Fermi Level Pinning at n-GaAs(110) Electrodes

Lăzărescu, Valentina; Gärtner, M.; Scurtu, Rareş; Anastasescu, Mihai; Ghiţă, Constantin; Lazarescu, M. F.; Schmickler, Wolfgang

doi:10.1016/b978-044452224-5/50042-1

Cited by 2 publications

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“…The electrified GaAs/solution interface provides further sources for the surface-specific nonlinear response. The large gradient in the electric field operating in the interfacial region and the high densities of surface states were found to play an important role in driving the surface sensitivity of the SHG signal at GaAs electrodes. − The application of an external bias not only stimulates second-harmonic production by the EFISH process but also activates the surface state contribution by their charging. Besides, because of their intrinsic susceptibility, adsorbates enhance the surface contributions, but often their electronic interaction with the substrate could be more important .…”

Section: Introductionmentioning

confidence: 99%

Potential-Induced Conformational Changes in an α-CN-terthiophene Thiolate Film on GaAs(110)

et al. 2009

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Second harmonic generation (SHG) investigations on alpha-CN-terthiophene-thiolate-covered GaAs(110) electrodes in 1 N H2SO4 solution revealed significant changes in the rotational anisotropy of the SH response. The enhancement of the 1- and the 3-fold contributions around -250 mV suggests changes in the symmetry properties of the delocalized electron system due to an alteration of the adsorption geometry induced by the applied potentials. The analysis of the EIS data showed that in the potential region where the SH signal exhibits the more important changes the Mott-Schottky plot undergoes a pronounced shift to more negative potentials as a result of the charging of the surface states grouped about 1.06 eV below the conduction band edge. Semiempirical MO calculations suggest that the most energetically favorable interaction implies electron transfer from the semiconductor conduction band to the lowest unoccupied molecular orbital of the organic molecule with epsilon(LUMO)=-1.707 eV. Such a chemisorption bond bringing the organic molecule to a quasi-planar position is well supported by the major changes in the XPS spectra of the electrochemically biased samples with respect to the as-prepared ones. Two distinct N 1s species instead of one and a shift of 1.6 eV to higher BE of the terthiophene S 2s core level are strong evidence for a potential-induced change in the adsorption geometry. Taking into account that the acceptor-like surface state group located close to the semiconductor valence edge (EC,S=-1.06 eV) may correspond to the LUMO level (shifted downward by the adsorption process), we assume that the organic molecule, initially adsorbed by the thiolate end, undergoes a conformational change from a tilted to an almost flat position when the applied potential brings the semiconductor Fermi level into its neighborhood. This assumption is in a very good agreement with the potential-induced variation in the thiol thickness estimated from the thiol capacitance.

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