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.     

Synthesis and luminescent properties of nanoparticles GdCaAl3O7:RE (RE=Eu, Tb) via the sol-gel method

By using metal nitrates as starting materials and citric acid as complexing agent, GdCaAl₃O₇:Eu³⁺ and GdCaAl₃O₇:Tb³⁺ powder phosphors were prepared by a citrate-gel method. Thermal analysis (TG-DTG), X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscope (SEM), photoluminescence excitation and emission, as well as kinetic decays were employed to characterize the resulting samples. The results of the XRD indicated the precursor samples began to crystallize at 800 °C and the crystallinity increased with elevation the annealing temperature. TEM images showed that the phosphor particles were basically of spherical shape, with good dispersion about a particle size of around 40-70 nm. Upon excitation with UV irradiation, it is shown that there is a strong emission at around 617 nm corresponding to the forced electric dipole ⁵D₀-⁷F₂ transition of Eu³⁺, and at around 543 nm corresponding to the ⁵D₄-⁷F₅ transition of Tb³⁺. The dependence of photoluminescence intensity on Eu³⁺ (or Tb³⁺) concentration and annealing temperature were also studied in detail.     

Heat-treatment-induced luminescence degradation in Tb-doped CePO4 nanorods

CePO₄:Tb nanorods were synthesized via a simple wet-chemical route. The as-synthesized CePO₄:Tb nanorods present high photoluminescence efficiency due to an efficient energy transfer form Ce³⁺ to Tb³⁺. However, heat treatment at 150 °C in air leads to a significant decrease of photoluminescence. X-ray photoelectron spectroscopy and excitation spectra revealed the oxidation of Ce³⁺ to Ce⁴⁺ in the heat-treatment process, which should be responsible for significant photoluminescence degradation due to the breakage of Ce³⁺→Tb³⁺ energy transfer. This conclusion is further supported by atmosphere and size effects of photoluminescence of CePO₄:Tb under the heat treatment.     

Photoluminescence properties and effects of dopant concentration in Bi2ZnB2O7:Tb phosphor

A novel green phosphor, Tb³⁺ doped Bi₂ZnB₂O₇ was synthesized by conventional solid state reaction method. The phase of synthesized materials was determined using the XRD, DTA/TG and FTIR. The photoluminescence characteristics were investigated using spectrofluorometer at room temperature. Bi₂ZnB₂O₇:Tb³⁺ phosphors excited by 270 nm and 485 nm wavelengths. The emission spectra were composed of three bands, in which the dominated emission of green luminescence Bi₂ZnB₂O₇:Tb³⁺ attributed to the transition ⁵D₄ → ⁷F₅ is centered at 546 nm. The dependence of the emission intensity on the Tb³⁺ concentration for the Bi_2−xTb_xZnB₂O₇ (0.01 ≤ x ≤ 0.15) was studied and observed that the optimum concentration of Tb³⁺ in phosphor was 13 mol% for the highest emission intensity at 546 nm.     

Synthesis and properties of submicron range CaSO4:Eu particles

CaSO₄:Eu with particle size in submicron range was synthesized. Radiation induced Eu³⁺↔Eu²⁺ conversion as well as thermal conversion was studied. The samples showed thermal conversion above 400 °C. However, no radiation induced conversion in submicron range particles was observed. Particles heated above 400 °C coalesce and when heated at 925 °C bigger particles of 20 μm size were formed. Optical microscopy of these particles reveals red inclusion of about 5 μm inside CaSO₄ particle. It is speculated that the red inclusion is CaS:Eu²⁺.     

Ionic liquid-assisted hydrothermal synthesis of dendrite-like NaY(MoO4)2:Tb phosphor

Micro-sized NaY(MoO₄)₂:Tb³⁺ phosphors with dendritic morphology was synthesized by a ionic liquid-assisted hydrothermal process. X-ray diffraction (XRD) indicated that the as-prepared product is pure tetragonal phase of NaY(MoO₄)₂. Field emission scanning electron microscopy (FE-SEM) images showed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors have dendritic morphology. The photoluminescent (PL) spectra displayed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors show a stronger green emission with main emission wavelength 545 nm corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺ ion, and the optimal Tb³⁺ doping concentration for obtaining maximum emission intensity was confirmed to be 10 mol%. Based on Van Uitert's and Dexter's models the electric dipole–dipole (D–D) interaction was confirmed to be responsible for the concentration quenching of ⁵D₄ fluorescence of Tb³⁺ in the NaY(MoO₄)₂:Tb³⁺ phosphors. The intrinsic radiative transition lifetime of ⁵D₄ level is found to be 0.703 ms.     

Fluorescence enhancement of oxide fluoride glass co-doped with TbF3 and SmF3

The fluorescence property of xTbF₃-BaF₂-AlF₃-GeO₂+ySmF₃ (x=0.01-40 mol%, y=0-5 wt%) glasses were investigated. The enhancement of Sm³⁺ fluorescence was recognized in the presence of Tb³⁺. Increasing Tb³⁺ content, the emission color changed from green to orange. When the intensity of fluorescence at 540 nm originated from Tb³⁺ is compared with that at 600 nm originated from Sm³⁺, the information about the concentration quenching of Tb³⁺ and Sm³⁺ was obtained. From these results, rare earth ions were dispersed identically in the glasses. After heating to 673 K or cooling to 77 K, the emission color of 20TbF₃-20BaF₂-10AlF₃-50GeO₂/mol%+0.05 wt% SmF₃ glass was reversibly changed from orange to green. In addition, while the emission from 10TbF₃-20BaF₂-10AlF₃-60GeO₂+0.01 wt% SmF₃ glass was green, its crystallized sample, prepared by annealing at 1073 K, exhibited an orange emission due to Sm³⁺ at room temperature.     

A white light emitting phosphor Sr1.5Ca0.5SiO4:Eu, Tb, Eu for LED-based near-UV chip: Preparation, characterization and luminescent mechanism

In this work, we report preparation, characterization and luminescent mechanism of a phosphor Sr_1.5Ca_0.5SiO₄:Eu³⁺,Tb³⁺,Eu²⁺ (SCS:ETE) for white-light emitting diode (W-LED)-based near-UV chip. Co-doped rare earth cations Eu³⁺, Tb³⁺ and Eu²⁺ as aggregated luminescent centers within the orthosilicate host in a controlled manner resulted in the white-light phosphors with tunable emission properties. Under the excitation of near-UV light (394 nm), the emission spectra of these phosphors exhibited three emission bands: one broad band in the blue area, a second band with sharp lines peaked in green (about 548 nm) and the third band in the orange-red region (588-720 nm). These bands originated from Eu²⁺ 5d→4f, Tb³⁺⁵D₄→⁷F_J and Eu³⁺⁵D₀→⁷F_J transitions, respectively, with comparable intensities, which in return resulted in white light emission. With anincrease of Tb³⁺ content, both broad Eu²⁺ emission and sharp Eu³⁺ emission increase. The former may be understood by the reduction mechanism due to the charge transfer process from Eu³⁺ to Tb³⁺, whereas the latter is attributed to the energy transfer process from Eu²⁺ to Tb³⁺. Tunable white-light emission resulted from the system of SCS:ETE as a result of the competition between these two processes when the Tb³⁺ concentration varies. It was found that the nominal composition Sr_1.5Ca_0.5SiO₄:1.0%Eu³⁺, 0.07%Tb³⁺ is the optimal composition for single-phased white-light phosphor. The CIE chromaticity calculation demonstrated its potential as white LED-based near-UV chip.     

Luminescent properties of Tb activated GdTaO4 with M and M′ type structure under UV-VUV excitation

The photoluminescence of Tb³⁺ doped M and M′ type gadolinium orthotantalate Gd_1−xTb_xTaO₄ (0.01≤x≤0.20) was investigated under ultraviolet and vacuum ultraviolet excitation. For the samples of Gd_1−xTb_xTaO₄ with different crystallographic structures, emission spectra were the same in addition to intensity; the optimal concentration for Tb³⁺ was about 10 mol % in M type Gd_1−xTb_xTaO₄ but 5 mol % in M′ type Gd_1−xTb_xTaO₄. These differences could be corresponding with the difference in structures. In addition, compared to commercial Zn₂SiO₄: Mn²⁺, the integrated intensity of M and M′ type GdTaO₄: Tb³⁺ could reach 67% and 85%, respectively, of that at 147 nm excitation, which indicates that GdTaO₄: Tb³⁺ would be a promising vacuum ultraviolet phosphor for application in PDP and Hg-free lamp.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.     

Effect of Eu,Tb codoping on the luminescent properties of Y2O3 nanorods

Red-emitting Y₂O₃:Eu³⁺ and green-emitting Y₂O₃:Tb³⁺ and Y₂O₃:Eu³⁺, Tb³⁺ nanorods were synthesized by hydrothermal method. Their structure and micromorphology have been analyzed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The photoluminescence (PL) property of Y₂O₃:Eu³⁺,Tb³⁺ phosphor was investigated. In the same host (Y₂O₃), upon excitation with ultraviolet (UV) irradiation, it is shown that there are strong emissions at around 610 and 545 nm corresponding to the forced electric dipole ⁵D₀-⁷F₂ transition of Eu³⁺ and ⁵D₄-⁷F₅ transition of Tb³⁺, respectively. Different qualities of Eu³⁺and Tb³⁺ ions are induced into the Y₂O₃ lattice. From the excitation spectrum, we speculate that there exists energy transfer from Tb³⁺ to Eu³⁺ ions .The emission color of powders reveals regular change in the separation of light emission. These powders can meet with the request of optical display material for different colors or can be potentially used as labels for biological molecules.     

Fabrication, structure and luminescence properties of polycrystalline Tb-doped Lu2SiO5 films by Pechini sol–gel method

Tb³⁺-doped lutetium oxyorthosilicate (Tb:Lu₂SiO₅, LSO) films have been successfully fabricated on carefully cleaned silicon (1 1 1) substrates by Pechini sol–gel method combined with the spin-coating technique. X-ray diffraction (XRD), photoluminescence (PL) spectra and atomic force microscopy (AFM) were employed to characterize the resultant films. XRD patterns indicated that the films were crystallized into A-type LSO phase at 1000 °C, followed by a phase transition from A-type LSO to B-type LSO occurred at 1100 °C. The AFM observation revealed that the phosphor films were uniform and crack-free, consisting of closely packed grains with an average size of 200–300 nm. The PL spectra showed the characteristic emission ⁵D₄ → ⁷F_J (J = 3–6) for Tb³⁺, The lifetime of Tb³⁺ in Tb:LSO films was 2.33 ms. The effect of heat-treatment temperature on the luminescent properties was also investigated.     

Intense ultraviolet upconversion luminescence of Yb and Tb co-doped glass ceramics containing SrF2 nanocrystals

The preparation and upconversion luminescence properties of the Yb³⁺ and Tb³⁺ co-doped glass ceramics containing SrF₂ nanocrystals were investigated. The formation of SrF₂ nanocrystals was confirmed by X-ray diffraction and transmission electron microscopy. Both microstructural and spectral analysis indicated that the Yb³⁺ and Tb³⁺ ions were enriched in the precipitated SrF₂ nanocrystals, which provide much lower phonon vibration energy than the glass matrix. Due to the efficient cooperative sensitization from Yb³⁺ to Tb³⁺ and the relatively low maximum phonon energy of SrF₂ nanocrystals, the Yb³⁺ and Tb³⁺ co-doped glass ceramics exhibited intense upconversion luminescence, including ultraviolet emission at 382 nm.     

Thermoluminescent and stuctural properties of BaAl2O4:Eu,Nd,Gdphosphors prepared by combustion method

BaAl₂O₄:Eu²⁺,Nd³⁺,Gd³⁺ phosphors were prepared by a combustion method at different initiating temperatures (400–1200 °C), using urea as a comburent. The powders were annealed at different temperatures in the range of 400–1100 °C for 3 h. X-ray diffraction data show that the crystallinity of the BaAl₂O₄ structure greatly improved with increasing annealing temperature. Blue-green photoluminescence, with persistent/long afterglow, was observed at 498 nm. This emission was attributed to the 4f⁶5d¹–4f⁷ transitions of Eu²⁺ ions. The phosphorescence decay curves were obtained by irradiating the samples with a 365 nm UV light. The glow curves of the as-prepared and the annealed samples were investigated in this study. The thermoluminescent (TL) glow peaks of the samples prepared at 600 °C and 1200 °C were both stable at ∼72 °C suggesting that the traps responsible for the bands were fixed at this position irrespective of annealing temperature. These bands are at a similar position, which suggests that the traps responsible for these bands are similar. The rate of decay of the sample annealed at 600 °C was faster than that of the sample prepared at 1200 °C.     

Growth and optical properties of Yb and Tb codoped BaB2O4 crystals

Optical absorption and luminescence spectra of ytterbium and terbium codoped BaB₂O₄ (β-BBO and α-BBO) crystals grown in different conditions have been studied. Low-temperature absorption peaks were observed in all samples. Features related to rare earth ions were observed in absorption and luminescence spectra. Absorption and emission in the range 860-1000 nm are caused by ²F_5/2↔²F_7/2 transitions in Yb³⁺ ions. Emission peaks at 500, 550, 590 and 630 nm correspond to ⁵D₄→⁷F₆, ⁷F₅, ⁷F₄, and ⁷F₃ transitions of Tb³⁺ ions, respectively. The probable reasons of variations in spectroscopic features related to Yb in BBO host are discussed. It has been shown that the replacement of Ва²⁺ by Yb³⁺ in the lattice of ВаВ₂О₄ results in the decrease in the symmetry of oxygen surrounding of Yb³⁺.     

Characterization of the VUV excitation spectrum of BaZr(BO3)2:Eu

The excitation spectra of M (M=Si⁴⁺, Ti⁴⁺) and Eu³⁺ co-doped BaZr(BO₃)₂, BaZrO₃:Eu and La₂Zr₂O₇:Eu in the vacuum ultraviolet (VUV) regions of 110-300 nm are investigated and the host-lattice absorption are characterized. The result indicated that BaZr(BO₃)₂:Eu³⁺ phosphor has a strong absorption under the VUV excitation, and in the host-lattice excitation, the strong band at 130-160 nm could be due to the BO₃ atomic groups; the band at 160-180 nm is related to the excitation of Ba-O; 180-200 nm corresponds to the charge transfer (CT) transition of Zr-O. The band at 200-235 nm due to the CT band of Eu³⁺-O²⁻ and a bond valence study explained the observed weak CT band of Eu³⁺-O²⁻ in the excitation spectra of BaZr(BO₃)₂:Eu³⁺. The emission results show that Si⁴⁺ can sensitize luminescence in the host of BaZr(BO₃)₂:Eu but Ti⁴⁺ has no improvement effect on luminescence.     

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.     

Solvothermal synthesis and luminescence properties of Tb-doped gadolinium aluminum garnet

Different concentrations of Tb³⁺ ion-doped gadolinium aluminum garnet (GAG) nanophosphors have been synthesized by solvothermal reaction method and sintered at 1300 °C. The XRD patterns confirm that the GAG phosphors sintered at 1300 °C have a garnet structure with single cubic phase. The calculated crystallite size is about 92 nm. The SEM images of the phosphors show the spherical morphology agglomerated with many small particles. The luminescence properties of these phosphors have been carried out by the emission and excitation spectra along with lifetime measurements. The excitation spectra of GAG:Tb³⁺ phosphors consist of three broad bands due to the 4f⁸→4f⁷5d¹ transition and some sharp peaks due to the 4f⁸→4f⁸ transition. The emission spectra of the phosphors reveal two colors, such as blue due to ⁵D₃→⁷F_J transitions and green due to the ⁵D₄→⁷F_J transitions. The dynamics of the phosphors have been investigated by decay curves and the cross-relaxation process and is observed at 0.5 mol% Tb³⁺ concentration.     

Synthesis and luminescent properties of nanoparticles LaSrAl3O7:Eu, Tb

Phosphors of nanoparticles LaSrAl₃O₇:RE³⁺(REEu, Tb) have been prepared by a sol–gel method. The structure and luminescent properties of LaSrAl₃O₇:Eu³⁺ and LaSrAl₃O₇:Tb³⁺ phosphors were characterized by X-ray diffraction and atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized. From X-ray diffraction (XRD) patterns, it is indicated that the phosphor LaSrAl₃O₇ forms without impurity phase at 900 °C. From atomic force microscopy (AFM) images, it is shown that the crystal size of the phosphores are about 60–80 nm. Upon excitation with UV irradiation, it is shown that there is a strong emission at around 617 nm corresponding to the forced electric dipole ⁵D₀–⁷F₂ transition of Eu³⁺, and at around 545 nm corresponding to the ⁵D₄–⁷F₅ transition of Tb³⁺. The dependence of photoluminescence intensity on Eu³⁺(or Tb³⁺) concentration and annealing temperature were also studied in detail.     

Red, green and blue (RGB) emission doped Y3Al5O12 (YAG) phosphors prepared by non-hydrolytic sol-gel route

An evolutionary optimization process involving combination chemistry was employed in an attempt to develop Y₃Al₅O₁₂ (YAG). The combination chemistry process utilized here consisted the doping of the YAG host with appropriate amounts of red (R), green (G), and blue (B) dopants in a single layer, for use in tricolor white light. The doped YAG was acieved by means of the non-hydrolytic sol-gel route. Four samples were prepared, three of which were mono-doped samples containing 1.0% of a certain lanthanide (Eu³⁺, Tb³⁺, or Tm³⁺) ion, while the fourth contained the three ions. The samples were characterized by X-ray diffractometry and photoluminescence. The diffraction pattern of the mono-doped samples synthered at 800 °C for 16 h displayed peaks corresponding to the Y₃Al₅O₁₂ (YAG) phase, while the sample doped with the three ions revealed the presence of a mixture of Y₃Al₅O₁₂ (YAG) and Y₄Al₂O₉ (YAM) phases. The emission spectra of the three mono-doped YAG samples displayed the typical bands of the blue, green, and red emission of the corresponding lanthanide ions. As for the sample doped with the three lanthanide ions; it simultaneously emitted R, G and B lights. The green emission (546 nm) was more intense and narrow in relation to the red and blue emissions, which may be due to differences in the size of the three incorporated ions.