Electrolytic coloration and spectral properties of hydroxyl-doped potassium chloride single crystals

Hydroxyl-doped potassium chloride single crystals are colored electrolytically at various temperatures and voltages using a pointed cathode and a flat anode. Characteristic OH⁻ spectral band is observed in the absorption spectrum of uncolored single crystal. Characteristic O⁻, OH⁻, U, V₂, V₃, O²⁻-V_a⁺, F, R₂ and M spectral bands are observed simultaneously in absorption spectra of colored single crystals. Current-time curve for electrolytic coloration of hydroxyl-doped potassium chloride single crystal and its relationship with electrolytic coloration process are given. Production and conversion of color centers are explained.     

Electrolytic coloration of O2-doped NaCl crystals

O₂²⁻-doped NaCl crystals are colored electrolytically by using a pointed cathode and a flat anode at various temperatures and voltages, which mainly benefit from appropriate coloration temperatures and voltages as well as anode structure of used electrolysis apparatus. Characteristic OH⁻, U, V₂^m, U_A, V₂, V₃, O²⁻-V_a⁺ complex, F, R₁, R₂ and M absorption bands are observed in absorption spectra of the colored crystals. Production and conversion of color centers in electrolytic coloration is explained. Current-time curves for electrolytic colorations and their relationships with electrolytic colorations were given.     

CrO43- centers in NH4Al(SO4)2.12H2 O single crystals

Electron paramagnetic resonance and optical absorption spectra of radiation damage products of undoped and CrO₄^2- doped ammonium alum are studied. On X-irradiation at room temperature several paramagnetic species like CrO₄^3-, SO₃^? and O₃^? are formed in the doped crystals. In the undoped crystals SO₃^? and O₃^? are the major radiation damage products.     

Electrolytic coloration of air-grown sodium fluoride crystals

Air-grown sodium fluoride crystals were colored electrolytically by using a pointed cathode at various temperatures and electric field strengths, which should mainly benefit appropriate coloration temperatures and electric field strengths. , F, M, N₁, N₂ color centers and O²⁻-F⁺ complexes were produced in the colored crystals. Current-time curves for the electrolytic colorations were given, and activation energy for the V color center migration was determined. The formation of the color centers was explained.     

Creation and optical properties of stable and metastable hole-trapped centres in beryllium oxide

Abstract

The paper is devoted to study of formation mechanisms and optical absorption of the hole-trapped centers in neutron, electron-impulse and X-irradiated BeO crystals. V⁰ and V^? centers are found out to be formed as a result of neutron irradiation creating cation Frenkel pairs. Within the transient absorption decay kinetics, we registered a component whose thermal-time properties coincide with those of the luminescence of triplet self-trapped excitons. A number of absorption bands from the V_B center and exciton hole nucleus are interpreted as transitions between the O^? ion p-levels splitted by the crystal field, as well as polaron transitions and transitions into the valence band.     

Electrolytic coloration and spectral properties of OH-doped KBr polycrystals

OH⁻-doped KBr polycrystals were colored electrolytically by using a pointed cathode and a flat anode. Characteristic O⁻, OH⁻, U, Cu⁺ and absorption peaks were observed in resolved absorption spectrum of uncolored polycrystals. Herein the position of the absorption peak at room temperature was determined by using a Mollwo-Ivey plot. Characteristic V₂, V₃, Cu⁺, , I₂ and F spectral bands were observed in Kubelka-Munk functions of colored polycrystals. Current-time curve for electrolytic coloration of an OH⁻-doped KBr polycrystal and its relationship with electrolytic coloration process were given. Formation and conversion of color centers were explained.     

F<Stack> <Subscript>3</Subscript> <Superscript>−</Superscript> </Stack> molecular ions in fluoride crystals

The UV absorption spectra of F₃^? molecular ions in LaF₃, SrF₂, CaF₂, and BaF₂ crystals doped with rare-earth elements are studied. Comparison of radiation-colored and additively colored crystals reveals the absorption bands of F₃^? hole centers in the region near 6 eV. Nonempirical calculations of optical transitions agree well with experimental results.     

Electrolytic coloration and spectral properties of OH- and Cu-codoped NaCl crystals

OH⁻- and Cu⁺-codoped NaCl crystals are colored electrolytically by using a pointed anode and a flat cathode at various temperatures and under various voltages. Absorption and fluorescence spectral properties of colored crystals are investigated. Absorption, excitation and fluorescence spectra reveal existence of V₂, V₂^m, V₃, OH⁻, U, U_A, O²⁻–V_a⁺, O₂⁺, Cu⁺, Cu⁰, Cu⁻ and OH⁻-perturbed Cu⁺ color centers in colored crystals. Formations of color centers are explained.     

Kinetics of tunneling electron transfer between antimorphous defects in optical crystals with mobile cations

The experimental data on the transient optical absorption of wide-band-gap optical crystals of lithium borates Li₂B₄O₇, LiB₃O₅, and Li₆Gd(BO₃)₃ and potassium (KH₂PO₄ (KDP)) and ammonium (NH₄H₂PO₄ (ADP)) dihydrogen phosphates in the visible and ultraviolet spectral regions are analyzed using the theory of diffusion-controlled tunneling recombination. A nanosecond pulsed radiation action on these crystals is shown to form defect pairs, such as polaron-type hole centers and electron centers based on interstitial cations. The relaxation kinetics of these centers over a wide time range of 10^?8?10 s is described by a proposed model of tunneling electron transfer between antimorphous defects in the cation sublattice under the thermally stimulated mobility of recombination partners. The numerical values of the kinetic parameters are determined and the time dependences of the reaction rate constants are calculated for all crystals under study. As a result, the dynamics of change in the optical properties of these crystals under a pulsed radiation action can be simulated.     

Formation of H<Subscript><Emphasis Type="Italic">a</Emphasis></Subscript><Superscript>-</Superscript> hydrogen centers upon additive coloration of alkaline-earth fluoride crystals

The mechanism of coloration of alkaline-earth fluoride crystals CaF₂, SrF₂, and BaF₂ in calcium vapors in an autoclave with a cold zone is studied. It was found that the pressure in the autoclave upon constant evacuation by a vacuum pump within the temperature range of 500–800°C increases due to evaporation of metal calcium. In addition to the optical-absorption bands of color centers in the additively colored undoped crystals or to the bands of divalent ions in the crystals doped with rare-earth Sm, Yb, and Tm elements, there appear intense bands in the vacuum ultraviolet region at 7.7, 7.0, and 6.025 eV in CaF₂, SrF₂, and BaF₂, respectively. These bands belong to the H_a ^- hydrogen centers. The formation of hydrogen centers is also confirmed by the appearance of the EPR signal of interstitial hydrogen atoms after X-ray irradiation of the additively colored crystals. Grinding of the outer edges of the colored crystals leads to a decrease in the hydrogen absorption-band intensity with depth to complete disappearance. The rate of hydrogen penetration inside the crystal is lower than the corresponding rate of color centers (anion vacancies) by a factor of tens. The visible color density of the outer regions of the hydrogen-containing crystals is several times lower than that of the inner region due to the competition between the color centers and hydrogen centers.     

V color centers in electrolytically colored hydroxyl-doped sodium chloride crystals

Hydroxyl-doped sodium chloride crystals were successfully colored electrolytically by using pointed anode and flat cathode at various temperatures and under various electric field strengths. V₂ and V₃ color centers were produced in the colored crystals. Current-time curves for the electrolytic colorations were given, and activation energy for the V₂ and V₃ color center migration was determined. Production of the V₂ and V₃ color centers and formation of current zones for the electrolytic colorations of the hydroxyl-doped sodium chloride crystals are explained.     

The Formation of Dimeric Centers of Copper,Iron and Gadolinium in Modified Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript>

It is discovered that the electron paramagnetic resonance (EPR) spectrum of the doubly charged copper centers occurs in single crystals of Pb₅Ge₃O₁₁ doped with gadolinium or iron after annealing in an atmosphere containing chlorine and bromine. Similar annealing of the crystals doped with copper in a chlorine and fluorine atmosphere leads to redistribution of the intensities of the EPR spectra of two types of Cu²⁺ centers. The influence of annealing on the ongoing intensity of spectra of the dimeric triclinic centers Fe³⁺–A, Gd³⁺–A (where A represent Cl^?, Br^?, O^2?, F^?) was the subject of this research. Consideration is given to the mechanisms for changing the charge state and association of copper center with defects.     

Radiation-Induced Paramagnetic Centers in the Glasses Of CaO-Ga2O3-GeO2 System

The X-band (v ? 9.4 GHz) ESR spectra of the UV-, X-, and γ-irradiated glasses of CaO-Ga₂O₃-GeO₂ system with compositions similar to Ca₃Ga₂Ge₃O₁₂, Ca₃Ga₂Ge₄O₁₄, and Ca₃Ga₂O₆ crystals have been investigated at 300 and 77 K. It was shown that X- and γ-irradiation of the Ge-contained glasses induce simultaneously electron and hole paramagnetic centers, stable at room temperature. The UV-irradiation of Ge-contained glasses leads to the generation of stable centers of electron type, whereas the X- and γ-irradiation of glasses with Ca₃Ga₂O₆ composition induces stable hole centers, exclusively. The electron centers are assigned to E′ (Ge) centers with different local environments. ESR spectrum of hole centers is ascribed to O^? centers, localized on non-bridging oxygen of the glass network. The E′ (Ge) and O^? centers show high thermal stability in the CaO-Ga₂O₃-GeO₂ glass network. The obtained ESR spectra are described by spin Hamiltonian with g-factor of axial and rhombic symmetry for the E′ (Ge) and O^? centers, respectively. The nature, electron structure and some formation peculiarities of the radiation defects in CaO-Ga₂O₃-GeO₂ glasses are discussed in comparison with other glasses as well as Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ crystals.     

Photochemistry and reactions of OH− defects and F centers in Alkali Halides

Additively colored KCl:OH^? crystals show under combined UV and visible irradiation an irreversible destruction of F centers and visible absorption. This process, which is effective over the whole temperature range 4–300 K, was studied systematically in terms of the reaction efficiency and products using UV-visible and IR (local mode) spectroscopy. The UV photo-dissociation of OH^? defects and photo-ionization of F centers produce a combined net effect, in which at higher temperatures all F centers are converted into U centers, thus completely bleaching the colored crystal. By these photo-reactions, high contrast visible images can be produced which are stable under visible light at RT, and are thermally stable up to 650°C. Besides the optical information-storage aspect, these photo-reactions can be used for controlled production of U_A centers if the crystal contains alkali-ion impurities like Na⁺.     

Observation of ultra-long lifetime UV-induced infrared absorption in undoped and magnesium-doped congruent lithium niobate crystals

We report experimental observation of ultra-long lifetime UV-induced absorption in undoped and 5 mol.% Mg-doped congruent lithium niobate crystals between 400 nm and 2500 nm wavelength range. The saturated absorption coefficient change in undoped congruent lithium niobate was about 3 to 7 times that in Mg-doped congruent lithium niobate in the mid-infrared spectrum. The UV-illuminated LiNbO₃:Mg was fully recovered in the dark after 2 days, whereas the undoped congruent LiNbO₃ still exhibited nontrivial infrared absorption. We attribute the cause of the UV-induced absorption to the creation of hole-trapped intermediate states O⁻ near lithium vacancies.     

Temperature behavior of the 6.05-eV band in optical absorption spectra of oxygen-deficient corundum

The effect of temperature on the 6.05-eV absorption band in α-Al₂O₃ has been studied in the 80–515 K region. The data obtained are analyzed in terms of a one-coordinate model with strong electron-phonon coupling. This band is shown to be formed by two peaks at 5.91 and 6.22 eV (T=293 K) originating from absorption at the F ⁺ and F centers, respectively. An analysis of the experimental temperature dependences has allowed us to calculate the energies of effective phonons responsible for the broadening and shift of the peaks. The energies calculated agree with the data obtained in other studies and lie in the region of corundum acoustic-vibration frequencies. The Huang-Rhys factors have been evaluated for both centers and found to be close to the estimates made by other authors. The results are discussed in detail and compared with independent data on optical absorption and luminescence of anion centers in colored and irradiated α-Al₂O₃ single crystals.     

Radiation-induced paramagnetic centers in Ca3Ga2Ge4O14 crystals

Studies of EPR spectra, additional optical absorption, and the kinetics of buildup and decay of radiation-induced paramagnetic centers in compositionally disordered crystals of trigonal Ca-gallogermanate are reported. The parameters of the spin-Hamiltonian describing the observed room-temperature EPR spectra are determined. It is established that the radiation-induced paramagnetic centers in Ca₃Ga₂Ge₄O₁₄ crystals are O⁻ centers in common 6g sites stabilized by the Ge⁴⁺ vacancy in tetrahedral 2d sites. Fiz. Tverd. Tela (St. Petersburg) 39, 1044–1049 (June 1997)     

Elastic strain and coloration pattern in natural quartz crystals

Very small elastic strains (tilts of the order of 0.25 sec of arc and dilationsΔd/d?10^?6, whered is the spacing of net planes) have been observed in natural quartz crystals. According to their rocking curves which are of almost theoretical width, these crystals were commonly expected to be practically perfect crystals. On double crystal X-ray topographs a pattern was revealed of uniformly strained layers parallel to the rhombohedron faces (10¯11) and with thickness ranging between 20 and 200 microns. This fine structure strain pattern was correlated to the pattern of the optical coloration which could be produced by irradiating the originally transparent crystals with X-rays. A localincrease of coloration matched with a localcontraction of the lattice. Tilts occurred in transition zones between adjacent layers with slightly different lattice spacings. Strain and coloration patterns probably have as a common cause the deposition of layers with different impurity concentrations during the growth process of the crystals. Although no change of the strain as a result of the X irradiation could be detected in the colored layers in particular, experimental evidence has been found for anoverall expansion of the lattice of the order ofΔd/d?5×10^?7 due to X irradiation. This expansion seems to saturate at this low value and is probably caused by electronic processes connected with the coloration. Some aspects concerning the nature of the color centers have been discussed. It seems likely from the results of the strain measurements that both sets of layers, colored and transparent ones, play a combined role in coloration.     

Oscillator strength of electron-type color centers in KCl single crystals irradiated with electrons and protons

The absorption spectra of KCl single crystals irradiated with electrons and protons at energies of 15 and 100 keV and a particle flux ranging from 5×10¹² to 10¹⁵ cm^?2 are investigated. The absorption bands attributed to simple (F, F _a, K) and complex (M, R ₂, R ₄, N) color centers are identified in the spectra. The correlation dependences of the absorption coefficients for M, R ₂, and R ₄ centers on the absorption coefficient of F centers and the correlation dependences of the absorption coefficients for R ₂ and R ₄ centers on the absorption coefficient of M centers are established. The oscillator strengths are calculated for M, R ₂, and R ₄ color centers.     

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.