saalfeld, H. Kuhlenbeck, M. Neumann, Structural dependence of the 5d-metal surface energies as deduced from surface core-level shift measurements. Phys. Rev. B 39(12), 8181–8186 (1989)
A.S.Y. Chan, G.K. Wertheim, H. Wang, M.D. Ulrich, J.E. Rowe, T.E. Madey, Surface atom core-level shifts of clean and oxygen-covered Re(1231). Phys. Rev. B 72(3), 035442 (2005)
Y. Wang, Y.G. Nie, J.S. Pan, L. Pan, Z. Sun, C.Q. Sun, Layer and orientation resolved bond relaxation and quantum entrapment of charge and energy at Be surfaces. Phys. Chem. Chem. Phys. 12(39), 12753–12759 (2010)
W.T. Zheng, C.Q. Sun, Underneath the fascinations of carbon nanotubes and graphene nanoribbons. Energy Environ. Sci. 4(3), 627–655 (2011)
C.Q. Sun, Size dependence of nanostructures: impact of bond order deficiency. Prog. Solid State Chem. 35(1), 1–159 (2007)
C. Kittel, Intrduction to Solid State Physics, 8th edn. (Willey, New York, 2005)
M. Zhao, W.T. Zheng, J.C. Li, Z. Wen, M.X. Gu, C.Q. Sun, Atomistic origin, temperature dependence, and responsibilities of surface energetics: an extended broken-bond rule. Phys. Rev. B 75(8), 085427 (2007)
X.J. Liu, M.L. Bo, X. Zhang, L. Li, Y.G. Nie, H. Tian, Y. Sun, S. Xu, Y. Wang, W. Zheng, C.Q. Sun, Coordination-resolved electron spectrometrics. Chem. Rev. 115(14), 6746–6810 (2015)
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Sun, C. (2020). Solid and Liquid Skins. In: Electron and Phonon Spectrometrics. Springer, Singapore. https://doi.org/10.1007/978-981-15-3176-7_4
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