The structure and luminescence properties of Mn2+/Eu2+/Er3+‐doped MgO‐Ga2O3‐SiO2 glasses and glass‐ceramics

The MgO–Ga₂O₃–SiO₂ glasses and glass‐ceramics samples doped with Eu²⁺/Mn²⁺/Er³⁺ and heated in reductive atmosphere were prepared by the sol–gel method. The structure, morphology and the luminescence properties were studied using X‐ray diffraction, high‐resolution transmission electron microscope, fluorescence spectra, and up‐conversion emission. The luminescence characteristics of doped ions could be influenced by temperature and matrix component. The characteristic emission of Mn²⁺, Eu²⁺ and Er³⁺ were seen and the energy transfer efficiency from Eu²⁺ to Mn²⁺ was enhanced as Mn²⁺ concentration was increased. In addition, the two‐photon process was determined for the Er³⁺‐doped samples.     

Luminescent properties of Ca3SiO4Cl2 co‐doped with Ce3+ and Eu2+ for near‐ultraviolet light‐emitting diodes

Ca₃SiO₄Cl₂ co‐doped with Ce³⁺,Eu²⁺ was prepared by high temperature reaction. The structure, luminescent properties and the energy transfer process of Ca₃SiO₄Cl₂: Ce³⁺,Eu²⁺ were investigated. Eu²⁺ ions can give enhanced green emission through Ce³⁺ → Eu²⁺ energy transfer in these phosphors. The green phosphor Ca_2.9775SiO₄Cl₂:0.0045Ce³⁺,0.018Eu²⁺ showed intense green emission with broader excitation in the near‐ultraviolet light range. A green light‐emitting diode (LED) based on this phosphor was made, and bright green light from this green LED could be observed by the naked eye under 20 mA current excitation. Hence it is considered to be a good candidate for the green component of a three‐band white LED. Copyright © 2015 John Wiley & Sons, Ltd.     

Energy transfer in M5(PO4)3 F:Eu2+,Ce3+ (M = Ca and Ba) phosphors

M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) co‐doped with Ce³⁺ phosphors were successfully prepared by the combustion synthesis method. The introduction of co‐dopant (Ce³⁺) into the host enhanced the luminescent intensity of the M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) efficiently. Previously, we have reported the synthesis and photoluminescence properties of same phosphors. The aim of this article is to report energy transfer mechanism between Ce³⁺?Eu²⁺ ions in M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) phosphors, where Ce³⁺ ions act as sensitizers and Eu²⁺ ions act as activators. The M₅(PO₄)₃ F:Eu²⁺ (M = Ca and Ba) co‐doped with Ce³⁺ phosphor exhibits great potential for use in white ultraviolet (UV) light‐emitting diode applications to serve as a single‐phased phosphor that can be pumped with near‐UV or UV light‐emitting diodes. Copyright © 2013 John Wiley & Sons, Ltd.     

Influence of Tl+ activator ions on the luminescence characteristics of KCl0.5Br0.5:Eu2+ powder phosphors

Photoluminescence (PL) of thallium co‐doped with KCl_0.5Br_0.5:Eu²⁺ powder phosphors display emission bands at 320 and 370 nm attributable to centres involving Tl⁺ ions in addition to characteristic Eu²⁺ emission around 420 nm. Additional PL excitation and emission bandS observed around 260 and 380 nm, respectively, were observed in the double‐doped KCl_0.5Br_0.5:Eu²⁺, Tl⁺ powder phosphors and are attributed to complex centres involving Tl⁺ and Eu²⁺ ions. The enhancement observed in the intensity of Eu²⁺ emission around 420 nm with the addition of TlBr in KCl_0.5Br_0.5:Eu²⁺ powder phosphors is attributed to the energy transfer from Tl⁺ → Eu²⁺ ions. Photostimulated luminescence (PSL) studies of γ‐irradiated KCl_0.5Br_0.5:Eu²⁺, Tl⁺ mixed phosphors are reported and a tentative PSL mechanism in the phosphors has been suggested. Copyright © 2009 John Wiley & Sons, Ltd.     

Photoluminescence and thermoluminescence characteristics of Sr3B2O6:Eu2+ yellow phosphor

Sr₃B₂O₆:Eu²⁺ yellow phosphor was prepared by the combustion method. The crystalline structure, photoluminescence and thermoluminescence properties of Sr₃B₂O₆:Eu²⁺ were investigated extensively. The X‐ray diffraction result indicates that the Sr₃B₂O₆:Eu²⁺ phosphor exhibited a rhombohedral crystal structure. The emission spectra under a 435 nm excited wavelength showed an intense broad band peaking at 574 nm, which corresponds to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ion. There were two different sites of Sr replaced by Eu in host lattice. The concentration quenching process between Eu²⁺ ions is determined and the corresponding concentration quenching mechanism was verified as dipole‐quadrupole interaction. The glow curve under 3 Gy β‐ ray irradiation had the glow peak at 160°C and the average activation energy was defined as about 0.98 eV. Copyright © 2015 John Wiley & Sons, Ltd.     

Tunable luminescence properties and energy transfer in LaAl11O18:Eu,Tb phosphor

Eu²⁺ and Tb³⁺ singly doped and co‐doped LaAl₁₁O₁₈ phosphors were prepared by a combustion method using urea as a fuel. The phase structure and photoluminescence (PL) properties of the prepared phosphors were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence excitation and emission spectra. When the content of Eu²⁺ was fixed at 0.01, the emission chromaticity coordinates could be adjusted from blue to green region by tuning the contents of Tb³⁺ ions from 0.01 to 0.03 through an energy transfer (ET) process. The fluorescence data collected from the samples with different contents of Tb³⁺ into LaAl₁₁O₁₈: Eu, show the enhanced green emission at 545 nm associated with ⁵D₄ –⁷F₅ transitions of Tb³⁺. The enhancement was attributed to ET from Eu²⁺ to Tb³⁺, and therefore Eu²⁺ ion acts as a sensitizer (an energy donor) while Tb³⁺ ion as an activator. The ET from Eu²⁺ to Tb³⁺ is performed through dipole–dipole interaction. The ET efficiency and critical distance were also calculated. The present Eu²⁺–Tb³⁺ co‐doped LaAl₁₁O₁₈ phosphor will have potential application for UV convertible white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Eu3+‐doped polystyrene and polyvinylidene fluoride nanofibers made by electrospinning for photoluminescent fabric designing

Eu³⁺‐doped polystyrene and polyvinylidene fluoride (PVDF/Eu³⁺ and PS/Eu³⁺) nanofibers were made using electrospinning. These fibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT‐IR), energy dispersive spectroscopy (EDX) and photoluminescence (PL). Spectral analysis of PVDF/Eu³⁺ and PS/Eu³⁺ nanofibers was based on their emission spectra. A bright red emission was noticed from Eu³⁺ that was assigned to the hypersensitive ⁵D₀ → ⁷F₂ transition. The enhanced intensity ratios of ⁵D₀ → ⁷F₂ to ⁵D₀ → ⁷F₁ transitions in the nanofibers indicated a more polarized chemical environment for the Eu³⁺ ions and greater hypersensitivity for the ⁵D₀ → ⁷F₂ transition, which showed the potential for application in various polymer optoelectronic devices. The Eu³⁺‐doped polymer (PVDF/Eu³⁺ and PS/Eu³⁺) nanofibers are suitable for the photoluminescent white light fabric design of smart textiles. This paper focuses on the potential application of smart fabrics to address challenges in human life.     

Germanium tetra(tertiary butoxide): Synthesis, structure and its utility as a precursor for the preparation of europium doped germanium oxide nanoparticles

Germanium tetra(tertiary butoxide), [Ge(O^tBu)₄], has been prepared by the reaction of GeCl₄ with KOBu^t in benzene. It is a monomeric crystalline solid having a distorted tetrahedral configuration, defined by the coordination of four OBu^t groups around germanium atom. The TG analysis showed that the compound is thermally stable and volatilizes at around 130 °C. Europium doped and un-doped germanium oxide nanoparticles were prepared based on the urea hydrolysis of Ge(O^tBu)₄/Eu(OOCCH₃)₃ in ethylene glycol medium at 150 °C followed by heating the resulting product at 750 °C. The nanoparticles were characterized by XRD, TEM and PL measurements. The europium doped nanoparticles, which were nearly monodispersed (∼30 nm), showed luminescence and the Eu³⁺ ions were occupying the surface of the GeO₂ nanoparticles.     

Synthesis and luminescence study of Eu3+‐doped SrYAl3O7 phosphor

Rare‐earth ions play an important role in eco‐friendly solid‐state lighting for the lighting industry. In the present study we were interested in Eu³⁺ ion‐doped inorganic phosphors for near ultraviolet (UV) excited light‐emitting diode (LED) applications. Eu³⁺ ion‐activated SrYAl₃O₇ phosphors were prepared using a solution combustion route at 550°C. Photoluminescence characterization of SrYAl₃O₇:Eu³⁺ phosphors showed a 612 nm emission peak in the red region of the spectrum due to the ⁵D₀→⁷F₂ transition of Eu³⁺ ions under excitation at 395 nm in the near‐UV region and at the 466 nm blue excitation wavelength. These red and blue emissions are supported for white light generation for LED lighting. Structure, bonding between each element of the sample and morphology of the sample were analysed using X‐ray diffraction (XRD) and scanning electron microscopy (SEM), which showed that the samples were crystallized in a well known structure. The phosphor was irradiated with a ⁶⁰Co‐γ (gamma) source at a dose rate of 7.2 kGy/h. Thermoluminescence (TL) studies of these Eu³⁺‐doped SrYAl₃O₇ phosphors were performed using a Nucleonix TL 1009I TL reader. Trapping parameters of this phosphor such as activation energy (E), order of kinetics (b) and frequency factor (s) were calculated using Chen's peak shape method, the initial rise method and Ilich's method.     

Spectral investigations on Eu3+,Sm3+‐doped and Sm3+/Eu3+ co‐doped potassium‐fluoro‐phosphate glass emitting intense orange‐red for lighting applications

Potassium fluoro‐phosphate (KFP) glass singly doped with different concentrations of europium (Eu³⁺) or samarium (Sm³⁺) or co‐doped (Sm³⁺/Eu³⁺) was prepared, and their luminescence spectra were investigated. The phase composition of the product was verified by X‐ray diffraction analysis. Optical transition properties of Eu³⁺ in the studied potassium phosphate glass were evaluated in the framework of the Judd–Ofelt theory. The radiative transition rates (A_R), fluorescence branching ratios (β), stimulated emission cross‐sections (σ_e) and lifetimes (τ_exp) for certain transitions or levels were evaluated. Red emission of Eu³⁺ was exhibited mainly by the ⁵D₀→⁷F₂ transition located at 612 nm. Concentration quenching and energy transfer were observed from fluorescence spectra and decay curves, respectively. It was found that the lifetimes of the ⁵D₀ level increased with increase in concentration and then decreased. By co‐doping with Sm³⁺, energy transfer from Sm³⁺ to Eu³⁺ occurred and contributed to the enhancement in emission intensity. Intense orange‐red light emission was obtained upon sensitizing with Sm³⁺ in KFP glass. This approach shows significant promise for use in reddish‐orange lighting applications. The optimized properties of the Sm³⁺/Eu³⁺ co‐doped potassium phosphate glass might be promising for optical materials.     

Luminescence and energy‐transfer properties of color‐tunable Ca2Mg0.25Al1.5Si1.25O7:Ce3+/Eu2+/Tb3+ phosphors for ultraviolet light‐emitting diodes

A series of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺/Eu²⁺/Tb³⁺ phosphors was been prepared via a conventional high temperature solid‐state reaction and their luminescence properties were studied. The emission spectra of Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺ and Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Tb³⁺ phosphors show not only a band due to Ce³⁺ ions (409 nm) but also as a band due to Eu²⁺ (520 nm) and Tb³⁺ (542 nm) ions. More importantly, the effective energy transfer from Ce³⁺ to Eu²⁺ and Tb³⁺ ions was confirmed and investigated by emission/excitation spectra and luminescent decay behaviors. Furthermore, the energy level scheme and energy transfer mechanism were investigated and were demonstrated to be of resonant type via dipole–dipole (Ce³⁺ to Eu²⁺) and dipole–quadrupole (Ce³⁺ to Tb³⁺) reactions, respectively. Under excitation at 350 nm, the emitting color could be changed from blue to green by adjusting the relative doping concentration of Ce³⁺ and Eu²⁺ ions as well as Ce³⁺ and Tb³⁺ ions. The above results indicate that Ca₂Mg_0.25Al_1.5Si_1.25O₇:Ce³⁺,Eu²⁺/Tb³⁺ are promising single‐phase blue‐to‐green phosphors for application in phosphor conversion white‐light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of Dy3+ or Eu2+ co‐activator on a BaCa(SO4)2:Ce3+ mixed alkaline earth sulfate phosphor

The individual emission and energy transfer between Ce³⁺ and Eu²⁺ or Dy³⁺ in BaCa(SO₄)₂ mixed alkaline earth sulfate phosphor prepared using a co‐precipitation method is described. The phosphor was characterized by X‐ray diffraction (XRD) and photoluminescence (PL) studies and doped by Ce;Eu and Dy rare earths. All phosphors showed excellent blue–orange emission on excitation with UV light. PL measurements reveal that the emission intensity of Eu²⁺ or Dy³⁺ dopants is greater than when they are co‐doped with Ce³⁺. An efficient Ce³⁺ → Eu²⁺ [²T_2g(4f⁶5d) → ⁸S_7/2(4f₇)] and Ce³⁺ → Dy³⁺ (⁴ F_9/2 → ⁶H_15/2 and ⁴ F_9/2 → ⁶H_13/2) energy transfer takes place in the BaCa(SO₄)₂ host. A strong blue emission peak was observed at 462 nm for Eu²⁺ ions and an orange emission peak at 574 nm for Dy³⁺ ions. Hence, this phosphor may be used as a lamp phosphor. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of blue long‐lasting BaCa2Al8O15:Eu2+, Dy3+ phosphor

We have synthesized and characterized a new BaCa₂Al₈O₁₅:Eu²⁺,Dy³⁺ phosphor prepared by the combustion method. X‐ray diffraction, thermoluminescence, scanning electron microscope, time decay and optical spectral analysis photoluminescence excitation, emission spectra were used to characterize the phosphors. Broadband ultraviolet excited luminescence of the BaCa₂Al₈O₁₅:Eu²⁺,Dy³⁺ was observed in the blue region (λ_max = 435 nm) due to transitions from the 4f⁶5d¹ to the 4f⁷ configuration of the Eu²⁺ ion. Scanning electron microscopy has been used for exploring the morphological properties of the prepared phosphors. The BaCa₂Al₈O₁₅:Eu²⁺ phosphor has a blue afterglow when Dy³⁺ ions were co‐doped. The thermoluminescence spectra show that the Dy³⁺ ion induces a proper trap in the phosphor with a depth of 0.67 eV and results in a long afterglow phosphorescence. Copyright © 2013 John Wiley & Sons, Ltd.     

Optical properties and energy transfer of Eu2+/Ce3+ co‐activated Na3Ca6(PO4)5 phosphor

Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ phosphors were prepared using a combustion‐assisted synthesis method. X‐Ray powder diffraction (XRD) analysis confirmed the formation of a Na₃Ca₆(PO₄)₅ crystal phase. Na₃Ca₆(PO₄)₅:Eu²⁺ phosphors have an efficient bluish‐green emission band that peaks at 489 nm, whereas Ce³⁺‐doped Na₃Ca₆(PO₄)₅ showed a bright emission band at 391 nm. Analysis of the experimental results suggests that enhancement of the Eu²⁺ emission intensity in co‐doped Na₃Ca₆(PO₄)₅:Eu²⁺,Ce³⁺ phosphors is due to a resonance‐type energy transfer from Ce³⁺ to Eu²⁺ ions, which is predominantly governed by an exchange interaction mechanism. These results indicate that Ce³⁺/Eu²⁺ co‐doped Na₃Ca₆(PO₄)₅ is potentially useful as a highly efficient, bluish‐green emitting, UV‐convertible phosphor for white‐light‐emitting diodes. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and effect of Ce and Mn co‐doping on photoluminescence characteristics of Ca6AlP5O20:Eu novel phosphors

A series of Ca₆AlP₅O₂₀ doped with rare earths (Eu and Ce) and co‐doped (Eu, Ce and Eu,Mn) were prepared by combustion synthesis. Under Hg‐free excitation, Ca₆AlP₅O₂₀:Eu exhibited Eu²⁺ (486 nm) emission in the blue region of the spectrum and under near Hg excitation (245 nm), Ca₆AlP₅O₂₀:Ce phosphor exhibited Ce³⁺ emission (357 nm) in the UV range. Photoluminescence (PL) peak intensity increased in Ca₆AlP₅O₂₀:Eu,Ce and Ca₆AlP₅O₂₀:Eu, Mn phosphors due to co‐activators of Ce³⁺ and Mn²⁺ ions. As a result, these ions played an important role in PL emission in the present matrix. Ca₆AlP₅O₂₀:Eu, Ce and Ca₆AlP₅O₂₀:Eu, Mn phosphors provided energy transfer mechanisms via Ce³⁺ → Eu²⁺ and Eu²⁺ → Mn²⁺, respectively. Eu ions acted as activators and Ce ions acted as sensitizers. Ce emission energy was well matched with Eu excitation energy in the case of Ca₆AlP₅O₂₀:Eu, Ce and Eu ions acted as activators and Mn ions acted as sensitizers in Ca₆AlP₅O₂₀:Eu, Mn. This study included synthesis of new and efficient phosphate phosphors. The impact of doping and co‐doping on photoluminescence properties and energy transfer mechanisms were investigated and we propose a feasible interpretation. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of cations on the temperature sensitivity of Ca2+ transport in rat-liver mitochondria and safranine uptake by liposomes

The activation energy of mitochondrial Ca²⁺ transport has been studied in various conditions by Arrhenius plots in the temperature range 6–20°C. In the presence of Mg²⁺ the activation energy is decreased to 18 kJ/mole from that of 40 kJ/mole found in a sucrose medium. In the presence of the polyamine spermine the activation energy is practically 0 kJ/mole. A lanthanide Eu³⁺, which is a potent inhibitor of Ca²⁺ transport, has no significant effect on the activation energy. In a KCl medium the activation energy is increased to 70 kJ/mole. When both K⁺ and Mg⁺ are present the activation energy is nonlinear between 11 and 18°C. In the presence of K⁺ and spermine it is about 0 kJ/mole between 6 and 13°C and at higher temperatures 68 kJ/mole. Neither Mg²⁺ nor spermine affect the slope of the Arrhenius plot for state 4 respiration. Spermine decreases slightly the activation energy of Ca²⁺-stimulated respiration. Spermine also decreases the activation energy of valinomycin- or gramicidin-induced safranine uptake by liposomes from 68 to almost 0 kJ/mole between 17 and 30°C. The results indicate that Ca²⁺ binding to the polar head groups of the phospholipids at the membrane surface is the rate-limiting step of mitochondrial Ca²⁺ transport, because agents that inhibit Ca²⁺ binding to these sites (Mg²⁺, spermine, K⁺) have the most marked effect, whereas Eu³⁺, which, because of the small concentration used, ought to interact mainly with the mitochondrial Ca²⁺ transport system, has no significant effect on the temperature sensitivity of mitochondrial Ca²⁺ transport.     

Effect of replacement of Ca by Zn on the structure and optical property of CaTiO3:Eu3+ red phosphor prepared by sol‐gel method

Eu³⁺‐doped calcium titanate red phosphors, Ca_1‐xZn_xTiO₃:Eu³⁺, were prepared by the sol‐gel method. The structure of prepared Ca_1‐xZn_xTiO₃:Eu³⁺ phosphors were investigated by X‐ray diffraction and infrared spectra. Due to the ⁵D₀ → ⁷F_1–3 electron transitions of Eu³⁺ ions, photoluminescence spectra showed a red emission at about 619 nm under excitation of 397 nm and 465 nm, respectively. When zinc was added to the host, the luminescent intensity of Ca_1‐xZn_xTiO₃:Eu³⁺ was markedly improved several fold compared with that of CaTiO₃:Eu³⁺. Ca_0.9Zn_0.1TiO₃:Eu³⁺ also had higher luminescence intensity than the commercially available Y₂O₃:Eu³⁺ phosphors under UV light excitation. Copyright © 2014 John Wiley & Sons, Ltd.     

7-Amino actinomycin D bound to single-stranded hairpin DNA enhanced by loop sequence-dependent luminescent Eu and Tb binding

Lanthanide Eu³⁺ and Tb³⁺ ions have been widely used in luminescent resonance energy transfer (LRET) for bioassays to study metal binding microenvironments. We report here that Eu³⁺ or Tb³⁺ can increase the binding affinity of antitumor antibiotic drug agent, 7-amino actinomycin D (7AACTD), binding to 5′-GT/TG-5′ or 5′-GA/AG-5′ mismatched stem region of the single-stranded hairpin DNA. Further studies indicate that the effect of Eu³⁺ or Tb³⁺ on 7AACTD binding is related to DNA loop sequence. Our results will provide new insights into how metal ions can enhance antitumor agents binding to their targets.     

Photoluminescent properties of Eu3+‐Eu2+ activated MAl2SixO2x + 4 (M = Mg,Ca, Sr,Ba) phosphors prepared in air

In this paper, MAl₂Si_xO_2x+4:Eu²⁺/Eu³⁺ (Eu²⁺ + Eu³⁺ = 2%, molar ratio; M = Mg, Ca, Sr, Ba; x = 0, 0.5, 1, 1.5, 2) phosphors with different SiO₂ concentrations (the ratio of SiO₂ to MAl₂O₄ is n%, n = 0, 50, 100, 150, 200, respectively) were prepared by high‐temperature solid‐state reaction under atmospheric air conditions. Their structures and photoluminescent properties were systematically researched. The results indicate that Eu³⁺ ions have been reduced and Eu²⁺ ions are obtained in air through the self‐reduction mechanism. The alkaline earth metal ions and doping SiO₂ strongly affect the crystalline phase and photoluminescent properties of samples, including microstructures, relative intensity of Eu²⁺ to Eu³⁺, location of emission lines/bands. It is interesting and important that the emission color and intensities of europium‐doped various phosphors which consist of aluminosilicate matrices prepared under atmospheric air conditions could be modulated by changing the kinds of alkaline earth metal and the content of SiO₂.     

Enhanced orange–red emission of SrZn2(PO4)2:Sm3+ via codoping Eu2+ as a sensitizer

A series of Eu²⁺‐, Sm³⁺‐ and Eu²⁺/Sm³⁺‐doped SrZn₂(PO₄)₂ samples were synthesized using a solid‐state reaction. SrZn₂(PO₄)₂:Eu²⁺ presented a broad emission band due to 4f⁶5d–4f⁷ transition of the Eu²⁺ ion. The spectra of SrZn₂(PO₄)₂:Sm sintered in air and H₂/N₂ were identical in every aspect, except for a very small difference in intensity. A Eu²⁺–Sm³⁺ energy transfer scheme was proposed to realize the sensitization of Sm³⁺ ion emission by Eu²⁺ ions, and UV‐convertible Sm³⁺‐activated red phosphor was obtained in SrZn₂(PO₄)₂:Eu²⁺, Sm³⁺. Copyright © 2015 John Wiley & Sons, Ltd.