Electronic holes

Irradiation of a semiconductor with light of quantum energy greater than the band gap can lead to electron-hole separation. This can affect adsorption and lead to photocatalyzed or photoassisted reactions [187]. See Section XVIII-9F for some specifics. 

The size of the electron-hole pair can be estimated from the Bolu radius for this system ... 

In n type semiconductors, electrons are tire majority carriers. Holes will also be present tlirough accidental incoriioration of acceptor impurities or, more importantly, tlirough tlie intentional creation of electron-hole pairs. Holes in n type and electrons in p type semiconductors are minority carriers. 

There are many ways of increasing tlie equilibrium carrier population of a semiconductor. Most often tliis is done by generating electron-hole pairs as, for instance, in tlie process of absorjition of a photon witli h E. Under reasonable levels of illumination and doping, tlie generation of electron-hole pairs affects primarily the minority carrier density. However, tlie excess population of minority carriers is not stable it gradually disappears tlirough a variety of recombination processes in which an electron in tlie CB fills a hole in a VB. The excess energy E is released as a photon or phonons. The foniier case corresponds to a radiative recombination process, tlie latter to a non-radiative one. The radiative processes only rarely involve direct recombination across tlie gap. Usually, tliis type of process is assisted by shallow defects (impurities). Non-radiative recombination involves a defect-related deep level at which a carrier is trapped first, and a second transition is needed to complete tlie process. 

If tlie level(s) associated witli tlie defect are deep, tliey become electron-hole recombination centres. The result is a (sometimes dramatic) reduction in carrier lifetimes. Such an effect is often associated witli tlie presence of transition metal impurities or certain extended defects in tlie material. For example, substitutional Au is used to make fast switches in Si. Many point defects have deep levels in tlie gap, such as vacancies or transition metals. In addition, complexes, precipitates and extended defects are often associated witli recombination centres. The presence of grain boundaries, dislocation tangles and metallic precipitates in poly-Si photovoltaic devices are major factors which reduce tlieir efficiency. 

Light is generated in semiconductors in the process of radiative recombination. In a direct semiconductor, minority carrier population created by injection in a forward biased p-n junction can recombine radiatively, generating photons with energy about equal to E. The recombination process is spontaneous, individual electron-hole recombination events are random and not related to each other. This process is the basis of LEDs [36]. 

Brus L E 1984 Electron-electron and electron-hole Interactions In small semiconductor crystallites the size dependence of the lowest excited electronic state J. Chem. Phys. 80 4403-9... 

In solid state materials, single-step electron transport between dopant species is well known. For example, electron-hole recombination accounts for luminescence in some materials [H]. Multistep hopping is also well known. Models for single and multistep transport are enjoying renewed interest in tlie context of DNA electron transfer [12, 13, 14 and 15]. Indeed, tliere are strong links between tire ET literature and tire literature of hopping conductivity in polymers [16]. 

Photovoltaic Devices. For many inorganic semiconductors, absorption of light can be used to create free electrons and holes. In an organic semiconducting soHd, however, absorption of a photon leads to the formation of a bound electron—hole pair. Separation of this pair in an electric field can... 

Fig. 14. Schematic of the Auger electron emission process induced by creation of a K level electron hole.

Fig. 16. Relative probabiUties of Auger electron emission and x-ray fluorescence for initial iClevel electron hole as a function of atomic number (19).

The primary photochemical act, subsequent to near-uv light (wavelengths <400 nm) absorption by Ti02 particles, is generation of electron—hole pairs where the separation (eq. 3) into conduction band electrons (e g ) and valence band holes (/lyB ) faciUtated by the electric field gradient in the space charge region. Chemically, the hole associated with valence band levels is constrained at... 

Experimental Values of Charge-Generation Efficiencies. In this section the charge-generation efficiencies of many polymeric photoconductors are compared (Table 3). When the experimental data has been fitted to the Onsager model, the initial electron—hole separation distance,... 

Fig. 8. The photodiode detector (a) band model where the photon generates electron—hole pairs that are separated by the built-in potential setting up a photocurrent (b) physical model for a planar diode. The passivation is typically Si02 for Si diodes, an In oxide for InSb diodes, and CdTe for HgCdTe...

Another common loss process results from electron—hole recombination. In this process, the photoexcited electron in the LUMO falls back into the HOMO rather than transferring into the conduction band. This inefficiency can be mitigated by using supersensitizing molecules which donate an electron to the HOMO of the excited sensitizing dye, thereby precluding electron—hole recombination. In optimally sensitized commercial products, dyes... 

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