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Journal of Solid State Electrochemistry

, Volume 23, Issue 11, pp 3099–3106 | Cite as

Electronic transfer mechanism in self-assembled monolayers of silicon

  • Carolina GarínEmail author
  • Alejandro León
  • Mónica Pacheco
  • Gonzalo Riveros
Original Paper
  • 116 Downloads

Abstract

This work presents a theoretical-experimental study on electronic transfer mechanism on crystal silicon surface modified with redox molecules derived from ferrocene. The surface modification consists in the reaction of hydrogenated silicon with decyl bromide (10-bromo-1-decene) activated with white light, and its subsequent reaction with monolithio-ferrocene. The samples were analyzed by X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The layers formed are electrochemically active and present a quasi-reversible electrochemical process which is attributed to the ferrocene molecules bound to the silicon surface. In the experimental results, we found an apparent discrepancy, with respect to the results of the cyclic voltammetry, indicating that the redox centers have a diffusive behavior, like to molecules in solution, in spite of these molecules are linked to the silicon surface. While another technique indicates that these redox centers could be attached to the substrate. To understand these results, we have formulated a phenomenological model, based on a cellular automaton, that describes the mechanism of electronic transfer in molecules attached to the substrate. The parameters of the model are obtained from calculations of first principles, based on the density functional theory (DFT). Our results show that the electronic transfer mechanism is influenced by the movement of the redox centers of the molecules attached to the substrate. The latter would explain the apparent discrepancy in the experimental results.

Keywords

Silicon Ferrocene Surface modification Electronic transfer 

Notes

Funding information

This work has been partially supported by Chilean FONDECYT Grant No.3140051 and No.1151316.

References

  1. 1.
    Ruff I, Friererich JV (1971) Transfer diffusion I. Theoretical J Phys Chem 75(21):3297–3302CrossRefGoogle Scholar
  2. 2.
    RuffI I, Friederich JV, Demeter K, Csillag K (1971) Transfer diffusion II. Kinetics of electron exchange reaction between ferrocene and ferricinium ion in alcohols. J Phys Chem 75(21):3303–3309CrossRefGoogle Scholar
  3. 3.
    Dahms H (1968) Electronic conduction in aqueous solution. J Phys Chem 72(1):362–364CrossRefGoogle Scholar
  4. 4.
    Blauch DN, Saveant JM (1992) Dynamic of electron hopping in assemblies of redox centers. Percolation and diffusion. J Am Chem Soc 114(9):3323–3332CrossRefGoogle Scholar
  5. 5.
    George CB, Szleifer I, Ratner MA (2010) Lateral transport in monolayers of short chains at interfaces: a Monte Carlo study. Chem Phys 375(2):503–507CrossRefGoogle Scholar
  6. 6.
    Olivier Y, Lemaur V, Brédas JL, Cornil J (2006) Charge hopping in organic semiconductors: influence of molecular parameters on macroscopic mobilities in model one-dimensional stacks. J Phys Chem A 110(19):6356–6364CrossRefGoogle Scholar
  7. 7.
    Hayashi S (2013) Cellular automata for electrochemistry. A practical approach to the understanding of voltammograms. Electrochemistry 81(1):16–18CrossRefGoogle Scholar
  8. 8.
    Hayashi S (2013) Cellular automata for electrochemistry sweep rate. Electrochemistry 81(9):688–690CrossRefGoogle Scholar
  9. 9.
    Hayashi S (2017) Cellular automata for electrochemistry: extension to two-dimensional models. Electrochemistry 85(1):23–26CrossRefGoogle Scholar
  10. 10.
    Pérez-Brokate CF, Di Caprio D, Mahé E, Féron D (2015) Cyclic voltammetry simulations with cellular automata. J Comput Sci 11:269–278CrossRefGoogle Scholar
  11. 11.
    Riveros G, Meneses S, Escobar S, Garín C, Chornik B (2010) Electron transfer rates of alkyl-ferrocene molecules forming incomplete monolayer on silicon electrodes. J Chil Chem Soc 55(1):61–66CrossRefGoogle Scholar
  12. 12.
    Riveros C, Garín C, Meneses S, Escobar S (2010) Silicon modification with molecules derived from ferrocene: effect of the crystallographic orientation of silicon in the electron-transfer rates. Mol Cryst Liq Cryst 521:187–194CrossRefGoogle Scholar
  13. 13.
    Bard JA, Faulkner LR (1980) Electrochemical method. Wiley, New YorkGoogle Scholar
  14. 14.
    Menolasina S (2004) Fundamentos y Aplicaciones de Electroquimica. Consejo de publicaciones de la Universidad de Los Andes, VenezuelaGoogle Scholar
  15. 15.
    Riveros G, González G, Chornik B (2010) Modification of silicon surface with redox molecules derived from ferrocene. J Braz Chem Soc 21(1):25–32CrossRefGoogle Scholar
  16. 16.
    Droz M, Chopard B (2005) Cellular automata modeling of physical systems. Cambridge University Press, CambridgeGoogle Scholar
  17. 17.
    Goles E, Martinez S (1994) Cellular automata dynamical systems and neural networks. Springer, LondonCrossRefGoogle Scholar
  18. 18.
    León A (2013) Heavy and light monopoles in magnetic reversion in artificial spin ice. Curr Appl Phys 13 (9):2014–2018CrossRefGoogle Scholar
  19. 19.
    Open source package for Material eXplorer (2003). http://www.openmx-square.org
  20. 20.
    Ozaki T, Kino H (2005) Efficient projector expansion for the ab initio LCAO method. Phys Rev B 72 (4):045121–8CrossRefGoogle Scholar
  21. 21.
    Morrison I, Bylander DM, Kleinman L (1993) Nonlocal Hermitian norm-conserving Vanderbilt pseudopotential. Phys Rev B 47(11):6728–6731CrossRefGoogle Scholar
  22. 22.
    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77(18):3865–3868CrossRefGoogle Scholar
  23. 23.
    Csaszar P, Pulay P (1984) Geometry optimization by direct inversion in the iterative subspace. J Mol Struct 114:31–34CrossRefGoogle Scholar
  24. 24.
    Webb LJ, Nemanick EJ, Biteen JS, Knapp DW, Michalak DJ, Traub MC, Chan ASY, Brunschwig BS, Lewis NS (2005) High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces. J Phys Chem B 109(9):3930–3937CrossRefGoogle Scholar
  25. 25.
    Marrani AG, Cattaruzza F, Decker F, Galloni P, Zanoni R (2010) Chemical routes to fine tuning the redox potential of monolayers covalently attached on H-Si(100). Electrochim Acta 55:5733–5740CrossRefGoogle Scholar
  26. 26.
    Marrani AG, Dalchiele EA, Zanoni R, Decker F, Cattaruzza F, Bonifazi D, Prato M (2008) Functionalization of Si(100) with ferrocene derivatives via click chemistry. Electrochim Acta 53:3903–3909CrossRefGoogle Scholar
  27. 27.
    Marrani AG, Cattaruzza F, Decker F, Galloni P, Zanoni R (2009) Chemical routes to molecular SAMs on H-Si(100) with distinct and well-defined redox potentials. Superlattices Microstruct 46(1):40–43CrossRefGoogle Scholar
  28. 28.
    Zanoni R, Cataruzza F, Coluzza C, Dalchiele EA, Decker F, Di Santo G, Flamini A, Funari L, Marrani AG (2005) An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(100) with vinylferrocene. Surf Sci 575(3):260– 272CrossRefGoogle Scholar
  29. 29.
    Dalchiele EA, Aurora A, Bernardini G, Cattaruzza F, Flamini A, Pallavicini P, Zanoni R, Decker F (2005) XPS and electrochemical studies of ferrocene derivatives anchored on n- and p-Si(100) by SiO or SiC bonds. J Electroanal Chem 579(1):133–142CrossRefGoogle Scholar
  30. 30.
    Decker F, Cattaruzza F, Coluzza C, Flamini A, Marrani AG, Zanoni R, Dalchiele EA (2006) Electrochemical reversibility of vinylferrocene monolayers covalently attached on H-terminated p-Si(100). J Phys Chem B 110(14):7374–7379CrossRefGoogle Scholar
  31. 31.
    Cossi M, Iozzi MF, Marrani AG, Lavecchia T, Galloni P, Zanoni R, Decker F (2006) Measurement and DFT calculation of Fe(Cp)2 redox potential in molecular monolayers covalently bound to H-Si(100). J Phys Chem B 110(46):22961–22965CrossRefGoogle Scholar
  32. 32.
    Zanoni R, Aurora A, Cattaruzza F, Coluzza C, Dalchiele EA, Decker F, Di Santo G, Flamini A, Funari L, Marrani AG (2006) A mild functionalization route to robust molecular electroactive monolayers on Si(100). Mater Sci Eng C 26(5):840–845CrossRefGoogle Scholar
  33. 33.
    Tagliazucchi M, Calvo EJ, Szleifer I (2008) Molecular theory of chemically modified electrodes by redox polyelectrolytes under equilibrium conditions: comparison with experiment. J Phys Chem C 112:458–471CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Instituto de Química, Facultad de CienciasPontificia Universidad Católica de ValparaísoCurauma-ValparaísoChile
  2. 2.Departamento de FísicaUniversidad Técnica Federico Santa MaríaValparaísoChile
  3. 3.Instituto de Ciencias Básicas, Facultad de IngenieríaUniversidad Diego PortalesSantiagoChile
  4. 4.Instituto de Química y Bioquímica, Facultad de CienciasPontificia Universidad Católica de ValparaísoPlaya Ancha-ValparaísoChile

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