Ranges and range theories

Irradiation of ionic crystals causes the displacement of lattice ions and the formation of primary defects in the form of vacancies and interstitials. At high temperatures when these defects are mobile secondary defect reactions will produce various types of defect clusters. In some compounds clustering can lead to the formation of small particles of the metal constituent, referred to as colloids. A well-known example of this effect occurs in the alkali halides, where the colloids form as the result of large-scale aggregation of the primary F centres, so that the metallic region in this case derives from primary defects on the anion sublattice. The latent image of the photographic process in silver halides is also an example of the formation of a small metal colloid, and other crystals such as hydrides and azides can also be partially decomposed into metallic particles by irradiation with ionizing radiation. Recently metal colloids have been found as a result of displacement damage in the oxides Li₂ and Al₂O₃. This article reviews some of the background properties of colloids in ionic crystals and describes some examples of colloid formation by irradiation. Colloid growth in NaCl is described in more detail, since recent experimental and theoretical work provides a more complete picture than in other compounds. The Jain-Lidiard theory explains many features of the behaviour observed during high dose irradiation at high temperatures, and some comments are made about ways in which the theory could be developed further.     

Approximate degeneracies of zone boundary phonons in alkali halide crystals

We point out the existence of a pervasive pattern of near degeneracies of phonon frequencies in isobaric alkali halide crystals (NaBr, KCl, RbBr, CsI) which strongly suggests that their dynamical matrices are almost invariant under transformations which exchange positive and negative ions. We extend this hypothesis to a relation between phonon properties of “mirror” alkali halides in which the ions of one crystal are replaced by the oppositely charged isobaric ions of the other, such as RbCl and KBr. Experimental evidence supporting this can also be adduced. Similar near degeneracies universally occurring in NaCl structure alkali halides and alkaline earth oxides are also noted and a possible dynamical basis for understanding these suggested.     

Dielectric properties of alkali halide and alkaline earth oxide crystals

The deviations of ionic charge and compressibility from their nominal values in alkali halides and alkaline earth oxide crystals have been discussed and explained in terms of a theory based on shell model and exchange charge interactions originally developed by Dick and Overhauser. The exchange charge polarization parameters have been evaluated in the present study using the appropriate values of overlap integrals. It has been concluded that the second neighbour short range forces have significnant magnitudes in alkaline earth oxides.     

Ion implantation in insulators

The modifications of insulating materials by ion implantation can be of considerable interest for many applications. If ion implantation has considerable potential for changing the properties of insulators, only a few experiments have determined the critical parameters which are important in the behaviour of the implanted layer. As a matter of fact, the ion implantation process is, by its very nature, a non-equilibrium process and, in addition, the injection of charged particles in a lattice determines a concomitant creation of intrinsic lattice defects. These defects are associated with the nuclear part of the energy loss of the particles and sometimes with the electronic one (halide compounds). The characterization of these intrinsic defects and the knowledge of their spatial distribution in the lattice are necessary because the formation or dissolution of phases precipitated in the implanted layer are strongly influenced by point or extended defects.

The main parameters which determine the charge state and site location of the implanted atoms in insulating targets are: ionicity of the chemical bond of the lattice, electronegativity, thermal or radiation enhanced diffusion processes, and intrinsic defects. For heavily implanted insulators, phase changes of compositional type can occur which can lead to strong modifications of the physical properties of the implanted layer. In order to obtain information on the relative extent of the critical parameters of chemical implantation in insulators it is necessary to combine analysis with different techniques such as, nuclear techniques, TEM, ESR, optical spectroscopy, X-ray diffraction at glancing angle, etc.

To illustrate the effects of these parameters, typical experimental results obtained in implanted binary or ternary compounds are reported (alkali halides, silver halides, alkaline earth oxides or fluorides, transition metal oxides, natural minerals, etc.).     

Diffusion measurement of implanted Sb into Si,using SiO2 encapsulation

Large, asymmetric atomic relaxations have been shown to play a crucial role in the structure and properties of several point defects in oxide materials. Examples include trapped hole centers in alkaline-earth oxides and E1′ and E4′ oxygen-vacancy centers and peroxy-radical defects in silicon dioxide. Schirmer's “bound small polaron” model, applied in particular to the alkaline-earth oxide defects, and model treatments of the E1′ center in SiO2 by Yip, Griscom and Fowler clearly illustrate the important spectroscopic consequences of such atomic relaxations. In fact, such effects had been incorporated in Lüty's classic model of the Type II FA center in alkali halides. Edwards and Fowler have recently applied MNDO and MINDO/3 quantum-chemistry approaches to the E1′, E4′, and peroxy radical defects in SiO2. These calculations generally corroborate suggested models and bear as well on possible creation mechanisms. Large relaxation effects are likely to be important in many other defects in oxide materials.     

Analysis of the photoelastic effect in ionic crystals

An analysis of the photoelastic effect in ionic crystals has been presented within the framework of Clausius-Mossotti theory of the dielectric constant. The values of the strain derivative of the electronic dielectric constant have been calculated in alkali halides and MgO crystals by taking into account the variation of electronic polarizabilities with compressive stress. The results obtained are found closer to the experimental values. The photoelastic behaviour of MgO crystal is predicted to be of opposite nature to that of alkali halides, in conformity with the experimental observations.     

Transverse optic mode Gruneisen parameter and dielectric properties of alkali halides

The well known Szigeti relations for the dielectric theory of ionic crystals have been critically examined by investigating the volume dependence of dielectric behaviour of alkali halides. It has been predicted that the strain derivative of effective ionic charge parameter should be nearly equal to zero. Values of transverse optic mode Gruneisen parameter for NaCl structure alkali halides have been estimated.     

Charge-Transfer Processes in Doped Alkali Halides

Defects formation under UV-irradiation in the impurity-induced absorption bands at 4.2 K has been studied for crystals with and without traps for electrons (CsI:Pb and Eu^2?-doped alkali halides, respectively). In both cases the results have been explained by an electron transfer from the impurity-perturbed halogen ion states, resulting in the appearance of electrons and holes in the crystal. In CsI:Pb, the electrons are trapped by lead ions and the holes are self-trapped. In Eu^2?-doped crystals, the electrons and the holes recombine with the formation of excitons, whose decay results in the creation of Frenkel defects.     

Colored LiF: an optical material for all seasons

Colored LiF salt has been always considered a singular optical material among alkali halides and other dielectric crystals for its peculiar characteristics, which in due time have been applied with success in thermoluminescence and laser technology. Lately, while the two previous topics have been revived, new relevant results have been obtained in the optoelectronic field by using both bulk crystals and newly characterized thin films. In practice, miniaturized photoluminescent patterns can be produced rather easily by using low-energy electron beams and soft X-rays. So, LiF salt is becoming a new interesting photonic material with promising developments in basic reasearch and applications as well.     

A simple formula for the fundamental optical absorption of alkali halide melts

Significant similarities — with respect to absorption of ultraviolet — between the crystalline and liquid phases of the alkali halides are considered. It is shown that a simple formula which emerged from an earlier application of local electron transfer concepts to the fundamental absorption of the alkali halide crystals appears to apply equally well (i.e. within experimental error) to their melts. This formula fits the observations relating to the fundamental absorption of five molten alkali halides and yields predictions for all the others — which will, it is hoped, stimulate experimental activity.     

Dynamics of replacement sequences and of crowdions

The theory of the formation of point defects by ionization in alkali halides has been extended to include the dynamics of the subsequent motion of replacement sequences and of crowdions (H-centers) at low temperatures. Particular attention is paid to the stochastic aspect of the motion of these centers, which appears to play a crucial role in interpreting recent experimental studies of interaction proesses of H-centers with other defects in alkali halides. It turns out that at not too low temperatures the rate controlling reaction is the rotation of the centers. A detailed analysis of the kinetics of the various competing processes is given.     

Cathodo-luminescence spectra of alkali halides

Cathodo-luminescence spectra of fourteen alkali halides and of some mixed crystals of NaCl and KCl have been studied. The spectra show broad structureless bands. In some ten halides it is possible to find a strong band whose peak position shifts towards longer wavelengths as the inter-atomic distance increases. For pottasium halides the relationship λ_max=1380d, where “d” is the inter-atomic distance, holds approximately but is not generally true. A mechanism of cathodo-luminescence in alkali halides has been postulated, and an interpretation of the above band and of some NaCl bands has been made on that basis.     

A new theory of compressible ions — structures of the alkali halides

Ions in ionic crystals are considered to exist in compressible space-filling polyhedral cells analogous to the Wigner-Seitz cell in metals. Repulsion arises from the compression energy of the ions written as a surface integral over the ionic cells. Two adjustable parameters are introduced per ion with the provision that the same parameters can be used in any crystal of any structure in which the ion occurs. The 18 parameters for the 5 alkali and 4 halogen ions have been determined from PV data on the 20 alkali halides. The important successes of the theory are: (i) All the twenty alkali halides are correctly predicted to occur in their observed structures (ii) The thermal transition in CsCl is explained (iii) The pressure transitions in the alkali halides are predicted well (iv) The calculated values of the variation of transition pressures with temperature agree well with experiment. These results are much better than those obtained by earlier theories.     

The fractional ionic character of alkali and silver halide crystals

The fractional ionic character of alkali and silver halide crystals is defined in terms of the deviations from the additivity rule for polarizabilities of ions. The electronic polarizabilities of ions are calculated using an empirical relationship according to which the electronic polarizability of an ion can be assumed to be directly proportional to the cube of its radius. The calculated ionicities indicate that the alkali halides are nearly or more than 90% ionic and silver halides are much less ionic which is also evident from the Phillips ionicity scale.     

On Hurter-Driffield characteristics and optical storage in mixed crystals of alkali halides

Hurter-Driffield characteristic curves and the quality of stored and retrieved information in coloured mixed crystals of alkali halides are presented.     

Absorption Spectrum Study on Colloidal Centers in KCl:NCO:K

The absorption spectrum study on metallic colloidal centers in KCl:NCO:K crystals have been performed as a function of annealing temperature in the temperature range of 500–750K. Conversion process between F-centers and colloidal centers was observed and it is found that the NCO ions play an important role in the formation and stability of aggregative centers in alkali halides.     

Absorption bands of lead in mixed KCl + KBr crystals

The absorption spectra of mixed KCl + KBr crystals with lead added were measured. The main attention was devoted to A bands and their fine structure. Measurements were made at different temperatures. The results are discussed from the point of view of the existence of lead complexes in crystals of alkali halides.     

Atomic hydrogen and muonium in alkali halides

Atomic hydrogen can be trapped at interstitial and substitutional cation and anion sites in alkali halides. The geometrical structure of these defects was established by electron nuclear double resonance (ENDOR). From the analysis of the ENDOR spectra also detailed information was obtained on the electronic structure. In this article the major experimental and theoretical results for atomic hydrogen in several alkali halides are briefly reviewed. Special emphasis is given to the isotope effects upon replacing hydrogen by deuterium. The nature of the dynamical hyperfine and superhyperfine interactions is discussed. Its magnitude to be expected for muonium is estimated. Recent results on muonium centres are discussed on the basis of the knowledge about the hydrogen centres.     

Thermally stimulated depolarization of Eu2+-cation vacancy dipoles in alkali halide single crystals

Ionic thermocurrent (ITC) measurements have been performed on eight alkali halide single crystals doped with divalent europium. In all cases, the observed ITC peaks were fitted with a mono-energetic model without to appeal to any dipole-dipole interaction. Values for the reorientation parameters have been calculated. The relationship T_M1nτ^?1 α E previously found for I–V complexes in alkali halides has been found to be very well obeyed for the experimental data obtained in this investigation. It is also reported that the logarithm of the experimentally determined energies for free dipole reorientation shows a linear dependence on the interaction distance between the Eu²⁺ ion and the surrounding halogen ions in the distorted cubic site occupied by this impurity in the alkali halides.