Semiconductors photocorrosion

An interesting example of the kinetic effect in semiconductor photocorrosion is photopassivation and photoactivation of silicon (Izidinov et al., 1962). Silicon is an electronegative element, so it should be dissolved spontaneously and intensively in water with hydrogen evolution. But in most of aqueous solutions the surface of silicon is covered with a nonporous passivating oxide film, which protects it from corrosion. The anodic polarization curve of silicon (dashed line in Fig. 20) is of the form characteristic of electrodes liable to passivation as the potential increases, the anodic current first grows (the... 

A greater percentage of photogenerated holes utilized in constructive oxidation of polysulfide results in enhanced photocurrents. This has the additional benefit of fewer oxidizing holes available for attack on the semiconductor (photocorrosion). As seen in Fig. 16, this results in enhanced photocurrent stability of the PEC. This study showed that with solution optimization, not only the photocurrent but also the polysulfide electrolyte exhibits enhanced lifetime, both approaching one-year operation outdoors [48]. 

There are difficulties in making such cells practical. High-band-gap semiconductors do not respond to visible light, while low-band-gap ones are prone to photocorrosion [182, 185]. In addition, both photochemical and entropy or thermodynamic factors limit the ideal efficiency with which sunlight can be converted to electrical energy [186]. 

A thorough insight into the comparative photoelectrochemical-photocorrosion behavior of CdX crystals has been motivated by the study of an unusual phenomenon consisting of oscillation of photocurrent with a period of about 1 Hz, which was observed at an n-type CdTe semiconductor electrode in a cesium sulfide solution [83], The oscillating behavior lasted for about 2 h and could be explained by the existence of a Te layer of variable width. The dependence of the oscillation features on potential, temperature, and light intensity was reported. Most striking was the non-linear behavior of the system as a function of light intensity. A comparison of CdTe to other related systems (CdS, CdSe) and solution compositions was performed. 

The direct photoelectrolysis of water requires that the v level be below the 02/H20 level and the ec level be above the H+/H2 level. This condition is satisfied, e.g. for CdS, GaP, and several large-band gap semiconductors, such as SrTi03, KTa03, Nb205 and Zr02 (cf. also Fig. 5.59). From the practical points of view, these materials show, however, other specific problems, e.g. low electrocatalytic activity, sensitivity to photocorrosion (CdS, GaP), and inconvenient absorption spectrum (oxides). 

The band-gap excitation of semiconductor electrodes brings two practical problems for photoelectrochemical solar energy conversion (1) Most of the useful semiconductors have relatively wide band gaps, hence they can be excited only by ultraviolet radiation, whose proportion in the solar spectrum is rather low. (2) the photogenerated minority charge carriers in these semiconductors possess a high oxidative or reductive power to cause a rapid photocorrosion. 

The theoretical solar conversion efficiency of a regenerative photovoltaic cell with a semiconductor photoelectrode therefore depends on the model used to describe the thermodynamic and kinetic energy losses. The CE values, which consider all the mentioned losses can generally only be estimated the full line in Fig. 5.65 represents such an approximation. Unfortunately, the materials possessing nearly the optimum absorption properties (Si, InP, and GaAs) are handicapped by their photocorrosion sensitivity and high price. 

Generation of hydrogen from H2S using cadmium sulfide with waste products as sacrificial agents to avoid photocorrosion of the semiconductor is expected to grow as a niche application. 

Another important photocatalytic application is the synthesis of hydrogen from water. However, low solar efficiency and photocorrosion have proven to be hindrances limiting the process economics of photocatalysis [325], The most efficient systems to date consist of compound semiconductor heterostructures that operate with efficiencies of approximately 16%, however, cost and stability are still problematic [325],... 

Upon excitation of a semiconductor, the electrons in the conduction band and the hole in the valence band are active species that can initiate redox processes at the semiconductor-electrolyte interface, including photocorrosion of the semiconductor, a change in its surface properties (photoinduced superhydrophilicity [13]), and various spontaneous and non-spontaneous reactions [14-19]. These phenomena are basically surface-mediated redox reactions. The processes are depicted in Fig. 16.1. Owing to the slow spontaneous kinetic of the reactions between the... 

Various approaches are being pursued to circumvent the poor solar light response of photocorrosion-stable wide band gap semiconductors. For example, in an experiment carried out by Karn... 

Like other non-oxidic semiconductors in aqueous solutions, surface oxidized and photocorrosive InP is a poor photoelectrode for water decomposition [19,27,32,33], To enhance properties several efforts have focused on coupling of the semiconductor with discontinuous noble metal layers of island-like topology. For example, rhodium, ruthenium and platinum thin films, less than 10 nm in thickness, have been electrodeposited onto p-type InP followed by a brief etching treatment to achieve an island-like topology on the surface [27,28]. In combination with a Pt counter electrode, under AM 1.5 illumination of 87 mW/cm the metal (Pt, Rh, Ru) functionalized p-InP photocathodes [27] see a reduction in the threshold voltage for water electrolysis from 1.23 V to 0.64 V, and in aqueous HCl solution a photocurrent density of 24 mA/cm with a photoconversion efficiency of 12% [27]. 

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