Semiconductors light absorption

Fig. 5.17 CdS-ZnO coupled semiconductor system (a) interaction between two colloidal particles showing the principle of the charge injection process and (b) light absorption and electron transfer on an electrode surface leading to the generation of photocurrent. (Reproduced from [330])...

The photovoltaic effect is initiated by light absorption in the electrode material. This is practically important only with semiconductor electrodes, where the photogenerated, excited electrons or holes may, under certain conditions, react with electrolyte redox systems. The photoredox reaction at the illuminated semiconductor thus drives the complementary (dark) reaction at the counterelectrode, which again may (but need not) regenerate the reactant consumed at the photoelectrode. The regenerative mode of operation is, according to the IUPAC recommendation, denoted as photovoltaic cell and the second one as photoelectrolytic cell . Alternative classification and terms will be discussed below. 

The term photovoltaic effect is further used to denote non-electrochemical photoprocesses in solid-state metal/semiconductor interfaces (Schottky barrier contacts) and semiconductor/semiconductor pin) junctions. Analogously, the term photogalvanic effect is used more generally to denote any photoexcitation of the d.c. current in a material (e.g. in solid ferroelectrics). Although confusion is not usual, electrochemical reactions initiated by light absorption in electrolyte solutions should be termed electrochemical photogalvanic effect , and reactions at photoexcited semiconductor electodes electrochemical photovoltaic effect . 

Silicon is the most popular material for photovoltaic (PV) power. Another material is gallium arsenide (GaAs), which is a compound semiconductor. GaAs has a crystal structure similar to that of silicon, but it consists of alternating gallium and arsenic atoms. It is well suited for PV applications since it has a high light absorption coefficient and only a thin layer of material is required, which reduces the cost. 

Carbon nanodots and other carbon surface species may act as efficient solid-state sensitizers to promote visible light absorption. In addition, various nanocarbons may act as semiconductors enabling to realize interesting Z-schemes for extended visible light activity. 

The antenna effect as it is found in natural photosynthetic systems is an attractive tool for increasing light absorption of solar cells. Some of the work done on dye sensitization of polycrystalline titanium dioxide shows aspects of antenna behavior [76,83-87]. Most of the problems in the systems where an electron is injected into the semiconductor arise in the regeneration process of... 

This cell involves the absorption of light by dye molecules spread on the surface of the semiconductor, which upon light absorption will inject electrons into the conduction band of the n-type semiconductor from their excited state. The photo-oxidized dye can be used to oxidize water and the complementary redox process can take place at the counter electrode [46,47]. Tandem cells such as these are discussed in Chapter 8. 

Light absorption by a semiconductor results in the creation of electron-hole pairs, by means of either direct or indirect momentum transitions depending on the crystal structure. Momentum is conserved in direct transitions, while a change in momentum is... 

While and 17 can be rationalized on the basis of kinetic parameters, LHE depends on the active surface area of the semiconductor and the cross section for light absorption of the molecular sensitizer. In practice, the IPCE measurements are performed with monochromatic light, and 1 ( ) values are calculated according to Equation 17.9. 

The discussion which follows is divided into two main sections. The first termed antenna sensitizers presents studies of polynuclear compounds with a surface bound unit that can accept energy from covalently linked chromophoric groups and inject electrons into the semiconductor from its excited state. The second describes supramolecular assemblies designed to promote intramolecular and interfacial electron transfer upon light absorption. 

Figure 1 Schematic representation of a Gratzel solar cell. Sub-band-gap light absorption leads to the formation of the sensitizer excited state, followed by electron injection into the conduction band of the high-area nanocrystalline semiconductor. The electrons can be drawn into a circuit to do useful work and returned to the system through the redox mediator, the I/Ij" couple, at the counterelectrode.

The basic mechanism was treated in a number of articles [6]. Following the light absorption, primary excited species are formed which can either recombine or migrate to the surface of the semiconductor, where several redox reactions may take place. Tlie organic substrate reacts widi formed active species (oxidant or reducing) depending on its initial oxidation state and the nature of substituents [7], forming radicals and other species that are further oxidized or reduced. Several complex networks of reaction have been reported on the basis of detailed chemical analyses of the time evolution of the substrate and formed intermediates or by-products [8-11],... 

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