Spatial structures based on color centers created by electrons in lithium fluoride crystals: Absorption and luminescence characteristics

We have shown that in spatial structures based on color centers created by electrons in a lithium fluoride crystal, the distances between centers reach 1.6 nm and 3.6 nm for F₁ and F₂ centers respectively. This suggests considerable potential opportunities for using electron technology to form structures in the crystals with spatial resolution of such an order of magnitude. We measured the decrease in fluorine content on the irradiated surface of the crystal. We found the concentrations of F₁, F₂, F₃⁺, F₃(R₂), and F₄(N₁) centers. We established that the specific characteristics of color center formation by electrons leads to an increase in the efficiency of creation of F₃ and F₄ centers. We determined the decrease in the average luminescence lifetimes of F₂ and F₃⁺ centers as a result of concentration quenching. We observed distortion of the luminescence contour for F₂ centers as a result of absorption of its short-wavelength portion by other centers and emission of radiation by the latter in its long-wavelength portion. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 102–110, January–February, 2008.     

Spectroscopic characteristics of anionic centers in α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> crystals bombarded by Cu<Superscript>+</Superscript> and Ti<Superscript>+</Superscript> ions

We have studied the effect of bombardment by Cu⁺ and Ti⁺ ions with energy 30 keV on the optical absorption and luminescence of F centers in oxygen-deficient aluminum oxide. We have shown that in the induced optical absorption spectra there are six components of gaussian shape, which can be assigned to absorption bands of F⁺, F², and F₂⁺ centers. We have established that bombardment of the samples by ion beams has a weak effect on the thermoluminescence parameters in the 3.0 eV and 2.4 eV bands, while in the 3.8 eV luminescence band for F⁺ centers, the thermoluminescent response increases considerably. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 422–424, May–June, 2008.     

Radiation-induced color centers in the near-surface layer of lithium fluoride crystals

For radiation-induced intrinsic color centers, we show that the concentrations of identical centers and the concentration ratios of different centers are quite different in the near-surface layer and within the interior volume of a lithium fluoride crystal. We have established that these differences also depend on the sign of the difference between the temperature at which the crystal was irradiated with γ photons and the vacancy mobility temperature. We provide an interpretation for the results obtained, based on the structural features of the near-surface layer and the concentration ratio of vacancies and electrons in the layer, serving as the starting components for color center formation. We found that the concentrations of centers change over the course of a few days by tens of percent in the layer “emerging” from the interior onto the surface as a result of cleavage of the crystal. We measured the luminescence lifetimes of F₃ (R2) and F₄ centers: 6.6 nsec and 11.7 nsec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 775–781, November–December, 2006.     

The absorption spectrum of radiation-colored SrCl2-Ce crystals

We investigate the spectra of the x-ray radiation-induced absorption of SrCl₂−Ce crystals over the spectral range 345–830 nm and their temperature transformations in the interval from 77 to 450 K. We found that radiative color centers are characterized by a complex spectrum of induced absorption that contains wide bands of photochromic PC (750, 519, 378 nm) and PC⁺ (620, 446, 340 nm) centers and quasi-linear bands of Ce²⁺ centers. The most significant thermal transformations of radiative color centers occur in the vicinity of the thermostimulated luminescence peak of 394 K, at which the holes of the PC⁺ centers recombine with the electrons of the Ce²⁺ centers. Ivan Franko L’vov State University, 8, Kirilla i Mefodiya St., L’vov 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 545–547, July–August, 1997.     

Characteristic features of thermoluminescence kinetics in dosimetric aluminum oxide crystals

We have studied the thermoluminescence curves in the 420 nm band (F centers) and the 330 nm band (F⁺ centers) within the temperature range of the dosimetric peak (T_max = 450 K) in anion-deficient aluminum oxide crystals. Assuming general-order kinetics, we have analyzed the thermoluminescence decay curves on the rising and falling sides of the dosimetric peak, in samples with different degrees of deep trap filling. We have established differences in the order of the kinetics within different temperature ranges of the dosimetric peak. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 187–190, March–April, 2006.     

Luminescence of aggregate centers in CsBr:Eu2+ single crystals

We have used the Bridgman method to grow CsBr:Eu²⁺ single crystals, adding an activator to the mix in the form of Eu₂O₃ in amounts of 0.0125, 0.0250, and 0.0500 mole %. At T = 300 K, we studied the absorption spectra, the photoluminescence (PL) spectra, and the photostimulated luminescence (PSL) spectra of the grown crystals. We have established that the structure of the photoluminescence and photostimulated luminescence centers in crystals grown from the CsBr:Eu₂O₃ mix includes isolated dipole centers Eu²⁺-V_Cs, emitting in bands with maxima at 432 nm and 455 nm respectively, and in crystals grown at activator concentrations of 0.025 and 0.050 mole % they also include aggregate centers (AC) based on CsEuBr₃ nanocrystals with emission bands at 515 m and 523 nm. We have shown that the maximum concentration of aggregate centers of the CsEuBr₃ nanocrystal type in CsBr:Eu²⁺ crystals is achieved for an activator content in the mix within the range 0.01–0.05 mole %. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 359–362, May–June, 2006.     

Spectroscopy of F 3 + -color centers in lithium fluoride crystals (review)

Results of investigations of radiative F ₃ ⁺ -color centers in lithium fluoride obtained by the methods of one- and two-photon absorption, polarization spectroscopy, and luminescence in singlet, triplet and triplet-singlet channels are reported. The scheme of energy levels of the F ₃ ⁺ -center is revised. The probabilities of singlet-triplet conversion and the rates of depletion of the lower triplet state in the range of 80–350 K are presented. Recommendations are given on the technology of radiative LiF coloration that provide an increase in the F ₃ ⁺ -center concentration and a decrease in the concentration of some other centers that prevent lasing on the LiF:F ₃ ⁺ active medium from being obtained. The phototransformations of color centers in LiF are analyzed. The parameters of lasers with LiF:F ₃ ⁺ active media that provide generation of radiation tunable in the green region of the spectrum are considered. Based on spectroscopic data the maximum attainable time characteristics of such lasers are discussed. The prospects for further investigations of LiF:F ₃ ⁺ lasers are outlined in brief. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 5, pp. 745–760, September–October, 1998.     

Analysis of the latent structure of luminescence and absorption spectra of thallium complexes

Comprehensive investigations of luminescence, excitation, and absorption spectra as well as of the luminescence kinetics of a frozen LiCl-Tl⁺ solution are carried out. It is established that the luminescence spectrum consists of four components. One component is caused by luminescence of the matrix and the remainder by luminescence of one luminescence center, namely, by the saturated complex of thallium TlCl₂(H₂O)Cl₄. The absorption spectrum consists of three components. Their parameters have been evaluated. Each component of the luminescence spectrum is excited in several components of the absorption spectrum. It is found that the luminescence spectrum components and their intrinsic absorption bands are located differently on the frequency axis. These data are similar to those obtained for other activated solutions of electrolytes. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 75–78, January–February, 2000.     

Luminescence of short-lived color centers induced in LiF crystals by a pulsed microwave discharge

A new phenomenon — intense luminescence of noncolored lithium fluoride (LiF) crystals excited by an electrodeless pulsed microwave discharge at the prebreakdown stage of development — is observed. This luminescence consists of the luminescence of short-lived aggregate F₂ and F ₃ ⁺ color centers at room temperature. It is shown that the density of short-lived color centers induced in the surface layer of LiF crystals by a microsecond microwave discharge reaches values of ∼10¹⁹−10²⁰ cm⁻³. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 163–167 (10 August 1997)     

Luminescence of CsBr:Eu films grown by liquid-phase epitaxy

By liquid-phase epitaxy from an aqueous alcoholic solution, we have obtained films of the well-known storage phospor CsBr:Eu, and we have studied their cathodoluminescence and photoluminescence (PL) spectra compared with the undoped CsBr films. We have established that the structure of the photoluminescence centers of the CsBr:Eu films when excited by laser radiation in the absorption band of the Eu²⁺ ions (λ = 337 nm) includes Eu²⁺-V_Cs isolated dipole centers and CsEuBr₃ aggregate centers, and also luminescence centers based on inclusions of hydroxyl group OH⁻ with the corresponding emission bands in the 440 nm, 520 nm, and 600 nm regions. We have studied the dependence of the spectra and the intensity of the photoluminescence for CsBr:Eu films on annealing temperature in air at 423–483 K, compared with analogous dependences for CsBr:Eu single crystals obtained from the melt. We have shown that annealing the films at T = 423–463 K leads to rapid formation of CsEuBr3 aggregate luminescence centers, while for T > 473 K thermal degradation of these centers occurs. We conclude that the observed differences between the photoluminescence spectra of CsBr:Eu films and CsBr:Eu single crystals may be due to additional doping of the films with OH⁻ ions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 191–194, March–April, 2006.     

Thermoluminescence of corundum containing anion defects following ultraviolet laser and x irradiation

The thermoluminescence of single crystals of corundum containing anion defects following x-ray and laser excitation is investigated. Its features in the luminescence bands of F, F⁺, and Cr³⁺ centers are studied. Synchronous measurements of the thermoluminescence and thermally stimulated exoelectron emission are performed by the fractional glow technique following x-ray and laser excitation of the samples. It follows from the results obtained that several traps are active in the temperature range of the principal dosimetric peak (400–500 K). The spectral sensitivity curve contains maxima corresponding to absorption bands of F, F⁺, and Al _i ⁺ centers. A possible mechanism for the recombination luminescence of F centers is discussed. It is found that the material exhibits high sensitivity to small doses of ultraviolet laser radiation. Zh. Tekh. Fiz. 67, 72–76 (July 1997)     

Aggregate color center formation processes in lithium fluoride crystals after irradiation

Lithium fluoride crystals were irradiated by different doses of gamma photons at a temperature of 77 K. We measured the aggregation kinetics for the color centers with different annealing temperatures above the temperature of anion vacancy mobility. We show that the lifetimes of the vacancies decrease while the lifetimes of the F₂⁺ F_2^{+} centers increase as the irradiation dose increases. We explain these types of dependences based on the aggregation processes for color centers in the post-radiation period. We determine the time constants and energies (analogous to activation energies in the Arrhenius equation) for the various processes involving rise and fall in the concentration of aggregate color centers. Based on the experimental data obtained, we have established the processes forming F ₂ and F₃⁺ F_3^{+} centers in the post-radiation period. The F ₂ centers are formed when vacancies ν_a add to F₁^- F_1^{-} centers. Vacancies arising during irradiation of the crystal participate in their creation in the first fast stage. In the long final stage, vacancies are used which appear in the post-radiation period on occurrence of the reaction F₂⁺ F_2^{+} + H → ν_a + fluoride ion at the lattice site, where H is an interstitial fluorine atom. The F₃⁺ F_3^{+} centers are formed both by merging F₂⁺ F_2^{+} and F ₁ centers and as a result of addition of vacancies to F ₂ centers. In this case, vacancies are used that are generated not only during irradiation of the crystal but also in the post-radiation period. The rise in the concentration of F₃⁺ F_3^{+} centers occurs faster than the rise in the concentration of F ₂ centers.     

Spectral luminescence properties of Eu(III) complexes with tetracycline antibiotics and hydrogen peroxide

We have studied the spectral luminescence properties of mixed-ligand complexes of Eu(III) ions with tetracyclines and hydrogen peroxide. We have established that incorporation of hydrogen peroxide into the inner sphere of these complexes leads to a significant increase (by a factor of 10–25) in the intensity of luminescence of the Eu(III) ions, redistribution of the intensities of the ⁵D₀ → ⁷F_j transitions, in particular to an anomalous increase in the intensity of the band for the forbidden transition ⁵D₀ → ⁷F₀. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 310–314, May–June, 2007.     

Recombination luminescence of CaSO4:Tb3+ and CaSO4:Gd3+phosphors

A comparative study of the excitation of luminescence by VUV radiation as well as of thermally and photostimulated luminescence has been carried out for CaSO₄:Tb³⁺ and CaSO₄:Gd³⁺ phosphors, where Na⁺ or F⁻ ions are used for charge compensation. The distinction in hole processes for the phosphors with Na⁺ or F⁻ compensators is determined by the differing thermal stability of the holes localized at/near Tb³⁺Na⁺ and Gd³⁺Na⁺ (up to 100–160 K) or at/near Tb³⁺F⁻ V _Ca and Gd³⁺F⁻ V _Ca centers involving also a cation vacancy (up to 400–550 K). Tunnel luminescence in the pairs of localized electrons and holes nearby Tb³⁺ or Gd³⁺ has been detected. The mechanisms of electron-hole, hole-electron and tunnel recombination luminescence as well as a subsequent released energy transfer to RE³⁺ ions are considered.     

Luminescence efficiency of aromatic carboxylates of europium and terbium when methylene bridges and nitro groups are present in the ligands

We discuss the possibility of optimizing the brightness of luminescence for phenylcarboxylates, naphthylcarboxylates, and indolylcarboxylates of europium and terbium and their adducts with 1,10-phenanthroline and 2,2′-bipyridine by modifying the ligands. We have studied the efficiency of luminescence and luminescence excitation. We consider the effect of blocking energy transfer from the ligands to the Eu³⁺ and Tb³⁺ ions by methylene (-CH₂-) bridges dividing the π-electron system of the ligands into two parts and by the electronacceptor nitro group (-NO₂). We have analyzed the pathways for transfer and degradation of the excitation energy at 77 K and 300 K. From the phosphorescence spectra of gadolinium salts, we have determined the energies of the lowest excited triplet states of the ligands. We consider the effect of the relative positions of the triplet levels of the ligands and the excited levels of the Eu³⁺ and Tb³⁺ ions on the luminescence efficiency. We found channels for dissipation of the excitation energy via the ππ* and nπ* states of the aromatic system of the carboxylate and the NO₂ group. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 48–54, January–February, 2007.     

Luminescence of europium and ytterbium ions in strontium hexaborate

We have studied the luminescent properties of Eu^2+/3+ and Yb²⁺ ions in strontium hexaborate SrB₆O₁₀ for excitation in the 120–400 nm region. The luminescence spectra of Ln²⁺ ions in SrB₆O₁₀ consist of overlapping bands in the 370–520 nm region, due to 5d → 4f transitions at several nonequivalent centers. In the excitation spectra, besides the bands associated with 4f → 5d transitions in the Ln²⁺ ions, we also observe a band in the 135–160 nm region due to the transitions O(2p) → B(2s,2p) within the borate anions. The luminescence of the Eu³⁺ ions is excited most efficiently in the region of the Eu³⁺ charge transfer band (λ_max = 226 nm). The results obtained are compared with data for Ln in other strontium borates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 770–774, November–December, 2006.     

Effect of finely dispersed platinum on the structure of luminescence spectra of the adsorbates of magnesium phthalocyanine on silicon dioxide

The luminescence and excitation spectra and kinetic characteristics of the luminescence of the adsorbates of magnesium phthalocyanine (MgPhc) on SiO₂ and the effect on them of surface hydration and finely dispersed platinum are studied. It is found that a structure that improves hydration of the adsorbent surface appears on the platinized surface in the luminescence and excitation spectra. It is assumed that the spectral structure is due to the complexes of MgPhc formed with water molecules, the hydroxyl cover of the surface, and the surface centers of SiO₂ modified by a Pt-catalyst. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 552–555, July–August, 1999.     

Time-resolved spectroscopy of natural and synthetic BeO crystals

The results of comparative luminescence investigation of natural and synthetic BeO crystals are presented. Time-resolved luminescence (2.5–8 eV) and luminescence excitation spectra, and the kinetics of glow decay were measured using ultraviolet-vacuum-ultraviolet (VUV) synchrotron radiation (5–22 eV) or x-radiation (50–620 eV or 3–62 keV) ranges. X-ray and thermostimulated luminescence of natural BeO crystals were compared to the glow of additively colored synthetic crystals. The characteristic luminescence of F and F ⁺ centers was found in natural crystals. In synthetic crystals similar luminescence is observed only after additive or radiation coloration by virtue of the creation of F ⁻ and F ⁺ centers on anion vacancies. The defects found in the crystal lattice of a natural BeO crystal testify to the degree of mineral metamictization of the given deposit.     

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.