Semiconductors photoelectrochemical processes

These three equations (11), (12), and (13) contain three unknown variables, ApJt kn and sr The rest are known quantities, provided the potential-dependent photocurrent (/ph) and the potential-dependent photoinduced microwave conductivity are measured simultaneously. The problem, which these equations describe, is therefore fully determined. This means that the interfacial rate constants kr and sr are accessible to combined photocurrent-photoinduced microwave conductivity measurements. The precondition, however is that an analytical function for the potential-dependent microwave conductivity (12) can be found. This is a challenge since the mathematical solution of the differential equations dominating charge carrier behavior in semiconductor interfaces is quite complex, but it could be obtained,9 17 as will be outlined below. In this way an important expectation with respect to microwave (photo)electro-chemistry, obtaining more insight into photoelectrochemical processes... 

In any case, no electrode material or approach fulfills the requirements for a successful photoelectrochemical process in all respects, i.e., for routine practical use hence novel materials and approaches are constantly pursued. Note that beside the robust performance needed, the most important figure of merit for a semiconductor photoelectrode used for water splitting is the photoconversion efficiency, which is... 

Fujishima, A., Narasinga Rao, T., and Ohko, Y., Photoelectrochemical processes of semiconductors, in Photocatalysis, Science and Technology, Kaneko, M. and Okura, I. (Eds), Kodansha/Springer, Berlin, 2002, Chap. 2. 

Prior to the 1970 s, electrochemical kinetic studies were largely directed towards faradaic reactions occurring at metal electrodes. While certain questions remain unanswered, a combination of theoretical and experimental studies has produced a relatively mature picture of electron transfer at the metal-solution interface f1-41. Recent interest in photoelectrochemical processes has extended the interest in electrochemical kinetics to semiconductor electrodes f5-151. Despite the pioneering work of Gerischer (11-141 and Memming (15), many aspects of electron transfer kinetics at the semiconductor-solution interface remain controversial or unexplained. 

Solar energy conversion in photoelectrochemical cells with semiconductor electrodes is considered in detail in the reviews by Gerischer (1975, 1979), Nozik (1978), Heller and Miller (1980), Wrighton (1979), Bard (1980), and Pleskov (1981) and will not be discussed. The present chapter deals with the main principles of the theory of photoelectrochemical processes at semiconductor electrodes and discusses the most important experimental results concerning various aspects of photoelectrochemistry of a semiconductor-electrolyte interface a more comprehensive consideration of these problems can be found in the book by the authors (Pleskov and Gurevich,... 

Photoelectrochemical processes may proceed in quite different regimes, depending on the relative magnitudes of the depth of light penetration into a semiconductor, the diffusion length and the thickness of the space-charge region, and also between the rates of electrode process and carrier supply to the surface. Nevertheless, in important particular cases relatively simple (but in no way trivial) relations can be obtained, which characterize a photoprocess, and the theory can be compared with experiment. 

In Part I the fundamental aspects of photocatalysis are described. Photoelectrochemical processes at semiconductors are the most important basics for all photocatalytic reactions (Chapter 2). Design, preparation and characterization of active photocatalysts have been an important research subject,... 

Besides such electronic surface states which can interact either with electrons in the bulk of the semiconductor or with a redox system in the electrolyte, we have to consider another type of excess charge at the surface. This stems from adsorbed ions or from ionic groups attached to the surface of the semiconductor. This is well known from the pH dependence of the flat band potential of semiconducting oxides (8) or the dependence of the flat band potential of sulfides on the sulfide concentration in solution (9). Since surfaces of different orientation will interact differently with such ionic charge, this again will affect the photoelectrochemical processes via the different barrier heights at different surface orientation. 

In spite of a great number of investigations aimed at the preparation of photocatalysts and photoelectrodes based on the semiconductors surface-modified with metal nanoparticles, many factors influencing the photoelectrochemical processes under consideration are not yet clearly understood. Among them are the role of electronic surface (interfacial) states and Schottky barriers at semiconductor / metal nanoparticle interface, the relationship between the efficiency of photoinduced processes and the size of metal particles, the mechanism of the modifying action of such nanoparticles, the influence of the concentration of electronic and other defects in a semiconductor matrix on the peculiarities of metal nanophase formation under different conditions of deposition process (in particular, under different shifts of the electrochemical surface potential from its equilibrium value), etc. 

Kinetic Photoelectrochemical Processes at High Surface State Semiconductors... 

The possible results and limitations of model experiments for semiconductor/electrolyte interfaces are discussed for non-reactive and reactive interfaces and related to the use of UHV techniques for obtaining microscopic information of interfacial processes in photoelectrochemical processes. 

Only a few studies [453,543-547] have been carried but on the photoelectrochemical behaviour of YBCO ceramics and single crystals. In nonaqueous media, in the absence of degradation, the data show that the usual concepts of photoelectrochemistry of p-type semiconductors apply to those systems. Such studies have not yet been actively developed, probably because of the high sensitivity of photoelectrochemical processes to the nature of materials. Reproducibility of data for such complex systems as HTSC oxides is an issue. At the same time, the photoassisted electrochemical processes on HTSC electrodes can lay the basis for certain effective technologies. This is especially true for the photoelectrochemical etching and metallization which prove to be extremely effective as applied to semiconductors [503,504]. 

One of the specificities of the photoelectrochemical processes, involving minority charge carriers photogenerated in the semiconductor electrode, is that the current-potential relationship is of rather limited usefulness with regard to the determination of reaction kinetics. This is connected with the fact that, under such conditions, changes in electrode... 

A. J. Bard, Semiconductor photoelectrochemical ceUs, in Proceedings on Electrode Processes, Vol. 

H. Gerischer, The role of semiconductor structure and surface properties in photoelectrochemical processes, J. Electroanal. Chem. 15B, 553, 1983. 

The photoelectrochemical process can be divided into the four reactions (Equations 1-4) involving photon excitation and charge separation in the Pc film (Equation 1) recombination events (Equation 2), charge transfer at the electrode substrate-Pc. interface (Equation 3) and charge transfer at the Pc-solution interface (Equation 4). The net process is the oxidation of hydroquinone with 0 to form quinone and R. If this is normally a thermodynamically uphill process where the dye is superimposed on a semiconductor substrate, then true photosensitized energy conversion has occurred. 

Because the light used for photoelectrochemical processes must have photon energy greater than the band gap of the semiconductor, UV irradiation is needed... 

This section presents results that show how the rates of photoelectrochemical processes can be derived from time resolved measurement of the photoinduced current or potential in the external circuit of a photoelectrochemical cell. The capacitance of the Helmholtz-double layer is of the order of lO Fcm , the depletion layer capacitance of an extrinsic semiconductor junction is typically 10 -10 Fcm , while the capacitance of an insulator is orders of magnitude lower. With a value of 100 Ohm for the resistance Rd + R of the cell, the time constant of photoelectrochemical cells is 10 s for metallic electrodes, 10 -10" s for semiconductor electrodes and much lower for insulator electrodes. The rates of photoelectrochemical processes also span a wide range. This makes photoelectrochemical kinetics a rich, albeit demanding, area for research. 

IMPS uses modulation of the light intensity to produce an ac photocurrent that is analysed to obtain kinetic information. An alternative approach is to modulate the electrode potential while keeping the illumination intensity constant. This method has been referred to as photoelectrochemical impedance spectroscopy (PEIS), and it has been widely used to study photoelectrochemical reactions at semiconductors [30-35]. In most cases, the impedance response has been fitted using equivalent circuits since this is the usual approach used in electrochemical impedance spectroscopy. The relationship between PEIS and IMPS has been discussed by a number of authors [35, 60, 64]. Vanmaekelbergh et al. [64] have calculated both the IMPS transfer function and the photoelectrochemical impedance from first principles and shown that these methods give the same information about the mechanism and kinetics of recombination. Recombination at CdS and ZnO electrodes has been studied by both methods [62, 77]. Ponomarev and Peter [35] have shown how the equivalent circuit components used to fit impedance data are related to the physical properties of the electrode (e.g. the space charge capacitance) and to the rate constants for photoelectrochemical processes. 

In recent years great interest has aroused in photoelectrochemical behaviour of the semiconductor dispersions, e g., suspensions, colloids, small particles embedded in membranes and vesicles, etc. Unlike PEC cells, they do not provide for special separation of products of the photoelectrochemical process. However, the microheterogeneous systems are superior in electrocatalytic activity (due to their giant surface area). 

Already at an early stage of the research in the semiconductor dispersions, attempts have been made to carry out water splitting, CO2 reduction, etc., in other words, the same photoelectrochemical processes as in the macroscopic PEC cells. The results obtained are summarized in [51-55]. We shall confine ourselves, however, to the processes that might underly some methods of purification, eg., of waste waters etc. These processes are stimulated by electrons and holes produced in the particles by light. As only one type of the current carriers is consumed in the "useful" reaction, measures should be taken to remove the other type from the particle in order to preserve its electroneutrality and sustain the process. For this purpose a sacrificial electron donor (or acceptor) is to be introduced into the electrolyte solution. Often it is the solvent that plays sacrifice. Some examples are listed below. 

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