Semiconductors charge separation

Solar cells, or photovoltaic devices, have been studied for many years [3], Most of the current work is focused on dye-sensitized nanocrystalline solar cells. These provide a technical and economically viable alternative to present-day photovoltaic devices. In contrast to conventional systems, in which the semiconductor assumes both the task of light absorption and charge carrier transport, the two functions are separated in dye-sensitized nanocrystalline solar cells [54] (cf. OPCs). Light is absorbed by the dye sensitizer, which is anchored to the surface of a wide-band-gap semiconductor. Charge separation takes place at the interface via photoinduced electron injection from the dye into the conduction band of the... 

FIGURE 29.3 Charge separation during photoexcitation of a semiconductor electrode. 

Let us now return to MMCT effects in semiconductors. In this class of compounds MMCT may be followed by charge separation, i.e. the excited MMCT state may be stabilized. This is the case if the M species involved act as traps. A beautiful example is the color change of SrTiOj Fe,Mo upon irradiation [111]. In the dark, iron and molybdenum are present as Fe(III) and Mo(VI). The material is eolorless. After irradiation with 400 nm radiation Fe(IV) and Mo(V) are created. These ions have optical absorption in the visible. The Mo(VI) species plays the role of a deep electron trap. The thermal decay time of the color at room temperature is several minutes. Note that the MMCT transition Fe(III) + Mo(VI) -> Fe(IV) -I- Mo(V) belongs to the type which was treated above. In the semiconductor the iron and molybdenum species are far apart and the conduction band takes the role of electron transporter. A similar phenomenon has been reported for ZnS Eu, Cr [112]. There is a photoinduced charge separation Eu(II) -I- Cr(II) -> Eu(III) - - Cr(I) via the conduction band (see Fig. 18). 

Tricot, Y.-M. and Fendler, J.H., Colloidal catalyst-coated semiconductors in surfactant vesicles In situ generation of Rh-coated CdS particles in dihexadecylphosphate vesicles and their utilization for photosensitized charge separation and hydrogen generation, /. Am. Chem. Soc., 106, 7359,1984. 

Space charge layers and contact potential for efficient charge carrier separation can be achieved with proper semiconductor structure in several ways. When possible semiconductor structures are considered, the charge separation can be attained in an active mode, i.e., by the use of a potential bias in a photoelectrochem-ical cell, or in a passive mode, i.e., with the use of proper contact between different phases. 

Finally, an interesting concept, recently advanced, is the implementation of active materials as nanotube arrays. These systems have high surface area to optimize contact between semiconductor and electrolyte, and good light trapping properties. Their inner space could also be filled with catalysts or sensitizers and/ or pn junctions to obtain charge separation and facilitate electron transport [136]. 

The interaction of semiconductor with nanocarbon induces a modification of the intrinsic properties of semiconductor particles (band gap, charge carrier density, lifetime of charge separation, non-radiative paths, etc.) [1] as well as of the surface properties which were discussed in detail in the previous section. 

To detail DSSC technologies, Fig. 18.1 illustrates the modus operandi of DSSCs. Initially, light is absorbed by a dye, which is anchored to the surface of either n- or p-type semiconductor mesoporous electrodes. Importantly, the possibility of integrating both types of electrodes into single DSSCs has evoked the potential of developing tandem DSSCs, which feature better overall device performances compared to just n-or p-type based DSSCs [19-26]. Briefly, n-type DSSCs, such as TiOz or ZnO mesoporous films, are deposited on top of indium-tin oxide (ITO) or fluorine-doped tin oxide (FTO) substrates and constitute the photoanodes. Here, charge separation takes place at the dye/electrode interface by means of electron injection from the photoexcited dye into the conduction band (cb) of the semiconductor [27,28]. A different mechanism governs p-type DSSCs, which are mainly based on NiO electrodes on ITO and/or FTO substrates... 

In this type of DSSCs, once the dye is photoexcited, charge separation drives electrons from the valence band (vb) of the semiconductor to the photoexcited dye. Common to both types of DSSCs is the regeneration of the oxidized or reduced dye by a redox mediating electrolyte. The latter is mainly in the form of a liquid and/or a solid. Platinum films deposited onto ITO or FTO are the most utilized counter-electrodes and are required to close the electronic circuit. 

Maximization of the available energy for electrolysis with a given semiconductor seems to require use of the most heavily doped material together with a minimal band bending consistent with efficient charge separation so that in the n-semiconductor, Ep(n) is as high as possible while E (n, surface) is as low as possible and in the p-semiconductor 2 (p) is as low as possible... 

This cell employs a solid state photovoltaic to generate electricity that is then passed to a commercial-type water electrolyzer (see Chapter 2). An alternative system involves the semiconductor photovoltaic cell configured as a monolithic structure and immersed directly in the aqueous solution, see Chapter 8 this cell involves a solid-state p-n or schottky junction to produce the required internal electric field for efficient charge separation and the production of a photovoltage sufficient to decompose water [49-51]. 

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