Formation and spectral probing of transparent oxyfluoride glass-ceramics containing (Eu2+, Eu3+:BaGdF5) nano-crystals

In the present study, we report the formation of transparent glass-ceramics containing BaGdF₅ nanocrystals under optimum ceramization of SiO₂–BaF₂–K₂O–Sb₂O₃–GdF₃–Eu₂O₃ based oxyfluoride glass and the energy transfer mechanisms in Eu²⁺ → Eu³⁺ and Gd³⁺ → Eu³⁺ has been interpreted through luminescence study. The modification of local environment surrounding dopant ion in glass and glass ceramics has been studied using Eu³⁺ ion as spectral probe. The optimum ceramization temperature was determined from the differential scanning calorimetry (DSC) thermogram which revealed that the glass transition temperature (T_g), the crystallization onset temperature (T_x), and crystallization peak temperature (T_p) are 563 °C, 607 °C and 641 °C, respectively. X-ray diffraction pattern of the glass-ceramics sample displayed the presence of cubic BaGdF₅ phase (JCPDS code: 24-0098). Transmission electron microscopy image of the glass-ceramics samples revealed homogeneous distribution of spherical fluoride nanocrystals ranging 5–15 nm in size. The emission transitions from the higher excited sates (⁵D_J, J = 1, 2, and 3) as well as lowered asymmetry ratio of the ⁵D₀ → ⁷F₂ transition (forced electric dipole transition) to that of the ⁵D₀ → ⁷F₁ transition (magnetic dipole) of Eu³⁺ in the glass-ceramics when compared to glass sample demonstrated the incorporation of dopant Eu³⁺ ions into the cubic BaGdF₅ nanocrystals with higher local symmetry with enhanced ionic nature. The presence of absorption bands of Eu²⁺ ions and Gd³⁺ ions present in the glass matrix or fluoride nanocrystals in the excitation spectra of Eu³⁺ by monitoring emission at 614 nm indicated energy transfer from (Eu²⁺ → Eu³⁺) and (Gd³⁺ → Eu³⁺) in both glass and glass-ceramics samples.     

Spectroscopic properties of Eu3+/Nd3+ co-doped phosphate glasses and opaque glass–ceramics

This paper reports the fabrication and characterization of Eu³⁺/Nd³⁺ co-doped phosphate (PNE) glasses and glass–ceramics as a function of Eu³⁺ concentration. The precursor glasses were prepared by the conventional melt quenching technique and the opaque glass–ceramics were obtained by heating the precursor glasses at 450 °C for 30 h. The structural and optical properties of the glass and glass–ceramics were analyzed by means of X-ray diffraction, Raman spectroscopy, UV–VIS–IR absorption spectroscopy, photoluminescence spectra and lifetimes. The amorphous and crystalline structures of the precursor glass and opaque glass–ceramic were confirmed by X-ray diffraction respectively. The Raman spectra showed that the maximum phonon energy decreased from 1317 cm⁻¹ to 1277 cm⁻¹ with the thermal treatment. The luminescence spectra of the glass and glass–ceramic samples were studied under 396 nm and 806 nm excitation. The emission intensity of the bands observed in opaque glass–ceramic is stronger than that of the precursor glass. The luminescence spectra show strong dependence on the Eu³⁺ ion concentration in the Nd³⁺ ion photoluminescence (PL) intensity, which suggest the presence of energy transfer (ET) and cross-relaxation (CR) processes. The lifetimes of the ⁴F_3/2 state of Nd³⁺ ion in Eu³⁺/Nd³⁺ co-doped phosphate glasses and glass–ceramics under 806 nm excitation were measured. It was observed that the lifetimes of the ⁴F_3/2 level of Nd³⁺ of both glasses and glass–ceramics decrease with the increasing Eu³⁺ concentration. However in the case of opaque glass–ceramics the lifetimes decrease only 16%.     

Frequency upconversion properties of Er3+/Yb3+-codoped lead–germanium–bismuth oxide glasses

The frequency upconversion properties of Er³⁺/Yb³⁺-codoped heavy metal oxide lead–germanium–bismuth oxide glasses under 975 nm excitation are investigated. Intense green and red emission bands centered at 536, 556 and 672 nm, corresponding to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively, were simultaneously observed at room temperature. The influences of PbO on upconversion intensity for the green (536 and 556 nm) and red (672 nm) emissions were compared and discussed. The optimized rare earth doping ratio of Er³⁺ and Yb³⁺ is 1:5 for these glasses, which results in the stronger upconversion fluorescence intensities. The dependence of intensities of upconversion emission on excitation power and possible upconversion mechanisms were evaluated and analyzed. The structure of glass has been investigated by means of infrared (IR) spectral analysis. The results indicate that the Er³⁺/Yb³⁺-codoped heavy metal oxide lead–germanium–bismuth oxide glasses may be a potential materials for developing upconversion fiber optic devices.     

Multicolor upconversion of Er3+/Tm3+/Yb3+ doped oxyfluoride glass ceramics

Er³⁺/Tm³⁺/Yb³⁺ tridoped oxyfluoride glass ceramics was synthesized in a general way. Under 980 nm LD pumping, intense red, green and blue upconversion was obtained. And with those primary colors, multicolor luminescence was observed in oxyfluoride glass ceramics with various dopant concentrations. The red and green upconversion is consistent with ⁴F_9/2 → ⁴I_15/2 and ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transition of Er³⁺ respectively. While the blue upconversion originates from ¹G₄ → ³H₆ transition of Tm³⁺. This is similar to that in Er³⁺/Yb³⁺ and/or Tm³⁺/Yb³⁺ codoped glass ceramics. However the upconversion of Tm³⁺ is enhanced by the energy transfer between Er³⁺ and Tm³⁺.     

VUV–UV luminescence of Ce3+, Tb3+, Eu3+, and Dy3+ doped GdOCl

The vacuum ultraviolet spectroscopic properties of GdOCl:Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, and Dy³⁺) are investigated in detail for the first time. The host absorption band is determined to be around 179 nm, and the f–d transition bands as well as the charge transfer bands are assigned. Upon 179 nm excitation, Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, Dy³⁺) ions shown their characteristic emissions. Energy transfers from Gd³⁺ to Re³⁺ ion were observed. A broad band ranging from 350 to 400 nm corresponding to the d–f transition of Ce³⁺ is observed. Eu³⁺ has typical red emission with the strongest peak at 620 nm; Tb³⁺ shows characteristic transition of ⁵D_3,4 → ⁷F_j, and its spin-forbidden and spin-allowed f–d transitions in VUV region are calculated with Dorenbos’ equations, these calculated values agree well with the experimental results. Dy³⁺ presents yellow emission (⁴F_9/2 → ⁶H_13/2) with the strongest peak at 573 nm.     

Spectroscopic investigations on Eu3+ ions in Li–K–Zn fluorotellurite glasses

Eu³⁺ ions incorporated Li–K–Zn fluorotellurite glasses, (70 − x)TeO₂ + 10Li₂O + 10K₂O + 10ZnF₂ + xEu₂O₃, (0 ⩽ x ⩽ 2 mol%) were prepared via melt quenching technique. Optical absorption from ⁷F₀ and ⁷F₁ levels of the Eu³⁺-doped glass has been studied to examine the covalent bonding characteristics, energy band gap and Judd–Ofelt intensity parameters. The emission spectra (⁵D₀ → ⁷F_0,1,2,3,4) of the glasses were used to estimate the luminescence enhancement, asymmetric environment in the vicinity of Eu³⁺ ions, stimulated emission cross section and branching ratios. The phonon side band mechanism of ⁵D₂ level of the Eu³⁺ ions in the prepared glass was examined by considering the excitation and Raman spectra. The radiative lifetime calculated using Judd–Ofelt parameters was compared with the experimental lifetime to estimate the quantum efficiency of ⁵D₀ level of Eu³⁺ ions in Li–K–Zn fluorotellurite glass.     

Direct observation of Nd3 + and Tm3 + ion distributions in oxy-fluoride glass ceramics containing PbF2 nanocrystals

Nd^3 + and Tm^3 +, doped oxy-fluoride glasses and glass ceramics were prepared by conventional melt-quenching and subsequent heat-treatment, respectively. β-PbF₂ nanocrystals with diameter 50 –100 nm formed in the glass matrix after heat treatment. The Stark splitting in absorption peaks, enhanced photoluminescence and prolonged lifetimes that β-PbF₂ nanocrystal formation increased the luminescence of rare earth ions. Both Nd^3 + and Tm^3 + ions were incorporated into nanocrystals that were enriched in lead and fluorine, and deficient in oxygen.     

Visible quantum cutting through downconversion in Eu3+-doped K2GdZr(PO4)3 phosphor

K₂Gd_1?xZr(PO₄)₃:Eu_x³⁺ (0.02 ≤ x ≤ 0.1, x is in mol.%) were prepared by solid-state reaction method and their photoluminescence properties were investigated in ultra-violet (UV) and vacuum ultra-violet (VUV) region. The phenomenon of visible quantum cutting through downconversion was observed for the Gd³⁺–Eu³⁺ couple in this Eu³⁺-doped K₂GdZr(PO₄)₃ system. Visible quantum cutting, the emission of two visible light photons per absorbed VUV photon, occurred upon the 186 nm excitation of Gd³⁺ at the ⁶G_J level via two-step energy transfer from Gd³⁺ to Eu³⁺ by cross-relaxation and sequential transfer of the remaining excitation energy. The results revealed that the efficiency of the energy transfer process from Gd³⁺ to Eu³⁺ in the Eu³⁺-doped K₂GdZr(PO₄)₃ system could reach to 155% and K₂GdZr(PO₄)₃:Eu³⁺ was effective quantum cutting material.     

Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4:Eu3+

It has been found that charge compensated CaMoO₄:Eu³⁺ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO₄:Eu³⁺ without charge compensation. Two approaches to charge compensation, (a) 2Ca²⁺ → Eu³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Ca²⁺ → 2Eu³⁺ + vacancy, are investigated. The influence of sintering temperature and Eu³⁺ concentration on the luminescent property of phosphor samples is also discussed.     

Bifunction in Er3+/Yb3+ co-doped BaTi2O5–Gd2O3 glasses prepared by aerodynamic levitation method

Novel Er³⁺/Yb³⁺ co-doped BaTi₂O₅–Gd₂O₃ spherical glasses have been fabricated by aerodynamic levitation method. The thermal stability, upconversion luminescence, and magnetic properties of the present glass have been studied. The glasses show high thermal stability with 763.3 °C of the onset temperature of the glass transition. Red and green emissions centered at 671 nm, 548 nm and 535 nm are obtained at 980 nm excitation. The upconversion is based on a two-photon process by energy transfer, excited-state absorption, and energy back transfer. Yb³⁺ ions are more than Er³⁺ ions in the glass, resulting in efficient energy back transfer from Er³⁺ to Yb³⁺. So the red emission is stronger than the green emissions. Magnetization curves indicate that magnetic rare earth ions are paramagnetic and the distribution is homogeneous and random in the glass matrix. Aerodynamic levitation method is an efficient way to prepare glasses with homogeneous rare earth ions.     

Influences of Er3+ content on structure and upconversion emission of oxyfluoride glass ceramics containing CaF2 nanocrystals

Transparent 45SiO₂–25Al₂O₃–5CaO–10NaF–15CaF₂ glass ceramics doped with different content of erbium ion (Er³⁺) were prepared. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses evidenced the spherical CaF₂ nanocrystals homogeneously embedded among the glassy matrix. With increasing of Er³⁺ content, the size of CaF₂ nanocrystals decreased while the number density increased. The crystallization kinetics studies revealed that CaF₂ crystallization was a diffusion-controlled growth process from small dimensions with decreasing nucleation rate. Er³⁺ could act as nucleating agent to lower down crystallization temperature, while some of them may stay at the crystal surfaces to retard the growth of crystal. Intense red and weak green upconversion emissions were recorded for glass ceramics and their intensities increased with the increasing of Er³⁺ content under 980 nm excitation. However, the concentration quenching effect appeared when Er³⁺ doping reached 2 mol%. These results could be attributed to the change of ligand field of Er³⁺ ions due to the incorporation of Er³⁺ ions into precipitated fluoride nanocrystals.     

Effects of ultraviolet excitation on the spectroscopic properties of Sm3+ and Tb3+ doped aluminophosphate glasses

Li₂O–BaO–Al₂O₃–La₂O₃–P₂O₅ glasses optically activated with rare earth ions with the 4f⁵, and 4f⁸ electronic configuration (Sm³⁺ and Tb³⁺, respectively) were analyzed by Raman spectroscopy, absorption, excitation photoluminescence, decay curves and temperature dependent photoluminescence. The spectroscopic characteristics of the as-prepared and heat treated samples at temperatures below and above T_g were studied as well as their room temperature photometric properties under ultraviolet excitation. All the doped glasses exhibit typical signatures of the lanthanides in their trivalent charge state. For the samarium doped glass heat treated at 250 °C (<T_g) the Sm²⁺ luminescence was also observed. The analysis of the luminescence efficiency was performed in the interval range of 14 K to room temperature, where the integrated intensity of the luminescence was found to decrease for the Sm³⁺ and Tb³⁺ ions in the studied temperature range. Luminescence decay curves were found to be non-exponential for the ⁴G_5/2 → ⁶H_7/2 and ⁵D₃ → ⁷F₄ transitions of the Sm³⁺ and Tb³⁺ ions, respectively. The results strongly suggest the occurrence of energy transfer processes through cross relaxation phenomena, mediated by dipole–dipole interaction in all the studied samples. The decay of the ⁵D₄ → ⁷F₅ emission of the Tb³⁺ ions was found to be single exponential with a time constant of ∼3.1 ms. Based on the spectroscopic characteristics, models for recombination processes are proposed. The room temperature luminance photometric properties with ultraviolet excitation show that the samarium doped glasses have much lower luminance intensity (around 0.3 Cd/m²) when compared with the 6–7 Cd/m² observed for the terbium doped ones.     

Photoluminescence of Eu3+-doped LaPO4 nanocrystals synthesized by combustion method

Eu³⁺-doped LaPO₄ nanocrystals were synthesized for the first time by a combustion method with urea as a fuel calcined at 700 °C. The diffraction profile of the obtained sample was indexed as a monoclinic monazite-structure by X-ray diffraction (XRD) data. The obtained nanocrystals appeared to be short rod-like with diameters of 5–10 nm and lengths of 20–70 nm. The luminescence intensities of Eu³⁺-doped LaPO₄ nanocrystals were found to be strongly dependent on the quantities of urea added and the concentration of Eu³⁺.     

Synthesis and two-color emission properties of BaGd2(MoO4)4:Eu3+,Er3+,Yb3+ phosphors

Eu³⁺, Er³⁺ and Yb³⁺ co-doped BaGd₂(MoO₄)₄ two-color emission phosphor was synthesized by the high temperature solid-state method. The structure of the sample was characterized by XRD, and its luminescence properties were investigated in detail. Under the excitation of 395 nm ultraviolet light, the BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ phosphor emitted an intense red light at 595 and 614 nm, which can be attributed to ⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂ transitions of Eu³⁺, respectively. The phosphor will also show bright green light under 980 nm infrared light excitation. The green emission peaks centred at 529 and 552 nm, were attributed to ⁴H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺, respectively. It indicated that the two-color emission can be achieved from the same BaGd₂(MoO₄)₄:Eu³⁺,Er³⁺,Yb³⁺ host system based on the different pumping source, 395 nm UV light and 980 nm infrared light, respectively. The obtained results showed that this kind of phosphor may be potential in the field of multi-color fluorescence imaging and anti-counterfeiting.     

EPR,optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Antimony phosphate glasses (SbPO) doped with 3 and 6 mol% of Cr³⁺ were studied by Electron Paramagnetic Resonance (EPR), UV–VIS optical absorption and luminescence spectroscopy. The EPR spectra of Cr³⁺-doped glasses showed two principal resonance signals with effective g values at g = 5.11 and g = 1.97. UV–VIS optical absorption spectra of SbPO:Cr³⁺ presented four characteristics bands at 457, 641, 675, and 705 nm related to the transitions from ⁴A₂(F) to ⁴T₁(F), ⁴T₂(F), ²T₁(G), and ²E(G), respectively, of Cr³⁺ ions in octahedral symmetry. Optical absorption spectra of SbPO:Cr³⁺ allowed evaluating the crystalline field Dq, Racah parameters (B and C) and Dq/B. The calculated value of Dq/B = 2.48 indicates that Cr³⁺ ions in SbPO glasses are in strong ligand field sites. The optical band gap for SbPO and SbPO:Cr³⁺ were evaluated from the UV optical absorption edges. Luminescence measurements of pure and Cr³⁺-doped glasses excited with 350 nm revealed weak emission bands from 400 to 600 nm due to the ³P₁ → ¹S₀ electronic transition from Sb³⁺ ions. Cr³⁺-doped glasses excited with 415 nm presented Cr³⁺ characteristic luminescence spectra composed by two broad bands, one band centered at 645 nm (²E → ⁴A₂) and another intense band from 700 to 850 nm (⁴T₂ → ⁴A₂).     

Structural and spectroscopic characteristics of Eu3+-doped tungsten phosphate glasses

Tungsten based phosphate glasses are interesting non-crystalline materials, commonly known for photochromic and electrochromic effects, but also promising hosts for luminescent trivalent rare earth ions. Despite very few reports in the literature, association of the host́s functionalities with the efficient emissions of the dopant ions in the visible and near-infrared spectra could lead to novel applications. This work reports the preparation and characterization of glasses with the new composition 4(Sb₂O₃)96−x(50WO₃ 50NaPO₃)xEu₂O₃ where x = 0, 0.1, 0.25, 0.5 and 1.0 mol%, obtained by the melt quenching technique. The glasses present large density (∼4.6 g cm⁻³), high glass transition temperature (∼480 °C) and high thermal stability against crystallization. Upon excitation at 464 nm, the characteristic emissions of Eu³⁺ ions in the red spectral region are observed with high intensity. The Judd–Ofelt intensity parameters Ω₂ = 6.86 × 10⁻²⁰, Ω₄ = 3.22 × 10⁻²⁰ and Ω₆ = 8.2 × 10⁻²⁰ cm² were calculated from the emission spectra and found to be higher than those reported for other phosphate glass compositions. An average excited state lifetime value of 1.2 ms, was determined by fitting the luminescence decay curves with single exponential functions and it is comparable or higher than those of other oxide glasses.     

Down-shifting in Ce3+–Tb3+ co-doped SiO2–LaF3 nano-glass–ceramics for photon conversion in solar cells

95SiO₂–5LaF₃ sol–gel derived nano-glass–ceramics single doped with Ce³⁺ or Tb³⁺ and co-doped with Ce³⁺–Tb³⁺ were synthesized by thermal treatment of precursor glasses. Precipitation of LaF₃ nanocrystals during ceramming process was confirmed by X-ray diffraction with mean size ranging from 12 to 15 nm. An exhaustive spectroscopic analysis has been carried out. As a result, it was found that the green emission of Tb³⁺ ions was greatly enhanced through down shifting process, due to efficient energy transfer from Ce³⁺ to Tb³⁺ ions in the glass–ceramics, which is favored by the reduction of the interionic distances when the dopant ions are partitioned into LaF₃ nanocrystals. These results suggest the use of these materials to improve the efficiency of solar cells.     

Synthesis and photoluminescence properties of NaLaMgWO6:RE3+ (RE = Eu,Sm, Tb) phosphor for white LED application

Single phase of NaLa_1?xMgWO₆:xRE³⁺ (0 < x ≤1) (RE = Eu, Sm, Tb) phosphors were prepared by solid-state reaction method. X-ray diffraction, scanning electron microscopy, the morphology energy-dispersive X-ray spectroscopy, UV–vis diffuse reflectance spectra and photoluminescence were used to characterize the samples. Under the light excitation, NaLaMgWO₆:Eu³⁺, NaLaMgWO₆:Sm³⁺ and NaLaMgWO₆:Tb³⁺, phosphors showed the characteristic emissions of Eu³⁺ (⁵D₀ → ⁷F_{4, 3, 2, 1}), Sm³⁺ (⁴G_5/2 → ⁶H_{5/2, 7/2, 9/2}), and Tb³⁺ (⁵D₄ → ⁷F_{6, 5, 4, 3}), respectively. The intensity of the red emission for Na(La_0.6Eu_0.4)MgWO₆ is 2.5 times higher than that of (Y_0.95Eu_0.05)₂O₃ under blue light irradiation. The quantum efficiencies of the entitled phosphors excited under 394 nm and 464 nm are also investigated and compared with commercial phosphors Y₂O₃:Eu³⁺, Sr₂Si₅N₈:Eu²⁺ and Y₃A₅G₁₂:Ce³⁺. The results demonstrated NaLaMgWO₆:RE³⁺ phosphors as potential candidates for white light emitting diode pumped by UV or blue chip.     

Novel red phosphors LaBSiO5 co-doped with Eu3+, Al3+ for near-UV light-emitting diodes

Red-emitting phosphors LaBSiO₅:Eu³⁺ and LaBSiO₅:Eu³⁺, Al³⁺ were synthesized by the conventional solid state method at 1100 °C. The structure and luminescent properties of these phosphors are investigated. LaBSiO₅:Eu³⁺ and LaBSiO₅:Eu³⁺, Al³⁺ could be efficiently excited by near ultraviolet light with the strongest excitation peak at 395 nm. The main emission peak is located at around 616 nm, which corresponds to the transition of ⁵D₀ → ⁷F₂ of Eu³⁺ ions. The emission intensity of LaBSiO₅:Eu³⁺ was enhanced by introducing Al³⁺ ions. Compared with Y₂O₂S:0.05Eu³⁺, the sample La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺ shares the intense red emission, and its emission intensity is about 3.8 times as strong as that of Y₂O₂S:0.05Eu³⁺ under 395 nm light excitation. Bright red light can be observed from the red LED based on La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺, hence La_0.70B_0.75SiO₅:0.30Eu³⁺, 0.25Al³⁺ maybe find application on near-UV InGaN-based white LEDs.     

The structural influence of aluminium ions on emission characteristics of Sm3+ ions in lead aluminium silicate glass system

Optical absorption and photoluminescence characteristics of Sm³⁺ ions in lead silicate glasses mixed with different concentrations of Al₂O₃ (5–10 mol%) have been investigated. From these studies, the radiative properties viz., spontaneous emission probability A, the total emission probability, the radiative lifetime τ_R, the fluorescent branching ratio β of emission transition of ⁴G_5/2 → ⁶H_7/2 along with other transitions for Sm³⁺ have been evaluated and found to be the highest for the glass mixed with 8.0 mol% of Al₂O₃.The IR spectral studies have indicated that Al³⁺ ions do participate in the glass network with AlO₄ and AlO₆ structural units and further revealed that the concentration of octahedral aluminium ions induce bonding defects in the glass network. Such bonding defects are assumed to be responsible for low phonon losses in these glasses and lead to higher values of radiative parameters for the glass mixed with 8.0 mol% of Al₂O₃.