Color centers energy bands

The F center absorption maximum for KC1 is at 565 nm and that for KF is 460 nm (Table 9.1). (a) What is the composition of a natural crystal with color centers showing an absorption peak at 500 nm (b) If the absorption peak for KF corresponds to the promotion of an electron from the F center to the conduction band, determine the energy of the color center with respect to the conduction band. (The band gap in KF is 10.7 eV.) If the relative position of the color center energy level remains the same throughout the KF-KC1 solid solution range, estimate (c) the band gap of KC1 and (d) the band gap for the natural crystal. 

Color from Color Centers. This mechanism is best approached from band theory, although ligand field theory can also be used. Consider a vacancy, for example a missing CF ion in a KCl crystal produced by irradiation, designated an F-center. An electron can become trapped at the vacancy and this forms a trapped energy level system inside the band gap just as in Figure 18. The electron can produce color by being excited into an absorption band such as the E transition, which is 2.2 eV in KCl and leads to a violet color. In the alkaU haUdes E, = 0.257/where E is in and dis the... 

A second kind of electronic defect involves the electron. Let us suppose that the second plane of the cubic lattice has a vacancy instead of a substitutional impurity of differing valency. This makes it possible for the lattice to capture and localize an extraneous electron at the vacancy site. This is shown in the following diagram. The captured electron then endows the solid structure with special optical properties since it ean absorb photon energy. The strueture thus becomes optically active. That is, it absorbs light within a well-defined band and is called a "color-center" since it imparts a specific color to the crystal. 

The alkali halides cire noted for their propensity to form color-centers. It has been found that the peak of the band changes as the size of the cation in the alkali halides increases. There appears to be an inverse relation between the size of the cation (actually, the polarizability of the cation) and the peak energy of the absorption band. These are the two types of electronic defects that are found in ciystcds, namely positive "holes" and negative "electrons", and their presence in the structure is related to the fact that the lattice tends to become charge-compensated, depending upon the type of defect present. 

It is often observed that ceramics, especially oxides, will turn black when they are heavily reduced or exposed to strong radiation for extended periods. In either case, the formation of color centers is responsible for the observed phenomena. A color center is an impurity or a defect onto which an electron or a hole is locally bound. For example, how the reduction of an oxide can result in the formation of both Vq and Vq defects was discussed in some detail in Chap. 6 (see Fig. 6.4a and b). In the context of this chapter, both are considered color centers. If for these defects is the energy needed to liberate the electron into the conduction band (see Fig. 7.12c), it follows that light of that frequency will be absorbed. Note here that all incident wavelengths with energies equal to or greater than and not just the ones that are w E, will be absorbed because electrons can be promoted into any level in the conduction band, because of the latter s finite width. 

F centers in alkali halides, which result from heating in alkali vapor. An F center in metal halides consists of a halide ion vacancy that has trapped an electron. This process creates additional energy levels between the valence band and the conduction band. A similar situation is found in MgO heated in Mg vapor the F center consists of two electrons trapped at an oxygen vacancy. F centers are one example of so-called color centers. There are other types of possible color centers in ionic materials involving electrons and holes. (See Section 11.9 F is Farben.)... 

Color centers in alkali halide crystals are based on a halide ion vacancy in the crystal lattice of rock-salt structure (Fig. 5.76). If a single electron is trapped at such a vacancy, its energy levels result in new absorption lines in the visible spectrum, broadened to bands by the interaction with phonons. Since these visible absorption bands, which are caused by the trapped electrons and which are absent in the spectrum of the ideal crystal lattice, make the crystal appear colored, these imperfections in the lattice are called F-centers (from the German word Farbe for color) [5.138]. These F-centers have very small oscillator strengths for electronic transitions, therefore they are not suited as active laser materials. 

Perhaps the most interesting pressure phenomena connected with the color centers is the appearance of a pressure-induced band in certain alkali halides on the high energy side of the F band. Figure 21 illustrates the phenomenon in KBr. At 8.5 kilobars the... 

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