Luminescence and radiation-induced color centers in anion-defective alumina crystals after high-dose irradiation

A method of UV spectroscopy was used to measure photoluminescence (PL) spectra and photoluminescence excitation (PLE) spectra in anion-defective alumina crystals exposed to high doses of gamma-radiation. An additional emission band in the range of 1.6–2.75 eV appears in the exposed crystals. Aggregate F₂-type centers in different charge states are responsible for this band. It was found that growing intensity of PL aggregate centers occurs at doses corresponding to saturation of dose response and is accompanied by a sharp drop in the intensity of F⁺-band in the PL spectrum resulting from combination of F⁺-centers into aggregates. Uncharged F₂-centers are formed when electrons are trapped by F₂⁺ and F₂²⁺-centers. The main role of F⁺-centers in radiation-induced transformations of color centers under high-dose irradiation of anion-defective alumina crystals was indicated.     

Electrochemical fabrication of arrayed alumina nanowires showing strong blue emission

Arrayed alumina nanowires having controlled uniform diameters of 30–90 nm and lengths of 2–10 μm have been fabricated electrochemically with a high yield using two-step anodized aluminum oxide membranes as templates. The observed photoluminescence of the arrayed alumina nanowires arising from the emission of F⁺ and F centers is strong and blue-shifted compared with that of porous alumina membranes due to the structural difference of Al₂O₃. Our synthesized alumina nanowires are also found to be chemically more stable than the templates.     

Effects of ordering quality of the pores on the photoluminescence of porous anodic alumina prepared in oxalic acid

Photoluminescence (PL) of the anodic alumina has been studied and related with quality of hexagonal ordering of the pores. The photoluminescence excitation (PLE) spectra have been successfully de-convoluted into primarily two sub-bands with peak positions at about 355 and 395 nm and maximum emission at about 450 and 500 nm, respectively; the former being assigned to F⁺ centers and the latter to the F-centers. A red shift in the PLE takes place, at a given anodizing voltage, when the quality of the hexagonal pore ordering deteriorates with an increase in number density of defects, i.e., pentagons and hexagons with missing pores. The metallic hills at these defects change the curvatures of the metal-oxide and the oxide-electrolyte interfaces that could affect the field distribution and hence the stress-state and other characteristics of the oxide at the defects. This allows a comparatively larger concentration of F centers (395 nm band), causing a red shift in the PLE with increase in defect density.     

Optical properties of alumina membranes prepared by anodic oxidation process

The luminescence property of anodic alumina membranes (AAMs) with ordered nanopore arrays prepared by electrochemically anodizing aluminum in oxalic acid solutions have been investigated. Photoluminescence emission (PL) measurement shows that a blue PL band occurs in the wavelength ranges of 300-600 nm. The PL intensity and peak position of AAMs depend markedly on the excitation wavelength. A new peak located at 518 nm can be observed under a monitoring wavelength at 429 nm in the photoluminescence excitation (PLE) spectra. Convincing evidences have been presented that the PLE would be associated with the residual aluminum ions in the membrane. The PLE and PL of AAMs, as a function of anodizing times, have been discussed. It is found that the oxalic impurities incorporated in the AAMs would have important influences on the optical properties of AAMs in the initial stage of anodization. The PL and PLE spectra obtained show that there are three optical centers, of which the first is originated from the F⁺ centers in AAMs, the second is correlated with the oxalic impurities incorporated in the AAMs, and the third is associated with the excess aluminum ions in the membrane.     

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.     

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.     

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.     

Thermal- and photo-induced transformations of luminescence centers in αd-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> anion-defective crystals

The thermal- and photo-induced transformations of luminescence centers in anion-defective crystals of α-Al₂O₃ have been investigated. It has been found that the exposure of crystals to ultraviolet light at temperatures in the range 50–900°C leads to substantial changes in their thermoluminescence and radioluminescence spectra. According to the optical absorption and photoluminescence data, the detected F-type centers have been identified and the temperature ranges of the F → F ⁺ → F ₂ transformations and their possible mechanisms have been determined. The special attention has been drawn to the detailed similarity in the formation of complex F ₂-type centers in the initially perfect α-Al₂O₃ crystals irradiated with fast neutrons and in the studied anion-defective crystals.     

Modification of erbium photoluminescence excitation spectra for the emission wavelength 1.54 μm in mesoscopic structures

Photoluminescence excitation (PLE) spectra for the emission wavelength 1.54 μm were studied for erbium-doped xerogels embedded in artificial opals and porous anodic alumina films. Opals were chosen with photonic stop-band in green spectral range, where excitation of 1.54 μm occurs most efficiently. In comparison to the structure erbium-doped titania xerogel/porous anodic alumina/silicon the photoluminescence excitation spectra for 1.54 μm emission wavelength significantly changes for the same xerogels embedded in artificial opals. Enhancement of erbium-related 1.54 μm emission was observed from the structure Fe₂O₃ xerogel/porous anodic alumina fabricated on silicon, having some incompletely anodized aluminium, under excitation with either the lasing source at 532 nm or xenon lamp. Evident difference in PLE spectra for erbium doped TiO₂ and Fe₂O₃ xerogels in porous anodic alumina is observed.     

White-light emission from Li<Subscript>2</Subscript>Sr<Subscript>1−3<Emphasis Type="Italic">x</Emphasis>/2</Subscript>Dy<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>SiO<Subscript>4</Subscript> phosphors

Li₂Sr_1−3x/2Dy _x SiO₄ phosphors were synthesized at 900°C in the normal atmosphere by a solid-state method. The synthesized phosphors were characterized by X-ray powder diffraction (XRD) and photoluminescence (PL) spectra. The photoluminescence excitation (PLE) spectra show excitation peaks ranging from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The predominant emission of Dy³⁺ ions under 349 nm excitation is observed at 479 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions and 572 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions, respectively. The PL results reveal that the optimal concentration of the Dy³⁺ ions in Li₂Sr_1−3x/2Dy _x SiO₄ phosphors is x=0.03 mol. The nature of the resonance energy transfer for the Dy³⁺ ions is confirmed by Huang’s rule. Simulation of the white light excited by 349 nm near-ultraviolet (n-UV) light is also performed for its potential for white LEDs.     

Luminescence of CaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>:Eu crystals

We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa₂Se₄:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f⁶ 5d–4f⁷ (⁸S_7/2) of the Eu²⁺ ions. From the temperature dependence of the intensity (log I–10³/T), we determined the activation energy (E _a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu²⁺ ions in the CaGa₂Se₄ crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.     

Luminescent properties of YVO4:Eu/SiO2 core–shell composite particles

We report an efficient process for preparing monodisperse SiO₂@Y_0.95Eu_0.05VO₄ core–shell phosphors using a simple citrate sol–gel method and without the use of surface-coupling silane agents or large stabilizers. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectra were used to characterize the resulting SiO₂@Y_0.95Eu_0.05VO₄ core–shell phosphors. The XRD results demonstrate that the Y_0.95Eu_0.05VO₄ particles crystallization on the surface of SiO₂ annealing at 800 °C is perfectly and the crystallinity increases with raising the annealing temperature. The obtained core–shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 500 nm and an average thickness of ~50 nm), are not agglomerated, and have a smooth surface. The thickness of the YVO₄:Eu³⁺ shells on the SiO₂ cores could be easily tailored by changing the mass ratio of shell to core (W = [YVO₄]/[SiO₂]) (~50 nm for W = 30%). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀ − ⁷F₂ red emission at 618 nm) under the excitation of 320 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the values of W.     

Visible photoluminescence from Ge+-implanted SiO2 films thermally grown on crystalline Si

+ -implanted SiO₂ films is studied as a function of different fabricating conditions (implantation dose, annealing temperature and time). The SiO₂ films containing Ge nanocrystals exhibit two photoluminescence (PL) bands peaked at 600 nm and 780 nm. There are two excitation bands in the PL excitation (PLE) spectra. With variation in Ge nanocrystal size, the PL and PLE peak energies show no appreciable shift. The PL and PLE spectral analyses suggest that during the PL process, electron–hole pairs are generated by the E(l) and E(2) direct transitions inside Ge nanocrystals, which then radiatively recombine via luminescent centers in the matrix or at the interface between the nanocrystal/matrix. Received: 27 January 1998/Accepted: 18 March 1998     

Photoluminescence of f-centers in films of anodic alumina

Results are reported from a study of the optical properties of porous alumina films obtained by anodizing in a water solution of sulfuric acid and modified by thermal annealing in air at T ≥ 850°C. A comparative analysis of the data shows that the near-UV and visible photoluminescence of alumina anodized in a sulfuric acid solution is caused primarily by oxygen divacancies (F₂, F₂⁺ _2^{+} , and F₂^{2 +} _2^{2 + } centers), while sulfate ions have little effect on the luminescence properties of anodic alumina in this spectral range.     

Transversely pumped laser using F 3 + and F2 mixed color centers in a LiF crystal at room temperature

A stable laser with F₃⁺ and F₂ mixed color centers in LiF crystal is constructed using a transversely pumped cavity at room temperature. The mixed color center laser is pumped with a nitrogen-laser-pumped dye laser. A pulse output of the laser is 0.23 mJ. The pulse widths of the F₃⁺ and F₂ color center lasers are about 12 and 8.5 ns, respectively. The optical–optical conversion efficiency is about 5.0%. The divergence of the F₃⁺ color center laser beam is about 2.2 mrad and that of the F₂ color center laser beam about 3.5 mrad. The polarization of the mixed color center laser is about 0.97. The output of the F₃⁺ color center laser extends from 515 to 575 nm and peaks at 540 nm, while that of the F₂ color center laser extends from 633 to 705 nm and peaks at 667 nm.     

Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

Up-Conversion Luminescence of the NaRF<Subscript>4</Subscript>-NaR′F<Subscript>4</Subscript> (R: Y,Yb, Er) Core-Shell Nanomaterials

Up-converting NaRF₄-NaR′F₄ (R: Y, Yb, Er) nanomaterials with different core-shell combinations were prepared with the co-precipitation method. The X-ray powder diffraction (XPD) measurements revealed the presence of both the cubic and hexagonal NaRF₄ phases. The crystallite sizes calculated with the Scherrer formula were 100 and 150 nm for the cubic and hexagonal phases, respectively. The FT-IR spectra showed water impurities. The up-conversion luminescence and luminescence decays were studied with NIR laser excitation at 970 nm. The up-conversion luminescence spectra showed strong red (640–685 nm) (⁴F_9/2 → ⁴I_15/2) and moderate green (515–560 nm) (²H_11/2, ⁴S_3/2 → ⁴I_15/2) Er³⁺ luminescence. The strongest up-conversion luminescence and longest red luminescence decay was obtained from the Na(Y,Yb)F₄-NaErF₄ core-shell combination.     

Photocontrolled magnetic resonance plasticity of γ-irradiated KCl:Fe crystals

A photocontrolled resonance decrease in microhardness, which is due to the application of mutually perpendicular static and microwave fields, in γ-irradiated KCl:Fe crystals has been revealed. It has been found that the magnetic plasticity of unirradiated γ-KCl:Fe crystals is due to the resonance effect of magnetic fields on two types of impurity centers: first, centers containing Fe²⁺-ν _c ion-vacancy pairs and, second, centers containing Fe⁺ ions. The illumination of γ-KCl:Fe crystals with F-light (with a wavelength of λ = 500–600 nm) is accompanied by rearrangement of the spectrum of electron paramagnetic resonance detected by a change in microhardness. The effect of F-light on the spectrum of magnetic resonance plasticity is manifested as the suppression of the spectra of Fe²⁺-ν _c ions with effective g-factors of 7.0 and 3.5 due to their recombination with F-electrons and reconstruction to Fe⁺ centers with g-factors of 2.2 and 4.1.     

Defect evolution and photoluminescence in anion-defective alumina single crystals exposed to high doses of gamma-rays

A method of luminescent UV and VUV spectroscopy was used to study the evolution of color centers in anion-defective alumina single crystals exposed to high doses of gamma-radiation. A sharp drop in the intensity of the emission bands and, therefore, the concentration of F⁺ and F-centers associated with the formation of aggregate F₂-type centers was found. The aggregate centers create an additional emission band in the range of (1.8–2.8) eV. When the crystals are exposed to middle and high doses, the photoluminescence (PL) intensity is the highest in the emission band of F₂²⁺-centers, which indicates a high concentration of the aggregates from singly charged oxygen vacancies (of F⁺-centers). When PL of the crystals exposed to high doses is excited with synchrotron radiation of the VUV range, a wide emission band in the red and near infrared (NIR) regions is registered. The centers related presumably to impurity defects, their aggregates and clusters consisting of several oxygen vacancies are responsible for this emission band.     

Synthesis and luminescent characteristics of one-dimensional europium doped Gd2O3 phosphors

One-dimensional (1D) Gd₂O₃:Eu³⁺ nano-rods and micro-rods were prepared using a facile sol-gel precipitation method, without a template and with a post-growth heat treatment in air. Based on scanning electron microscopy (SEM) and X-ray diffraction (XRD) data, hexagonal Gd(OH)₃:Eu³⁺ micro-rods, 60∼90 nm in diameter and 700 nm to 1 μm in length, were synthesized and then transformed by calcining (800°C, 2 hr) to cubic Gd₂O₃:Eu³⁺ with the same morphology and dimensions. Nano-rods of Eu³⁺ doped Gd(OH)₃ and calcined Gd₂O₃, 60∼90 nm diameter and 150∼300 nm length, were prepared by adding polyethylene glycol (PEG) as a capping agent during the sol-gel synthesis. Photoluminescence (PL) spectra exhibited the ⁵D₀–⁷F₂ transitions of Eu³⁺ at 612 and 627 nm from excitation at 280 nm. Photoluminescence excitation (PLE) data showed that a small fraction of PL from Eu³⁺ resulted from direct excitation, but most PL resulted from the oxygen to europium charge-transfer band (CTB) between 250 and 280 nm.