Fermi level control

Figure 22.24 Possible effect of doping. Top Catalysis on metal clusters. The gas reaction takes place entirely on the cluster. Hence, the conductance remains unaffected. Left Spillover Metallic clusters promote the dissociation of certain ambient gases. The reactive particles reach the tin dioxide surface, where the reaction takes place. The conductance is affected due to this. Right Fermi level control. Metallic clusters are partially oxidised in the gaseous atmosphere. The ambient gases affect the stoichiometry. Changes in the Fermi level position of the clusters change the depletion layer and the band bending inside the tin dioxide, reproduced from [30] by permissions of Shaker Verlag...

It has been proven by experiment that there are donor acceptor atoms and molecules of absorbate and their classification as belonging to one or another type is controlled not only by their chemical nature but by the nature of adsorbent as well (see, for instance [18, 21, 203-205]). From the standpoint of the electron theory of chemisorption it became possible to explain the effect of electron adsorption [206] as well as phenomenon of luminescence of radical recombination during chemisorption [207]. The experimental proof was given to the capability of changing of one form of chemisorption into another during change in the value of the Fermi level in adsorbent [208]. 

In this chapter we introduce and discuss a number of concepts that are commonly used in the electrochemical literature and in the remainder of this book. In particular we will illuminate the relation of electrochemical concepts to those used in related disciplines. Electrochemistry has much in common with surface science, which is the study of solid surfaces in contact with a gas phase or, more commonly, with ultra-high vacuum (uhv). A number of surface science techniques has been applied to electrochemical interfaces with great success. Conversely, surface scientists have become attracted to electrochemistry because the electrode charge (or equivalently the potential) is a useful variable which cannot be well controlled for surfaces in uhv. This has led to a laudable attempt to use similar terminologies for these two related sciences, and to introduce the concepts of the absolute scale of electrochemical potentials and the Fermi level of a redox reaction into electrochemistry. Unfortunately, there is some confusion of these terms in the literature, even though they are quite simple. 

Electrical cells based on semiconductors that produce electricity from sunlight and deliver the electrical energy to an external load are known as photovoltaic cells. At present most commercial solar cells consist of silicon doped with small levels of controlled impurity elements, which increase the conductivity because either the CB is partly filled with electrons (n-type doping) or the VB is partly filled with holes (p-type doping). The electrons have, on average, a potential energy known as the Fermi level, which is just below that of the CB in n-type semiconductors and just above that of the VB in p-type semiconductors (Figure 11.2). 

For p-type electrodes, the cathodic current is carried at low overvoltages by the minority carriers (electrons) in the conduction band and is controlled at high overvoltages by the limiting current of electron diffusion the anodic current is carried by the mtqority carriers (holes) in the valence band and the concentration of interfacial holes increases with increasing anodic overvoltage until the Fermi level is pinned in the valence band at the electrode interface, where the anodic current finally becomes an electron injection current into the electrode. 

In the active state, the dissolution of metals proceeds through the anodic transfer of metal ions across the compact electric double layer at the interface between the bare metal and the aqueous solution. In the passive state, the formation of a thin passive oxide film causes the interfadal structure to change from a simple metal/solution interface to a three-phase structure composed of the metal/fUm interface, a thin film layer, and the film/solution interface [Sato, 1976, 1990]. The rate of metal dissolution in the passive state, then, is controlled by the transfer rate of metal ions across the film/solution interface (the dissolution rate of a passive semiconductor oxide film) this rate is a function of the potential across the film/solution interface. Since the potential across the film/solution interface is constant in the stationary state of the passive oxide film (in the state of band edge level pinning), the rate of the film dissolution is independent of the electrode potential in the range of potential of the passive state. In the transpassive state, however, the potential across the film/solution interface becomes dependent on the electrode potential (in the state of Fermi level pinning), and the dissolution of the thin transpassive film depends on the electrode potential as described in Sec. 11.4.2. 

An externally applied potential controls the Fermi level of the semiconductor with respect to the reference electrode in the solution. Changes of the potential affect the potential drop across the semiconduc-tor/electrolyte interface. In most situations of electrochemical reactions, the potential drop in the solution Helmholtz layer can be neglected, and thus a gradient of potential is generated in the space charge... 

We depart briefly from our discussion of SI GaAs to consider an example that better illustrates some of the features of temperature-dependent Hall measurements. This example (Look et al., 1982a) involves bulk GaAs samples that have sc — F — 0-15 eV. We suppose, initially, that the impurity or defect controlling the Fermi level is a donor. Then any acceptors or donors above this energy (by a few kT more) are unoccupied and any below are occupied. Also, p n for kT eG. From Eq. (B34), Appendix B, we get... 

In order to take advantage of nanometer-sized semiconductor clusters, one must provide an electron pathway for conduction between the particles. This has been achieved by sintering colloidal solutions deposited on conductive glasses. The resulting material is a porous nanostructured film, like that shown in Fig. 1, which retains many of the characteristics of colloidal solutions, but is in a more manageable form and may be produced in a transparent state. Furthermore, the Fermi level within each semiconductor particle can be controlled potentiostati-cally, a feature which is fundamental for the functioning of the electrochromic devices described in Section III. 

Dietl et al. 2001c). There exists another mechanism by which strain may affect 7c. It is presently well known that the upper limit of the achievable carrier concentration is controlled by pinning of the Fermi level by impurity or defect states in virtually all compound semiconductors. Since the energies of such states in respect to bands vary strongly with the bond length, the hole concentration and thus 7c will depend on strain. 

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