F" center

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... 

X-ray diffraction experiments revealed a psendo-cubic orthorombic unit cell with cell dimensions similar to the expected cubic F centered arrangement of the predesigned diamond-like crystal. 

In this case, we use 6 as a small fraction since the actual number of defects is small in relation to the overall number of ions actually present. For the F-Center, the brackets enclose the complex consisting of an electron captured at an anion vacancy. Note that these equations encompass all of the mechanisms that we have postulated for each of the individual reactions. That is, we show the presence of vacancies in the Schottlqr case and interstitial cations for the Frenkel case involving either the cation or anion. The latter, involving an interstitlcd anion is called, by convention, the "Anti-Frenkel" case. The defect reaction involving the "F-Center" is also given. 

Actually, the formation of an F-center is more complicated than this. Although F-centers can be formed by severed methods, the best way to do so is by exposing a sodium chloride ciystal to sodium metal vapors. In that case, the following defect reactions have been observed to take place ... 

These equations illustrate how the crystal responds to the presence of sodium vapor, i.e.- excess Na- -, by forming anion vacaneies, to form the F-center. 

In the heterogeneous solid, a different mechanism concerning charge dominates. If there are associated vacancies, a different type of electronic defect, called the "M-center", prevails. In this case, a mechanism similcu to that already given for F-centers operates, except that two (2) electrons occupy neighboring sites in the crystal. The defect equation for formation of the M-center is ... 

They are usually joined along the 110 plane of the lattice of the face-centered salt crystal, although we have not shown them this way (The 100 plane is illustrated in the diagram). Note that each vacancy has captured an electron in response to the charge-compensation mechanism which is operative for all defect reactions. In this case, it is the anion which is affected whereas in the "F-center", it was the cation which was affected (see equation 3.2.8. given above). These associated, negatively-charged, vacancies have quite different absorption properties than that of the F-center. 

What is the nature of the defects seen in the EPR spectra For alkali and alkali earth halogenides it is well known that irradiation with X-ray, neutrons, gamma-radiation, or electrons produce paramagnetic color centers (F-center) [109-111]. If these centers are created in large amounts, they can be stabilized by the formation of metal clusters as observed for MgCl2 films after prolonged electron radiation [106]. From the temperature dependence... 

In Sections III(l) and 111(2) the lability principle has been illustrated for processes involving the transfer of weakly bound electrons, including the reactions of solvated and trapped electrons and F-centers and processes of electrochemical generation of solvated electrons. In Sections IV and V, it will be illustrated also by atom transfer reactions and, in particular, by reactions involving adsorbed atoms. 

Image plates use stimulated luminescence from storage phosphor materials. The commercially available plates are composed of extremely fine crystals of BaFBrEu2+. X-rays excite an electron of Eu2+ into the conduction band, where it is trapped in an F-center of the barium halide with a subsequent oxidation of Eu2+ to Eu3+. By exposing the BaFBrEu" complex to light from a HeNe laser the electrons are liberated with the emission of a photon at 390 nm [38]. 

In alkali halide crystals containing color-centers (F-centers) illumination with light of appropriate energy causes transient changes of hardness (Nadeau, 1964). This effect apparently results from changes in the effective sizes of the F-centers when they become excited. 

When a crystal of an alkali halide has the vapor of the alkali metal passed over it, the alkali halide crystal becomes colored. The reason for this is that a type of defect that leads to absorption of light is created in the crystal. Such a defect is known as an F-center because the German word for "color" is Farbe. It has been shown that such a defect results when an electron occupies a site normally occupied by an anion (an anion "hole"). This arises as a result of the reaction... 

The potassium ions that are produced occupy cation lattice sites, but no anions are produced so electrons occupy anion sites. In this situation, the electron behaves as a particle restricted to motion in a three-dimensional box that can absorb energy as it is promoted to an excited state. It is interesting to note that the position of the maximum in the absorption band is below 4000A (400nm, 3.1 eV) for LiCl but it is at approximately 6000 A (600 nm, 2eV) for CsCl. One way to explain this observation is by noting that for a particle in a three-dimensional box the difference between energy levels increases as the size of the box becomes smaller, which is the situation in LiCl. Schottky, Frenkel, and F-center defects are not the only types of point defects known, but they are the most common and important types. 

Subsequent to the advent of the dye laser, tunable lasers based upon other lasing media were developed which operate over various wavelength ranges. Nobable among these are the f-center lasers and diode lasers which are tunable in the infrared. 

Coherent optical phonons can couple with localized excitations such as excitons and defect centers. For example, strong exciton-phonon coupling was demonstrated for lead phtalocyanine (PbPc) [79] and Cul [80] as an intense enhancement of the coherent phonon amplitude at the excitonic resonances. In alkali halides [81-83], nuclear wave-packets localized near F centers were observed as periodic modulations of the luminescence spectra. 

Point defects can have a profound effect upon the optical properties of solids. The most important of these in everyday life is color,3 and the transformation of transparent ionic solids into richly colored materials by F centers, described below, provided one of the first demonstrations of the existence of point defects in solids. 

The first experiments that connected color with defects were carried out in the 1920s and 1930s by Pohl, who studied synthetic alkali halide crystals. A number of ways were discovered by which the colorless starting materials could be made to display intense colors. These included irradiation by X rays, electrolysis (with color moving into the crystal from the cathode), or heating the crystals at high temperatures in the vapor of an alkali metal. Pohl was a strict empiricist who did not openly speculate upon the mechanics of color formation, which he simply attributed to the presence of Farbzentren (lit. color centers), later abbreviated to F centers. 

Leading theoreticians were, however, attracted to the phenomenon and soon suggested models for F centers. In 1930 Frenkel suggested that an F center was an electron trapped in a distorted region of crystal structure, an idea that was incorrect in this instance but led directly to development of the concepts of excitons and... 

The origin of the color is as follows. The electron trapped at an anion vacancy in an alkali halide crystal is an analog of a hydrogen atom. The electron can occupy one of a number of orbitals, and transitions between some of these levels absorb light and hence endow the solid with a characteristic color. F centers and related defects are discussed further in Chapter 9. 

Exposure of transparent solids, both glasses and crystals, to high-energy radiation frequently makes them colored. The defects responsible for this are known as color centers. The first of these defects to be characterized was the F center, a term derived from the German Farbzentrum (color center). 

Figure 9.24 Schematic illustration of an F center, an anion vacancy plus a trapped electron, in an alkali halide crystal.

Since the original studies of F centers many other color centers have been characterized that may be associated with either trapped electrons or trapped holes. These are called electron excess centers when electrons are trapped and hole excess centers when holes are trapped. 

The F center is an electron excess center and arises because the crystal contains a small excess of metal. Similar metal excess F centers exist in compounds other than... 

The concept of color centers has been extended to surfaces to explain a number of puzzling aspects of surface reactivity. For example, in oxides such as MgO an anion vacancy carries two effective charges, V(2. These vacancies can trap two electrons to form an F center or one electron to form an F+ center. When the vacancy is located at a surface, the centers are given a subscript s, that is, Fs+ represents a single electron trapped at an anion vacancy on an MgO surface. As the trapping energy for the electrons in such centers is weak, they are available to enhance surface reactions. 

The fabrication of lasers based upon color centers adds a further dimension to the laser wavelengths available. Ordinary F centers do not exhibit laser action, but F centers that have a dopant cation next to the anion vacancy are satisfactory. These are typified by FLi centers, which consist of an F center with a lithium ion neighbor (Fig. 9.26a). Crystals of KC1 or RbCl doped with LiCl, containing FLi centers have been found to be good laser materials yielding emission lines with wavelengths between 2.45 and 3.45 p,m. A unique property of these crystals is that in the excited state an anion adjacent to the FLi center moves into an interstitial position... 

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