Spectral, band transparency

Silicon is not as prominent a material in optoelectronics as it is in purely electronic applications, since its optical properties are limited. Yet it finds use as a photodetector with a response time in the nanosecond range and a spectral response band from 0.4 to 1.1 im, which matches the 0.905 im photoemission line of gallium arsenide. Silicon is transparent beyond 1.1 im and experiments have shown that a red light can be produced by shining an unfocused green laser beam on a specially prepared ultrathin crystal-silicon slice.CVD may prove useful in preparing such a material. 

The extinction features at energies where water is transparent are rapidly squelched in the ultraviolet as the onset of electronic transitions greatly increases bulk absorption. In the infrared, however, vibrational absorption bands in water are carried over into similar bands in extinction (dominated by absorption if a A) by a water droplet. Unlike MgO there are no appreciable spectral shifts in going from the bulk to particulate states. The reason for this lies in the strength of bulk absorption and will be discussed more thoroughly in Chapter 12. 

The calculated extinction spectrum of a polydispersion of small aluminum spheres (mean radius 0.01 jam, fractional standard deviation 0.15) is shown in Fig. 11.4 both scales are logarithmic. In some ways spectral extinction by metallic particles is less interesting than that by insulating particles, such as those discussed in the preceding two sections. The free-electron contribution to absorption in metals, which dominates other absorption bands, extends from radio to far-ultraviolet frequencies. Hence, extinction features in the transparent region of insulating particles, such as ripple and interference structure, are suppressed in metallic particles because of their inherent opacity. But extinction by metallic particles is not without its interesting aspects. 

A compound that is transparent within a spectral domain when in its isolated state can sometimes absorb when in the presence of a species with which it can interact through a donor-acceptor relationship (D-A). This phenomenon is related to the passage of an electron from a bonding orbital of the donor (which becomes a radical cation) to an unoccupied orbital of the acceptor (which becomes a radical anion), which has a close energy level (Fig. 11.6). The position of the absorption band in the spectrum is a function of the ionisation potential of the donor and the electron affinity of the acceptor. The value of e for these transitions is usually large. 

Table 6.2 lists the ultraviolet cutoff for a variety of solvents commonly used in UV-VIS spectroscopy. The solvent chosen must dissolve the sample, yet be relatively transparent in the spectral region of interest. Typically, very low concentrations of sample will be present in the solvent. It is therefore important to avoid solvents that have even weak absorptions near the solute s bands of interest. Methanol and ethanol are two of the most commonly used solvents. Care must be exercised when using the latter that no benzene (an azeotropic drying agent) is present as this will alter the solvent s transparency. Normally, this will not be a problem in spectral grade solvents. 

---