Semiconducting n-type

Fujishima A., Honda K. and Kikuchi S. (1969), Photosensitized electrolytic oxidation on semiconducting n-type Ti02 electrode , J. Chem. Soc. Jpn. 72, 108-113. 

Free-electron lasers have long enabled the generation of extremely intense, sub-picosecond TFlz pulses that have been used to characterize a wide variety of materials and ultrafast processes [43]. Due to their massive size and great expense, however, only a few research groups have been able to operate them. Other approaches to the generation of sub-picosecond TFlz pulses have therefore been sought, and one of the earliest and most successfid involved semiconducting materials. In a photoconductive semiconductor, carriers (for n-type material, electrons)... 

Modifications of the conduction properties of semiconducting carbon nanotubes by B (p-type) and N ( -type) substitutional doping has also been dis-cussed[3l] and, in addition, electronic modifications by filling the capillaries of the tubes have also been proposed[32]. Exohedral doping of the space between nanotubes in a tubule bundle could provide yet an-... 

Ceria is another type of mixed conducting oxide which has been shown already to induce electrochemical promotion.71 Ceria is a catalyst support of increasing technological importance.73 Due to its nonstoichiometry and significant oxygen storage capacity it is also often used as a promoting additive on other supports (e.g. y-A Cb) in automobile exhaust catalysts.79 It is a fluorite type oxide with predominant n-type semiconductivity. The contribution of its ionic conductivity has been estimated to be 1-3% at 350°C.71... 

Gallium arsenide is a semiconducting material. If we wish to modify the sample by replacing a small amount of the arsenic with an element to produce an n-type semiconductor, which element would we choose selenium, phosphorus, or silicon Why ... 

Anodization generally results in the formation of films with limited thickness, uncertain composition, defects, and small crystallite size. Thus, the barrier nature of the n-type semiconducting CdS film obtained in the previous manner makes it too thin to form the basis of Cu2S/CdS or CdTe/CdS solar cells by the normal dipping process. Heterojunction cells of low efficiency have, however, been made by anodization followed by vacuum deposition of the added layer (CU2S). 

Bolts JM, Wrighton MS (1978) Chemically derivatized n-type semiconducting germanium photoelectrodes. Persistent attachment and photoelectrochemical activity of ferrocene derivatives. J Am Chem Soc 100 5257-5262... 

Elhs AB, Kaiser SW, Bolts JM, Wrighton MS (1977) Study of n-type semiconducting cadmium chalcogenide-based photoelectrochemical cells employing polychalcogenide electrolytes. J Am Chem Soc 99 2839-2848... 

Kubiak CP, Schneemeyer LF, Wrighton MS (1980) Visible fight driven generation of chlorine and bromine. Photooxidation of chloride and bromide in aqueous solution at illuminated n-type semiconducting molybdenum diselenide and molybdenum disulfide electrodes. J Am Chem Soc 102 6898-6900... 

Schneemeyer LF, Wrighton MS (1979) Flat-band potential of n-type semiconducting molybdenum disulfide by cyclic voltammetry of two-electron reductants Interface energetics and the sustained photooxidation of chloride. J Am Chem Soc 101 6496-6500... 

Figure 13 shows the irreversible conversion of a nonconjugated poly (p-phenylene pentadienylene) to a lithiun-doped conjugated derivative which has a semiconducting level of conductivity (0.1 to 1.0 S/cm) (29). Obviously, the neutral conjugated derivative of poly (p-phenylene pentadienylene) can then be reversibly generated from the n-type doped material by electrochemical undoping or by p-type compensation. A very similar synthetic method for the conversion of poly(acetylene-co-1,3-butadiene) to polyacetylene has been reported (30), Figure 14. This synthesis of polyacetylene from a nonconjugated precursor polymer containing isolated CH2 units in an otherwise conjugated chain is to be contrasted with the early approach of Marvel et al (6) in which an all-sp3 carbon chain was employed.

Various other semiconductor materials, such as CdSe, MoSe, WSe, and InP were also used in electrochemistry, mainly as n-type photoanodes. Stability against photoanodic corrosion is, naturally, much higher with semiconducting oxides (Ti02, ZnO, SrTi03, BaTi03, W03, etc.). For this reason, they are the most important n-type semiconductors for photoanodes. The semiconducting metal oxide electrodes are discussed in more detail below. 

In addition to the stoichiometry of the anodic oxide the knowledge about electronic and band structure properties is of importance for the understanding of electrochemical reactions and in situ optical data. As has been described above, valence band spectroscopy, preferably performed using UPS, provides information about the distribution of the density of electronic states close to the Fermi level and about the position of the valence band with respect to the Fermi level in the case of semiconductors. The UPS data for an anodic oxide film on a gold electrode in Fig. 17 clearly proves the semiconducting properties of the oxide with a band gap of roughly 1.6 eV (assuming n-type behaviour). 

Aliovalent additives are often called donor dopants, when they tend to provide electrons and enhance intrinsic n-type semiconducting behavior, or acceptor dopants, when they tend to give a population of mobile holes and enhance /j-typc semiconducting behavior. The process of creating electronic defects in a crystal in this way is called valence induction. 

Tin oxide is a semiconductor with a wide band gap of Eg 3.7 eV, which can easily be doped with oxygen vacancies and chlorine acting as donor states. It is stable in aqueous solutions and hence a suitable material for n-type semiconducting electrodes. 

An example is shown in Fig. 8.9, where the photocurrent generated in n-type semiconducting WO3 is plotted for three different wavelengths... 

The speed of p- and n-type doping and that of p-n junction formation depend on the ionic conductivity of the solid electrolyte. Because of the generally nonpolar characteristics of luminescent polymers like PPV, and the polar characteristics of solid electrolytes, the two components within the electroactive layer will phase separate. Thus, the speed of the electrochemical doping and the local densities of electrochemically generated p- and n-type carriers will depend on the diffusion of the counterions from the electrolyte into the luminescent semiconducting polymer. As a result, the response time and the characteristic performance of the LEC device will highly depend on the ionic conductivity of the solid electrolyte and the morphology and microstructure of the composite. 

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