Degradation of phosphors under cathode-ray excitation

A systematic analysis of phosphor degradation is presented. An increase of the self-absorption of the luminescence, destruction of luminescence centres, a decreased energy flow to these centres, and increased energy losses in the phosphor host lattice - both in the bulk and at the surface - can be distinguished as causes of the deterioration of the external radiant efficiency of phosphors. Simple measurements are suggested to disentangle the contribution of each of these parameters to the observed degradation effects. As an illustration degradation effects of Zn₂SiO₄ : Mn, Y₂SiO₅ : Ce, Sr₂Al₆O₁₁ : Eu and a Tb³⁺ activated borate glass are analyzed.     

Candoluminescence and radical-excited luminescence

The literature on the emission of solids heated in flames or excited by gases containing free radicals or excited molecules is reviewed. Many different emission processes can occur, including selective thermal radiation, candoluminescence, surface chemiluminescence, adsorboluminescence, and chemisorptive luminescence. These effects occur in a wide variety of materials, including BN, various oxides (MgO, ZnO, Y₂O₃, etc.), many impurity-activated phosphors (CaO:Bi, ZnS: Cu, Zn₂SiO₄:Mn, etc.), and organic compounds. Emission may be excited by a number of radicals, including H, O, OH, N, CO and CH. In a flame, the catalytic activity of the solid surface for radical recombination or de-excitation influences both the excitation of luminescence and the temperature of the solid (and hence the incandescence). An outstanding example of high-temperature candoluminescence is the Welsbach mantle (ThO₂ : Ce).     

Synthesis of Y2Si2O7:Eu nanocrystal and its optical properties

Nanocrystalline Y₂Si₂O₇:Eu phosphor with an average size about 60 nm is easily prepared using silica aerogel as raw material under ultrasonic irradiation and annealing temperature at 300-600 °C and this nanocrystalline decomposes into Y₂O₃:Eu and silica by heat treatment at 700-900 °C. The excitation broad band centered at 283 and 254 nm results from Eu³⁺ substituting for Y³⁺ in Y₂Si₂O₇ and Y₂O₃/SiO₂, respectively. Compared with Y₂O₃:Eu/SiO₂ crystalline, the PL excitation and emission peaks of Y₂Si₂O₇:Eu nanocrystalline red-shift and lead to the enhance of its luminescence intensity due to the different chemical surroundings of Eu³⁺ in above nanocrystallines. The decrease of PL intensity may be ascribed to quenching effect resulting from more defects in Y₂O₃:Eu/SiO₂ crystalline.     

Evaluating Zn2SiO4:Mn phosphor for use in medical imaging radiation detectors

2 SiO₄:Mn phosphor was evaluated for use in radiation detectors of medical imaging systems. Zn₂SiO₄:Mn was used in the form of laboratory-prepared fluorescent layers (screens) with coating weights from 18 to 150 mg/cm². The phosphor was excited to luminescence by low-energy X-raysusing X-raytube voltages ranging from 15 to 50 kVp. The number of emitted optical photons per incident X-rayquantum was thus determined for various X-rayenergies and phosphor coating weights. The optical emission spectrum was also measured and it was used to evaluate the spectral compatibility of Zn₂SiO₄:Mn with radiographic films, photocathodes and the Si photodiode. Finally, phosphor optical properties were estimated by fitting a theoretical model to experimental data. Results showed that Zn₂SiO₄:Mn is more efficient for low-energy X-rays. Its intrinsic conversion efficiency was found equal to 0.08, which is comparable to that of actually used phosphors. Zn₂SiO₄:Mn was also adequately compatible with orthochromatic films and the ES-20 photocathode, thus being appropriate for low-voltage radiography and fluoroscopy. Received: 31 July 1998/Accepted: 3 August 1998     

XPS analysis for degraded Y2SiO5:Ce phosphor thin films

X-ray photoelectron spectroscopy (XPS) results were obtained for standard Y₂SiO₅:Ce phosphor powders as well as undegraded and 144 h electron degraded Y₂SiO₅:Ce pulsed laser deposited (PLD) thin films. The two Ce 3d peaks positioned at 877.9 ± 0.3 and 882.0 ± 0.2 eV are correlated with the two different sites occupied by Ce in the Y₂SiO₅ matrix. Ce replaced the Y in the two different sites with coordination numbers of 9 and 7. The two Ce 3d XPS peaks obtained during the thin film analysis were also correlated with the luminescent mechanism of the broad band emission spectra of the Y₂SiO₅:Ce X₁ phase. These two different sites are responsible for the two main sets of cathodoluminescent (CL) and photoluminescence (PL) peaks situated at wavelengths of 418 and 496 nm. A 144 h electron degradation study on the Y₂SiO₅:Ce thin film yielded an increase in the CL intensity with a second broad emission peak emerging between 600 and 700 nm. XPS analysis showed the presence of SiO₂ on the surface that formed during prolonged electron bombardment. The electron stimulated surface chemical reaction (ESSCR) model is used to explain the formation of this luminescent SiO₂ layer.     

Silica-coated Y2O3:Eu nanoparticles and their luminescence properties

Crystalline Y₂O₃:Eu is of paramount significance in rare earth materials and research on luminescence spectra. In this work, the nanocrystalline Y₂O₃:Eu was coated with silica by a facile solid state reaction method at room temperature. The transmission electron microscope (TEM) photographs showed that the prepared Y₂O₃:Eu particle is polycrystalline with the size of 20 nm, the size of silica-coated particle is about 25 nm. The XPS spectra indicated that the silica layer is likely to interact with Y₂O₃:Eu by a Si-O-Y chemical bond. The luminescence spectra showed that the intensity of ground samples is lower than that of unground ones, the intensity of silica-coated phosphors is higher than that of the ground samples, while almost the same as that of the unground ones. Therefore, the silica coating decreases the surface defects of nanoparticles of the nanocrystalline Y₂O₃:Eu, thus increasing their luminescent intensity.     

Method for the analysis of saturation effects of cathodoluminescence in phosphors; applied to Zn2SiO4:Mn and Y3Al5O12:Tb

Saturation of the luminescence of phosphors under stationary cathode-ray excitation is due to activator ground-state depletion and an increased importance of higher order recombination processes at high excitation density. A method based on model considerations is presented to determine the kinetics of the dominating superlinear energy-loss process. The method is illustrated to analyse the saturation of the luminescence of Zn₂SiO₄:Mn and the blue ⁵D₃→⁷F emission of Y₃Al₅O₁₂:Tb. Quadratic energy-loss processes related to excited activator ions (Mn, Tb) are found. With this result the emitted optical flux under stationary excitation conditions and the rise time and the decay time of the luminescence can be quantitatively interpreted. When activator ground-state depletion occurs excited-state absorption cannot be excluded.     

Pulsed laser deposition of silicate phosphor thin films

Three types of silicate phosphor thin films, emitting in the red-green-blue (RGB) primary colors, were fabricated by pulsed laser deposition, including manganese and lead doped calcium silicate (CaSiO₃:MnPb) for red color, manganese doped zinc silicate (Zn₂SiO₄:Mn) for green color and cerium doped yttrium silicate (Y₂SiO₅:Ce) for blue color. A correlation was observed between photoluminescence intensity with film crystallinity and surface morphology. RGB phosphor thin films with excellent color saturation were obtained. Luminescence mechanisms for these phosphor thin films are discussed.     

Luminescence centers in thin films of yttrium oxide and yttrium-aluminum garnet activated with bismuth

Luminescence spectra and photoluminescence excitation spectra of Y₂O₃:Bi and Y₃Al₅O₁₂:Bi thin films were investigated. Luminescence was stimulated by the emission from two types of centers that were associated with the substitution of Bi³⁺ for Y³⁺ in sites of the crystal lattice of Y₂O₃ (Y₃Al₅O₁₂) with point symmetries C₂ and C_3i (D₂ and C_3i). The emission of Bi³⁺ in the site with point symmetry C_3i causes blue luminescence in both Y₂O₃:Bi and Y₃Al₅O₁₂:Bi films with maxima at 3.03 eV and 3.15 eV, respectively, that is related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry C₂ gives green luminescence in Y₂O₃:Bi with the maximum at 2.40 eV that is also related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry D₂ leads to ultraviolet luminescence in Y₃Al₅O₁₂:Bi with the maximum at 3.75 eV that corresponds to the ³P₁-¹S₀ transition. The red luminescence band with the maximum at 1.85 eV in Y₂O₃:Bi is due to the presence of structural defects. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 202–207, March–April, 2008.     

Luminescence properties of green emission of SiO2/Zn2SiO4:Mn nanocomposite prepared by sol–gel method

Green light emitting Mn²⁺ doped Zn₂SiO₄ particles embedded in SiO₂ host matrix were synthesized by a sol–gel method. After the incorporation of ZnO:Mn nanoparticles in a silica monolith using sol–gel method with supercritical drying of ethyl alcohol in two steps, it was heat treated in air at 1200 °C for 2 h in order to obtain the SiO₂/α-Zn₂SiO₄:Mn nanocomposites. The microstructure of phosphor crystals was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). XRD results indicate that the pure phase α-Zn₂SiO₄ with rhombohedral structure was obtained after thermal treatment at 1200 °C. The SiO₂/α-Zn₂SiO₄:Mn nanocomposites with a Mn doping concentration of 1.5 at% exhibit two broadband emissions in the visible range: a strong green emission at around 525 nm and a second one in the range between 560 and 608 nm. This nanocomposite with a Mn doping concentration of 0.05 shows the highest relative emission intensity. Upon 255 nm excitation, the luminescence decay time of the green emission of Zn₂SiO₄:Mn around 525 nm is 11 ms. The luminescence spectra at 525 nm (⁴T₁–⁶A₁) and lifetime of the excited state of Mn²⁺ ions-doped Zn₂SiO₄ nanocrystals are investigated.     

Luminescence of excitons in single-crystal garnets

Comparative studies of the luminescence of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and their volume analogues—Y₃Al₅O₁₂ and Y₃Al₅O₁₂:Ce single crystals, excited by synchrotron radiation with energy E=120–150 eV, have been performed. The films were grown from melt-solution by liquid-phase epitaxy and the crystals were grown from melt. The single-crystal films and single crystals studied are characterized by different degrees of structural order, in particular, different concentrations of substitutional defects of the Y _Al ³⁺ and LU _Al ³⁺ types. It was ascertained that the bands at 260 and 250 nm in the intrinsic luminescence spectra of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and single crystals are due to the emission of self-trapped excitons. The luminescence band with λ_max=300 nm and τ=0.36 μs, which is present in the luminescence spectrum of single crystals and absent in the spectra of single-crystal films, is due to the recombination of electrons with holes localized at Y _Al ³⁺ centers. It is shown that an efficient energy transfer by excitons to activator ions occurs in Y₃Al₅O₁₂ and Lu₃Al₅O₂ single-crystal films doped with Ce³⁺ ions.     

Luminescence and scintillation properties of Y<Subscript>3</Subscript>A<Subscript>l5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

Luminescence and scintillation properties of Y₃A_l5O₁₂:Ce single crystals grown from the melt by the Czochralski and horizontal directed crystallization methods in various gas media and Y₃A_l5O₁₂:Ce single-crystal films grown by liquid-phase epitaxy from a melt solution based on a PbO-B₂O₃ flux have been comparatively analyzed. The strong dependence of scintillation properties of Y₃A_l5O₁₂:Ce single crystals on their growth conditions and concentrations of Y_Al antisite defects and vacancy defects has been established. Vacancy defects are involved in Ce³⁺ ion emission excitation as the centers of intrinsic UV luminescence and trapping centers. It has been shown that Y₃A_l5O₁₂:Ce single-crystal films are characterized by faster scintillation decay kinetics than single crystals and a lower content of slow components in Ce³⁺ ion luminescence decay during high-energy excitation due to the absence of Y_Al antisite defects in them and low concentration of vacancy defects. At the same time, the light yield of Y₃A_l5O₁₂:Ce single-crystal films is comparable to that of single crystals grown by directed crystallization due to the quenching effect of the Pb²⁺ ion impurity as a flux component and is slightly lower (∼25%) than the light yield of single crystals grown by the Czochralski method.     

Luminescence study of some yttrium tantalate-based phosphors

Yttrium tantalate (YTaO₄), yttrium niobium-tantalate (YTaNbO₄), yttrium niobate (YNbO₄), europium and terbium activated yttrium tantalate (YTaO₄:Eu, YTaO₄:Tb) and europium activated yttrium niobate (YNbO₄:Eu) phosphors were prepared by solid-state reaction, from a homogeneous mixture consisting of Y₂O₃, Eu₂O₃, Tb₄O₇, Ta₂O₅, Nb₂O₅ and Na₂SO₄ as flux. Photoluminescence (PL), thermally stimulated luminescence (TSL), X-ray diffraction (XRD) and scanning electron microscopy (SEM) of yttrium tantalate based phosphors are reported. In the present study TSL characteristics of these phosphors were first investigated and reported after exposure to beta, UV (311 nm) and X-ray radiations.     

Investigation of luminescence spectra of the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single-crystal films

The luminescence spectra of single-crystal films and bulk crystals of yttrium-aluminum garnet Y₃Al₅O₁₂ and Ce³⁺-activated Y₃Al₅O₁₂ were investigated. It was shown that the room-temperature luminescence intensity of the Ce³⁺-free single-crystal Y₃Al₅O₁₂ film was considerably lower than that of the bulk crystals, while the luminescence intensity of the Ce³⁺ ions in the Y₃Al₅O₁₂:Ce films was considerably higher than that one for the corresponding bulk crystal.     

High luminance of new green emitting phosphor, Mg2SnO4:Mn

Mg₂SnO₄, which has an inverse spinel structure, was adopted as the host material of a new green emitting phosphor. Luminescence properties of the manganese-doped magnesium tin oxide prepared by the solid state reaction were investigated under vacuum ultraviolet (VUV) ray and low-voltage electron excitation. The Mg₂SnO₄:Mn phosphor exhibited green luminescence with the emission spectrum centered at 500 nm due to spin flip transition of the d-orbital electron associated with the Mn²⁺ ion. Optimum Mn concentration of Mg₂SnO₄:Mn under VUV excitation with 147 nm wavelength and electron beam excitation with 800 V excitation voltage are 0.25 and 0.6 mol%, respectively. The emission intensities of Mg₂SnO₄:Mn phosphors under the two excitation sources are higher than those of Zn₂SiO₄:Mn and ZnGa₂O₄:Mn phosphors. At 0.25 mol% of Mn concentration, on the other hand, the decay time is shorter than 10 ms.     

Lu2SiO5:Ce and Y2SiO5:Ce single crystals and single crystalline film scintillators: Comparison of the luminescent and scintillation properties

The paper is dedicated to development of scintillators based on the single crystalline films of Ce³⁺ doped Lu₂SiO₅ (LSO:Ce) and Y₂SiO₅ (YSO:Ce) orthosilicates grown by Liquid Phase Epitaxy method onto YSO substrates from melt-solutions based on the PbO–B₂O₃ flux. We also compare the luminescent and scintillation properties of Ce doped LSO:Ce and YSO:Ce single crystalline films with those of their single crystal counterparts, grown by the Czochralski method.     

Brightness and decay time of Zn2SiO4:Mn phosphor particles with spherical shape and fine size

Green-light-emitting Zn₂SiO₄:Mn phosphor particles were synthesized by modified large-scale spray pyrolysis using a colloidal solution containing fumed silica particles. The particles had a fine size, filled morphology, spherical shape and non-aggregation characteristics even after post-treatment at 1150 °C. The luminescence characteristics of Zn₂SiO₄:Mn phosphor particles having spherical shape, such as brightness and decay time under VUV excitation light, were investigated as a function of Mn content. The luminescence intensity exhibits a maximum at 5 mol% Mn-doped powder. The decay time increases consistently with decreasing Mn content and more saturated color coordinates are obtained with the composition having 12 mol% Mn. As a consequence, the 10 mol% Mn-doped powder proved to provide a good combination of favorable luminance and acceptable decay time. The influence of post-treatment temperature on the decay time and photoluminescence characteristics of Zn₂SiO₄:Mn particles was also investigated. Particles post-treated at 1155 °C had the maximum photoluminescence intensity, which was identical to 113% that of the commercial product, and a comparable decay time of 5.8 ms. PACS 81.20.Rg; 78. 55.Hx; 78.40.Ha; 81.05.Hd; 81.40.Tv     

Intense visible luminescence from Nd-doped yttrium oxysulfide

We report on a novel luminescent phenomenon in Y₂O₂S doped with Nd³⁺. After irradiation by a 261 nm ultraviolet (UV) light into the Y₂O₂S host lattice, the Nd³⁺-doped Y₂O₂S phosphor emits intense blue luminescence in the visible light region. Moreover, this blue luminescence can also be obtained by exciting directly into the Nd³⁺ energy absorption itself. XRD, photoluminescence, and fluorescence decay curve are used to characterize the synthesized phosphor. The spectroscopic data indicate that all the visible emission peaks are originated from the electrical transitions of Nd³⁺, and the strong luminescence of the Nd³⁺ is considered to be due to an efficient energy transfer from the Y₂O₂S host lattice to the Nd³⁺ in Y₂O₂S:Nd³⁺. The optimum concentration for the luminescence Nd³⁺ is determined to be 1 mol% of Y³⁺ in Y₂O₂S host. The critical energy transfer distance has been calculated by the concentration quenching and the possible luminescent process of this blue luminescence-emitting phosphor is also investigated.     

Eu red long afterglow in Y2O2S:Ti, Eu phosphor through afterglow energy transfer

Eu,Ti co-doped Y₂O₂S:0.03Ti,0.03Eu phosphors and single Eu or Ti doped Y₂O₂S phosphors were prepared and their luminescent properties were investigated in detail by photoluminescence (PL) spectra, long afterglow spectra and thermoluminescence spectra measurements. The results showed that Y₂O₂S:Ti,Eu phosphors possess orange-red afterglow color with afterglow time above 5 h. The reddish afterglow color, which corresponds to a set of linear Eu³⁺ emissions at low-energy range (540-630 nm), was demonstrated to come from the energy transfer process from yellow Ti afterglow emissions, the proposed energy transfer mechanism may well explain the Eu³⁺ afterglow emission.     

Degradation of Y2SiO5:Ce phosphor powders

The degradation of the cathodoluminescence (CL) intensity of cerium-doped yttrium silicate (Y₂SiO₅:Ce) phosphor powders was investigated for possible application in low voltage field emission displays (FEDs). Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and CL spectroscopy were used to monitor changes in the surface chemical composition and luminous efficiency of commercially available Y₂SiO₅:Ce phosphor powders. The degradation of the CL intensity for the powders is consistent with a well-known electron-stimulated surface chemical reaction (ESSCR) model. It was shown with XPS and CL that the electron stimulated reaction led to the formation of a luminescent silicon dioxide (SiO₂) layer on the surface of the Y₂SiO₅:Ce phosphor powder. XPS also indicated that the Ce concentration in the surface layer increased during the degradation process and the formation of CeO₂ and CeH₃ were also part of the degradation process. The CL intensity first decreased until about 300 C cm⁻² and then increased due to an extra peak arising at a wavelength of 650 nm.