Farbzentrenassoziate mit (100)-Symmetrie (A und B-Zentren)

By light absorption in additively colored KCl A-centers can be developped under certain conditions. Irradiation with (100) polarized F-light produces a reorientation of these centers, which is observed by a characteristic dichroic absorption. From these measurements the symmetry and the two optical transitions A₁ und A₂of the A-center are derived. Experiments with Na-doped crystals suggest as a model for the A-centeran F-center assoziated to a single Na ⁺ ion in the KCl lattice. From A-centers a new center can optically be developped, which has again (100) symmetry and two optical transitions. This ?B-center“ is interpreted as the assoziation oftwo F-Centers to a Na ⁺ion in KCl.     

The photoacoustic effect and non-radiative transitions OF F-centers in alkali halides

The common photoacoustic spectrum (PAS) is wider than the optical absorption spectrum in KCl crystals. A photoacoustic experiment was performed with a solid KCl sample that was additively colored according to the Van Doorn technique. The sample had about 10 17 v [F/cm 3 ]. It was determined that the PAS is composed of many bands of the F and aggregate centers. It is explained here, using the configuration coordinate model, that the photoacoustic effect in alkali halides with F-centers shows experimental broadening of the photoacoustic band relative to the F -band. Furthermore, experimental data is added resolving the photoacoustic bands of the agglomerates and also the bands of higher excited states of the F-center. Finally, assuming a configuration coordinate model and the F-centers as sources of heat, an estimation is made for the increase of the sample temperature.     

Zur Bildungskinetik der F-Folgezentren in KCl

Following the same procedure as in part I the formation of Z₁-centers under Flight irradiation was investigated in additively colored KCl crystals doped with Ca⁺⁺ and Sr⁺⁺ ions. The measurements show that again F′-centers and empty anion vacancies are the first reaction product and determine the rate of Z₁-center formation. The temperature dependence and rate of the Z₁-center formation is in agreement with the corresponding results on F _A -center formation, demonstrating that Z₁-centers are formed as the consequence of an ionic process and not a mere electronic transfer. It is concluded that again empty anion vacancies or F′ centers diffuse randomly in the lattice (activation energy 0.6 eV) until they are captured at an impurity site. Arguments are presented that these impurities are divalent cation/vacancy complexes, so that the model of the Z₁-center should be a combination of the F-center with this complex. The independence of the Z₁-band of the nature of the divalent cation indicates the assoziation of the F-center to the vacancy-side of the complex. A characteristic delay period in the Z₁-center formation can be accounted for by a non-statistical distribution of F-centers and divalent cations to each other. This is a necessary consequence of the high temperature dynamical equilibrium between these imperfections which is frozen in by the quenching of additively colored crystals. A direct proof for this interpretation is the absence of the delay period in crystals where the F-centers are formed by x-irradiation at room temperature.     

Deformation Luminescence in gamma-irradiated KCl single crystals

Abstract

Deformation Luminescence(DL) is studied on KCl crystal colored by γ-irradiation. The spectra analysis of DL and thermoluminescence reveals that F-center plays a role as electron donor through the interaction with moving dislocation and V₂-center is a probable luminescence center. A theory is presented for understanding the deformation rate and temperature dependences of DL intensity.     

Zur Bildungskinetik der F-Folgezentren in KCl

The process of F-center aggregation under light irradiation, which involves ionic movement at low temperatures (observable down to — 60°C), is not at all understood in its mechanism. It is the aim of this work to evaluate quantitatively the kinetics of this process for different F-aggregate centers. In part I the assoziation of F-centers in KCl crystals with isolated Na⁺ or Li⁺ ions was thoroughly investigated as the clearest model case of F-center-aggregation. The reaction product in these crystals after light irradiation, an F-center associated to a Na⁺ or Li⁺ ion as nearest (100) neighbor (F _A -center), is well established in its model and can be detected by its double peak absorption structure. By optical measurements of the rate of F _A -center formation in dependence on light-intensity, time, Na⁺ or Li⁺-concentration, F→F′ conversion rate and temperature, the kinetics of this reaction could be evaluated in a simple equation of bimolecular type. The analysis leads to the conclusion, that either the anion vacancy or the F′-center must be regarded as a unit of high thermal mobility (activation energy 0·6±0·05 eV, jump frequency about 10² sec^?1 at room temperature) which diffuses randomly in the lattice and can be captured by a Na⁺ or Li⁺ ion.     

Negative photoplastic effect due to the relaxed excited state of the F-center in alkali halides

Abstract

To make clear the mechanism of the photoplastic effect (PPE) in alkali halides containing F-centers, on the basis of the photochemical reaction of the F-center, temperature dependence of the PPE in KC1, and KBr and NaCl was studied from 95 K up to RT. The characteristic critical points θ _ts in colored KC1 and KBr were determined to be 110 and 190 K, respectively. Below θ _t the sign of the PPE in both crystals was negative, i.e., decrement of the flow stress during light illumination was observed. Moreover, the θ _ts were in good agreement with the temperature where the photoconductivities show remarkable increase in the course of the measurements. The negative PPE is explained in terms of the rotation of the principal strain axis of the relaxed state of the F-center having ?100? tetragonarity as to relax the stress around the edge dislocation coming closely.     

Color center formation by synchrotron radiation in the Na6Al6Si6O24(Nal)1.6 optical ceramic

The spectrum of F-center excitation by 5-to 27-eV photons in the Na₆Al₆Si₆O₂₄(NaI)_2x sodalite optical ceramic (x=0.8) was measured at 80 K by high-sensitivity photoexcited luminescence techniques. The F-centers are created by photons with an energy of 5.6-to 8.5 eV through the excitation and ionization of iodine centers of two types; in the 8.2-to 27-eV region, through the generation of electronic excitations in the aluminosilicate framework of alternating Al³⁺ and Si⁴⁺ ions, each coordinated tetrahedrally by oxygen ions. At the low irradiation doses used, the F centers are created primarily through photoelectron capture by the iodine vacancies which exist before irradiation. In the 23-to 25-eV region, the efficiency of F-center formation doubles as a result of the multiplication of electron-hole pairs.     

Electron-lattice interaction of Ag− and Cu− centers in alkali halides

Absorption, emission, and excitation spectra of Ag^? centers in KCl, RbCl, CsCl, and CsBr are measured at low temperatures. The positions of theA emission bands are slightly different afterC andA band excitation, respectively. This is believed to be due to the existence of two different types of minima in the adiabatic potential energy surface of the³ T _1u state. The symmetry of the energy minima in the¹ T _1u state is trigonal for KCl∶Ag^? and Cu^?, but tetragonal for CsBr∶Ag^?. This becomes evident from the polarization properties of the emission. The energy and temperature dependence of the polarization is discussed. Uniaxial stress causes polarized emission of Ag^? and Cu^? centers measured from LHeT to 100 K. This is due to a splitting and mixing of the relaxed excited states by the stress. The effects are used to calculate the coupling constants between thep electron and theE _g andT _2g lattice modes. They are compared with predictions from the point-charge model for different lattice structures. A new assignment of the absorption bands of KCl∶Cu^? to the excited states of Cu^? is established on measurements of emission spectra and lifetimes.     

Dichteänderung und F-Zentrenbildung in KCl durch Röntgenbestrahlung bei Raumtemperatur

F-center concentrations and density changes in KCl single crystals, brought about by X-irradiation at room temperature, were measured. The density measurements were made using a flotation technique. Both undoped KCl crystals and crystals doped with KH were investigated. The following results were obtained:

1. 1.
   In Korth-KCl crystals (undoped) the volume change per F-center in stage I of the coloration — i.e. where the so-called fast coloration process is predominant — was (1.34±0.04)a ³ (a: interionic distance).     
   
   

O−−-Lücken-Dipole in Alkalihalogenidkristallen

Dielectric loss measurements are reported for KBr, KCl, and NaCl crystals containing O^?? ions. The frequency and temperature dependences can be well represented by a Debye curve. The dipole moment found immediately after quenching is interpreted as being due to O^?? ions associated with anion vacancies. Activation energies for reorientation of the ion are E₀=0.59 eV for KCl, 0.54 eV for KBr and 0.61 eV for NaCl. Fluorescence bands were found in freshly quenched KCl crystals at 470 nm and 1.05 μm and are attributed to isolated dipoles. Dielectric losses decreased and the optical absorption changed during annealing due to the collection of centers into aggregates. A detailed analysis of the kinetics for KCl indicates the formation of double dipoles as the first step. The energy of association is E_A=0.85 eV. Earlier measurements of absorption, fluorescence and photochemical coloring are reinterpreted on the basis of the proposed model in which an O^?? center is thought of as a O^?? ion associated with an anion vacancy.     

Two photoplastic effects and their temperature dependence in alkali halides

The characteristic critical temperatures for the sign of the photoplastic effect (PPE) in KCl and KBr, using also photoconductivity measurements, were determined to be 110 K and 190 K, respectively. Negative PPE is explained in terms of elastic interaction between a moving dislocation and the relaxed excited state of the F-center.     

Comparative investigations of TL and OSL in KCI:Eu2+ crystals irradiated with UV and X-rays

Abstract

We present thermoluminescence (TL) glow curves and optical stimulated luminescence (OSL) response from both KCl:Eu²⁺ crystals irradiated with soft X-rays (20 KV, 80 μA) and ultraviolet light (230 nm). Two situations take place. First, we observed that for long time F-light bleaching (560 nm) the typical TL glow curve of X-rays irradiated KCl:Eu²⁺ resembles the TL glow curve of UV-irradiated samples. Second, along with OSL measurements, we have performed a thermal bleaching and we have addressed F and F_z participation in OSL. These results provide us a supportable correlation between F and F_z as responsible centers for OSL and TL processes.     

Dislocation spectroscopy of crystals

A new method of studying the energy characteristics of dislocations is proposed, which is based on the investigation of the interaction of moving dislocations with purposefully introduced electronic and hole centers. A study has been made of KCl, NaCl, KBr, LiF, and KI alkali halide crystals containing electronic F and hole V _K and Me ⁺⁺ (Cu⁺⁺, Ag⁺⁺, Tl⁺⁺, In⁺⁺) centers. Investigation of the temperature dependence of the dislocation interaction with the F centers permitted determination of the position of the dislocation-induced electronic band (DEB) in the band diagram of the crystal. In KCl, the DEB is separated by ≈2.2 eV from the conduction-band minimum. It is shown that dislocations transport holes from the centers lying below the dislocation-induced hole band (DHB) (X ⁺, In⁺⁺, Tl⁺⁺, V _K) to those above the DHB (the Cu⁺ and Ag⁺ centers). Such a process is temperature independent. The DHB position in the crystal band diagram has been determined; in KCl it is separated by ≈1.6 eV from the valence-band top. The effective radii of the dislocation interaction with the electronic F and hole X ⁺, V _K, and Tl⁺⁺ centers have been found. Fiz. Tverd. Tela (St. Petersburg) 41, 2139–2146 (December 1999)     

Vibrational fluorescence of CN− centers in KCl by electronic excitation of neighbouring Tl+ centers

Abstract

Infrared emission from higher vibrational states of CN^? in KCl has been achieved by optically exciting nearby Tl⁺ ions with an excimer laser. The electronic vibrational energy transfer, already known from F_H(CN^?) in alkali halides, leads to population of vibrational states up to at least the tenth level.     

Role of Ti in the luminescence process of Al2O3:Si,Ti

Al₂O₃:Si,Ti, prepared under oxidizing condition at high temperature, gives PL emission around 430 nm when excited with 240 nm. The Al₂O₃:C, TL/OSL phosphor, also shows emission around 430 nm, which corresponds to characteristic emission of F-center. Thus, to identify the exact nature of luminescent center in Al₂O₃:Si,Ti, fluorescence lifetime measurement studies were carried out along with the PL,TL and OSL studies. The PL and TL in Al₂O₃:Si,Ti show emission around 430 nm and the time-resolved fluorescence studies show lifetime of about 43 μs for the 430 nm emission, which is much smaller than the reported lifetime of ∼35 ms for the 430 nm emission (F-center emission) in Al₂O₃:C phosphor. Therefore, the emission observed in Al₂O₃:Si,Ti phosphor was assigned to Ti⁴⁺ charge transfer transition. Fluorescence studies of Al₂O₃:Si,Ti do not show any traces of F and F⁺ centers. Also, Ti⁴⁺ does not show any change in the charge state after gamma-irradiation. On the basis of the above studies, a mechanism for TSL/OSL process in Al₂O₃:Si,Ti is proposed.     

De-excitation process and hot luminescence in the FA(type I) center in KCl:Na

The de-excitation process of F_A(type I) centers in KCl:Na has been investigated by measuring the hot luminescence spectrum from optically excited F_A centers with time-resolved spectroscopy. The experimental results are analyzed by using a model that describes a time evolution of the phonon wave packet during the vibronic relaxation process from the Franck-Condon state to a relaxed excited state. From the analysis of the experimental data, information on the vibronic mixing between 2p and 2s states, whose magnitude varies during the relaxation process, and the adiabatic potential energy curves of 2s and 2p states are extracted. The present results are compared with the already known ones of the F_A(type II) centers.     

The two-photon transition of the fully-ionized muonic boron migrating in helium

In recent experiments performed at the Paul Scherrer Institute (PSI) measurements were made of the yield of the two-photon transition of the fully-ionized muonic boron formed and quenched in a gaseous mixture of diborane B₂H₆ and helium. In the present work this yield is calculated for an idealized case of a very low diborane density when the main 2 s state decay modes competing with the two-photon transition are due to the electron transfer from helium to the μ-ion. As the rate of this transfer depends strongly on the relative velocity, a treatment is needed of the whole kinetics of processes occurring with the μ-ion in helium. Accordingly, within the optical model with a complex potential constructed before we calculate cross-sections of the elastic scattering and electron transfer. Then the time evolution of the μ-ion energy is considered and, finally, the yield is calculated. It proves that at helium pressures Torr this yield may be written in the form: ,where the factor C is greater than unity and increases rapidly with the initial energy E₀ which the μ-ion has after its formation in the diborane molecule. Thus measurement of the pressure dependence of allows E₀ to be estimated. The results obtained make it possible to suggest a similar parametrization of the PSI data. Received: 21 October 1997 / Revised: 16 January 1998 / Accepted: 2 March 1998     

Vibronic scheme of the franck-condon state of F centers that consistently elucidates MCD and resonance raman scattering

Abstract

The resonance Raman scattering (RRS) of F centers, particularly the photon-energy dependence of linear polarization of the RRS, has been studied on the basis of a vibronic viewpoint. With combinination of previous results that have explained magnetic circular dichroism (MCD) spectra, a vibronic scheme of the Franck-Condon state of F centers for KCl, KBr and KI crystals is established.     

Determination of the refractive index difference caused by the birefringence of FA (II) centers in KCl:Li

Abstract

A method is described for determining the refractive index difference caused by the birefringence of oriented F_A (II) centers in KCl:Li crystals. It is shown that the portion induced by the birefringence can be separated from an absorption spectrum measured through a polarizer-analyzer system. From this portion the refractive index difference can then be calculated with ease.