Cluster centers in forsterite laser crystals Mg2SiO4 : Cr and Mg2SiO4 : Cr : Li

The structures of chromium-containing cluster centers in forsterite laser crystals Mg₂SiO₄ : Cr and Mg₂SiO₄ : Cr : Li have been simulated using the interatomic potential method. A system of position-dependent parameters of interatomic interaction potentials in forsterite has been developed. In the ionic approximation, this system adequately describes the structure, properties, and defects of the crystal with correct representation of the preferred positional arrangement of chromium ions. The preferred mechanisms of chromium dissolution in forsterite crystals have been evaluated from a comparison of the energies of formation of chromium-containing clusters with different configurations. It has been demonstrated that the results of the simulation of interatomic interaction potentials are consistent with the experimental data obtained from electron paramagnetic resonance and optical spectroscopy studies.     

Effects of annealing treatment and gamma irradiation on the absorption and fluorescence spectra of Cr:GSGG laser crystal

The influence of annealing treatments and gamma-ray irradiation on the absorption and fluorescence spectra of Cr:GSGG crystals grown by the Czochralski method has been investigated. Two absorption bands located near 686 nm and 1050 nm were weakened markedly after the crystal was re-annealed in H₂ atmosphere, which is due to the Cr⁴⁺ ions being de-oxidized into Cr³⁺ ions. The other two weak additional absorption bands induced by gamma-ray irradiation appearing near 310 nm and 480 nm are ascribed to the Fe²⁺ ions and F-type color centers, respectively. In particular, the gamma-ray irradiation with a dose of 100 Mrad has an effect of improving slightly the luminescence properties of Cr:GSGG crystals. The improvement mechanism is analyzed and discussed.     

Interaction of impurity and intrinsic defects in forsterite and its role in the formation of spectral and luminescence properties

This paper reports on the results of investigations of the coefficients of chromium distribution between a crystal and a melt of forsterite, the absorption and luminescence spectra, and the electron paramagnetic resonance spectra of chromium centers in Mg₂SiO₄: Cr, Mg₂SiO₄: Cr: Sc, and Mg₂SiO₄: Cr: Li crystals. It has been established that the concentration dependences of these properties vary upon changing over from the range of trace concentrations of chromium, scandium, or lithium impurities in the melt to the range of higher concentrations of these impurities. The observed phenomenon is explained by the interaction of impurities with intrinsic defects of the crystal, which is called as the microimpurity trapping effect. According to the performed estimations, the concentration of predominant intrinsic defects (magnesium Frenkel defects) in the forsterite crystals grown from the melt is equal to (7.5 ± 0.3) × 10⁻⁶ atomic fractions. The energy of the formation of magnesium Frenkel defects can be estimated as 4.2 ± 0.2 eV.     

Study of divalent and trivalent chromium in forsterite by high-frequency EPR spectroscopy

Divalent and trivalent chromium ions Cr²⁺ and Cr³⁺ replacing magnesium ions at octahedral positions in Mg₂SiO₄: Cr and Mg₂SiO₄: Cr: Li crystals are investigated by submillimeter EPR spectroscopy in the frequency range 65–230 GHz. The crystals are grown from the melt by the Czochralski method. The content of mixed-valence chromium species in forsterite is analyzed. It is demonstrated that, in crystals grown in argon (the oxygen partial pressure is \(P_{O_2 } \) = 0.01 kPa), approximately half of the chromium ions are in the divalent form. The Cr²⁺ ions are distributed over the M1 and M2 positions in a ratio of approximately 2: 1. A change in the oxygen partial pressure \(P_{O_2 } \) and the chromium concentration, as well as an additional doping with lithium, does not lead to substantial changes in the distribution of divalent chromium ions over the positions. It is shown that an increase in the oxygen partial pressure \(P_{O_2 } \) from 0.01 to 2.00 kPa results in a decrease in the coefficient of divalent chromium distribution between the crystal and the melt. Doping with lithium also decreases the concentration of Cr²⁺ centers. In crystals grown without lithium, approximately half of the trivalent chromium ions are associated with magnesium vacancies. The addition of lithium leads to the destruction of these associates, an increase in the concentration of individual Cr³⁺ centers, and the formation of lithium associates with trivalent chromium ions. The conditions for the formation of associates of trivalent chromium ions with lithium ions are optimum when the crystal contains approximately identical amounts of Cr³⁺ and Li⁺ ions. Doping with lithium increases the concentration of Cr³⁺ ions and, thus, decreases the fraction of Cr²⁺ and Cr⁴⁺ ions in the total content of chromium centers.     

Simulation of the structure of oxygen hole centers in Mg2SiO4 and Mg2SiO4: Cr forsterite crystals by the interatomic potential method

The structure of oxygen hole centers in forsterite crystals has been simulated using the interatomic potential method. The energies of isolated oxygen hole centers, as well as the energies of their clusters with intrinsic and extrinsic defects of the crystal, have been estimated for different arrangements of point defects in the structure. It has been shown that the most energetically favorable position for isolated oxygen hole centers is the O3 position, in which the gain in the formation energy is equal to 0.17 eV as compared to the O2 position and 1.66 eV as compared to the O1 position. The maximum energy gain due to the association energy can be achieved when the oxygen hole centers are located at the vertices of the tetrahedron with a silicon vacancy. The presence of chromium in the forsterite crystal can increase the probability of the formation of silicon vacancies. The obtained results have been discussed in terms of the experimental investigations of the color centers generated in the Mg₂SiO₄ and Mg₂SiO₄: Cr crystals under ionizing radiation.     

Absorption and emission spectra of yttria-stabilized zirconia and magnesium oxide

We have investigated the luminescence and absorption spectra of doped and undoped ZrO₂-Y₂O₃ and MgO crystals at room- and low temperatures. The crystals used are partly doped with the transition metals Ni, Co, Cr and the rare earth Pr. The emission spectra were obtained under laser excitation at different wavelengths. The observed optical emission and absorption bands of the MgO crystals doped with Ni, Co and Cr correspond to transitions between spin-orbit split crystal field levels of the transition metals. Luminescence and absorption bands of undoped yttria-stabilized zirconia (YSZ) crystals are due to color centers, absorption bands of the doped YSZ correspond to the well known transitions of the Ni²⁺, Co²⁺ and Pr³⁺ ions, respectively. The emission spectra of the doped YSZ obtained under various laser excitations can be explained by an energy transfer process between the color center and the doping materials. The influence of annealing on the absorption and emission of Pr³⁺/Pr⁴⁺ is investigated.     

First-principles study on electronic structures of BaWO4 crystals containing F-type color centers

The electronic structures of BaWO₄ crystals containing F-type color centers are studied within the framework of the fully relativistic self-consistent Dirac-Slater theory, using a numerically discrete variational (DV-Xα) method. It is concluded that F and F⁺ color centers have donor energy level in the forbidden band. The optical transition energies are 2.449 and 3.101 eV, which correspond to the 507 and 400 nm absorption bands, respectively. It is predicted that 400-550 nm absorption bands originate from the F and F⁺ color centers in BaWO₄ crystals.     

Gamma-ray induced color centers in Yb:YAG crystals grown by Czochralski method

20 at.% Yb:YAG single crystals have been grown by the CZ method and gamma-ray irradiation induced color centers and valence change of Fe³⁺ and Y b³⁺ ions in Yb:YAG have been studied. One significant 255 nm absorption band was observed in as-grown crystals and was attributed to Fe³⁺ ions. Two additional absorption (AA) bands located at 255 nm and 345 nm, respectively, were produced after gamma irradiation. The changes in the AA spectra after gamma irradiation and air annealing are mainly related to the charge exchange of the Fe³⁺, Fe²⁺, oxygen vacancies and F-type color centers. Analysis shows that the broad AA band is associated with Fe²⁺ ions and F-type color centers. The transition Y b³⁺→Y b²⁺ takes place as an effect of recharging of one of the Y b³⁺ ions from a pair in the process of gamma irradiation.     

Elektronenspin-Resonanz und Photochemie des U2-Zentrums in Alkalihalogenid-Kristallen

The photochemical reactions involved in the production and in the bleaching of U₂ centers (interstitial hydrogen atoms) in KCl, KBr and NaCl crystals are investigated by measuring the optical absorption spectra of the crystals at low temperatures. The U₂ centers are prepared by UV irradiation of hydroxide- and hydride-doped crystals. The electron spin resonance of KCl, KBr and NaCl crystals with U₂ centers at low temperatures reveals a well-resolved hyperfine splitting due to interactions of the hydrogen atom with four neighbouring halogen ions. The U₂ center can be described as a tetrahedal [HX₄]^4?-molecule ion, in which one hole, bound mainly at the hydrogen atom and partially at the surrounding halogen ions, gives rise to the spin resonance.     

Thermoluminescence and opitical absorption of BaF2 crystals

Abstract

Nominally pure and Dy-doped BaF₂ crystals were investigated concerning their optical absorption (OA) and thermoluminescence (TL) properties. Peaks at 120—150 and 200°C were observed for a heating rate of 1.7°C/s. The TL response for γ-rays and the TL emission spectra were obtained for these peaks. Except for the purest crystal, all BaF₂ crystals produced OA bands before irradiation typical of Ce³⁺ ions. After irradiation, Dy doped crystals showed bands due to Dy²⁺ ions. A nominally pure sample gave bands related to Ce²⁺ ions and photochromic centers of Ce³⁺ ions. and photochromic centres of Ce³⁺ ions. The correlation between some OA bands and TL peaks is discussed.     

CaWO4晶体中F型色心电子结构的研究

运用相对论的密度泛函离散变分法(DV-Xα)研究了CaWO₄晶体中F型色心的电子结构. 计算结果表明，F和F⁺心在禁带中引入了新的施主能级；分析了晶体内可能存在的光学跃迁模式，并通过过渡态的方法计算了F，F⁺心跃迁到导带底的能量分别为1.92eV和2.42eV. 因此，从理论上推断了F和F⁺心在CaWO₄晶体中可能引起650nm和515nm的吸收，由此说明CaWO₄晶体中650nm和515nm吸收带起源于晶体中的F和F⁺心. 关键词： 4晶体')" href="#">CaWO₄晶体 +心')" href="#">F和F⁺心 DV-Xα     

Concentration of Cr<Superscript>4+</Superscript> impurity ions and color centers as an indicator of saturation of forsterite crystals Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> with oxygen

The influence of the oxygen partial pressure P _{O 2} in the growth atmosphere on the coefficient of chromium distribution between the crystal and the melt of forsterite, the Cr³⁺ and Cr⁴⁺ ion contents in crystals, and the concentration of color centers induced by irradiation has been investigated. It has been established that the crystals grown at low oxygen partial pressures P _{O 2} (0.01–0.05 kPa) are characterized by low concentrations of Cr⁴⁺ ions and color centers. A change in the oxygen partial pressure to P _{O 2} ∼ 0.85 kPa leads to an increase in the Cr⁴⁺ center concentration by a factor of ∼10 and in the color center concentration by a factor of ∼5. A further increase in the oxygen partial pressure to P _{O 2} to 12 kPa remains the concentration of these centers almost unchanged. A model has been proposed according to which the intrinsic defects formed under conditions of a relative excess of oxygen leads to both the self-oxidation of chromium and the formation of color centers in the forsterite crystals under irradiation.     

Changes induced by ion implantation in forsterite Sio4 Mg2

Abstract

The various methods of optical absorption spectroscopy, Rutherford back-scattering, transmission electron microscopy and X-ray diffraction, have been associated to study the high-dose ion implantation (150 keV, 10¹⁷ ions cm^?2) phenomena in SiO₄Mg₂ single crystals. After thermal annealing at high temperature under vacuum or in atmosphere, different new phases appear:

For an under vacuum anneal, the formation of solid solution is observed: SiO₄ (Mg, Fe)₂ by X-ray diffraction;

For atmospheric anneal precipitates a spinelle phase of Fe₃O₄ or Mg Fe₂O₄.

Preliminary results on the mechanical properties studied by creep technique will be discussed for these implanted and annealed crystals.     

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.     

Irradiation and heating effects in amethyst crystals from brazil

Abstract

In this work we report optical absorption spectroscopy study of thermal and irradiation effects on samples of amethyst from Minas Gerais and Rio Grande do Sul, Brazil. Three bands were studied: 10500 cm^?1 (k), 18300 cm^?1 (θ) and 28000 cm^?1 (ζ). Thermal and irradiation effects shows that the θ and ζ bands belongs to a same center and the k band to another center. The isothermal decay and irradiation growth of these band reveal a complex kinetics. The optical absorption bands of amethyst from Minas Gerais do not recover the prmitive absorbance after being bleached at 470°C and irradiated. This sample heated at 470°C in highly reducing atmosphere gets a yellow-brown color. The amethyst from Rio Grande do Sul treated at 400°C gets, also, a yellow-brown color. We suggest this color is probalbly due to the formation of Fe₂O₃ submicroscopc segregate crystals due to the diffusion of Fe ions and oxygen vacancies.     

Thermal decay of photochromic color centers in CaF2, SrF2, and BaF2 crystals doped by La and Y impurities

The absorption spectra of photochromic centers in CaF₂, SrF₂, and BaF₂ crystals doped by La and Y impurities and thermal decay of the centers in the temperature range 80–600 K are investigated. Under low-temperature x-ray irradiation, ionized photochromic color (PC⁺) centers are generated in La- and Y-doped CaF₂ crystals and in a La-doped SrF₂ crystal. It is revealed that, upon heating of the CaF₂-LaF₃ crystal, PC⁺ centers are transformed into photochromic color (PC) centers. In the SrF₂-YF₃ crystal irradiated at room temperature, photochromic color centers are generated as well. All color centers decay at a temperature of approximately 600 K. After irradiation of the BaF₂-YF₃ crystal at a temperature of 80 K, absorption bands are observed at energies of 2.25 and 3.60 eV, which are related to neither PC centers nor PC⁺ centers.     

First-principles study on the origin of optical transitions to be associated with F colour centers for PbWO4 crystals

The electronic structures of PbWO₄ crystals containing F type color centers with the lattice structure optimized are studied within the framework of the fully relativistic self-consistent Direc–Slater theory, using a numerically discrete variational (DV-Xα) method. The calculated results show that F and F⁺ centers have donor energy level in forbidden band. Their optical transition energy are 1.84 eV, 2.21 eV, respectively, which corresponds to the 680 nm, 550 nm absorption bands. It predicts that the 680 nm, 550 nm absorption bands originate form the F and F⁺ centers in PbWO₄ crystals.     

Polar-center phase nuclei in He+-irradiated CuO single crystals

Irradiation of various single-crystal CuO faces [ac,bc,(110)] with 4.6-MeV He⁺ ions has been found to result in reduction of CuO to Cu₂O and Cu on the irradiated and unirradiated sides, lifting of forbiddenness from optical transitions in the [CuO₄]⁷⁻ electron center in the 0.7–0.95-eV energy range, a change in dichroism near the bands corresponding to transitions in the hole centers, [CuO₄]⁵⁻, and electron centers, [CuO₄]⁷⁻, as well as in a resonant increase of absorption at 0.95–1.30 eV with an unusual polarization dependence. The results of He⁺ irradiation of CuO single crystals are discussed in terms of a model of the nucleation of the phase of polar (electron and hole) centers in copper-oxygen systems. Fiz. Tverd. Tela (St. Petersburg) 40, 419–424 (March 1998)     

Study of color centers produced in thulium doped YLF crystals irradiated by electron beam and femtosecond laser pulses

In this work, we report the influence of the presence of photochromic and color centers in the photobleaching of thulium ions blue emission in YLF (YLiF₄) crystals doped with 1 mol% Tm (3+). The samples were irradiated at room temperature both with electron beam and high intensity ultrashort pulses from a Ti:Sapphire CPA laser system. In both irradiations the production of photochromic and color centers was observed via the absorption bands in the UV and visible ranges. Pure LiF and pure and oxygen doped YLF crystals were used to identify the color centers produced and their optical properties. From a phenomenological model it was possible to study the interaction between color centers and thulium ions, and their effect in photobleaching and photodarkening behaviors. Finally, the blue up laser level population was computed using a rate equation analysis.     

Spectroscopy of radiation-induced and structural defects in garnet crystals with V and Cr impurity ions

The optical absorption spectra of crystals with garnet structure (A₃B₂C₃O₁₂), containing V or Cr impurity ions, before and after oxidation annealing, γ irradiation, and coactivation with Ca and Mg ions have been experimentally and theoretically investigated. It is shown that V³⁺ and Cr⁴⁺ ions are incorporated into both octahedral and tetrahedral sites of the garnet lattice. The absorption spectra and energy level diagrams of impurity ions are identified.