Alkali halides vacancy pairs

For a 1 1 solid MX, a Schottky defect consists of a pair of vacant sites, a cation vacancy, and an anion vacancy. This is presented in Figure 5.1 (a) for an alkali halide type structure the number of cation vacancies and anion vacancies have to be equal to preserve electrical neutrality. A Schottky defect for an MX2 type structure will consist of the vacancy caused by the ion together with two X anion vacancies, thereby balancing the electrical charges. Schottky defects are more common in 1 1 stoichiometry and examples of crystals that contain them include rock salt (NaCl), wurtzite (ZnS), and CsCl. 

Particle irradiation effects in halides and especially in alkali halides have been intensively studied. One reason is that salt mines can be used to store radioactive waste. Alkali halides in thermal equilibrium are Schottky-type disordered materials. Defects in NaCl which form under electron bombardment at low temperature are neutral anion vacancies (Vx) and a corresponding number of anion interstitials (Xf). Even at liquid nitrogen temperature, these primary radiation defects are still somewhat mobile. Thus, they can either recombine (Xf+Vx = Xx) or form clusters. First, clusters will form according to /i-Xf = X j. Also, Xf and Xf j may be trapped at impurities. Later, vacancies will cluster as well. If X is trapped by a vacancy pair [VA Vx] (which is, in other words, an empty site of a lattice molecule, i.e., the smallest possible pore ) we have the smallest possible halogen molecule bubble . Further clustering of these defects may lead to dislocation loops. In contrast, aggregates of only anion vacancies are equivalent to small metal colloid particles. 

At small radiation doses (the number of radiation-produced defects), the mean distance l between components of such geminate pairs (the vacancy and an interstitial atom) is much less than the mean distance between different pairs Iq = n-1/3, where n is defect concentration. The initial defect distribution is described by the distribution function f(r). Below a certain temperature (typically < 30 K for interstitial atoms and 200 K for vacancies in alkali halides), defects are immobile. With a temperature increase, the defects perform thermally activated random hops between the nearest lattice sites. This is usually considered to be continuous diffusion. 

As it is known, I centres are the most mobile radiation-induced radiation defects in alkali halides and therefore they play an essential role in low-temperature defect annealing. It is known, in particular, from thermally-stimulated conductivity and thermally-stimulated luminescence measurements, that these centres recombine with the F and F electron centres which results in an electron release from anion vacancy. This electron participates in a number of secondary reactions, e.g., in recombination with hole (H, Vk) centres. Results of the calculations of the correlated annealing of the close pairs of I, F centres are presented in Fig. 3.11. The conclusion could be drawn that even simultaneous annealing of three kinds of pairs (Inn, 2nn and 3nn in equal concentrations) results in the step-structure of concentration decay in complete agreement with the experimental data [82]. 

Ideas about the tunneling mechanism of the recombination of donor acceptor pairs in crystals seem to be first used in ref. 51 to explain the low-temperature of photo-bleaching (i.e. decay on illumination) of F-centres in single crystals of KBr. F-centres are electrons located in anion vacancies and are generated simultaneously with hole centres (centres of the Br3 type which are called H-centres) via radiolysis of alkali halide crystals. 

Let us say a few words on non-selective techniques which have been employed in the study of Li+ systems [93,152]. If this impurity moves off-centre in a alkali halide lattice the pair formed by the positive vacancy and the Li+ ion gives rise to an electric dipole, p. It is well known that free dipoles under an applied electric field, E, tend to place p parallel to E while thermal disorder is opposed to this effect. For this reason, if the average value of p at a given temperature is designated by... 

Besides alkali halides, alkali and alkaline earth azides have been most thoroughly inveistigated for radiation coloration. By irradiation of freshly precipitated potassium azide at 196°C with radiation of A = 2537 A, Tompkins and Young19 obtained bands due to the presence of F-centres and V-centres. Ageing was found to have marked influence on these bands. The proposed mechanism of ageing involves the formation of anion and cation vacancy pairs... 

Some defects may contribute to D but not to o (paired cation and anion vacancies in the alkali halides, for example). 

An example of covalent interaction of defects is the pairing of vacancies in alkali halides (see also Volume 2, Chapter 2). Neutral F centers (anion vacancies) may form divacancy pairs with an enthalpy of association of about —4 kcal/mole. Neutral cation vacancies also may attract each other with an even greater association enthalpy, ranging from about —40 kcal/mole for iodides to about — 75kcal/ mole for chlorides. This is even larger than the Coulomb attraction between oppositely charged vacancies. 

Intrinsic point defects are deviations from the ideal structure caused by displacement or removal of lattice atoms [106,107], Possible intrinsic defects are vacancies, interstitials, and antisites. In ZnO these are denoted as Vzn and Vo, Zn and 0 , and as Zno and Ozn, respectively. There are also combinations of defects like neutral Schottky (cation and anion vacancy) and Frenkel (cation vacancy and cation interstitial) pairs, which are abundant in ionic compounds like alkali-metal halides [106,107], As a rule of thumb, the energy to create a defect depends on the difference in charge between the defect and the lattice site occupied by the defect, e.g., in ZnO a vacancy or an interstitial can carry a charge of 2 while an antisite can have a charge of 4. This makes vacancies and interstitials more likely in polar compounds and antisite defects less important [108-110]. On the contrary, antisite defects are more important in more covalently bonded compounds like the III-V semiconductors (see e.g., [Ill] and references therein). 

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