The origin of 3.55 eV emission band of RbCl:Tl

Fluorescence spectra of KCl:Tl, RbCl:Tl and NH₄Cl:Tl under A band excitation at room temperature (300 K) and liquid nitrogen temperature (77 K) have been re-examined in order to ascertain the origin of the 3.55 eV emission band of RbCl:Tl. The emission band at RT is found to show two components and the weaker component becomes dominant at LNT. The observations are explained in terms of Patterson's model of two local environments for Tl⁺ ion. One of them is a Tl⁺ having local CsCl like environment. The 3.55 eV emission band at 300 K is assigned to electronic transition in the Tl⁺ having local CsCl like environment.     

Compound synthesis in TiO2 implanted with Rubidium

Rubidium ions, with energy in the range 0.1 MeV, 2.0 MeV have been implanted in TiO₂ single crystals at RT and LNT.

Defects induced by implantation have been studied by optical spectroscopy, X-ray diffraction, RBS, TEM and electrical conductivity.

During implantation, the implanted samples are blue colored after irradiation. This coloration is due to an optical absorption band localized at 900 nm which corresponds to optical transition of intrinsic defects identified as Ti³⁺. These defects are induced by a chemical reaction between the implanted ions and the oxygen of the lattice as in the case of D⁺, H⁺, Li⁺, Na⁺ and K⁺ implanted in rutile.^1-3

The synthesis of a new phase in heavily implanted rutile is exhibited by using a thermal treatment and by combining techniques such as RBS, TEM and X-ray diffraction at glancing angle in the temperature range 300°C-700°C.

This compound does not correspond to metallic precipitates of rubidium which are observed in MgO implanted with Rb ions.

Planar defects have been observed in the implanted area. A correlation is exhibited between these defects and the precipitates of the new phase. From X-ray diffraction measurements and TEM observations, the composition of the synthetized compound is likely Rb₂TiO₃.     

Luminescence and defects creation under photoexcitation of CsI : Tl crystals in Tl-related absorption bands

Characteristics of the defects created at 4.2 K by the UV-irradiation of CsI : Tl crystals in the Tl⁺-related absorption bands (by photons of 5.8-4.8 eV energy) have been studied. The dependences of the intensities of the thermally stimulated luminescence peaks appearing near 60, 90 and 125 K and of the recombination luminescence photostimulation bands peaking at 2.35, 1.92, 1.33 and 0.89 eV on the irradiation energy and duration, uniaxial stress and thallium concentration have been examined. The mechanisms of the processes, responsible for the appearance of the intense visible (2.55 and 2.25 eV) luminescence of excitons localized near Tl⁺ ions and creation of defects pairs of the type of Tl⁰-V_K and Tl⁺-V_K with various distances between the components, have been discussed.     

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.     

Comparison of the Kinetics of the Exchange Mechanism of the Thallium Ion with 18C6 and with Pentaglyme in Acetonitrile Solutions

Abstract

In acetonitrile solutions, the exchange reaction is bimolecular in the Tl⁺ + 18C6 system, while in the Tl⁺ + pentaglyme system the associative-dissociative and the bimolecular mechanisms coexist at room temperature and the bimolecular exchange reaction dominates at 263° K. For the bimolecular mechanism in the case of Tl⁺ + 18C6 and the associative-dissociative mechanism in the case of Tl⁺ + pentaglyme, the activation energies of the exchange reactions change with temperature. At 298° K, in the Tl⁺ + 18C6 system the activation energy for the bimolecular exchange reaction is ≈ 2 kcal.mol^?1 and exchange rate constant (k₁) is (4.1 ± 0.1) × 10⁷ s^?1mol^?1; in the Tl⁺ + pentaglyme system, the activation energy for the associative-dissociative exchange reaction is ≈ 5 kcal mol^?1 and the decomplexation rate constant (k_?2) is (2.2 ± 0.4) X 10⁵ s^?1. The activation energy for the bimolecular exchange in the Tl⁺ + pentaglyme system was determined to be 3.00 ± 0.05 kcal.mol_?1 and the exchange rate constant (3.0 ± 0.1) X 10⁸ s^?1 mol^?1.     

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.     

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.     

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.     

Atomic 6p-Tl0 centers in ferroelectric Rb2ZnCl4 crystals

Abstract

Several Tl⁰ (6s²6p ¹)-type paramagnetic centers, produced by low temperature X-ray irradiation, were observed and studied by electron spin resonance (ESR) in the orthorhombic ferroelectric phase of thallium doped Rb₂ZnCl₄ crystals. The centers were formed by electron trapping at Tl⁺ ions localized substitutionally at Rb⁺ sites. The number and properties of the observed centers account for the tripling of the unit cell in the ferroelectric phase.     

Mn2+ and Tl+ luminescence in β-aluminas

The compounds AGa₁₁O₁₇ (A = K, Rb, Cs) and AAl₁₁O₁₇ (A = Na, K, Rb) have the β-alumina structure. The Mn²⁺-activated gallates show efficient luminescence under 254 nm excitation with an emission peaking at 498 nm and a quantum efficiency up to 70%. The Tl⁺-activated aluminates show efficient luminescence under 254 nm excitation with an emission peaking at 380–390 nm and a quantum efficiency up to 70%. In AAl₁₁O₁₇: Tl⁺ energy is transferred from Tl⁺ to Mn²⁺, resulting in an emission peaking at 512 nm with a quantum efficiency up to 55%.     

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.     

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)     

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.     

Luminescence and energy migration in a two-dimensional system: NaEuTiO4

Energy transfer processes in compounds NaGd_1-xEu_xTiO₄ (0 < x ? 1) have been evaluated. It is shown that in these compounds energy migration to quenching centres occurs down to the lowest temperatures if x > 0.3. Transfer from intrinsic Eu³⁺ ions to extrinsic Eu³⁺ ions has been observed. The nature of quenching centres and trap centres has been clarified. The characteristics of the energy migration processes can be explained using a two-dimensional diffusion model. The temperature dependence of the hopping rate can be explained assuming phonon-assisted energy transfer.     

Diode-pumped colour-centre lasers tunable in the 1.5 µm range

Under pumping with a 990 nm, 1 W laser diode, continuous-wave (cw) tunable laser emission in the 1.5 µm wavelength range was obtained from two different colour centres: Tl⁰(1) in NaCl:Tl⁺ and (F ₂ ⁺ )_H in NaCl:OH^–. The results are compared to those recently obtained with a similar apparatus and Tl⁰(1) centres in KCl:Tl⁺. The highest output power (30 mW) and the broadest tuning range (1.48–1.68 µm) were achieved with (F ₂ ⁺ )_H centres.     

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.     

Ion implantation damage and crystalline-amorphous transition in Ge

Experimental studies on the damage produced in (100) Ge substrates by implantation of Ge⁺ ions at different energies (from 25 to 600 keV), fluences (from 2×10¹³ to 4×10¹⁴ cm⁻²) and temperature (room temperature, RT, or liquid-nitrogen temperature, LN₂T) have been performed by using the Rutherford backscattering spectrometry technique. We demonstrated that the higher damage rate of Ge with respect to Si is due to both the high stopping power of germanium atoms and the low mobility of point defects within the collision cascades. The amorphization of Ge has been modeled by employing the critical damage energy density model in a large range of implantation energies and fluences both at RT and LN₂T. The experimental results for implantation at LN₂T were fitted using a critical damage energy density of ∼1 eV/atom. A fictitious value of ∼5 eV/atom was obtained for the samples implanted at RT, essentially because at RT the damage annihilation plays a non-negligible role against the crystalline–amorphous transition phase. The critical damage energy density model was found to stand also for other ions implanted in crystalline Ge (Ar⁺ and Ga⁺).     

Pre-resonant enhancement of the Raman scattering from KI:Tl+

E_g and T_2g spectra at room and nitrogen temperature at several laser wavelengths are reported for KI:Tl⁺. As resonance with Tl⁺ -absorption bands is approached the optic phonon parts of the spectra are enhanced relative to the acoustic phonon parts, and distortions occur within the acoustic and optic parts of the spectra. A model for the scattering is employed which involves electron-phonon coupling to nearest and nn neighbors. Exchange and crystal field contributions to the electron-phonon coupling are distinguished.     

Electrical conductivity and colour centres in Tl-doped KCl crystal

The electrical conductivity and optical absorption of potassium chloride crystals doped with different concentrations of thallium have been measured before and after X-irradiation. The optical absorption spectrum exhibits the characteristic Tl⁺ ion band at 247 nm. The extrinsic conductivity and the absorption coefficient at 247 nm increase with impurity addition upto a certain concentration. Further increase in impurities decreases them. Room temperature X-irradiation decreases the Tl⁺ ion band and produces the F band. F centre concentration is higher in lightly doped crystal compared to pure or heavily doped KCl. These results have been interpreted in terms of formation of interstitial potassium ions and positive ion vacancies in the Tl-doped KCl lattice due to large ionic radius of Tl⁺ ions. The impurity ions precipitate into TlCl phase when the doping is heavy.