Synthesis, Characterization and Photophysical Properties of Eu3+ Doped in BaMoO4

In this work Ba_0.99Eu_0.01MoO₄ (BEMO) powders were prepared by the first time by the Complex Polymerization Method. The structural and optical properties of the BEMO powders were characterized by Fourier Transform Infra-Red (FTIR), X-ray Diffraction (XRD), Raman Spectra, High-Resolution Scanning Electron Microscopy (HR-SEM) and Photoluminescent Measurements. XRD show a crystalline scheelite-type phase after the heat treatment at temperatures greater than 400 °C. The ionic radius of Eu³⁺ (0.109 nm) is lower than the Ba²⁺ (0.149 nm) one. This difference is responsible for the decrease in the lattice parameters of the BEMO compared to the pure BaMoO₄ matrix. This little difference in the lattice parameters show that Eu³⁺ is expected to occupy the Ba²⁺ site at different temperatures, stayed the tetragonal (S₄) symmetry characteristic of scheelite-type crystalline structures of BaMoO₄. The emission spectra of the samples, when excited at 394 nm, presented the ⁵D₁→⁷F_{0, 1 and 2} and ⁵D₀→⁷F_{0, 1, 2, 3 and 4} Eu³⁺ transitions at 523, 533, 554, 578, 589, 614, 652 and 699 nm, respectively. The emission spectra of the powders heat-treated at 800 and 900 °C showed a marked increase in its intensities compared to the materials heat-treated from 400 to 700 °C. The decay times for the sample were evaluated and all of them presented the average value of 0.61 ms. Eu³⁺ luminescence decay time follows one exponential curve indicating the presence of only one type of Eu³⁺ symmetry site.     

The Role of the Eu<Superscript>3+</Superscript> Concentration on the SrMoO<Subscript>4</Subscript>:Eu Phosphor Properties: Synthesis,Characterization and Photophysical Studies

SrMoO₄ doped with rare earth are still scarce nowadays and have attracted great attention due to their applications as scintillating materials in electro-optical like solid-state lasers and optical fibers, for instance. In this work Sr_1−xEu_xMoO₄ powders, where x = 0.01; 0.03 and 0.05, were synthesized by Complex Polymerization (CP) Method. The structural and optical properties of the SrMoO₄:Eu³⁺ were analyzed by powder X-ray diffraction patterns, Fourier Transform Infra-Red (FTIR), Raman Spectroscopy, and through Photoluminescent Measurements (PL). Only a crystalline scheelite-type phase was obtained when the powders were heat-treated at 800 °C for 2 h, 2θ = 27.8° (100% peak). The excitation spectra of the SrMoO₄:Eu³⁺ (λ_Em. = 614 nm) presented the characteristic band of the Eu^3 + 5L₆ transition at 394 nm and a broad band at around 288 nm ascribed to the charge-transfer from the O (2p) state to the Mo (4d) one in the SrMoO₄ matrix. The emission spectra of the SrMoO₄:Eu³⁺ powders (λ_Exc. = 394 and 288 nm) show the group of sharp emission bands among 523–554 nm and 578–699 nm, assigned to the ⁵D₁→⁷F_{0,1and 2} and ⁵D₀→⁷F_{0,1,2,3 and 4}, respectively. The band related to the ⁵D₀→⁷F₀ transition indicates the presence of Eu³⁺ site without inversion center. This hypothesis is strengthened by the fact that the band referent to the ⁵D₀→⁷F₂ transition is the most intense in the emission spectra.     

Photoluminescence of fluoroacrylate polymers impregnated with Eu(bta)<Subscript>3</Subscript> using supercritical CO<Subscript>2</Subscript>

Optical properties (photoluminescence and absorption) of Eu(bta)₃(B) _n (B = H₂O or 1,10-phenanthroline) polycrystalline powders and fluoroacrylate polymers (FAPs) impregnated with these compounds using supercritical CO₂ (SC CO₂) were investigated. It was established that impregnation of Eu(bta)₃phen into the FAPs using an SC CO₂ solution was difficult to achieve. The type of B (ancillary ligand) and the polymer matrix were shown to influence the temperature quenching of photoluminescence of Eu³⁺ ions in the range 25–100°C. A comparative analysis of quantum yields (λ_ex = 300 and 380 nm) and photoluminescence decay times (λ_ex = 337.1 nm) for Eu(bta)₃B _n and for Eu(bta)₃B _n -doped FAPs was performed.     

Preparation of phosphors AEu(MoO4)2 (A?=?Li, Na, K and Ag) by?sol-gel method

A series of double molybdates phosphors AEu(MoO₄)₂ (A = Li, Na, K and Ag) have been prepared by sol-gel method. Their crystal structure and luminescent properties have also been investigated in a comparable way. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA). Field emission scanning electron microscopy (FE-SEM) was also used to characterize the shape and size distribution of the phosphors. Samples except KEu(MoO₄)₂ showed tetragonal scheelite structure in the range of our experiments, and no phase transition appeared. Phosphor KEu(MoO₄)₂ possessed two structures, and the phase transition took place at about 800°C. All samples with high purity could be obtained at about 500°C for 5 hours, and they all showed intense red light peaked at 616 nm originated from ⁵D₀→⁷F₂ emission of Eu³⁺ under the excitation of 465 nm or 394 nm light. The excitation spectra of phosphors AEu(MoO₄)₂ (A = Li, Na, and K) are composed of a strong broad charge transfer (CT) band and some sharp lines, and the relative intensity of CT band, the two strongest absorption lines at 395 nm and 465 nm are comparative, so these three phosphors are good red phosphor candidates for violet or blue LEDs. For the excitation spectrum of phosphor AgEu(MoO₄)₂, intensities of CT band and the absorption line at 395 nm are much weaker than that of line at 465 nm, thus phosphor AgEu(MoO₄)₂ is only suit for GaN-based blue LED.     

Synthesis and photoluminescence properties of?novel red-emitting phosphors for light emitting diodes

The novel red-emitting phosphors K₂Ba_1−x (MoO₄)₂: xEu³⁺(0.02≤x≤0.15) phosphors were prepared by solid-state reaction and their crystal structures, photo luminescent characteristics were investigated. The results show that all samples can be efficiently excited by UV (396 nm) and blue (466 nm) light, which are coupled well with the characteristic emission from UVLED and blue LED, respectively. Their emission spectra show intense red emission at 616 nm with line spectra due to the ⁵D₀–⁷F₂ transition of Eu³⁺. The XRD and photoluminescence experimental results indicate that the K₂Ba(MoO₄)₂: Eu³⁺ phosphor crystallization optimum annealing temperature occurs at about 800°C. The optimum doping concentration of Eu³⁺ is 0.10 mol, and the critical transfer distance (Rc) among Eu³⁺ ions is calculated to be about 11.126 ?. The approach to charge compensation was used: Ba²⁺→Eu³⁺+X⁻ (X=F, Cl, Br), and the charge compensation influence on the luminescent intensity of phosphors is investigated.     

KGd(MoO4)2:Eu as a promising red phosphor for light-emitting diode application

A red phosphor KGd(MoO₄)₂:Eu³⁺ was prepared by solid-state reaction technique at high temperature. Its photoluminescent property was investigated and the optimum concentration of Eu³⁺ doped in the KGd(MoO₄)₂ is 25 mol%. Compared with Y₂O₂S:0.05Eu³⁺, the obtained KGd(MoO₄)₂:Eu³⁺ shows wider excitation band around 400 nm, higher intensity of Eu^{3+ 5}D₀–⁷F₂ emission upon excitation 393 nm, and the CIE chromaticity coordinates (x = 0.655, y = 0.345) are closer to the standard of National Television Standard Committee (NTSC). The optical properties of KGd(MoO₄)₂:Eu³⁺ suggest that it is an efficient red-emitting phosphor for light-emitting diode applications.     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Spectral-luminescent properties of AgLa<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Eu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> solid solutions

The luminescent properties of AgLa_{1 − x} Eu _x (MoO₄)₂ (x = 0.1, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0) under laser excitation (λ = 337.1 nm) are studied. It is shown that, upon substitution of Eu³⁺ for La³⁺, the symmetry of luminescence centers does not vary. According to the X-ray diffraction data, all samples have scheelite-like structure; the pattern of variation in volumes of their unit cells counts in favor of the presence of a continuous series of solid solutions. It is found that an increase in the europium concentration in AgLa_{1 − x} Eu _x (MoO₄)₂ leads to an increase in the luminescence intensity with a maximum at x = 0.9.     

Determination of Ofloxacin using a Highly Selective Photo Probe Based on the Enhancement of the Luminescence Intensity of Eu3+—Ofloxacin Complex in Pharmaceutical and Serum Samples

A rapid, simple and sensitive spectrofluorimetric method for determination of trace amount of ofloxacin was developed. At pH 5.1 the ofloxacin enhances the luminescence intensity of the Eu³⁺ ion in Eu³⁺- ofloxacin complex at λ_ex = 365 nm. The produced luminescence intensity of Eu³⁺-ofloxacin complex was in proportional to the concentration of ofloxacin. The working range for the determination of ofloxacin was 5.0 × 10^-9–5.0 × 10^-6 mol L^-1 with lower detection limit (LOD) and quantitative detection limit (QDL) of 3 × 10^-9 and 9 × 10^-9 mol L^-1, respectively. The enhancement mechanism of the luminescence intensity in the Eu³⁺-ofloxacin system has been also explained. The method revealed good selectivity for ofloxacin in the presence of coexisting substances and used successfully for the assay of ofloxacin in pharmaceutical preparations and serum. A comparison with other standard methods was also discussed.     

Determination of Meloxicam Using Europium Sensitized Luminescence in the Presence of Co-Luminescence Reagents

A sensitive time- resolved luminescence method for the determination of meloxicam (MX) in methanol and in aqueous solution is described. The method is based on the luminescence sensitization of europium (Eu³⁺) by formation of ternary complex with MX in the presence of 1,10- phenanthroline as coligand, Tween-80 as surfactant and gadolinium ion as a co-luminescence reagent. The signal for Eu- MX-1, 10- phenanthroline is monitored at λ_ex = 360 nm and λ_em = 620 nm. Optimum conditions for the formation of the complex in aqueous system were 0.01 M TRIS buffer, pH 8.0, 1,10- phenanthroline (6.0 × 10⁻⁶ M) , Gd³⁺ (7.0 × 10⁻⁶ M), Tween-80 (0.28%) and 1.75 mM of Eu³⁺ which allows the determination of 20–800 ppb of MX with limit of detection (LOD) of 7 ppb. The relative standard deviations of the method range between 0.1 and 1.1% indicating excellent reproducibility of the method. The proposed method was successfully applied for the assay of MX in pharmaceutical formulations, plasma and in urine samples. Average recoveries of 99.8 ± 1.1%, 100.2 ± 0.9% and 100.9 ± 1.1% were obtained for MX in tablet, plasma and urine sample respectively.     

Luminescence Properties of Dual Valence Eu Doped Nano-crystalline BaF2 Embedded Glass-ceramics and Observation of Eu2+ → Eu3+ Energy Transfer

Europium doped glass-ceramics containing BaF₂ nano-crystals have been prepared by using the controlled crystallization of melt-quenched glasses. X-ray diffraction and transmission electron microscopy have confirmed the presence of cubic BaF₂ nano-crystalline phase in glass matrix in the ceramized samples. Incorporation of rare earth ions into the formed crystalline phase having low phonon energy of 346 cm⁻¹ has been demonstrated from the emission spectra of Eu³⁺ ions showing the transitions from upper excitation states ⁵D_J (J = 1, 2, and 3) to ground states for the glass-ceramics samples. The presence of divalent europium ions in glass and glass-ceramics samples is confirmed from the dominant blue emission corresponding to its 5d-4f transition under an excitation of 300 nm. Increase in the reduction of trivalent europium (Eu³⁺) ions to divalent (Eu²⁺) with the extent of ceramization is explained by charge compensation model based on substitution defect mechanisms. Further, the phenomenon of energy transfer from Eu²⁺ to Eu³⁺ ion by radiative trapping or re-absorption is evidenced which increases with the degree of ceramization. For the first time, the reduction of Eu³⁺ to Eu²⁺ under normal air atmospheric condition has been observed in a BaF₂ containing oxyfluoride glass-ceramics system.     

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.     

Spectral-luminescent properties of LiRbLa<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Eu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>(MoO<Subscript>4</Subscript>)<Subscript>4</Subscript> solid solutions

The luminescent properties of LiRbLa_{2 − x} Eu _x (MoO₄)₄ (x = 0.002, 0.02, 0.1, 0.2, 0.5, 1.0, 1.5, 2.0) solid solutions are investigated under laser excitation {λ_ex = 337.1 nm). It is established that the composition containing 50 at % Eu³⁺ is the brightest of the considered set of phosphors and has the highest quantum yield.     

Spectrofluorimetric Determination of Dopamine Using Chlorosulfonylthenoyltrifluoroacetone–Europium Probe

A new spectrofluorimetric method was developed for the determination of trace amounts of dopamine (DA). Using chlorosulfonylthenoyltrifluoroacetone (CTTA)–europium ion (Eu³⁺) as a fluorescent probe, in a buffer solution at pH = 10.0, DA can remarkably enhance the fluorescence intensity of the CTTA-Eu³⁺ complex at λ = 612 nm; the enhanced fluorescence intensity of Eu³⁺ is proportional to the concentration of DA. Optimum conditions for the determination of DA were also investigated. The linear range and detection limit for the determination of DA were 5.0 × 10⁻⁸∼1.6 × 10⁻⁵ mol/l and 3.2 × 10⁻⁸ mol/l. This method is simple, practical and relatively free of interference from coexisting substances, and can be applied to assess DA in injection and human serum samples with good precision and accuracy.     

A potential red phosphor LiGd(MoO4)2:Eu for light-emitting diode application

Eu³⁺-doped LiGd(MoO₄)₂ red phosphor was synthesized by solid-state reaction, and its photoluminescent properties were measured. The effect of Eu³⁺ doping concentration on PL intensity was investigated, and the optimum concentration of Eu³⁺ doped in LiGd(MoO₄)₂ was found to be 30 mol%. Compared with Y₂O₂S:0.05Eu³⁺, Na_0.5Gd_0.5MoO₄:Eu³⁺ and KGd(MoO₄)₂:Eu³⁺, the LiGd(MoO₄)₂:Eu³⁺ phosphor showed a stronger excitation band around 395 nm and a higher intensity red emission of Eu³⁺ under 395 nm light excitation. For the first time, intensive red light-emitting diodes (LEDs) were fabricated by combining phosphor and a 395 nm InGaN chip, confirming that the LiGd(MoO₄)₂:Eu³⁺ phosphor is a good candidate for LED applications.     

Spectrofluorimetric Assessment of Doxycycline Hydrochloride in Pharmaceutical Tablets and Serum Sample Based on the Enhancement of the Luminescence Intensity of the Optical Sensor Sm<Superscript>3+</Superscript> Ion

A simple and sensitive spectrofluorimetric method for determination of trace amount of doxycycline hydrochloride (DC) in pharmaceutical tablets and serum samples was developed. In ammonia buffer solution of pH 8.9 the doxycycline hydrochloride can remarkably enhance the luminescence intensity of the Sm³⁺ ion in Sm³⁺- DC complex at λ_ex = 400 nm. The produced luminescence intensity of Sm³⁺- DC complex in DMSO is in proportion to the concentration of DC and used as optical sensor for its determination. The dynamic range for the determination of DC is 1 × 10⁻⁸ – 5 × 10⁻⁶ mol L⁻¹ and in case of quantum yield calculations is 7 × 10⁻⁹ – 5 × 10⁻⁶ mol L⁻¹ with detection limit of 6.5 × 10⁻¹⁰ mol L⁻¹. The enhancement mechanism of the luminescence intensity in the Sm³⁺- DC system has been also discussed. A comparison with other spectrofluorimetric methods for tetracycline derivatives in which Eu³⁺ ion is used instead of Sm³⁺ ion is also studied.     

Terbium Sensitized Luminescence for the Determination of Ketoprofen in Pharmaceutical Formulations

This paper explores an ultra-sensitive luminescence method for the determination of Ketoprofen (KP) in pharmaceutical formulations. The technique is indirect and exploits the luminescence enhancement of terbium (Tb³⁺) by complexation with KP (Tb³⁺–KP), which was monitored at respective excitation and emission wavelengths of λ _ex = 258 nm and λ _em = 549 nm. The effect of varying the Tb³⁺ concentration and using multiple solvents was examined to determine optimal experimental conditions. Maximum sensitization was accomplished in the presence of methanol where the most favourable condition for the formation of the complex was recorded at a level of 1.0 × 10⁻⁵ M of Tb³⁺. Under these optimum experimental conditions, linear calibration curve was obtained in the range of 2.8 × 10⁻⁷–3.1 × 10⁻⁶ M with a detection limit of 8.7 × 10⁻⁸ M. The technique was validated with ‘working’ reference standards and produced relative standard deviations < 2% indicating that the reproducibility was highly acceptable. The proposed method was successfully applied to assays of KP in pharmaceutical formulations with average recoveries of 92–98%. The results were found to be in good agreement with those obtained by HPLC. The method is highly suited for general applications of this nature.     

Crystal structure and photoluminescence correlations in white emitting nanocrystalline ZrO2:Eu3+ phosphor: Effect of doping and annealing

White emitting nanocrystalline ZrO₂:Eu³⁺ phosphors were synthesized by a simple precipitation route without using a capping agent. X-ray diffraction (XRD) study of ZrO₂ and ZrO₂:Eu³⁺samples revealed the presence of monoclinic and tetragonal phases. The monoclinic phase increases with increase in the annealing temperature while the tetragonal phase increases with increase in the concentration of Eu³⁺. This can be attributed to the presence of oxygen vacancy evolved when Zr⁴⁺ is replaced by Eu³⁺. Photoluminescence (PL) emission peaks of Eu³⁺ are observed at 591, 596, 606 and 613 nm on monitoring excitation wavelengths at 250, 286, 394 and 470 nm. The peaks at 591 and 606 nm were found to correlate with the tetragonal phase and those at 596 and 613 nm with the monoclinic phase. Intensities of these peaks are found to change as the crystal structure changes. The lifetime value corresponding to 591 nm peak increases with Eu³⁺ concentration at a particular heating temperature indicating increase of tetragonal phase with respect to monoclinic phase. The CIE co-ordinates of the doped samples were found to be close to that of white color (0.33, 0.33). The changes in the crystal structure of the doped samples due to doping and annealing did not affect the white color emission.     

Emission analysis of RE3+ (Eu3+, Tb3+ & Ho3+): B2O3-BaO-LiF/AIF3 glasses

We report here the luminescence spectra of certain rare earth ions (Eu³⁺, Tb³⁺ & Ho³⁺) doped B₂O₃-BaO-LiF/AiF₃ based on the measurements of emission and decay curves of prominent emission transitions. For both the reference host glasses, FTIR, XRD, DTA-TG profiles have been recorded to understand their structural and thermal properties. Eu³⁺ doped glasses have shown five emission transitions of ⁵D₀ → ⁷F_{01,2,3 & 4} located at 580nm, 593nm, 615nm, 655nm and 704nm respectively with an excitation at λ_exci = 392 nm (⁷F₀ → ⁵L₆). Also under an UV source, these europium glasses have displayed a bright red emission from their surfaces. Tb³⁺ glasses have exhibited four emission bands of ⁵D₄ → ⁷F_6,5,4,3 at 491nm, 547nm, 588nm and 625nm respectively with an excitation at λ_exci = 376 nm (⁷F₆ → ⁵G₆). Intense green emission from the glass surfaces has been noticed upon exposure to the UV source. Prominently bluish-green emission has been noticed from the surfaces of the holmium glasses under an UV source and same emission transition (⁵F₄ → ⁵I₈) at 519 nm with an excitation at λ_exci = 389 nm (⁵I₈ − ⁵G₄) has also been obtained from their measured emission spectra. For all the prominent emissions of the rare earth glasses, decay curves have been measured to compute their lifetimes.     

Luminescence of Eu<Superscript>2+</Superscript> ions in alkaline earth dilithiosilicates

Spectral-luminescent properties of Eu²⁺ ions in alkaline earth dilithiosilicates of composition MLi₂SiO₄ (M = Ca, Sr, Ba) have been studied at 77 K. The reasons for the different positions of the Eu²⁺ 4f ⁶5 d → 4f ⁷ emission band maximum in spectra of MLi₂SiO₄ were found based on the obtained results. It was shown that the increase in the decay time of the Eu²⁺ emission on going from CaLi₂SiO₄ (0.41μs) through BaLi₂SiO₄ (0.64 μs) to Sr-silicate (1.11μs) correlates with the shift of the emission maximum to longer wavelengths.