Conduction band, semiconductor electrodes

In a light-emitting MSM structure the two metal electrodes selected such that the work functions of the electrodes are near the edge of the valence band (VB) and the conducting band (CB) of the semiconductor, respectively, so that oppositely charge carriers are injected from the opposite electrodes. An ohmic and a rectifying contact is therefore formed in the MSM structure (see Fig. 9-22). 

Figure 13-4. Encigy level diagnim of a single-layer OLED, where the organic malerial is depicted as a fully depleted semiconductor. The valence band Ey corresponds to the HOMO and the conduction band Ec corresponds to the LUMO. Tile Fermi levels of the two metal electrodes are marked as Et-. Upon contact a built-in potential is established and needs to be compensated for, before the device will begin to operating.

Fig. 5.14 Inoue et al. carried out a systematic study of the photocatalytic reduction of CO2 by different semiconductor powders in aqueous suspensions. Shown here is the energy correlation between semiconductor catalysts and redox couples in water, as presented in their paper. In principle, the solution species with more positive redox potential with respect to the conduction band level of the semiconductor is preferably reduced at the electrode. Photoexcited electrons in the more negative conduction band certainly have greater ability to reduce CO2 in the solution. (Reproduced from [240])...

Depending on the nature of the electrode and reaction, the carriers involved in an electrochemical reaction at a semiconductor electrode can be electrons from the conduction band (in the following to be called simply electrons), electrons from the valence band (holes), or both. The concentration of the minority carriers in semiconductors (electrons in p-type, and holes in n-type semiconductors) is always much... 

The electrons produced in the conduction band as a result of illumination can participate in cathodic reactions. However, since in n-type semiconductors the quasi-Fermi level is just slightly above the Fermi level, the excited electrons participating in a cathodic reaction will almost not increase the energy effect of the reaction. Their concentration close to the actual surface is low hence, it will be advantageous to link the n-type semiconductor electrode to another electrode which is metallic, and not illuminated, and to allow the cathodic reaction to occur at this electrode. It is necessary, then, that the auxiliary metal electrode have good catalytic activity toward the cathodic reaction. 

The band edges are flattened when the anode is illuminated, the Fermi level rises, and the electrode potential shifts in the negative direction. As a result, a potential difference which amounts to about 0.6 to 0.8 V develops between the semiconductor and metal electrode. When the external circuit is closed over some load R, the electrons produced by illumination in the conduction band of the semiconductor electrode will flow through the external circuit to the metal electrode, where they are consumed in the cathodic reaction. Holes from the valence band of the semiconductor electrode at the same time are directly absorbed by the anodic reaction. Therefore, a steady electrical current arises in the system, and the energy of this current can be utilized in the external circuit. In such devices, the solar-to-electrical energy conversion efficiency is as high as 5 to 10%. Unfortunately, their operating life is restricted by the low corrosion resistance of semiconductor electrodes. 

Finally cells containing a p-type semiconductor electrode should be mentioned. In principle the application of p-type electrodes would be even more favorable because electrons created by light excitation are transferred from the conduction band to the redox system. Stability problems are less severe because most semiconductors do not show cathodic decomposition (see e.g. earlier review article. However, there is only one system, p-InP/(V " /V ), with which a reasonable efficiency was obtained (Table 1) . There are mainly two reasons why p-electrodes were not widely used (i) not many materials are available from which p-type electrodes can be made (ii)... 

Various attempts have been made to produce methanol by photoreduction of CO2 at semiconductor electrodes and particles (see e.g.) . In principle there is a good chance to produce methanol at a semiconductor because the conduction band can be... 

The above mechanistic aspect of electron transport in electroactive polymer films has been an active and chemically rich research topic (13-18) in polymer coated electrodes. We have called (19) the process "redox conduction", since it is a non-ohmic form of electrical conductivity that is intrinsically different from that in metals or semiconductors. Some of the special characteristics of redox conductivity are non-linear current-voltage relations and a narrow band of conductivity centered around electrode potentials that yield the necessary mixture of oxidized and reduced states of the redox sites in the polymer (mixed valent form). Electron hopping in redox conductivity is obviously also peculiar to polymers whose sites comprise spatially localized electronic states. 

Semiconductor electrodes seem to be attractive and promising materials for carbon dioxide reduction to highly reduced products such as methanol and methane, in contrast to many metal electrodes at which formic acid or CO is the major reduction product. This potential utility of semiconductor materials is due to their band structure (especially the conduction band level, where multielectron transfer may be achieved)76 and chemical properties (e.g., C02 is well known to adsorb onto metal oxides and/ or noble metal-doped metal oxides to become more active states77-81). Recently, several reports dealing with C02 reduction at n-type semiconductors in the dark have appeared, as described below. 

The charge carriers may reduce or oxidize the semiconductor itself leading to decomposition. This poses a serious problem for practical photoelectrochemical devices. Absolute thermodynamic stability can be achieved if the redox potential of oxidative decomposition reaction lies below the valence band and the redox potential of the reductive decomposition reaction lies above the conduction band. In most cases, usually one or both redox potentials lie within the bandgap. Then the stability depends on the competition between thermodynamically possible reactions. When the redox potentials of electrode decomposition reactions are thermodynamically more favored than electrolyte redox reactions, the result is electrode instability, for example, ZnO, Cu20, and CdS in an aqueous electrolyte. 

There is a fundamental difference between electron-transfer reactions on metals and on semiconductors. On metals the variation of the electrode potential causes a corresponding change in the molar Gibbs energy of the reaction. Due to the comparatively low conductivity of semiconductors, the positions of the band edges at the semiconductor surface do not change with respect to the solution as the potential is varied. However, the relative position of the Fermi level in the semiconductor is changed, and so are the densities of electrons and holes on the metal surface. 

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