Semiconductor/liquid electrolyte

One additional problem at semiconductor/liquid electrolyte interfaces is the redox decomposition of the semiconductor itself.(24) Upon Illumination to create e- - h+ pairs, for example, all n-type semiconductor photoanodes are thermodynamically unstable with respect to anodic decomposition when immersed in the liquid electrolyte. This means that the oxidizing power of the photogenerated oxidizing equivalents (h+,s) is sufficiently great that the semiconductor can be destroyed. This thermodynamic instability 1s obviously a practical concern for photoanodes, since the kinetics for the anodic decomposition are often quite good. Indeed, no non-oxide n-type semiconductor has been demonstrated to be capable of evolving O2 from H2O (without surface modification), the anodic decomposition always dominates as in equations (6) and (7) for... 

The band bending at the semiconductor/liquid (electrolyte solution) interface can be understood by considering the potential distribution at this interface. In a case where the electrolyte solution contains a redox couple (R/Ox), which causes an electrochemical redox reaction,... 

In any case, it is perceived from the above discussion that the problem of longterm chemical stability of polycrystalline semiconductor liquid junction solar cells is far from being solved. Still, as already pointed out in the early research, any practical photovoltaic and PEC device would have to be based on polycrystalline photoelectrodes. Novel approaches mostly involving specially designed PEC systems with alternative solid or gel electrolytes and, most importantly, hybrid/sensitized electrodes with properties dictated by nanophase structuring - to be discussed at the end of this chapter - promise new advances in the field. 

Koval CA, Howard JN (1992) Electron transfer at semiconductor electrode-liquid electrolyte interfaces. Chem Rev 92 411 33... 

The photoelectrolysis of H2O can be performed in cells being very similar to those applied for the production of electricity. They differ only insofar as no additional redox couple is used in a photoelectrolysis cell. The energy scheme of corresponding systems, semiconductor/liquid/Pt, is illustrated in Fig. 9, the upper scheme for an n-type, the lower for a p-type electrode. In the case of an n-type electrode the hole created by light excitation must react with H2O resulting in 02-formation whereas at the counter electrode H2 is produced. The electrolyte can be described by two redox potentials, E°(H20/H2) and E (H20/02) which differ by 1.23 eV. At equilibrium (left side of Fig. 9) the electrochemical potential (Fermi level) is constant in the whole system and it occurs in the electrolyte somewhere between the two standard energies E°(H20/H2) and E°(H20/02). The exact position depends on the relative concentrations of H2 and O2. Illuminating the n-type electrode the electrons are driven toward the bulk of the semiconductor and reach the counter electrode via the external circuit at which they are consumed for Hj-evolution whereas the holes are dir tly... 

Similar photovoltaic cells can be made of semiconductor/liquid junctions. For example, the system could consist of an n-type semiconductor and an inert metal counterelectrode, in contact with an electrolyte solution containing a suitable reversible redox couple. At equilibrium, the electrochemical potential of the redox system in solution is aligned with the Fermi level of the semiconductor. Upon light excitation, the generated holes move toward the Si surface and are consumed for the oxidation of the red species. The charge transfer at the Si/electrolyte interface should account for the width of occupied states in the semiconductor and the range of the energy states in the redox system as represented in Fig. 1. 

Solid state materials that can conduct electricity, are electrochemically of interest with a view to (a) the conduction mechanism, (b) the properties of the electrical double layer inside a solid electrolyte or semiconductor, adjacent to an interface with a metallic conductor or a liquid electrolyte, (c) charge-transfer processes at such interfaces, (d) their possible application in systems of practical interest, e.g. batteries, fuel cells, electrolysis cells, and (e) improvement of their operation in these applications by modifications of the electrode surface, etc. 

So-called wet solar cells show promise, particularly because of their relative ease of fabrication. In this type of photovoltaic cell, the junction is formed, between a semiconductor and a liquid electrolyte. No doping is required because a junction forms spontaneously when a suitable semiconductor, such as GaAs, is contacted with a suitable electrolyte, Three knotty problems (accelerated oxidation of surface of semiconductor exchange of ions between semiconductor and electrolyte forming a blocking layer and deposition of ions of impurities on the surface of the semiconductor) all have been solved and thus the concept now appears technically viable,... 

By contrast, electrolyte states are much more limited in their distribution than metal conduction band states so that in many cases electron transfer through surface states may be the dominant process in semiconductor-electrolyte junctions. On the other hand, in contrast to vacuum and insulators, liquid electrolytes allow substantial interaction at the interface. Ionic currents flow, adsorption and desorption take place, solvent molecules fluctuate around ions and reactants and products diffuse to and from the surface. The reactions and kinetics of these processes must be considered in analyzing the behavior of surface states at the semiconductor-electrolyte junction. Thus, at the semiconductor-electrolyte junction, surface states can interact strongly with the electrolyte but from the point of view of the semiconductor the reaction of surface states with the semiconductor carriers should still be describable by equations 1 and 2. 

Electrochemical reactions usually occur at the interface between a solid electrode and a liquid electrolyte. The electrode is an electron conductor, such as metals and semiconductors, and is immersed in an electrolyte. In practice the electrode is partially immersed in an electrolyte, but in theory it is convenient to define that the electrode is a multiphase system in which an electronic conductor is fully immersed in an electrolyte as shown in Fig. 9.4. 

In the presence of a redox system dissolved in the electrolyte, as long as there exists an energy difference between the Fermi level of the semiconductor and the redox couple, to reach the equilibrium conditions charge-carrier transfer occurs across the semiconductor-liquid interface via the energy bands, i.e., the conduction or valence band of the semiconductor. At the equilibrium point, the Fermi level of the redox... 

Galvanic cell (or galvanic element) — A galvanic cell is an - electrochemical cell in which reactions occur spontaneously at the -> electrodes when they are connected externally by a conductor. In these cells chemical energy can be converted into electrical energy [i, ii]. The galvanic cell consists of two electrodes, i.e., electron conductors (-> metal, carbon, semiconductor etc.) in contact with one or more ionic conductors (which may be - electrolyte solutions, ionic liquids, electrolyte melts, or - solid electrolytes). 

Photovoltaic cells based on the sensitization of mesoporous titanium dioxide by Ru(II) complex dyes in conjunction with the I.3 /U redox couple as a mediator have proved very efficient at exploiting this principle. In such systems, the ionic mediator travels back and forth by diffusion from the working electrode to the counterelectrode, to shuttle to the sensitizer the electrons that have gone through the electrical circuit [18, 21, 84]. Recently, solid-state devices have been described where the liquid electrolyte present in the pores of the nanocrystalline oxide film is replaced by a large-bandgap p-type semiconductor acting as a hole-transport medium [85 88]. 

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