Excitation process and photoluminescence properties of Tb and Eu ions in SnO2 and in SnO2: Porous silicon hosts

Tin oxide (SnO₂)-layers-doped terbium and europium ions are elaborated by the sol-gel method on silicon substrates. After annealing at 500 °C, the transmission electron microscopy revealed a crystallization of tin oxide.The emission properties of rare-earth in SnO₂ are studied systematically against temperature annealing and Tb³⁺ concentration. The PL spectrum is optimal after annealing at 900 °C and the corresponding photoluminescence (PL) decay is nearly exponential, showing that the sample is homogenous and the PL process can be described by two levels system.The concentration effect shows a quenching of the PL intensity for Tb³⁺ concentration above 4%. From the investigation of the decay rate from the ⁷F₅ state within terbium concentration, we show that self-quenching is insured by dipole - dipole interaction. The evolutions of both PL intensity and PL lifetime versus temperature are studied. The PL intensity and PL lifetime are enhanced by deposing SnO₂:Tb³⁺ and SnO₂:Eu³⁺ in porous silicon. We show that an efficient excitation transfer from Si nanocrystallites to RE ions can occur.     

Photoluminescence properties of europium-doped porous silicon nanocomposites

We present new results concerning the photoluminescence properties of europium (Eu³⁺) incorporated in porous silicon (PS) matrix. Eu³⁺ ions were embedded in the matrix by simple impregnation of PS layers in chloride solution of europium. Complete and uniform penetration of Eu³⁺ into the pores is proved from RBS study.The PL spectrum shows the existence of several peaks superposed to the PL band of PS. These peaks are related to level transitions in Eu³⁺. The effect of the ray excitation on the PL shows that energy transfer is not the principal route for radiative recombination.A systematic study of the PL versus annealing temperature was performed. It was found that the optimised PL spectrum is found after annealing at 1000°C. Low-temperature study of the PL shows an important increase of the intensity and a broadness of the peaks due to the appearance of a second crystallographic site.     

Excitation and emission processes of Tb in porous anodic alumina

The strong photoluminescence (PL) of porous anodic alumina (PAA) with terbium deposition is reported. PAA, which has a regular pore morphology, is considered an effective template for fabricating luminescent composites. Tb was deposited onto PAA films by immersion in alcoholic solution with terbium chloride followed by heat treatment. The PL spectra demonstrate typical bands of Tb³⁺ corresponding to ⁵D₄ → ⁷F_j (j = 3, 4, 5, 6,) electron transition, with the maximum at 18,360 cm⁻¹ (⁵D₄ → ⁷F₅). The PL mechanism of Tb³⁺ was systematically studied with annealing temperature. The non-radiative relaxation channel is provided by OH hydroxyls at the surface of porous anodic alumina and, after annealing at 900 °C, the PL yield is highly improved. The PL intensity of Tb³⁺ increases with laser power and a saturation phenomenon, associated with the ratio of Tb³⁺ to Tb⁴⁺ ions, is observed at approximately 90 W/cm². Based on a theoretical model, the optical cross-section σ of terbium in PAA is estimated, with a value close to that of other porous materials doped with the rare-earth elements.     

UV-induced photoluminescence and thermally stimulated luminescence of CaSO4:Eu and CaF2:Tb3+ phosphors

Ultraviolet radiation induced changes in photoluminescence (PL) and thermally stimulated luminescence (TSL) of europium activated calcium sulphate (CaSO₄:Eu³⁺, Eu²⁺) and terbium doped calcium fluoride (CaF₂:Tb³⁺) phosphors have been studied. PL measurements suggest conversion of Eu³⁺ to Eu²⁺ on 254 nm irradiation corresponding to charge transfer band of Eu³⁺ ions and reduction of Eu²⁺ ions with 365 nm illumination representing a f–d transition of Eu²⁺ ions. Similar studies carried out on CaF₂:Tb³⁺ phosphor, however, do not show any significant wavelength specific changes. The integrated TSL output appears to be rate-dependent for both phosphors. The wavelength dependent changes in TSL output observed for CaSO₄:Eu phosphor have been correlated with those obtained in PL studies. The changes in TSL and PL characteristics of CaF₂:Tb³⁺ phosphor have been explained on the basis of stabilisation of traps based on matrix specific charge similarities.     

The effects of added foreign ions in Gd2O2S : Tb; crystal field calculations, lifetimes, photo-luminescence and absorption spectra

A spectroscopic study is carried out in which the effects of added Ca²⁺ and Ru⁴⁺ transition metal ions on some characteristics of the emission of Gd₂O₂S : Tb³⁺ phosphors (energy levels, intensities, lifetimes) are examined and compared. In order to distinguish the Tb³⁺ emissions from impurity ones, the electronic energy levels of trivalent terbium are determined and the energy level scheme is completed by a crystal field analysis. The optical spectra reveal no terbium doped impurity phase; however, other rare earth ions present as impurities in the starting materials are detected. They are identified, and the influence of the added Ca²⁺ and Ru⁴⁺ on their emission lines is also examined.     

Thermoluminescence properties of rare earth doped lithium magnesium borate phosphors

This paper reports the thermoluminescence (TL) properties of rare earth doped lithium magnesium borate (LMB) polycrystalline phosphor. LMB phosphor has been prepared by high temperature solid state diffusion method. Among all the rare earth doped LMB phosphors, terbium doped material has shown maximum TL sensitivity with a broad dosimetric glow peak at 240 °C. near the tissue equivalent TL phosphor with terbium dopant has about four times the TL sensitivity of TLD-100. The main dosimetric properties such as glow curve stability, TL response versus absorbed dose, post-irradiation storage stability, and reusability are investigated. This TL material has a linear dose response up to 10³ Gy, negligible storage fading and a simple annealing procedure for reuse. The TL emission spectra of LMB:Tb³⁺ showed broad green emission at 544 nm, which merged with host emission. The characteristic Tb³⁺ emissions are seen in the photoluminescence (PL) spectra.     

A novel green phosphor GdCaAlO4:Tb for PDP application

A novel green-emitting nano-sized phosphor, Tb³⁺-doped GdCaAlO₄ was synthesized with a precursor prepared by citrate sol-gel method at relatively low temperature. Powder X-ray diffraction (XRD) analysis confirmed the formation of GdCaAlO₄. Field-emission scanning electron microscopy (FE-SEM) observation indicated a narrow size-distribution of about ∼100 nm for the particles with a spherical shape. Upon excitation with near UV and vacuum ultraviolet (VUV) light, the phosphor showed strong green-emission peaked at around 546 nm, corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺, and the highest photoluminescence (PL) intensity at 546 nm was found at a content of about 12 mol% Tb³⁺. As the Tb³⁺ concentration increases, the fast diffusion of energy among terbium ions toward traps or impurities resulting in a decrease of the lifetime. The optical properties study suggests that it is a potential candidate for plasma display panels (PDPs) application.     

Synthesis, photoluminescence, thermoluminescence and dosimetry properties of novel phosphor Zn(BO2)2:Tb

Polycrystalline powder samples of terbium doped Zn(BO₂)₂ phosphors were prepared by solid state reaction in the thermal carbon reducing atmosphere at high temperature. The photoluminescence (PL), three-dimensional (3D) TL emission spectrum and dosimetric characteristics following ⁶⁰Co gamma-rays irradiation were studied. Characteristic emission bands of Tb³⁺ at about 490, 543, 584 and 620 nm, attributed to the ⁵D₄→⁷F_J (J=3, 4, 5, 6) transitions of Tb³⁺ ions, were observed in the TL and PL emission spectrum. No emission from Tb⁴⁺ ions was observed in the TL emission spectrum. The TL-dose response of the powder samples Zn(BO₂)₂:Tb to ⁶⁰Co gamma-rays radiation in the dose range from 1 to 100 Gy for clinical dose levels was almost linear. The experiment results showed that Zn(BO₂)₂:Tb has potential use as the materials of gamma-rays thermoluminescence dosimeter (TLD) for clinical dosimetry.     

Sensitized luminescence through nanoscopic effects of ZnO encapsulated in SiO2:Tb sol gel derived phosphor

Terbium (1 mol%) doped ZnO-SiO₂ binary system was prepared by a sol-gel process. Nanoscopic effects of ZnO on the photoluminescence (PL) and the cathodoluminescence (CL) properties were studied. Defects emission from ZnO nanoparticles was measured at 560 nm and the line emission from Tb³⁺ ions in SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺ with a major peak at 542 nm was measured. The PL excitation wavelength for 542 nm Tb³⁺ emission was measured at ∼320 nm in both SiO₂:Tb³⁺ and ZnO-SiO₂:Tb³⁺. The CL data showed quenched luminescence of the ZnO nanoparticles at 560 nm from a composite of ZnO-SiO₂:Tb³⁺ and a subsequent increase in 542 nm emission from the Tb³⁺ ions. This suggests that energy was transferred from the ZnO nanoparticles to enhance the green emission of the Tb³⁺ ions. The PL and CL properties of ZnO-SiO₂:Tb³⁺ binary system and possible mechanism for energy transfer from the ZnO nanoparticles to Tb³⁺ ions are discussed.     

Syntheses of optically efficient (La1−x−yCexTby)F3 nanocrystals via a hydrothermal method

Optically efficient cerium and terbium doped lanthanide fluoride (La_1−x−yCe_xTb_y)F₃ nanocrystals with different doping concentrations have been synthesized by a hydrothermal route in the presence of ethylenediamine tetraacetic acid disodium salt (EDTA). The results showed that the formation of nanocrystals with different morphologies depends on terbium ion Tb³⁺ doping concentration, but independent of cerium ion Ce³⁺ doping concentration. With increase in Tb³⁺ doping concentration, the morphologies of nanocrystals evolved from a spherical shape to a plated-like one. In addition, both the photoluminescence quantum yield (PL QY) and the fluorescence lifetime of nanocrystals increased with the increase in Ce³⁺ doping concentration in cerium and terbium co-doped system. The PL QY reached up to 55%, and the lifetime up to 7.3 ms. Transmission electron microscopy (TEM), X-ray diffraction (XRD), selected area electron diffraction (SAED), X-ray fluorescence (XRF), energy dispersive spectroscopy (EDS), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) and infrared (IR) spectroscopies were employed to characterize the properties of nanocrystals. The growth mechanism of nanocrystals with different morphologies and optical properties of nanocrystals with different doping concentrations were investigated.     

Eu/Tb ions co-doped white light luminescence Y2O3 phosphors

Y₂O₃:Eu³⁺, Tb³⁺ phosphors with white emission are prepared with different doping concentration of Eu³⁺ and Tb³⁺ ions and synthesizing temperatures from 750 to 950 °C by the co-precipitation method. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the crystallinity of the synthesized samples increases with enhancing the firing temperature. The photoluminescence spectra indicate the Eu³⁺ and Tb³⁺ co-doped Y₂O₃ phosphors show five main emission peaks: three at 590, 611 and 629 nm originate from Eu³⁺ and two at 481 and 541 nm originate from Tb³⁺, under excitation of 250-320 nm irradition. The white light luminescence color could be changed by varying the excitation wavelength. Different concentrations of Eu³⁺ and Tb³⁺ ions were induced into the Y₂O₃ lattice and the energy transfer from Tb³⁺→Eu³⁺ ions in these phosphors was found. The Commission International de l’Eclairage (CIE) chromaticity shows that the Y₂O₃:Eu³⁺, Tb³⁺ phosphors can obtain an intense white emission.     

Thermoluminescence and optical studies on X-irradiated terbium-doped potassium bromide crystals

This paper reports the thermoluminescence (TL) and other optical studies made on terbium-doped KBr crystals X-irradiated at room temperature. Photoluminescence studies confirm the presence of terbium ions in the KBr matrix in their trivalent form. Formation of Z₁ centres on F-bleaching of X-irradiated crystals is observed. The characteristic emission due to Tb³⁺ ions in the spectral distribution under optically stimulated emission and thermoluminescence emission confirm the participation of the Tb ions in the recombination process. TL process has been identified to be due to the thermal mobilization of electrons produced during the colouration process.     

Influences of Doping and Annealing on the Structural and Photoluminescence Properties of Y2O3 Nanophosphors

This paper reports the structural and optical properties of rare earth doped and codoped yttrium oxide nanophosphors. Dysprosium (Dy³⁺) and Terbium (Tb³⁺) doped and codoped yttrium oxide (Y₂O₃) phosphors were prepared by combustion synthesis method and subsequently annealed to high temperature to eliminate the hydroxyl group (?OH) and to get more crystallinity. The formation of compounds was confirmed by the X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR). The diffuse reflectance spectra (DRS) of doped and codoped Y₂O₃ powder phosphors were measured and it is observed that the absorption edge of the doped samples is shifted towards blue region with respect to undoped sample. The bandgap of the prepared samples were evaluated with the help of Kubelka-Munk function using Diffuse Reflectance Spectra (DRS) and an increase in bandgap was observed with the decrease in crystallite size. A strong characteristics emission from Tb³⁺ and Dy³⁺ ions was identified and the influence of doping concentration and annealing temperature on photoluminescence properties was systematically studied. Transfer of energy was observed in dysprosium–terbium codoped Y₂O₃ nanophosphor at room temperature from Dy³⁺ ions toTb³⁺ ions.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

White light generation through the zinc metaphosphate glass activated by Ce, Tb and Mn ions

The photoluminescence of Ce³⁺, Tb³⁺ and Mn²⁺ ions was investigated in the Zn(PO₃)₂ glass. The blue and green emissions of Tb³⁺ ions and the red emission of Mn²⁺ ions are enhanced upon UV excitation through a non-radiative energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions. The efficiency of this transfer was estimated in at least 62%. It is demonstrated that this glass activated with three ions (Ce³⁺, Tb³⁺ and Mn²⁺) can generate white light emission (x=0.420 and y=0.423 chromaticity coordinates and 3440 K colour temperature) under excitation at 254 nm, i.e., using an AlGaN-based LED as excitation source.     

D3→FJ emission of Tb doped sol–gel silica

Amorphous silica samples doped with 0.1 and 1 mol% of terbium (Tb) were synthesized by the sol–gel method. In addition to the green light associated with ⁵D₄→⁷F_J transitions of Tb³⁺, the sample containing 0.1 mol% also emitted blue light as a result of ⁵D₃→⁷F_J transitions during photoluminescence (PL) measurements. As a result of concentration quenching this blue emission was not observed for the samples doped with the higher concentration (1 mol%). However the blue ⁵D₃ →⁷F_J emission was observed in the 1 mol% doped samples during cathodoluminescence (CL) measurements. Since a rough calculation indicated that the excitation rate in the CL system where the blue emission is observed may be similar to a laser PL system under conditions where the blue emission is not observed, the difference is attributed to the nature of the excitation sources. It is suggested that during the CL excitation incident electrons can reduce non-luminescent Tb⁴⁺ ions in the silica, substituting for Si⁴⁺ ions, to the excited (Tb³⁺)? state and that these are responsible for the blue emission, which does not occur during PL excitation.     

Role of Bi ions for Er ions efficient 1.54 μm light emission in Er/Bi codoped SiO2 thin film prepared by sol-gel method

Er/Bi codoped SiO₂ thin films were prepared by sol-gel method and spin-on technology with subsequent annealing process. The bismuth silicate crystal phase appeared at low annealing temperature while vanished as annealing temperature exceeded 1000 °C, characterized by X-ray diffraction, and Rutherford backscattering measurements well explained the structure change of the films, which was due to the decrease of bismuth concentration. Fine structures of the Er³⁺-related 1.54 μm light emission (line width less than 7 nm) at room temperature was observed by photoluminescence (PL) measurement. The PL intensity at 1.54 μm reached maximum at 800 °C and decreased dramatically at 1000 °C. The PL dependent annealing temperature was studied and suggested a clear link with bismuth silicate phase. Excitation spectrum measurements further reveal the role of Bi³⁺ ions for Er³⁺ ions near infrared light emission. Through sol-gel method and thermal treatment, Bi³⁺ ions can provide a perfect environment for Er³⁺ ion light emission by forming Er-Bi-Si-O complex. Furthermore, energy transfer from Bi³⁺ ions to Er³⁺ ions is evidenced and found to be a more efficient way for Er³⁺ ions near infrared emission. This makes the Bi³⁺ ions doped material a promising application for future erbium-doped waveguide amplifier and infrared LED.     

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 studies on lanthanide ions (Eu, Dy and Tb) doped YAG:Ce nano-phosphors

Yttrium aluminum garnet nanoparticles both undoped and doped with lanthanide ions (Ce³⁺, Eu³⁺, Dy³⁺ and Tb³⁺) having average size around 30 (±3 nm) nm were prepared by glycine nitrate combustion method followed by annealing at a relatively low temperature of 800 °C. Increase in the annealing temperature has been found to improve the luminescence intensity and for 1200 °C heated samples there exists strong energy transfer from Tb³⁺ to Ce³⁺ ions in YAG:Ce(2%),Tb(2%) nanoparticles as revealed by luminescence studies. Co-doping the YAG:Ce nanoparticles with Eu³⁺ results in significant decrease in the emission intensity of both Ce³⁺ and Eu³⁺ ions and this has been attributed to the oxidation of Ce³⁺ to Ce⁴⁺ and reduction of Eu³⁺ to Eu²⁺ ions. Dy³⁺ co-doping did not have any effect on the Ce³⁺ emission as there is no energy transfer between Dy³⁺ and Ce³⁺ ions.     

Luminescence of Mn ions in Tb3Al5O12 garnet

The paper is dedicated to investigation of the Mn²⁺ luminescence in Tb₃Al₅O₁₂ (TbAG) garnet, as well as the processes of excitation energy transfer between host cations (Tb³⁺ ions) and activators (Mn²⁺ and Mn²⁺-Ce³⁺ pair ions) in single crystalline films of TbAG:Mn and TbAG:Mn,Ce garnets which can be considered as promising luminescent materials for conversion of LED's radiation. Due to the effective energy transfer between TbAG host and activator, Mn²⁺ ions in TbAG possess the bright orange luminescence in the bands peaked at 595 nm with a lifetime of 0.64 ms which are caused by the ⁴T₁→⁶A₁ radiative transitions. The simultaneous process of energy transfer is realized in TbAG:Mn,Ce: (i) from Tb³⁺ to Mn²⁺ ions; (ii) from Tb³⁺ cations to Ce³⁺ ions and then partly to Mn²⁺ ions through Tb³⁺ ion sublattice and Ce-Mn dipole-dipole interaction.