Luminescence Spectra of Poly(methylmethacrylate)/ZnS:Eu(III),Tb(III) Composites

Colloidal zinc sulfide solutions have been prepared by reacting zinc trifluoroacetate and thioacetamide in methyl methacrylate as a reaction medium, and europium and terbium salts have been added to the solution. Using methyl methacrylate block polymerization, we have synthesized PMMA/ZnS, PMMA/ZnS:Eu(III), PMMA/ZnS:Tb(III), and PMMA/ZnS:Eu(III),Tb(III) composites. The luminescence of the composites is due to charge recombination at energy levels of structural defects and impurities in ZnS and also to ⁵D₀ → ⁷F _j and ⁵D₄ → ⁷F _j electronic transitions of the Eu³⁺ and Tb³⁺ ions. It depends on the composition and structure of the composites, excitation wavelength, and other factors. The mutual effects of the ZnS and the Eu³⁺ and Tb³⁺ ions show up as changes in the position and relative intensity of luminescence bands in the spectra of the composites.     

Synthesis and luminescence spectra of (Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–YOF):Ln(III) composites

Sols were prepared by reacting yttrium, europium, and terbium trifluoroacetates with thioacetamide in ethyl acetate. The Eu³⁺ and Tb³⁺ concentrations in the sols were 0.10 to 10 wt % relative to yttrium, which corresponded to 0.061 (0.059) to 6.1 (5.9) at % Eu (Tb). The sols were converted into a gel-like state by slowly evaporating the solvent. After ripening, the gels were heat-treated at a temperature of 800°C. X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and IR spectroscopy results showed that the resultant composites consisted predominantly of a mixture of Y₂O₃ and YOF. The Eu³⁺ and Tb³⁺ ions were shown to substitute for Y³⁺ ions in the crystal lattices of the yttrium oxide and yttrium oxyfluoride. The formation of the (Eu_0.6Y_0.4)₂O₃, Eu₂O₃, and EuOF phases was demonstrated. We determined the types and parameters of the crystal lattices of the synthesized materials in relation to activator concentrations. The luminescence of the composites is due to the ⁵ D ₀ → ⁷ F _j and ⁵ D ₄ → ⁷ F _j electronic transitions of the Eu³⁺ and Tb³⁺ ions and depends on the host and activator compositions, the excitation wavelength, and other factors.     

Tb<Superscript>3+</Superscript> photoluminescence in mesoporous glasses,terbium nitrate and terbium chloride hexahydrates,and coordination compounds

We have compared the intensity and shape of photoluminescence spectra of Tb³⁺ ions in mesoporous glasses, inorganic phosphors (terbium nitrate and terbium chloride hexahydrates), and coordination compounds (terbium benzoate, terbium o-phenoxybenzoate, and terbium terephthalate). The excitation sources used were a repetitively pulsed nitrogen laser with an emission wavelength of 337 nm and cw semiconductor light-emitting diodes with wavelengths of 369 and 385 nm. It has been shown that the highest photoluminescence intensity normalized by the percentage of terbium is offered by terbium terephthalate and terbium- doped mesoporous glass. We are thus led to conclude that introducing terbium terephthalate into the pores of mesoporous photonic glass and mesoporous photonic crystals is a promising approach for obtaining efficient laser operation in the green spectral region on the ⁵D₄–7F₅ transition of the terbium ion.     

Green electroluminescence from AlN:Tb thin film devices on glass

Electroluminescence (EL) properties of AlN:Tb thin film EL device (TFELD) prepared on a glass substrate by a rf-magnetron sputtering method have been studied. The AlN:Tb emission layer consists of hexagonal (110)-oriented poly-crystals of AlN with a high transparency in visible region. Four emission peaks originating from ⁵D₄ → ⁷F _j (j = 6, 5, 4, 3) transitions of Tb³⁺ were found in both photoluminescence (PL) and EL spectra of the AlN:Tb thin film. The peak emission intensity of the ⁵D₄ → ⁷F₆ transitions is almost the same magnitude with that of the ⁵D₄ → ⁷F₅ transitions, being largely different from the intensity ratio of Tb³⁺in other host materials.     

Synthesis and luminescence spectra of poly(methyl methacrylate)/CdS:Ln(III) composites

Cadmium sulfide was prepared by colloidal synthesis in methyl methacrylate (MMA). Europium and terbium salts were added to the colloidal solutions. Using MMA radical polymerization, we synthesized PMMA/CdS:Eu(III), PMMA/CdS:Tb(III), and PMMA/CdS:Eu(III):Tb(III) luminescent composites. Their luminescence is due to defects in the CdS crystals and the ⁵ D _о → 7Fj and ⁵ D ₄ → ⁷ F _j electronic transitions of the Eu³⁺ and Tb³⁺ ions, respectively. It depends on the composition of the materials, complexation on the surface of the colloidal particles, heat treatment time during synthesis, excitation wavelength, and other factors.     

Luminescence performance of Eu<Superscript>3+</Superscript>-doped lead-free zinc phosphate glasses for red emission

In this study, the luminescence performance of zinc phosphate glasses containing Eu³⁺ ion with the chemical compositions (60–x)NH₄H₂PO₄-20ZnO-10BaF₂-10NaF–x Eu₂O₃ (where x = 0.2, 0.5, 1.0 and 1.5 mol%) has been studied. These glasses were characterized by several spectroscopic techniques at room temperature. All the glasses showed relatively broad fluorescence excitation and luminescence spectra. Luminescence spectra of these glasses exhibit characteristic emission of Eu³⁺ ion with an intense and most prominent red emission (614 nm), which is attributed to ⁵D₀ → ⁷F₂ transition. Judd-Ofelt (Ω₂, Ω₄) parameters have been evaluated from the luminescence intensity ratios of ⁵D₀ → ⁷F_J (where J = 2 and 4) to ⁵D₀ → ⁷F₁ transition. Using J-O parameters and excitation spectra, the radiative parameters are calculated for different Eu³⁺-doped glasses. Effect of γ-irradiation at fixed dose has been studied for all the Eu³⁺-doped glass matrices. The lifetimes of the excited level, ⁵D₀, have been measured experimentally through decay profiles. The colour chromaticity coordinates are calculated and represented in the chromaticity diagram for Eu³⁺-doped zinc phosphate glasses for all concentrations.     

Temperature effect on the photoluminescence intensity and Eu<Superscript>2+</Superscript> excited state lifetime in EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript> and EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript>:Er<Superscript>3+</Superscript>

The photoluminescence (PL) spectra and Eu²⁺ excited state lifetime of EuGa₂S₄ and EuGa₂S₄:Er³⁺ have been studied in the range 78–500 K. The spectra show a band at 545 nm, due to the 4f ⁶5d → 4f ⁷(⁸ S _7/2) transition. With increasing temperature, the full width at half maximum Γ(T) of the PL band of EuGa₂S₄ and EuGa₂S₄:Er³⁺ crystals increases from 0.15 to 0.22 and from 0.13 to 0.19 eV, respectively. Over the entire temperature range studied, Γ(T) is a linear function of T ^1/2. The 545-nm emission intensity and Eu²⁺ excited state lifetime in EuGa₂S₄ and EuGa₂S₄:Er³⁺ vary exponentially with temperature. The luminescence quenching energies evaluated from the Arrhenius plots of I(10³/T) and τ(10³/T) coincide (0.10 eV) within the error of determination.     

Rapid synthesis and enhancement in down conversion emission properties of BaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>,RE<Superscript>3+</Superscript> (RE<Superscript>3+</Superscript>=Y,Pr) nanophosphors

BaAl₂O₄:Eu²⁺,RE³⁺ (RE³⁺=Y, Pr) down conversion nanophosphors were prepared at 600 °C by a rapid gel combustion technique in presence of air using boron as flux and urea as a fuel. A comparative study of the prepared materials was carried out with and without the addition of boric acid. The boric acid was playing the important role of flux and reducer simultaneously. The peaks available in the XPS spectra of BaAl₂O₄:Eu²⁺ at 1126.5 and 1154.8 eV was ascribed to Eu²⁺(3d _5/2) and Eu²⁺(3d _3/2) respectively which confirmed the presence of Eu²⁺ ion in the prepared lattice. Morphology of phosphors was characterized by tunneling electron microscopy. XRD patterns revealed a dominant phase characteristics of hexagonal BaAl₂O₄ compound and the presence of dopants having unrecognizable effects on basic crystal structure of BaAl₂O₄. The addition of boric acid showed a remarkable change in luminescence properties and crystal size of nanophosphors. The emission spectra of phosphors had a broad band with maximum at 490–495 nm due to electron transition from 4f ⁶5d ¹ → 4f ⁷ of Eu²⁺ ion. The codoping of the rare earth (RE³⁺=Y, Pr) ions help in the enhancement of their luminescent properties. The prepared phosphors had brilliant optoelectronic properties that can be properly used for solid state display device applications.     

Photoluminescence of terbium nitrate hexahydrate incorporated into pores of opal photonic crystals

We have measured photoluminescence (PL) and broadband reflection spectra of the surface of an opal photonic crystal (OPC) filled with terbium nitrate hexahydrate (TNH). The excitation sources used were a halogen lamp, lasers with emission wavelengths of 266 and 337 nm, and semiconductor light-emitting diodes (369 and 385 nm). It has been shown that resonance excitation of the TNH (Tb(NO₃)₃ · 6H₂O) filled OPC by pulsed laser light at a wavelength of 266 nm gives rise to superluminescence: an increase in the relative intensity of the 545-nm PL band, corresponding to the Tb^{3+ 5} D ₄–⁷ F ₅ transition. The efficiency of pumping the upper laser level of the OPC increases due to the increase in the density of photon states (Purcell effect) near the bandgap edge in the OPC. The lack of clear superluminescence under excitation by the other excitation sources is related to specific features of the absorption of incident light by the rare-earth ion and to the low output power of the cw light sources.     

Absorption spectra of bulk aluminum nitride crystals doped with Er<Superscript>3+</Superscript> ions

This Letter presents results of analysis of the absorption spectra of AlN:Er³⁺ bulk crystals. In the spectral of 370–700 nm, absorption lines responsible for intraconfiguration electron transition from the ground state ⁴I_15/2 to the excited states of Er³⁺ ions are found. Transitions to the levels of the ⁴F_9/2, ²H_11/2, and ⁴G_11/2 states at 2 K are studied in detail. The number of observed lines for these transitions fully agrees with that theoretically possible for f–f electron transitions in Er³⁺ ions found in a noncubic crystal field. The small width of the observed lines and their number indicate that erbium ions displace mostly one regular crystal position. Most probably, Er³⁺ occupies the position of Al. Energy positions of excited states for the considered transitions are determined.     

Influence of Nd doping on microwave dielectric properties of SrTiO<Subscript>3</Subscript> ceramics

Sr_1?x Nd _x TiO₃ (x?=?0.08–0.14) ceramics were prepared by conventional solid-state methods. The analysis of crystal structure suggested Sr_1?x Nd _x TiO₃ ceramics appeared to form tetragonal perovskite structure. The relationship between charge compensation mechanism, microstructure feature and microwave dielectric properties were investigated. Trivalent Nd³⁺ substituting Sr²⁺ could effectively decrease oxygen vacancies. This reduction and relative density were critical to improve Q?×?f values of Sr_1?x Nd _x TiO₃ ceramics. For ε _r values, incorporation of Nd could restrain the rattling of Ti⁴⁺ cations and led to the reduction of dielectric constant. The τ _f values were strongly influenced by tilting of oxygen octahedral. The τ _f values decreased from 883 to 650 ppm/°C with x increasing from 0.08 to 0.14. A better microwave dielectric property was achieved for composition Sr_0.92Nd_0.08TiO₃ at 1460 °C: ε _r ?=?160, Q?×?f?=?6602 GHz, τ _f ?=?883 ppm/°C.     

Photoluminescence and electrical properties of Eu3+-doped Na0.5Bi4.5Ti4O15-based ferroelectrics under blue light excitation

Na_0.5Bi_4.5?x Eu _x Ti₄O₁₅ (NBT- _x Eu³⁺) ceramics with x = 0, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30 and 0.40 were prepared by conventional ceramics processing. NBT-0.25Eu³⁺ ceramics show the strongest red and orange emissions corresponding to the ⁵D₀ → ⁷F₂ (617 nm) and ⁵D₀ → ⁷F₁ (596 nm) transitions, respectively. The strongest excitation band around 465 nm matches well with the emission wavelength of commercial InGaN-based blue LED chip, indicating that Eu³⁺-doped NBT ceramics may be used as potential environmental friendly red-orange phosphor for W-LEDs application. As an inherent ferroelectric and piezoelectric material, the electrical properties of this potentially multifunctional electro-optical material have been also studied. The introduction of Eu³⁺ distinctly increased the Curie temperature (T _C ) of NBT- _x Eu³⁺ ceramics from 640°C to 711°C as x ranges from 0 to 0.40. For higher temperature applications, the electrical conductivity was also investigated. The conduction of charge carriers in high-temperature range originates from the conducting electrons from the ionization of oxygen vacancies. High T _C and low tanδ makes Eu³⁺-doped NBTceramic also suitable for high temperature piezoelectric sensor applications and electro-optical integration.     

Strong up-conversion luminescence and electrical properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> multifunctional ceramics by Er<Superscript>3+</Superscript> doping

Novel green-emitting piezoelectric ceramics of SrBi_4?x Er _x Ti₄O₁₅ (SBT-xEr) were prepared. Strong up-conversion with bright green (524 and 548 nm) and a relatively weak red (660 nm) emission bands were obtained under 980 nm excitation at room temperature, which is attributed to the intra 4f–4f electronic transition of (²H_11/2, ⁴S_3/2)–⁴I_15/2 and the transition from ⁴F_9/2 to ⁴I_15/2 of Er³⁺ ions, respectively. Simultaneously, Er³⁺ doping promotes the electrical properties. At 0.8 mol%Er, the optimal electric properties with high Curie temperature of T _c?~527?°C, large remanent polarization of 2P _r?~14.92 μC/cm² and piezoelectric constant of d ₃₃?~17 pC/N was achieved. As a multifunctional material, Er³⁺ doped SBT showed a great potential to be used in 3D-display, bio-imaging, solid state laser and optical temperature sensor.     

Facile synthesis and characterization of TiO<Subscript>2</Subscript>–graphene–ZnFe<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Tb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>4</Subscript> ternary nano-hybrids

Rare earth ion (Tb³⁺)-doped zinc ferrite (ZnFe₂O₄) nanoparticles grown on reduced graphene oxide (RGO) prepared through sol–gel method have been reported. During the sol–gel process, graphene oxide was reduced to RGO, and, subsequently, anatase TiO₂ and cubic spinel ZnFe_2?x Tb _x O₄ were grown in situ on the surfaces of the RGO nano-sheets. The structure, surface morphology and chemical composition of ternary nano-composites were studied using scanning electron microscopy, energy-dispersive X-ray, X-ray diffraction (XRD), Fourier transform infrared spectroscopy, photoluminescence spectra and vibrating sample magnetometer (VSM). XRD results showed that the produced TiO₂ was composed of anatase and some rutile phases and ZnFe₂O₄ with a cubic spinel structure. The particle sizes of ZnFe₂O₄ and TiO₂ nanoparticles were in the ranges of ~65–80 and ~17–20 nm, respectively. The saturation magnetization (M _S) determined from VSM was found to linearly increase with Tb³⁺ concentration.     

Luminescent properties of europium-activated yttrium gadolinium phosphates

Nanocrystalline Y_{1 ? x ? y} Gd _x Eu _y PO₄ phosphors have been prepared via precipitation from aqueous solutions. From their luminescence and excitation spectra, the intensity ratio I ₆₁₅/I ₅₉₄ of the Eu³⁺ luminescence bands corresponding to electric dipole and magnetic dipole transitions has been determined as a function of Gd³⁺ content. The critical concentration and effective energy transfer radius in Y_{1 ? x ? y} Gd _x Eu _y PO₄ have been evaluated. Excitation of Gd³⁺⁸ S _J ?⁶ D _J and ⁸ S _J ?⁶ J _J transitions to Eu³⁺ luminescence excitation levels in Y_{0.99 ? x} Gd _x Eu_0.01PO₄ involves efficient energy transfer. Under 250-nm excitation, the Eu³⁺ luminescence yield in Y_{0.99 ? x} Gd _x Eu_0.01PO₄ is a factor of 2.5–3 higher than that in Y_0.99Eu_0.01PO₄.     

New,thermally stable Gd<Subscript>11</Subscript>(GeO<Subscript>4</Subscript>)(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>O<Subscript>10</Subscript>-based upconversion phosphors

A series of Gd_11–x–y Yb _x Er _y GeP₃O₂₆ germanate phosphates differing in the ratio of the Yb³⁺ and Er³⁺ active ions have been synthesized, and their luminescence spectra have been measured. According to X-ray diffraction characterization results, all of the synthesized germanate phosphates are single-phase and have a triclinic structure (sp. gr. P1). We have measured upconversion luminescence spectra due to the Er^{3+ 2}H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 radiative transitions in the synthesized gadolinium ytterbium erbium germanate phosphates and determined the luminescence upconversion energy yield (B _en) in Gd_11–x–y Yb _x Er _y GeP₃O₂₆. The effects of the concentrations and ratio of the dopants in the Gd₁₁(GeO₄)(PO₄)₃O₁₀ germanate phosphate host on B _en and the ratio of the luminescence intensities in the red and green spectral regions (R/G) have been assessed.     

Synthesis and luminescence properties of Tb<Superscript>3+</Superscript>-doped LiMgPO<Subscript>4</Subscript> phosphor

Polycrystalline sample LiMg_(1?x)PO₄:xTb³⁺ (x = 0.001, 0.002, 0.005, 0.01, 0.02) phosphor was synthesized via modified solid state method (MSSM). The prepared sample was characterized through XRD pattern (X-ray diffraction) and SEM (scanning electron microscope). Additionally, photoluminescence (PL), optically stimulated luminescence (OSL), thermoluminescence (TL) and other dosimetric properties including dose linearity, reusability and fading were studied. In OSL mode, sensitivity of prepared phosphor was found to be 2.7 times that of LiMgPO₄:Tb³⁺, B (BARC) phosphor and 4.3 times that of α-Al₂O₃:C (BARC) phosphor. The TL glow consists of overlapping peaks in temperature range of 50–400^°C and first peak (P₁) was observed at 150^°C, second peak (P₂) at 238^°C, third peak (P₃) at 291^°C and fourth peak (P₄) at 356^°C. The TL sensitivity of second peak (P₂) of LiMgPO₄:Tb³⁺ phosphor was compared with α-Al₂O₃:C (BARC) phosphor and found to be 100 times that of the α-Al₂O₃:C (BARC) phosphor. The minimum detectable dose (MDD) was found to be 5.6 μGy. Moreover, photoionization cross-sections, linearity, reusability, fading and kinetic parameters were calculated. Also, photoluminescence spectra of LiMgPO₄: Tb³⁺ shows characteristic green–yellow emission exciting at 224 nm UV source.     

Optical properties of europium-activated hafnium fluoride-based glasses

We have studied the optical absorption, luminescence, and electron paramagnetic resonance of EuF₃- and EuF₂-activated fluorohafnate glasses. The glasses prepared with EuF₂ contain both di- and trivalent europium. The fraction of divalent europium clusters in the glass host decreases with decreasing EuF₂ concentration. Eu²⁺ luminescence in the fluorohafnate glasses is quenched, which is due the overlap of Eu²⁺ excited state levels with the conduction band of the glass, resulting in nonradiative relaxation through Hf³⁺ levels in the conduction band. The Eu³⁺ luminescence spectra contain lines corresponding to transitions from several levels of the ⁵D multiplet to levels of the ⁷F multiplet. The relationship between transitions from different ⁵D levels depends on europium concentration and temperature.     

Recombination processes in the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> scintillator

The roentgenoluminescence spectra, temperature-dependent activator luminescence, optically stimulated luminescence, and the effect of IR irradiation on the yield and spectral composition of the low-temperature roentgenoluminescence and thermoluminescence curves of the Y₃Al₅O₁₂:Ce³⁺ scintillator have been studied in the temperature range 85–295 K. The results, coupled with earlier data, suggest that the Ce³⁺ ions in the garnet crystal studied form Ce³⁺ p hole centers and increase the concentration of electronic F ^?-centers responsible for the IR stimulation band at 940 nm. The reduction in roentgenoluminescence yield on cooling Y₃Al₅O₁₂:Ce³⁺ to below 230 K is due to the significant localization of excited carriers at defects, which show up in thermoluminescence peaks and optical stimulation spectra. The low-temperature Ce³⁺ luminescence in Y₃Al₅O₁₂:Ce₃₊ seems to result from the recombination of activator-bound excitons.     

Upconversion Luminescence of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocrystals Doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> Ions

The upconversion luminescence (UCL) of nanocrystalline gadolinium oxide (Gd₂O₃) doped with Er³⁺ and Yb³⁺ ions has been studied in the temperature range of 90–400 K. The nanocrystals were synthesized by chemical vapor deposition and possessed a cubic crystalline structure with an average particle size within 48–57 nm. It is established that the USL intensity in the red (⁴F_9/2 → ⁴I_15/2 transition in Er3+ ion) and green (⁴S_3/2 → ⁴I_15/2 transition) spectral regions depends on the sample temperature and concentration of dopant ions, as well as on the additional structural defects (anion vacancies) created in the crystal lattice by the introduction of Zn²⁺ ions or irradiation with high-energy (10 MeV) electrons. The luminescence efficiency and spectrum of the upconversion phosphor are determined by energy transfer processes.