Electronic carrier recombination

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]. 

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... 

The photovoltage is esentially determined by the ratio of the photo- and saturation current. Since io oomrs as a pre-exponential factor in Eq. 1 it determines also the dark current. Actually this is the main reason that it limits the photovoltage via Eq. 2, The value of io depends on the mechanism of charge transfer at the interface under forward bias and is normally different for a pn-junction and a metal-semiconductor contact. In the first case electrons are injected into the p-region and holes into the n-region. These minority carriers recombine somewhere in the bulk as illustrated in Fig. 1 c. In such a minority carrier device the forward current is essentially determined... 

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. 

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

In addition, the rate of Oz reduction, forming 02 by electron, is of importance in preventing carrier recombination during photocatalytic processes utilizing semiconductor particles. 02 formation may be the slowest step in the reaction sequence for the oxidation of organic molecules by OH radicals or directly by positive holes. Cluster deposition of noble metals such as Pt, Pd, and Ag on semiconductor surfaces has been demonstrated to accelerate their formation because the noble metal clusters of appropriate loading or size can effectively trap the photoinduced electrons [200]. Therefore, the addition of a noble metal to a semiconductor is considered as an effective method of semiconductor surface modification to improve the separation efficiency of photoinduced electron and hole pairs. 

The overall process performance, as measured by photon efficiency (number of incident photon per molecule reacted, like the incident photon to current conversion efficiency, or IPCE, for PV cells), depends on the chain from the light absorption to acceptor/donor reduction/oxidation, and results from the relative kinetic of the recombination processes and interfacial electron transfer [23, 28]. Essentially, control over the rate of carrier crossing the interface, relative to the rates at which carriers recombine, is fundamental in obtaining the control over the efficiency of a photocatalyst. To suppress bulk- and surface-mediated recombination processes an efficient separation mechanism of the photogenerated carrier should be active. 

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. 

However, there are a number of difficulties associated with the synthesis of colloidal semiconductor particles. The preparation of stable, monodispersed, well-characterized populations of nanosized, colloidal semiconductor particles is experimentally demanding and intellectually challenging. Small and uniform particles are needed to diminish non-productive electron-hole recombinations the mean distance by which the charge carriers need to diffuse to reach the particle surface from which they are released is necessarily reduced in small particles. Monodispersity is a requirement for the observation of many of the spectroscopic and electro-optical manifestations of size quantization in semiconductor particles. Small semiconductor particles are difficult to maintain in solution in the absence of stabilizers flocculations and Ostwald ripening... 

Fig. 3.7. Trap-controlled carrier recombination 1 - excitation of solid with creation of electron ( ) and hole (0) pair 2, 3 - their localization (trapping) by defects 4 - thermal ionization of electron from a trap 5 - its recombination with the recombination centre.

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