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Current issue   Ukr. J. Phys. 2017, Vol. 62, N 7, p.605-614
https://doi.org/10.15407/ujpe62.07.0605    Paper

Lytovchenko V.G., Gorbanyuk T.I., Solntsev V.S.

V.E. Lashkaryov Institute of Semiconductor Physics, Nat. Acad. of Sci. of Ukraine
(41, Prosp. Nauky, Kyiv 03028, Ukraine; e-mail: lvg@isp.kiev.ua)

Mechanism of Adsorption-Catalytic Activity at the Nanostructured Surface of Silicon Doped with Clusters of Transition Metals and Their Oxides

Section: Solid Matter
Original Author's Text: Ukrainian

Abstract: echanisms of adsorption-catalytic activation of composites fabricated on the basis of porous
silicon with incorporated nanoparticles of transition metals (Pd, W, Cu) and their oxides have
been analyzed theoretically. The infuence of adsorbed atoms of acceptor elements (O, S, F,
Cl) on the catalytic activity of transition metals during the formation of surface nanoclusters
of transition metal oxides is revealed. The enhancement of the catalytic activity of transition
metals with the completely flled �-band may consist in a change of the flling of �-states with
electrons (the appearance of holes above the Fermi level) at the formation of surface nanoclus-
ters of transition metal oxides. The results of experimental researches of the adsorption-electric
efect in gas-sensitive structures with Schottky barriers obtained within the method of high-
frequency volt-farad characteristics are presented. The experimental adsorption isotherms of
hydrogen and hydrogen sulfde on the surface of nanostructured silicon composites with copper,
tungsten, palladium, and their oxides in the pores are analyzed. An increased adsorption sen-
sitivity of those composites to various gases (H2, H2S, H2O) in comparison with an ordinary
porous silicon layer is found. It is established that the mechanism of physical adsorption is
realized at low gas pressures (≤ 25 ppm) and/or short times of the adsorbate-substrate inter-
action, and the chemisorption mechanism at higher pressures and in the course of long-term
processes. This conclusion agrees with the theoretical data calculated for the adsorption heat
from experimental isotherms (0.3–0.5 eV).

Key words: nanostructured silicon, nanoparticles, transition metals and their oxides, adsorption sensitivity, hydrogen sulfde, gas sensor.

References:

  1. F.F. Volkenshtein, The Electronic Theory of Catalysis on Semiconductors (Pergamon Press, 1963).
  2. V.F. Kiselev, O.V. Krilov. Adsorption and Catalysis on Transition Metals and Their Oxides (Springer, 1989).
    https://doi.org/10.1007/978-3-642-73887-6
  3. V.G. Litovchenko, Electroadsorption effects in layered systems insulator-semiconductor. Zh. Fiz. Khim. 52, 3063 (1978).
  4. Advanced Sensor and Detection Materials, edited by A. Tiwari, M.M. Demir (Wiley, 2014).
    https://doi.org/10.1002/9781118774038
  5. G. Bozzolo, J.E. Garces, R.D. Noebe, P. Abel, H.O. Mosca. Atomistic modeling of surface and bulk properties of Cu, Pd and the Cu–Pd system. Prog. Surf. Sci. 73, 79 (2003).
    https://doi.org/10.1016/j.progsurf.2003.08.034
  6. W.A. Harrison, Solid State Theory (McGraw-Hill, 1970).
  7. J.C. Bertolini, P. Miegge, P. Hermann, J.L. Rousset, B. Tardy. On the reactivity of 2D Pd surface alloys obtained by surface segregation on deposition technique. Surf. Sci. 331, 651 (1995).
    https://doi.org/10.1016/0039-6028(95)00144-1
  8. J. Greeley, J.K. Norskov. A general scheme for the estimation of oxygen binding energies on binary transition metal surface alloys. Surf. Sci. 592, 104 (2005).
    https://doi.org/10.1016/j.susc.2005.07.018
  9. N. Lopez, T.V.W. Janssens, B.S. Clausen, Y. Xu, M. Mavrikakis, T. Bligard, J.K. Norskov. On the origin of the catalytic activity of gold nanoparticles for low-temperature CO oxidation. J. Catal. 223, 232 (2004).
    https://doi.org/10.1016/j.jcat.2004.01.001
  10. A. Nilsson, L.G.M. Petersson, B. Hammer, T. Bligaard, C.H. Christensen, J.K. Norskov. The electronic structure effect in heterogeneous catalysis. Catal. Lett. 3–4, 111 (2005).
    https://doi.org/10.1007/s10562-004-3434-9
  11. V.G. Litovchenko, T.I. Gorbanyuk, O.O. Yefremov, A.A. Yevtukh, Yu.G. Ptushinskyy, V.A. Ischuk, O.V. Kanash. Catalytic peculiarities of ultra-thin palladium films and its alloys. Ukr. Fiz. Zh. 48, 565 (2003) (in Ukrainian).
  12. V.G. Litovchenko, V.S. Solntsev. Sensing effects in the nanostructured systems. In Proceedings of the NATO Advanced Research Workshop on Electron Transport in Nanosystems 22, 373 (2008).
  13. V.G. Litovchenko, T.I. Gorbanyuk, V.S. Solntsev. New adsorption active nanoclusters for ecological monitoring. In Nanodevices and Nanomaterials for Ecological Security – NATO for Peace and Security. Series B: Physics and Biophysics (Springer, 2012), p. 297.
    https://doi.org/10.1007/978-94-007-4119-5_27
  14. J. Kukkola, J. Moklin, N. Halonen et al. Gas sensors based on anodic tungsten oxide. Sens. Actuat. B 153, 293 (2011).
    https://doi.org/10.1016/j.snb.2010.10.043
  15. A.K. Nayak, R. Ghosh, S. Santra, P.K. Guha, D. Pradhan. Hierarchical nanostructured WO3–SnO2 for selective sensing of volatile organic compounds. Nanoscale 7, 12460 (2015).
    https://doi.org/10.1039/C5NR02571K
  16. Synthesis, Properties, and Applications of Oxide Nanomaterials, edited by J.A. Rodriguez, M. Fern’andez-Garc’ıa (Wiley, 2007).
    https://doi.org/10.1002/0470108975
  17. V.G. Litovchenko, T.I. Gorbanyuk, V.S. Solntsev, A.A. Evtukh. Mechanism of hydrogen, oxygen and humidity sensing by Cu/Pd-porous silicon–silicon structures. Appl. Surf. Sci. 234, 262 (2004).
    https://doi.org/10.1016/j.apsusc.2004.05.146
  18. V.G. Litovchenko, T.I. Gorbanyuk, A.A. Efremov, A.A. Evtukh, D. Schipanski. Investigation of MIS gas sensitive structures with Pd and Pd/Cu metal layers. Sens. Actuat. A 74, 233 (1999).
    https://doi.org/10.1016/S0924-4247(98)00314-8
  19. R.S. Niranjan, V.A. Chaudhary, I.S. Mulla, K. Vijayamohanan. A novel sulfide room sensor based on copper nanocluster functionalized tin oxide thin films. Sens. Actuat. B 85, 26 (2002).
    https://doi.org/10.1016/S0925-4005(02)00046-1
  20. A. Ruban, B. Hammer, P. Stoltze, H.L. Skriver, J.K. Norskov. Surface electronic structure and reactivity of transition and noble metals. J. Mol. Catalys. A 115, 421 (1997).
    https://doi.org/10.1016/S1381-1169(96)00348-2
  21. A.I. Manilov, V.A. Skryshevsky. Hydrogen in porous silicon – A review. Mater. Sci. Eng. B 178, 942 (2013).
    https://doi.org/10.1016/j.mseb.2013.05.001
  22. T.I. Gorbanyuk, A.A. Evtukh, V.G. Litovchenko, V.S. Solntsev. Porous silicon microstructure and composition characterization depending on the formation conditions. Thin Solid Films 495, 134 (2006).
    https://doi.org/10.1016/j.tsf.2005.08.188
  23. O.L. Syshchyk, V.A. Skryshevsky, O.O. Soldatkin, A.P. Soldatkin. Enzyme biosensor systems based on porous silicon photoluminescence for detection of glucose, urea and heavy metals. Biosens. Bioelectron. 66, 89 (2015).
    https://doi.org/10.1016/j.bios.2014.10.075
  24. A.I. Manilov, S.A. Alekseev, V.A. Skryshevsky, S.V. Litvinenko, G.V. Kuznetsov, V. Lysenko. Influence of palladium particles impregnation on hydrogen behavior in meso-porous silicon. J. Alloys Comp. 492, 466 (2010).
    https://doi.org/10.1016/j.jallcom.2009.11.141
  25. M.S. Shivaraman. Detection of H2S with Pd-gate MOS field-effect transistors. J. Appl. Phys. 47, 3591 (1976).
    https://doi.org/10.1063/1.323162