Recombination, electron-hole

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]. 

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]. 

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... 

Amorphous Silicon. Amorphous alloys made of thin films of hydrogenated siUcon (a-Si H) are an alternative to crystalline siUcon devices. Amorphous siUcon ahoy devices have demonstrated smah-area laboratory device efficiencies above 13%, but a-Si H materials exhibit an inherent dynamic effect cahed the Staebler-Wronski effect in which electron—hole recombination, via photogeneration or junction currents, creates electricahy active defects that reduce the light-to-electricity efficiency of a-Si H devices. Quasi-steady-state efficiencies are typicahy reached outdoors after a few weeks of exposure as photoinduced defect generation is balanced by thermally activated defect annihilation. Commercial single-junction devices have initial efficiencies of ca 7.5%, photoinduced losses of ca 20 rel %, and stabilized efficiencies of ca 6%. These stabilized efficiencies are approximately half those of commercial crystalline shicon PV modules. In the future, initial module efficiencies up to 12.5% and photoinduced losses of ca 10 rel % are projected, suggesting stabilized module aperture-area efficiencies above 11%. 

In a subsequent work [182], it was shown that the photoelectrochemical performance of InSe can be considerably improved by means of selective (photo)electrochemical etching. Interestingly, whereas the cleavage vdW plane showed little improvement, the photocurrent in the face parallel to the c-axis was doubled. Note that, in contrast to InSe crystals cleaved in the plane perpendicular to the c-axis that are almost defect free, the crystals cut in the plane parallel to the c-axis contain a high density of defects on their surface which leads to a high rate of electron-hole recombinations and inferior quantum efficiency. The asymmetry in the role of electrons and holes, as manifested, e.g., in the fact that surface holes carry out the selective corrosion of the semiconductor surface in both cleavage orientations, was discussed. 

An important aspect of semiconductor photochemistry is the retardation of the electron-hole recombination process through charge carrier trapping. Such phenomena are common in colloidal semiconductor particles and can greatly influence surface corrosion processes occurring particularly in small band gap materials, such... 

Nosaka and Fox determined the quantum yield for the reduction of methyl viologen adsorbed on colloidal CdS particles as a function of incident light intensity. Electron transfer from CdS to MV " competes with electron-hole recombination. They derived a bimolecular rate constant of 9 10 cm s for the latter process. 

The emission spectmm of Co, as recorded with an ideal detector with energy-independent efficiency and constant resolution (line width), is shown in Fig. 3.6b. In addition to the expected three y-lines of Fe at 14.4, 122, and 136 keV, there is also a strong X-ray line at 6.4 keV. This is due to an after-effect of K-capture, arising from electron-hole recombination in the K-shell of the atom. The spontaneous transition of an L-electron filling up the hole in the K-shell yields Fe-X X-radiation. However, in a practical Mossbauer experiment, this and other soft X-rays rarely reach the y-detector because of the strong mass absorption in the Mossbauer sample. On the other hand, the sample itself may also emit substantial X-ray fluorescence (XRF) radiation, resulting from photo absorption of y-rays (not shown here). Another X-ray line is expected to appear in the y-spectrum due to XRF of the carrier material of the source. For rhodium metal, which is commonly used as the source matrix for Co, the corresponding line is found at 22 keV. 

The Auger effect is the phenomenon involving electron-hole recombination in an inner-shell vacancy causing the emission of another electron. 

In order to minimize the fast electron-hole recombination, Calzolari et al. [50] attached a donor-acceptor boronic acid spacer between the anthocyanins and a gold electrode, and the same molecule between the dye and a P-cydodextrin which is able to bind I3 dissolved in the electrolyte near the chromophore. In that configuration, the device shows an increase in the quantum yield of the photocurrent from a negligible value to 1.75%. Such studies were not repeated on Ti02 layers. 

While most of the research in metastable defect formation has focussed on light-induced defects, there has recently been growing interest in thermally generated defects. Smith and Wagner (1985 Smith et al., 1986) extended the proposed Staebler-Wronski mechanism of electron-hole recombination via band tail states, resulting in the formation of dangling... 

Loss of carriers either by electron-hole recombination or by trapping at localized states in the band gap or at the surface. 

S Ramasesha, S Mazumdar, K Tandon, and M Das, Electron correlation effects in electron-hole recombination and triplet-triplet scattering in organic light emitting diodes, Synth. Met., 139 917— 920, 2003. 

It should also be briefly recalled that semiconductors can be added to nanocarbons in different ways, such as using sol-gel, hydrothermal, solvothermal and other methods (see Chapter 5). These procedures lead to different sizes and shapes in semiconductor particles resulting in different types of nanocarbon-semiconductor interactions which may significantly influence the electron-transfer charge carrier mobility, and interface states. The latter play a relevant role in introducing radiative paths (carrier-trapped-centers and electron-hole recombination centers), but also in strain-induced band gap modification [72]. These are aspects scarcely studied, particularly in relation to nanocarbon-semiconductor (Ti02) hybrids, but which are a critical element for their rational design. 

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