Electrons and positive holes

The valence electrons in metals have considerable freedom of movement (see Section 1.3.4). This contrasts with ionic crystals where the bonding electrons are normally locahzed within the ions, and with covalent and molecular crystals where electrons are localized in the constituent bonds. 

PHONONS (vibrations of atoms about mean positions). 

EXCITONS (energetic combinations of electrons and positive holes). 

ELECTRONS and POSITIVE HOLES ( excess or missing electrons). 

Imperfections localized in the vicinity of a small number of lattice sites 

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The relative contributions of ions, electrons and positive holes to the conductivity is described drrough the transport number which is related to a partial conductivity defined by... 

At the other end of the conduction spectrum, many oxides have conductivities dominated by electron and positive hole contributions to the extent that some, such as Re03, SnOa and tire perovskite LaCrOs have conductivities at the level of metallic conduction. High levels of p-type semiconduction are found in some transition metal perovskites especially those containing alio-valent ions. Thus the lanthairum-based perovskites containing transition metal ions, e.g. LaMOs (M-Cr, Mn, Fe, Co, Ni) have eirlranced p-type semiconduction due to the dependence of the transition metal ion valencies on the ambient... 

If there is more than one type of carrier, i.e. electrons and positive holes, as in MWCNT, the contribution of each type of carrier should be taken into account. In that case, the total electrical conductivity is given by the sum of the partial conductivities. 

Excitons (energetic combination of electron and positive hole)... 

Measurements of photoconductivity and of the Hall potential [367] are accurate and unambiguous methods of detecting electronic conduction in ionic solids. Kabanov [351] emphasizes, however, that the absence of such effects is not conclusive proof to the contrary. From measurements of thermal potential [368], it is possible to detect solid-solution formation, to distinguish between electronic and positive hole conductivity in semi-conductors and between interstitial and vacancy conductivity in ionic conductors. 

Optical Detection of Electrons and Positive Holes in TiOj.149... 

Small semiconductor particles also act like microelectrodes upon illumination. Electrons and positive holes are created in the particles which initiate redox reactions. The charge carriers may also recombine and emit fluorescence light. Reaction with a solute leads to quenching of the fluorescence. 

In studies of this kind, methods developed in radiation chemistry and photochemistry are often applied The methods of pulse radiolysis and flash photolysis allow one to investigate the mechanism of reactions in which free radicals, electrons and positive holes are the intermediates. In order to understand the mechanisms of processes that occur on colloidal particles it is important to know how free radicals... 

Generally speaking the mobilities of electrons and positive holes decrease and the band gaps increase as the bonding in the semiconductors becomes more... 

On the absorption of light and the trapping of electrons and positive holes in crystalline dielectrics. Physik. Z. Sowjetunion 9, 158 (1936). 

It is now known that dark- and photoconductivity is connected with the structure of organic compounds 10>. The conductivity of organic dyes and other organic compounds, like that of inorganic semiconductors, is attributable to electronic charge carriers, i.e. electrons and positive holes. The dark conductivity [Pg.87]

Intrinsic Semiconductors. Excitation of electrons from the filled band will introduce electrons into the empty conduction band, leaving positive holes in the previously filled band, and both electrons and positive holes will contribute to the electrical conductivity. 

Many dyes are decolorized and ultimately mineralized by photocatalysis. In the degradation of azo dye,18 21) the degradation rate decreases in the order monoazo > diazo > triazo.1819) Three processes including oxidation and reduction are considered to occur simultaneously in the photocatalytic degradation of dye. These are illustrated in Fig. 9.9. Process 1 is the common photocatalytic degradation process of organic compounds. Process 2 is spectral sensitization as observed in a wet-type solar cell. In process 3 one moiety of dye molecule serves as the electron acceptor, suppressing recombination between electron and positive hole. 

Photocatalytic oxidation is accelerated by scavenging conduction band electrons thus preventing the recombination between electron and positive hole. Several oxidants such as H202, K2S2Or and KI(V3) are used for tnis purpose. Among them H202 may be the best from a practical point of view, because no reaction product is left aftei the treatment. Several observations have been maae (a) (b)... 

Fig. 6, and the results for numerous dopants in anthracene compared with calculated trap depths are given in Fig. 7. One notes that the general agreement is good considering the often approximate values of Ic and Ac available and also that particular impurities, notably tetracene, may function both as electron and positive hole traps of depths 0.17 eV and 0.42 eV respectively.

Electrical conductivity of metals is very high and is of the order of 106 108 ohm-1 cm-1 while that of insulators is of the order of 10-12 ohm-1 cm-1. Semi-conductors have intermediate conductivity which lies in the range 102 10-9 ohm-1 cm1. Electrical conductivity of solids may arise through the motion of electrons and positive holes (electronic conductivity) or through the motion of ions (ionic conductivity). The conduction through electrons is called n-type conduction and through positive holes is called p-type conduction. Pure ionic solids where conduction can take place only through motion of ions are insulators. However, the presence of defects in the crystal structure increases their conductivity. 

Unlike metals, the conductivity of semi-conductors and insulators is mainly due to the presence of interstitial electrons and positive holes in the solids due to imperfections. The conductivity of semiconductors and insulators increases with increase in temperature while that of metals decreases. 

Johnson and Willson interpreted the main feature of the observations on solid polyethylene doped with aromatic solutes in terms of an ionic mechanism it was analogous to that proposed for irradiated frozen glassy-alkane-systems in which ionization occurred with G = 3 — 4 [96], The produced charged species, electron and positive hole, were both mobile as indicated by the radiation-induced conductivity. The production of excited states of aromatic solutes was caused mainly by ion-electron neutralization. The ion-ion recombination was relatively slow but it might contribute to the delayed fluorescence observed. On the basis of Debye-Simoluchovski equation, they evaluated the diffusion coefficients of the radical anion of naphthalene and pyrene as approximately 4 x 10 12 and 1 x 10 12 m2 s 1 respectively the values were about three orders of magnitude less than those found in typical liquid systems. 

Although simple in concept, semiconductor detectors are rather complex in construction, because of practical difficulties whith have to be overcome. These problems derive from the small numbers of electrons and positive holes produced in the initial interactions. To enable the electrical pulses to be... 

The principle of photocatalysis is often explained with an illustration like Fig. 2, a schematic representation of the electronic structures of semiconducting materials, a band model. An electron in an electron-filled valence band (VB) is excited by photoirradiation to a vacant conduction band (CB), which is separated by a forbidden band, a band gap, from the VB, leaving a positive hole in the VB (Section III.B). These electrons and positive holes drive reduction and oxidation, respectively, of compounds adsorbed on the surface of a photocatalyst. Such an interpretation accounts for the photocatalytic reactions of semiconducting and insulating materials absorbing photons by the bulk of materials. In the definition of photocatalysis given above, however, no such limitation based on the electronic structure of a photocatalyst is included. For example, isolated... 

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