Semiconductor electrolyte interface measurements

Since the metal can be treated as a nearly perfect conductor, C is high compared with C, and cannot influence the value of the measured doublelayer capacitance. The role of the metal in the double layer structure was discussed by Rice, who suggested that the distribution of electrons inside the metal decides the properties of the double-layer. This concept was later used to describe double-layer properties at the semiconductor/electrolyte interface. As shown later, the electron density on the metal side of the interface can be changed under the influence of charged solution species (dipoles, ions). ... 

Electrons, generated near the semiconductor-electrolyte interface are unable to stay in this region because of the electric field there which drives them into the bulk of the TiOz crystal, out through the metallic contact, the external circuit (where the photo-current may be measured) and into the catalytically active metal. At the interface of this metal with the electrolyte solution, reaction occurs ... 

Most often, the electrochemical impedance spectroscopy (EIS) measurements are undertaken with a potentiostat, which maintains the electrode at a precisely constant bias potential. A sinusoidal perturbation of 10 mV in a frequency range from 10 to 10 Hz is superimposed on the electrode, and the response is acquired by an impedance analyzer. In the case of semiconductor/electrolyte interfaces, the equivalent circuit fitting the experimental data is modeled as one and sometimes two loops involving a capacitance imaginary term in parallel with a purely ohmic resistance R. 

It is the electrode potential

electrochemical experiments it represents a potential difference between two identical metallic contacts of an electrochemical circuit. Such a circuit, whose one element is a semiconductor electrode, is shown schematically in Fig. 2. Besides the semiconductor electrode, it includes a reference electrode whose potential is taken, conventionally, as zero in reckoning the electrode potential (for details, see the book by Glasstone, 1946). The potential q> includes potential drops across the interfaces, i.e., the Galvani potentials at contacts—metal-semiconductor interface, semiconductor-electrolyte interface, etc., and also, if current flows in the circuit, ohmic potential drops in metal, semiconductor, electrolyte, and so on. (These ohmic drops are negligibly small under experimental conditions considered below.)... 

There is a growing tendency to invoke surface states to explain electron transfer at semiconductor-electrolyte interfaces. Too frequently the discussion of surface states is qualitative with no attempt to make quantitative estimates of the rate of surface state reactions or to measure any of the properties of these surface states. This article summarizes earlier work in which charge transfer at the semiconductor-electrolyte interface is analyzed as inelastic capture by surface states of charge carriers in the semiconductor bands at the surface. This approach is shown to be capable of explaining the experimental results within the context of established semiconductor behavior without tunneling or impurity conduction in the bandgap. Methods for measuring the density and cross section of surface states in different circumstances are discussed. 

Buhks, A New Theoretical Approach to Photoelectron Transfer Across Semiconductor-Electrolyte Interfaces, in Photoelectro-chemistry Fundamental Processes and Measurement Techniques, W. L. Wallace, A. Nozik, and S. K. Debb, eds., Proc. 

Unpinning of band edges at the semiconductor/electrolyte interface is understood as a common phenomenon for n- and p-type materials. Thus, the band edge positions as obtained from Hatband potential measurements in the dark, cannot be taken as a fixed value for the interpretation of charge transfer processes. More investigations in this direction are necessary. 

Light and potential modulated microwave reflectivity measurements offer a novel approach to the study of the semiconductor electrolyte interface. Perturbation of the density of electrons and holes in a semiconductor influences the conductivity and hence the imaginary component of the dielectric constant at microwave frequencies. For small perturbations, the change ARm in microwave reflectivity depends linearly on the change in conductivity [27, 28, 75). The application of frequency response analysis to light modulated microwave reflectance is relatively new [30]. Although the technique is analogous to IMPS, it provides additional information. 

If c = 0, then VJ,h gives a measure of the flat-band potential provided r/re(i()x is known. In fact, this formula is very rarely obeyed in practice and deviations are both common and complex. Detailed theories of the potential distribution at the semiconductor-electrolyte interface have been presented, based on photovoltage measurements, but immense care needs to be taken in the interpretation of the photovoltage since kinetic effects apparently play a major role. This is especially true if surface recombination plays an important role [172]. 

The Mott-Schottky regime spans about 1 V in applied bias potential for most semiconductor-electrolyte interfaces (i.e., in the region of depletion layer formation of the semiconductor space-charge layer, see above) [15]. The simple case considered here involves no mediator trap states or surface states at the interface such that the equivalent circuit of the interface essentially collapses to its most rudimentary form of Csc in series with the bulk resistance of the semiconductor. Further, in all the discussions above, it is reiterated that the redox electrolyte is sufficiently concentrated that the potential drop across the Gouy layer can be neglected. Specific adsorption and other processes at the semiconductor-electrolyte interface will influence Ffb these are discussed elsewhere [29, 30], as are anomalies related to the measurement process itself [31]. Figure 7 contains representative Mott-Schottky... 

A relatively recent development in frequency-resolved techniques is the perturbation of an electrochemical system (that is initially in a steady-state condition) by a periodic nonelectrical stimulus. One member in this family of techniques (IMPS, entry 7 in Table 2) has provided a wealth of information on charge transfer across semiconductor-electrolyte interfaces. Reviews are available [2, 9, 10], as is a summary of progress on the use of its electrical predecessor (AC impedance spectroscopy, entry 3 in Table 2) for the study of these interfaces [81]. These accounts should also be consulted for a discussion of the relevant time-scales in dynamic measurements on semiconductor electrolyte interfaces. 

Capacitance measurements are generally regarded as the most reliable method for determination of the band edge positions at a sensitized semiconductor-electrolyte interface [14]. The Mott-Schottky relationship, Eq. 7 ... 

The semiconductor electrode must be ideally polarizable over the potential range of interest. This means that there is no leakage current or Faradaic reaction to allow charge transfer across the semiconductor-electrolyte interface. This restriction is not too important if measurements are taken at sufficiently high frequency that the effects of Faradaic reactions are suppressed. 

In-situ luminescence measurements have been used to study the semiconductor/ electrolyte interface for many years (e.g. Petermann et al., 1972). Luminescence may result from optical excitation of electron/hole pairs that subsequently combine with the emission of light (photoluminescence). Alternatively, minority carriers injected from redox species in the electrolyte can recombine with majority carriers and give rise to electroluminescence. The review by Kelly et al. (1999) summarises the main features of photoluminescence (PL) and electroluminescence (EL) at semiconductor electrodes. The experimental arrangements for luminescence measurements are relatively straightforward. Suitable detectors include a silicon photodiode placed close to the sample, a conventional photomultiplier or a cooled charge-coupled silicon detector (CCD). The CCD system is used with a grating spectrograph to obtain luminescence spectra. 

Tafalla D., Pujadas M. and Salvador P. (1989), Direct measurements of flat-band potential shifts under illumination of the semiconductor electrolyte interface by electrolyte electroreflectance , Surface Sci. 215, 190-200. 

Surfce states at the semiconductor-electrolyte interface under illumination can be calculated from the impedance measurements using the new equivalent circuit proposed. 

Hu K, Fan FRF, Bard AJ, Hillier AC. Direct measurement of diffuse doublelayer forces at the semiconductor/electrolyte interface using an atomic force microscope. J Phys Chem B 1997 101 8298—8303. 

In the case of light modulated microwave reflectivity measurements, is a linear function of the change in the photogenerated charge that accumulates at the semiconductor/electrolyte interface... 

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