On the origin of the visible emission in KBr:Tl and KCl:Tl crystals

The intensity of the visible emission of KBr:Tl at 440 nm is shown to increase linearly with the absorption in the A₁ band at 4.64 eV (267 nm). The latter band increased with the square of the Tl⁺ ions concentration, which supports its assignment to thallium dimers. Similarities in behavior between the 440 nm emission of KBr:Tl and the 475 nm emission of KCl:Tl suggest that the latter is also related to dimers. This is supported by the superlinear dependence of this emission on the Tl⁺ ion concentration. Deviations ofthe superlinearity from the square dependence expected for dimers is explained by the overlap between the weak dimer absorption and the very strong A-band.The 440 nm emission of KBr:Tl was found to be excited only in the A₁ component of the dimer absorption and not in the stronger A₂ component. This indicates that the emission process may be compound.     

First stage f centre formation in pure and doped KCl crystals by room temperaure X-irradiation

The electrical conductivity and optical absorption of potassium chloride crystals, pure and doped with divalent cation impurities, have been measured before and after X-irradiation at room temperature. The concentration of free positive ion vacancies at room temperature has been calculated from conductivity for each crystal before irradiation and is found to be much less than the first stage F centre concentration. This shows that both free and associated positive ion vacancies are the latent source of F centres in the first stage colouration. Pb^{+ +} ions trap electrons producing Pb^{+ +} and Pb⁰ centres and making free the associated cation vacancies. Such centres are not produced in Ca-doped crystals where impurity-vacancy complexes trap F centres producing Z centres. The higher ratio of F centres to positive ion vacancies in Pb-doped crystals indicates that free cation vacancies are more effective in producing F centres. However, the concentration of divalent cations is found to decrease in both the crystals after irradiation, the decrease being more in Ca-doped crystals.The author is indebted to Prof. H. N. Bose for helpful discussions. Thanks are also due to Dr. M. L. Mukherjee for providing the crystals.     

Dimer centres in variously pretreated thallium doped sodium halides

A detailed examination of the luminescent characteristics of variously pretreated heavily doped NaBr:Tl phosphors has been carried out. A prominent emission band at 420 nm exhibited by the phosphor is attributed to the electronic transitions within Tl⁺ ion perturbed by the presence of another Tl⁺ ion occupying nearest neighbour alkali ion site, the centre so formed being known as dimer. It is rather surprising that the dimers are conspicuous by their absence in heavily doped NaCl:Tl phosphors. This aspect of the result is discussed on the basis of the relative sizes of the ions in the phosphors.     

Ionic conduction and effect of cation doping in Tl<Subscript>4</Subscript>HgI<Subscript>6</Subscript>

The ionic conduction properties of undoped and doped Tl₄HgI₆ were investigated using electrical conductivity, dielectrics, differential scanning calorimetry, and X-ray diffraction techniques. The heavy Tl⁺-ions diffusion was activated at high temperature, whereas low conductivity at the lower temperature suggested electronic contribution in undoped Tl₄HgI₆. The partial replacement of heavy Tl⁺ ion by suitable cations (Ag⁺ and Cu⁺) enhanced the conductivity by several orders of magnitude, whereas diminution in conductivity results with increasing dopants’ concentration in Tl₄HgI₆. These results can be interpreted in terms of a lattice contraction and vacancy–vacancy interaction (leading to the cluster formation), respectively. The dielectric values of undoped Tl₄HgI₆ system gradually increasing with temperature, followed by a sharp change, were observed around 385 K and can be explained on the basis of increasing number of space charge polarization and ions jump orientation effects. The activation energy of undoped and doped Tl₄HgI₆ systems were calculated, and it was found that ionic conductivity activation energy for 5 mol% of cation dopants is much lower than that of undoped one, and also 10 mol% doped Tl₄HgI₆ systems.     

Photo- and thermo-stimulated luminescence of CsI—Tl crystal after UV light irradiation at 80 K

Abstract

Thermo- and photo-stimulated luminescence are studied for CsI—Tl crystal after the irradiation with the UV light at 80 K. Creation spectrum of the photostimulated luminescence coincides with the D absorption band of Tl⁺ ions. Nature of the defects created by UV light at low temperatures is discussed basing on the correspondence between the thermostimulated glow curve peaks and thermal evolution of the photostimulation spectra observed after irradiation in the D absorption band. Three bands at 1400, 950 and 580 nm have been observed in the stimulation spectrum at 80 K. The 1400 and 950 nm stimulation bands are presumably explained as the optical transitions in the Tl⁰ centre forming the spatially correlated defect pair with V_k centre while the 580 nm stimulation band is connected with the unperturbed Tl⁰ centres. It is concluded that the Tl⁺ luminescence at low temperature is connected with the electron recombination with the Tl²⁺ centre.     

Electronic excitation energy transfer and nonstationary processes in KH<Subscript>2</Subscript>PO<Subscript>4</Subscript>:Tl crystals

We report the results of our experimental study and numerical simulation of the electronic excitation energy transfer to impurity centers under conditions where nonstationary processes take place in the hydrogen sublattice of potassium dihydrogen phosphate (KH₂PO₄) single crystals doped with mercury-like Tl⁺ ions (KDP:Tl). We present the experimental results of our investigation of the decay kinetics of the transient optical absorption (100 ns–50 s) of intrinsic defects in the hydrogen sublattice of KDP:Tl obtained by pulsed absorption spectroscopy and the results of our study of the dynamics of the change in steady-state luminescence intensity with irradiation time (1–5000 s). To explain the transfer of the energy being released during electron recombination involving intrinsic KDP:Tl lattice defects, we formulate a mathematical model for the transfer of this energy to impurity Tl⁺ luminescence centers. Within the model being developed, we present the systems of differential balance equations describing the nonstationary processes in the electron subsystem and the hydrogen sublattice; provide a technique for calculating the pair correlation functions Y(r, t) of dissimilar defects based on the solution of the Smoluchowski equation for the system of mobile hydrogen sublattice defects; calculate the time-dependent reaction rate constants K(t) for various experimental conditions; and outline the peculiarities and results of the model parametrization based on our experimental data. Based on our investigation, the dramatic and significant effect of a gradual inertial increase by a factor of 50–100 in steady-state luminescence intensity in the 4.5-eV band in KDP:Tl crystals due to the luminescence of mercury-like Tl⁺ ions has been explained qualitatively and quantitatively.     

FA(Ga+,In+,Tl+) tunable laser activity and interaction of halogen atoms (F,Cl,Br,I,At) at the (001) surface of KCl crystal: ab initio calculations

An attempt has been made to examine F_A(Ga⁺,In⁺,Tl⁺) tunable laser activity and adsorptivity of halogen atoms (F,Cl,Br,I,At) at the (0 0 1) surface of KCl crystal using an embedded cluster model, CIS and density functional theory calculations with effective core potentials. The ion clusters were embedded in a simulated Coulomb field that closely approximates the Madelung field at the host surface. The nearest neighbor ions to the defect site were then allowed to relax to equilibrium. Based on the calculated strength of electron–phonon coupling and Stokes-shifted optical transition bands, The F_A(Tl⁺) center was found to be the most laser active in agreement with the experimental observation that the optical emissions of F_A(In⁺) and F_A(Ga⁺) centers were strongly quenched. The disappearance of the anisotropy and np splitting observed in the absorption of F_A(Ga⁺,In⁺,Tl⁺) centers were monotonically increasing functions of the size of the impurity cation. The F_A(Ga⁺,In⁺,Tl⁺) defect formation energies followed the order F_A(Ga⁺)>F_A(In⁺)>F_A(Tl⁺). The Glasner–Tompkins empirical relationship between the principal optical absorption of F centers in solids and the fundamental absorption of the host crystal was generalized to include the positive ion species. As far as the adsorptivity of the halogen atoms is concerned, the F and F_A(In⁺,Tl⁺) centers were found to change the nature of adsorption from physical adsorption to chemical adsorption. The adsorption energies were monotonically increasing functions of the electronegativity of the halogen and the amount of charge transferred from the defect-free surface. The calculated adsorption energies were explainable in terms of the electron affinity, the effective nuclear charge and the electrostatic potentials at the surface. The spin pairing mechanism played the dominant role in the course of adsorbate–substrate interactions and the KCl defect-free surface can be made semiconducting by F or F_A(In⁺,Tl⁺) surface imperfections.     

Optical absorption behavior of Tl<Superscript>+</Superscript> DOPED Rb(Br<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>I<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>) system

The optical absorption behavior of Tl⁺ doped Rb(Br_1–x I _x ) mixed crystals (with x = 0.00, 0.05, and 0.10) grown under vacuum by slow cooling from the melt has been studied. Absorption spectra of the mixed crystals recorded at room temperature showed that the characteristic A-absorption band of Tl⁺ ions in the Rb(Br_1–x I _x ) system (0.1 mol. %) with x = 0.00 (i.e., RbBr:Tl⁺) broadened with the iodine content towards the low energy side. Changes in the absorption spectra of the mixed crystals are due to creation of some complex centers involving Tl⁺, Br^–, and I^- ions with energy levels inside the band gap while forming the mixed crystal. The absorption spectra of gamma-irradiated mixed crystals showed the F-band, which shifted towards the low energy side due to the existence of iodine ions in the mixed crystals.     

Optical absorption spectrum of X-irradiated CaF2:Cr and SrF2:Cr

The optical absorption spectra of X-irradiated CaF₂:Cr and SrF₂:Cr are studied. X-irradiation induces the formation of a prominent band in the u.v. region (centered at 277 nm in CaF₂ and 285 nm in SrF₂) as well as a weak absorption in the visible region. Combined EPR and optical absorption measurements together with some optical bleaching experiments suggest that the u.v. absorption bands are related with either Cr⁺ or Cr³⁺ ions. Several arguments are presented in order to tentatively associate these bands with an interconfigurational transition of Cr⁺ in a cubal environment.     

Photoluminescence of a silver-doped glass

The absorption, emission and excitation spectra of Ag⁺ ions in a soda lime glass doped with two different concentration of silver are investigated. Absorption spectra exhibit a main broad band peaked at about 260 nm (4.77 eV) with a shoulder at about 227 nm (5.46 eV). The relative height of the shoulder depends on silver concentration in the glass. Emission spectra of Ag⁺ are dominated by an ultraviolet broad band at about 330 nm (3.76 eV). The excitation spectra for this emission show a preponderant broad band peaked at about 227 nm (5.46 eV) which coincides with peak position of the shoulder displayed in the optical absorption spectra. A weak broad featureless emission band centred at about 550 nm (2.25 eV) with an excitation peak at about 242 nm (5.12 eV) is tentatively related to an impurity from the host silica glass rather than originated in silver-type centres. Comparison of the luminescence decay curves for both emissions show substantial differences between them. Consequently, the emissions in the time-resolved spectra can easily be discriminated.     

Luminescence studies on gamma irradiated KCl: Ce crystals

This paper reports thermoluminescence(TL), optical absorption and TL emission studies that are made on Ce³⁺ doped KCl single crystals irradiated at room temperature. The glow curve and optical absorption studies indicate the participation of Ce³⁺ ions in the TL process. The TL study suggests the presence of low concentration of Ce³⁺ ions which reduces the TL efficiency with respect to pure KCl samples. On F bleaching γ irradiated crystals Z₁ centers are observed. A broader and strongly intense violet blue emission at 290, 370, 423 and 488 nm has been observed with 240 nm excitation. This emission has been attributed due to the transition from 5d(2D) excited energy level to the 4f¹ ground stable energy level (2F_5/2 and 3F_7/2) of Ce³⁺ doped KCl crystals.     

Optical and Conductivity Studies of Cr3+ Doped Polyvinyl Pyrrolidone Polymer Electrolytes

Abstract

Polymer electrolyte films of polyvinyl pyrrolidone (PVP) embedded with various concentrations of Cr³⁺ ions were prepared by a solution casting technique. The complexation between the Cr³⁺ ions and the polymer was confirmed by Fourier transform infrared (FTIR) spectroscopy and UV–vis spectroscopy. The electrical conductivity of the films was measured using an impedence analyzer in the frequency range of 42?Hz to 5?MHz at ambient temperature. It was observed that the conductivity increased with the increase in the Cr³⁺ ion concentration. UV–visible absorption spectra in the wavelength range of 200–800?nm were used to determine the direct and indirect optical energy band gaps and optical absorption edge. Both of the optical band gaps decreased with the increase in Cr³⁺ ion concentration. FTIR studies on pure and Cr³⁺ doped PVP polymer films revealed the vibrational changes that occurred due to the effect of the dopant Cr³⁺ ions in the polymer. Our results suggested that Cr³⁺, as a dopant, is a good choice to improve the electrical properties of PVP polymer electrolytes.     

First-Principles Study on the Electronic Structures for Y^3＋：PbWO4 Crystals

The possible defect models of Y^3＋：PbWO4 crystals are discussed by defect chemistry and the most possible substituting positions of the impurity Y^3＋ ions are studied by using the general utility lattice program （GULP）. The calculated results indicate that in the lightly doped Y^3＋ ：PWO crystal, the main compensating mechanism is [2Ypb^＋ ＋ VPb^2-], and in the heavily doped Y^3＋ ：PWO crystal, it will bring interstitial oxygen ions to compensate the positive electricity caused by YPb^＋, forming defect clusters of [2Ypb^＋ ＋Oi^2-] in the crystal. The electronic structures of Y3＋ ：PWO with different defect models are calculated using the DV-Xα method. It can be concluded from the electronic structures that, for lightly doped cases, the energy gap of the crystal would be broadened and the 420nm absorption band will be restricted; for heavily doped cases, because of the existence of interstitial oxygen ions, it can bring a new absorption band and reduce the radiation hardness of the crystal.     

Electron-lattice interaction in the absorption spectra of thallium doped alkali halides

The electron-lattice interaction of NaCl:Tl⁺, KCl:Tl⁺, KBr:Tl⁺, and KI:Tl⁺ is discussed using the moments of the absorption bands. The discussion is based on a theory ofToyozawa andInoue andHonma. Consistency of the data is found for the absorption measurements. An analysis of the band shift under applied stress shows for theA-band in KCl and KBr and for theA- andB-band in KI that the electronlattice coupling constants derived from these data assuming next neighbour interaction differ considerably from those derived from the second moments of the bands.     

Radiation induced defects in KBr:Tl+ crystals

The defects produced in KBr:Tl⁺ crystals during x-irradiation at 77 K were studied using thermoluminescence (TL), thermally stimulated currents (TSC), and absorption and emission spectra. Three main glow peaks at 165, 193 and 258 K were observed both in the TL and in the TSC curves. A variety of irradiation induced absorption bands were observed in the UV, visible and infrared up to about 2 microns. The 165 K TL peak was found to emit only the 440 nm band assigned to thallium dimers, while the peaks at 193 and 258 K exhibited the UV bands at 310 and 365 nm as well as the 440 nm band.The defects produced during the irradiation were the V_k hole center, the Tl° and the Tl⁺₂ electron centers. Smaller concentrations of Tl²⁺ and (Tl⁺)⁺₂ centers were also produced.An analysis of the results including measurements on lightly and heavily doped crystals enabled to draw conclusions on the nature of the defects and on the recombination processes involved. A close correlation has been found between the temperatures at which changes in the various absorption bands take place and the temperatures of the TL peaks. The analysis enabled also a full classification of the absorption bands.     

Anionische Silberzentren („B-Zentren“) in Alkalihalogeniden

It is proposed that negatively charged silver ions on anion sites are responsible for theB bands found in silver doped alkalihalides. Experimental investigations confirming this model of theB center are presented. Optical absorption and emission ofB centers were measured in seven alkalihalides in the temperature range from 450 to 4 °K. Configuration coordinate diagrams were obtained for KCl, KBr, and KI. A chemical method was used to determine the charge of theB center. Thermal or optical excitation causes theB centers to dissociate into neutral silver atoms andF centers. The Ag⁰ centers are bound to interstitial positions at low temperature. At high temperature they collect together forming colloidal centers. TetragonalB _A centers were formed during optical bleaching of theB band in mixed crystals of the type KCl+ΔNaCl. Their absorption and emission spectra, optical orientation, and polarized emission were investigated. These properties are shown to be similar to those ofF _A centers.B _A fluorescence polarized almost completely in the [100] direction was observed. A Jahn-Teller splitting of theB absorption band was resolved in RbCl at low temperature. The splitting confirms the configuration5s² for the Ag^? ion. The results are compared with those for the isoelectronic centers In⁺ and Sn⁺⁺. Thin films of alkalihalides containing small amounts of silver, copper, or thallium were condensed simultaneously with alkali vapor. New bands in the UV region were found, possibly due to Cu^? and Tl^? centers.     

Hydrogen maser atomic beam resonances

Au^? ions at anionic places are formed in gold doped crystals by a reducing treatment withF centers. The ultraviolet absorption consists of 4 bands, which are namedA, B, C, andD in analogy to the isoelectronic centers of the s² type, like Tl⁺. TheB band oszillator strength strongly increases with temperature in accordance with a phonon allowed transition. The ratio of the dipole strength of theC band to that of theA band as a function of the relative position of theB band is compared with Suganos prediction. Zero phonon lines are found at helium temperatures for theA band in NaCl (2,985 Å), KCl (3,068 Å), and KBr (3,145 Å) and for theC band in KCl (2,329 Å). In KCl the Huang-Rhys factor isg=3.4 for theA band. The vibronic structure comes from the relatively large radius 6s ² state of the negative ion. Uniaxial stress splits the zero phonon line. The results definitely agree with the stress splitting behaviour of a degenerateΓ ₁→Γ ₄ transition. Inversion symmetry of the center is confirmed by the absence of a linear Stark effect.     

Absorption,excitation and fluorescence spectra of thallium activated cesium bromide

Absorption, excitation and fluorescence spectra of T1⁺ doped cesium bromide have been investigated at various thallium concentrations. At very low thallium concentration two absorption bands are obtained at 225 nm and 264 nm. With rise of thallium concentration additional absorption bands are obtained at 230, 244, 258, 270 and 285 nm. A single bell-shaped fluorescence band at 357 nm in the ultraviolet region is obtained at low thallium concentration. Two additional visible fluorescence bands appear at 440 and 540 nm with rise in thallium content. The excitation spectra for ultraviolet emission band and visible emission bands are found to be different. Accordingly the ultraviolet emission band is attributed to the characteristic A emission in T1⁺ ion and the visible bands are attributed to dimer centers havingD _4h site symmetry.     

NMR study of both 19F and 205Tl motions in TlZrF5

Spin-lattice relaxation times in the laboratory T_l and rotating frames T_l? for both ¹⁹F and ²⁰⁵Tl nuclei were measured as a function of temperature. Comparison of the temperature dependence of longitudinal NMR relaxation rates of both ¹⁹F and ²⁰⁵Tl suggests that Tl⁺ ions are more mobile than F^? ones at high temperatures. Furthermore Fourier transform experiments show that two kinds of Tl⁺ ion can be distinguished at high temperatures, one of them being more mobile than the other one and probably responsible for the ionic conductivity of this material.     

Optical absorption in crystals and solutions of potassium halides with lead halide impurity

Using a spectrophotometric method of determining lead concentrations, the relation between the optical absorption of alkali-halide crystals with PbCl₂ impurity and that of the corresponding aqueous solutions was investigated. It was shown that the differences in the position of absorption maxima of (MHal_n)^m- complexes are determined by the effect of water molecules, and not by the structure of the complexes. It is established that the long-wave absorption band in the crystal (273 nm in KCl + PbCl₂) is due to the interaction of lead ions with anions, independently of the nature of the distribution of the impurity in the crystal.Translated from Izvestiya VUZ. Fizika, No. 12, pp. 71–76, December, 1971.