Photoconductivity hole conduction

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. 

Nd is the concentration of photoactive centers filled with electrons (species X), and NA is the concentration of sites filled with holes (species X ). The factor f = (C-l)/(C+l) accounts for the competing photoconductivity contributions due to electrons and holes, and has a value of -1 when electron photoconductivity dominates and +1 when hole conductivity dominates. Intermediate values occur when mixed conductivity is present. C is defined by... 

Fig. 3 Schematic illustration of acceptor doping that gives rise to extrinsic hole conductivity and long-wavelength photoconductivity in metal phthalocyanines...

Another interesting applications area for fullerenes is based on materials that can be fabricated using fullerene-doped polymers. Polyvinylcarbazole (PVK) and other selected polymers, such as poly(paraphcnylene-vinylene) (PPV) and phenylmethylpolysilane (PMPS), doped with a mixture of Cgo and C70 have been reported to exhibit exceptionally good photoconductive properties [206, 207, 208] which may lead to the development of future polymeric photoconductive materials. Small concentrations of fullerenes (e.g., by weight) lead to charge transfer of the photo-excited electrons in the polymer to the fullerenes, thereby promoting the conduction of mobile holes in the polymer [209]. Fullerene-doped polymers also have significant potential for use in applications, such as photo-diodes, photo-voltaic devices and as photo-refractive materials. 

Polysilanes can be regarded as one-dimensional analogues to elemental silicon, on which nearly all of modern electronics is based. They have enormous potential for technological uses [1-3]. Nonlinear optical and semiconductive properties, such as high hole mobility, photoconductivity, and electrical conductivity, have been investigated in some detail. However, their most important commercial use, at present, is as precursors to silicon carbide ceramics, an application which takes no advantage of their electronic properties. 

Some polymeric materials become conductive when illuminated with light. For instance, poly(A -vinylcarbazole) is an insulator in the dark, but when exposed to UV radiation it becomes conductive. Addition of electron acceptors and sensitizing dyes allows the photoconductive response to be extended into the visible and near-IR (NIR) regions. In general, such photoconductivity is dependent on the material s ability to create free-charge carriers, electron holes, through absorption of light, and to move these carriers when a current is applied. 

Electrical conductivity is due to the motion of free charge carriers in the solid. These may be either electrons (in the empty conduction band) or holes (vacancies) in the normally full valence band. In a p type semiconductor, conductivity is mainly via holes, whereas in an n type semiconductor it involves electrons. Mobile electrons are the result of either intrinsic non-stoichiometry or the presence of a dopant in the structure. To promote electrons across the band gap into the conduction band, an energy greater than that of the band gap is needed. Where the band gap is small, thermal excitation is sufficient to achieve this. In the case of most iron oxides with semiconductor properties, electron excitation is achieved by irradiation with visible light of the appropriate wavelength (photoconductivity). 

Therefore an increase in conductivity upon illumination (photoconductivity) can be due to either an increase in carrier concentration and/or an increase in mobility. In general, it is believed that an increase in carrier (hole) concentration is the dominant cause for room-temperature photoconductivity for the lead chalco-genides and that an increase in mobility becomes increasingly important at low temperatures. The dark conductivity of films deposited with or without added oxidant were similar the difference in photoconductivity between them was ascribed to the formation of sensitizing centers (interband states) due to the oxidant. 

An important application of polydimethylsilane is as a source of silicon carbide (SiC) fibres, which are manufactured under the trade-name Nicalon by Nippon Carbon in Japan. Heating in an autoclave under pressure converts polydimethylsilane to spinnable polycarbosilane (-Me2Si-CH2-) with elimination of methane. The spun fibres are then subjected to temperatures of 1200-1400 °C to produce silicon carbide fibres with very high tensile strengths and elastic moduli." As a result of their conductivity, polysilanes have also been used as hole transport layers in electroluminescent devices. In addition, the photoconductivity of polymethylphenylsilane doped with Cgo has been found to be particularly impressive. ... 

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]

Whereas in good-conducting doped or polymeric dyes ft-or -type conductivity can be explained without difficulty by analogy with inorganic semiconductors, the p- and -type photoconductivity in insulating (intrinsic) dye films cannot be explained in this manner. It is necessary to take into consideration the existence of defect states (lattice defects, dislocations, impurities etc.) distributed at different depths in the forbidden zone between valence and conduction band these defect states are able to trap electrons and holes, respectively, with different probability 10,11,88),... 

When a semiconductor is illuminated, electrons may be excited into the conduction band and/or holes into the valence band, producing photoconductivity. This excited condition is not generally permanent, and when the illumination ceases, the excess current carriers will decay, or recombine. The average time which a photoelectron remains in the conduction band is termed the lifetime. As the lifetime increases, the photocurrent, for a given intensity of illumination, increases. 

A photoconductive detector is a semiconductor whose conductivity increases when infrared radiation excites electrons from the valence band to the conduction band. Photovoltaic detectors contain pn junctions, across which an electric field exists. Absorption of infrared radiation creates electrons and holes, which are attracted to opposite sides of the junction and which change the voltage across the junction. Mercury cadmium telluride (Hg,. Cd/Te, 0 < x < 1) is a detector material whose sensitivity to different wavelengths is affected by the stoichiome-try coefficient, x. Photoconductive and photovoltaic devices can be cooled to 77 K (liquid nitrogen temperature) to reduce thermal electric noise by more than an order of magnitude. 

If, instead of thermal excitation, a photon of light excites an electron from the valence band to the conduction band, the same situation of electron and hole carriers obtains, and one observes the phenomenon of photoconductivity, useful in photocells and similar devices. 

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