Semiconductor nanosized

Nanosize particles (e.g., metals, semiconductors, etc.) are of continuing interest because they possess fascinating catalytic, electronic, and optical properties. Larger particles decorated with smaller nanoparticles on their surface are of interest because of their potential use as heterogeneous catalysts and their relevance in electronic and optical sensor applications as well as surface-enhanced Raman scattering [39,72-75]. 

Many different topics are involved in the study of metallic nanoparticles and many fundamental issues can be present for example, which is the infiuence of the nanoparticle size, shape and composition on the chemical activity of heterogeneous catalysts Or, considering another problem, at what size does a small particle behave like the bulk material, for example, changing from an insulator to a semiconductor [9-12] An enormous amount of literature is published on metallic nanoclusters this review is focusing on the relevant problem concerning the characterization of metallic nanosized materials from the morphological and... 

Nanotechnology involves the manipulation of matter on atomic and molecular scales. This technology combines nanosized materials in order to create entirely new products ranging from computers to micromachines and includes even the quantum level operation of materials. The structural control of materials on the nanometer scale can lead to the realization of new material characteristics that are totally different from those realized by conventional methods, and it is expected to result in technological innovations in a variety of materials including metals, semiconductors, ceramics, and organic materials. 

Nanosized functional materials made of semiconductors promise the prospect of application in many high-technique fields such as photovoltaic conversion and energy storage because of their characteristics of surface structure and high surface area [318-322],... 

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... 

Particles in the nanometer-size regime necessarily have large surface-to-volume ratios approximately one-third of the atoms are located on the surfaces of 40 A CdS particles, for example. Furthermore, colloid chemical preparations typically result in the development of surface imperfections and in the incorporation of adventitious or deliberately added dopants. Such surface defects act as electron and/or hole traps and, thus, substantially modify the optical and electro-optical properties of nanosized semiconductor particles. Altered photostabilities [595], fluorescence [579, 594, 596, 597], and non-linear optical properties [11, 598-600] are manifestations of the surface effects in colloidal semiconductors. 

Separation of bulk and surface properties in macroscopic semiconductors is less than straight forward and requires highly sensitive experimental techniques. In contrast, the large surface-to-volume ratios in nanosized semiconductor particles render the examination of surface processes in and/or on these colloids to be experimentally feasible. Advantage has been taken of pulse radiolysis to inject electrons (in aqueous, N20-saturated solutions which contained 2-propanol see Eqs. 22,23, and 25) or holes (in aqueous, N20-saturated solutions which did not contain 2-propanol see Eqs. 22 and 23) into nanosized semiconductor particles [601, 602], Electron injection into CdS particles, for example, decreased the extinction coefficient at 470 nm (the absorption onset) by — 5 x 104 M-1cm-1 (Fig. 98) [576]. Hole injection resulted in the appearance of a transient absorption band in the long-wavelength region and in much less... 

The supporting medium (aqueous or organic solvents membrane-mimetic compartments) also has a profound influence on the optical and electro-optical properties of nanosized semiconductor particles. This dielectric confinement (or local field effect) originates, primarily, in the difference between the refractive indices of semiconductor particles and the surrounding medium [573, 604], In general, the refractive index of the medium is lower than that of the semiconductor particle, which enhances the local electric field adjacent to the semiconductor particle surface as compared with the incident field intensity. Dielectric confinement of semiconductor particles also manifests in altered optical and electro-optical behavior. 

The experimental set-up used in the generation and in situ monitoring of semiconductor particulate films is identical to that used for nanosized, metallic, particulate films. Evolution of a nanocrystalline particulate film, illustrated by the formation of sulfide semiconductor particulate films (Fig. 110), has been discussed in terms of the following steps [639] ... 

Fig. 4.9 Schematic cross-sectional view of a semiconductor (n-Si) electrode coated with sparsely scattered nanosized metal particles...

In nanosized particle film electrodes, photogenerated holes can be rapidly transferred to the semiconductor/electrolyte interface and there be captured by the redox species in the electrolyte. In this way, the recombination losses can be diminished. This is of great importance for semiconductors like hematite with a very short hole diffusion length (2-4 nm). Another advantage is the large internal surface area, which characterize nanostructured semiconductor film electrodes. The latter decreases the current density per unit area of semiconductor / electrolyte interface. 

Studies of nitrogen oxide radicals in various condensed media by means of the EPR technique started about 45 years ago. Initial results were collected in [88, 28]. NxOy radicals are of interest first of all because of their toxicity and a key role in atmospheric chemistry. From this point of view, formation, stability and reactivity of these species adsorbed on the surface of nanosized metal-oxide semiconductor particles, which are photoactive and widely presented in atmosphere, are of essential importance. Principal values of g- and A-tensors for some cases are picked up in the following Table 8.4. 

ESR is known to be a very sensitive tool and can therefore be used in studying structural features of nanosized semiconductor particles doped with paramagnetic metal ions. In many studies vanadium impurities inside the Ti02 matrix or on the particle s surface were used as dopants. Moreover, V4+ ions are very convenient ESR probes since the 51V nuclei have a large magnetic moment leading to informative hyperfine structures (S = 1/2 / = 7/2). At low vanadium concentration, the EPR spectrum has well resolved sharp lines (Fig. 8.10) allowing precise measurement of spin-Hamiltonian parameters. 

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