Schottky—Frenkel defects

Dislocation theory as a portion of the subject of solid-state physics is somewhat beyond the scope of this book, but it is desirable to examine the subject briefly in terms of its implications in surface chemistry. Perhaps the most elementary type of defect is that of an extra or interstitial atom—Frenkel defect [110]—or a missing atom or vacancy—Schottky defect [111]. Such point defects play an important role in the treatment of diffusion and electrical conductivities in solids and the solubility of a salt in the host lattice of another or different valence type [112]. Point defects have a thermodynamic basis for their existence in terms of the energy and entropy of their formation, the situation is similar to the formation of isolated holes and erratic atoms on a surface. Dislocations, on the other hand, may be viewed as an organized concentration of point defects they are lattice defects and play an important role in the mechanism of the plastic deformation of solids. Lattice defects or dislocations are not thermodynamic in the sense of the point defects their formation is intimately connected with the mechanism of nucleation and crystal growth (see Section IX-4), and they constitute an important source of surface imperfection. 

By analogy with similar materials in which free elecU ons and electron holes are formed, NiO is called a p-type compound having vacant site Schottky defects, and ZnO is an n-type compound having interstitial Frenkel defects. The concentrations of these defects and their relation to the oxygen pressure in the suiTounding atmosphere can be calculated, for a dilute solution of defects by the application of a mass action equation. The two reactions shown above are represented by the equations... 

Point defects (Schottky, Frenkel, unoccupied lattice sites, misplaced units)... 

Thus, if Frenkel Defects predominate in a given solid, other defects are usually not present. Likewise, for the Schottky Defect. Note that this applies for associated defects. If these are not present, there will still be 2 types of defects present, each having an opposite effect upon stoichiometry. 

Write a series of equations for the Frenkel defect, similar to those given for the Schottky defect, i.e.- Equations 3.7.2 to 3.7.3. 

Draw a heterogeneous lattice, using circles and squares to indicate atom positions in a simple cubic lattice. Indicate both Schottky and Frenkel defects, plus the simple lattice defects. Hint- use both cation and anion sub-lattices. 

Yakov Frenkel showed in 1926 that ideal crystals could not exist at temperatures above the absolute zero. Part of the ions leave their sites under the effect of thermaf vibrations and are accommodated in the interstitial space, leaving vacancies at the sites formerly taken up. Such point defects have been named Frenkel defects. These ideas were developed further by Walter Schottky in 1929, who pointed out that defects will also arise when individual ions or ion pairs are removed from the bulk... 

Intrinsic Defects The simplest crystalline defects involve single or pairs of atoms or ions and are therefore known as point defects. Two main types of point defect have been identified Schottky defects and Frenkel defects. A Schottky defect consists of a pair of vacant sites a cation vacancy and an anion vacancy. A Schottky defect is... 

FIGURE 25.1 Schematic representations of (a) a Schottky defect in NaCl and (b) a Frenkel defect in AgCl. (From Gelings and Bouwmeester, 1997, Fig. 3.36, with permission from CRC Press LLC via CCC.)... 

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. 

BALANCED POPULATIONS OF POINT DEFECTS SCHOTTKY AND FRENKEL DEFECTS... 

Figure 1.15 Balanced populations of point defects in an ionic crystal of formula MX (schematic) (a) Schottky defects and (b) Frenkel defects.

A point defect is a localized defect that consists of a mistake at a single atom site in a solid. The simplest point defects that can occur in pure crystals are missing atoms, called vacancies, or atoms displaced from the correct site into positions not normally occupied in the crystal, called self-interstitials. Additionally atoms of an impurity can occupy a normal atom site to form substitutional defects or can occupy a normally vacant position in the crystal structure to form an interstitial. Other point defects can be characterized in pure compounds that contain more than one atom. The best known of these are Frenkel defects, Schottky defects, and antisite defects. 

The estimation of the number of Frenkel defects in a crystal can proceed along lines parallel to those for Schottky defects by estimating the configurational entropy (Supplementary Material S4). This approach confirms that Frenkel defects are thermodynamically stable intrinsic defects that cannot be removed by thermal treatment. Because of this, the defect population can be treated as a chemical equilibrium. For a crystal of composition MX, the appropriate chemical equilibrium for Frenkel defects on the cation sublattice is... 

Some experimental values for the formation enthalpy of Frenkel defects are given in Table 2.2. As with Schottky defects, it is not easy to determine these values experimentally and there is a large scatter in the values found in the literature. (Calculated values of the defect formation energies for AgCl and AgBr, which differ a little from those in Table 2.2, can be found in Fig. 2.5.)... 

Despite the fact that not all details of the photographic process are completely understood, the overall mechanism for the production of the latent image is well known. Silver chloride, AgBr, crystallizes with the sodium chloride structure. While Schottky defects are the major structural point defect type present in most crystals with this structure, it is found that the silver halides, including AgBr, favor Frenkel defects (Fig. 2.5). 

Figure 2.5 Calculated variation of the formation energy of Schottky and Frenkel defects in the halides AgCl and AgBr as a function of temperature. [Redrawn from data in C. R. A. Catlow, Mat. Res. Soc. Bull., XIV, 23 (1989).]...

At all temperatures above 0°K Schottky, Frenkel, and antisite point defects are present in thermodynamic equilibrium, and it will not be possible to remove them by annealing or other thermal treatments. Unfortunately, it is not possible to predict, from knowledge of crystal structure alone, which defect type will be present in any crystal. However, it is possible to say that rather close-packed compounds, such as those with the NaCl structure, tend to contain Schottky defects. The important exceptions are the silver halides. More open structures, on the other hand, will be more receptive to the presence of Frenkel defects. Semiconductor crystals are more amenable to antisite defects. 

An intrinsic defect is one that is in thermodynamic equilibrium in the crystal. This means that a population of these defects cannot be removed by any forms of physical or chemical processing. Schottky, Frenkel, and antisite defects are the best characterized intrinsic defects. A totally defect-free crystal, if warmed to a temperature that allows a certain degree of atom movement, will adjust to allow for the generation of intrinsic defects. The type of intrinsic defects that form will depend upon the relative formation energies of all of the possibilities. The defect with the lowest formation energy will be present in the greatest numbers. This can change with temperature. 

The energy of formation of defects in PbF2 are anion Frenkel defect, 0.69 eV cation Frenkel defect, 4.53 eV Schottky defect, 1.96 eV. (a) What point defects do these consist of (b) What are (approximately) the relative numbers of these defects in a crystal at 300 K (Data from H. Jiang et al., 2000). 

When Schottky defects are present in a crystal, vacancies occur on both the cation and anion sublattices, allowing both cation and anion vacancy diffusion to occur (Fig. 5.12a). In the case of Frenkel defects interstitial, interstitialcy, and vacancy diffusion can take place in the same crystal with respect to the atoms forming the Frenkel defect population (Fig. 5.12b). 

Figure 5.12 Diffusion in crystals of composition MX containing (a) Schottky and (b) Frenkel defects, schematic V, vacancy, i, interstitial, iy, interstitialcy.

In densely packed solids without obvious open channels, the transport number depends upon the defects present, a feature well illustrated by the mostly ionic halides. Lithium halides are characterized by small mobile Li+ ions that usually migrate via vacancies due to Schottky defects and have tc for Li+ close to 1. Similarly, silver halides with Frenkel defects on the cation sublattice have lc for Ag+ close to 1. Barium and lead halides, with very large cations and that contain... 

Frenkel defects on the anion sublattice show only anion migration and hence have fa close to 1. The alkali halides NaF, NaCl, NaBr, and KC1 in which Schottky defects prevail and in which the cations and anions are of similar sizes have both cation and anion contributions to ionic conductivity and show intermediate values of both anion and cation transport number. 

It is important that the complete diagram displays prominently information about the assumptions made. Thus, the assumption that Schottky defect formation was preferred to the formation of electronic defects is explicitly stated in the form Ks > Ke (Fig. 7.9e). As Frenkel defect formation has been ignored altogether, it is also possible to write Ks > Ke > > Kt , where A p represents the equilibrium constant for the formation of Frenkel defects in MX. 

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