Semiconductor/electrolyte

Figure Bl.28.10. Schematic representation of an illuminated (a) n-type and (b) p-type semiconductor in the presence of a depletion layer fonned at the semiconductor-electrolyte interface.

Zegenhagen J, Kazimirov A, Scherb G, Kolb D M, Smilgies D-M and Feidenhans l R 1996 X-ray diffraction study of a semiconductor/electrolyte interface n-GaAs(001)/H2S04( Cu) 1996 Surf. Sc/. 352-354 346-51... 

Figure 12. Energy diagram of a semiconductor/electrolyte interface showing photogeneration and loss mechanisms (via surface recombination and interfacial charge transfer for minority charge carriers). The surface concentration of minority...

Figure 27. Minority charge carrier profiles near the semiconductor/electrolyte junction. calculated for a silicon interface at two different electrode potentials. Uf- -0.25 V and Uf= 5.0 V10 ((//= forward bias = t/ - Ufl>).

Following the same procedure, the kinetic constants have been determined for very different electrochemical conditions. When n-WSe2 electrodes are compared in contact with different redox systems it is, for example, found9 that no PMC peak is measured in the presence of 0.1 M KI, but a clear peak occurs in presence of 0.1 M K4[Fe(CN)6], which is known to be a less efficient electron donor for this electrode in liquid junction solar cells. When K4[Fe(CN)6] is replaced by K3[Fe(CN)6], its oxidized form, a large shoulder is found, indicating that minority carriers cannot react efficiently at the semiconductor/electrolyte junction (Fig. 31). 

The PMC transient-potential diagrams and the equations derived for PMC transients clearly show that bending of an energy band significantly influences the charge carrier lifetime in semiconductor/electrolyte junctions and that an accurate interpretation of the kinetic meaning of such transients is only possible when the band bending is known and controlled. 

How can such problems be counterbalanced Since a large capacitance of a semiconductor/electrolyte junction will not negatively affect the PMC transient measurement, a large area electrode (nanostructured materials) should be selected to decrease the effective excess charge carrier concentration (excess carriers per surface area) in the interface. PMC transient measurements have been performed at a sensitized nanostructured Ti02 liquidjunction solar cell.40 With a 10-ns laser pulse excitation, only the slow decay processes can be studied. The very fast rise time cannot be resolved, but this should be the aim of picosecond studies. Such experiments are being prepared in our laboratory, but using nanostructured... 

The reason for the exponential increase in the electron transfer rate with increasing electrode potential at the ZnO/electrolyte interface must be further explored. A possible explanation is provided in a recent study on water photoelectrolysis which describes the mechanism of water oxidation to molecular oxygen as one of strong molecular interaction with nonisoenergetic electron transfer subject to irreversible thermodynamics.48 Under such conditions, the rate of electron transfer will depend on the thermodynamic force in the semiconductor/electrolyte interface to... 

Jaegermann, W. The Semiconductor/Electrolyte Interface A Surface Science Approach 30... 

Semiconductor-electrolyte interface, photo generation and loss mechanism, 458 Semiconductor-oxide junctions, 472 Semiconductor-solution interface, and the space charge region, 484 Sensitivity, of electrodes, under photo irradiation, 491 Silicon, n-type... 

Boddy PJ (1965) The structure of the semiconductor-electrolyte interface. J Electroanal Chem 10 199-244... 

Lemasson P, Etcheberry A, Gautron J (1982) Analysis of photocurrents at the semiconductor-electrolyte junction. Electrochim Acta 27 607-614... 

Lemasson P, Boutry AE, Tiiboulet R (1984) The semiconductor-electrolyte junction Physical parameters determination by photocurrent measurement throughout the Cdi xZnxTe alloy series. J Appl Phys 55 592-594... 

The diffuse charge distribution in the semiconductor s surface layer leads to a drastically lower cell capacitance at the semiconductor-electrolyte interface. Typical... 

Fig. 3a—c. Charge transfer processes at semiconductor-electrolyte interface a) and b) under forward bias. 

Between 0.20 and 0.30 V, a decay of the initial photocurrent and a negative overshoot after interrupting the illumination are developed. This behavior resembles the responses observed at semiconductor-electrolyte interfaces in the presence of surface recombination of photoinduced charges [133-135] but at a longer time scale. These features are in fact related to the back-electron-transfer processes within the interfacial ion pair schematically depicted in Fig. 11. 

Equation (45) resembles the generalized expression of IMPS for semiconductor-electrolyte interfaces [149,164]. This similarity between the dynamic photoresponses for both types of interfaces is only valid in phenomenological terms, as the natures of the... 

R. H. Wilson, in Photo-Effects at Semiconductor-Electrolyte Interfaces (A. E. Nozik, ed.), ACS Publishers, Washington DC, 1981. 

Fig. 4.1 Structure of the electric double layer and electric potential distribution at (A) a metal-electrolyte solution interface, (B) a semiconductor-electrolyte solution interface and (C) an interface of two immiscible electrolyte solutions (ITIES) in the absence of specific adsorption. The region between the electrode and the outer Helmholtz plane (OHP, at the distance jc2 from the electrode) contains a layer of oriented solvent molecules while in the Verwey and Niessen model of ITIES (C) this layer is absent...

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