Polyvinylpyrrolidone (PVP)-assisted solvothermal synthesis of flower-like SrCO3:Tb3+ phosphors

Well-crystallized flower-like SrCO₃:Tb³⁺ phosphors have been synthesized by an inexpensive and friendly solvothermal process using polyvinylpyrrolidone (PVP, K30) as an additive without further annealing treatment. X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FESEM) as well as photoluminescence spectroscopy (PL) were used to characterize the resulting samples. The amount of PVP and the reaction time have strong effect on the morphology of the SrCO₃:Tb³⁺ particles. The results of XRD confirm the formation of a well-crystallized SrCO₃ phase with an orthorhombic structure. The possible formation mechanism for flower-like SrCO₃:Tb³⁺ phosphor is proposed. The SrCO₃:Tb³⁺ phosphors show the characteristic ⁵D₄–⁷F_J (J = 6, 5, 4, 3) emission lines with green emission ⁵D₄–⁷F₅ (544 nm) as the most prominent group under ultraviolet excitation.     

Photoluminescence properties of Y2O3:Tb and YBO3:Tb green phosphors synthesized by hydrothermal method

In this work, two Tb³⁺ activated green phosphors: Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺ were prepared by hydrothermal method. Photoluminescence properties of both phosphors were studied in details. Both phosphors exhibit similar luminescent characteristics symbolized by the dominant green emission at 545 nm. Concentration quenching occurs at the Tb³⁺ concentration of 1.60 atomic% and 2.57 atomic% for Y₂O₃:Tb³⁺ and YBO₃:Tb³⁺, respectively. Luminescence decay properties were characterized to better understand the mechanism of concentration quenching. Based on the calculation, the concentration quenching in both phosphors was caused by the dipole–dipole interaction between Tb³⁺ ions.     

Self-assembled 3D flower-like NaY(MoO4)2:Eu microarchitectures: Hydrothermal synthesis, formation mechanism and luminescence properties

Self-assembled 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were successfully synthesized by a glycine-assisted hydrothermal method at 180 °C. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were employed to characterize the as-obtained products. It was found that morphology modulation could be easily realized by changing the time of hydrothermal reaction system. 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were formed with 72 h reaction time. The formation mechanism for flower-like architecture was proposed on the basis of a series of time-dependent experiments. The NaY(MoO₄)₂:Eu³⁺ powders obtained can be effectively excited by 396 nm light, and exhibit strong red emission around 615 nm, attributed to the Eu³⁺⁵D₀ → ⁷F₂ transition. An investigation on the photoluminescence (PL) properties of NaY(MoO₄)₂:Eu³⁺ obtained revealed that the luminescence properties were correlated with the morphology and size.     

Hydrothermal synthesis and luminescent properties of Y2O3:Tb and Gd2O3:Tb microrods

One-dimensional (1D) Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods have been successfully prepared through a large-scale and facile hydrothermal method followed by a subsequent calcination process in N₂/H₂ mixed atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (IR), thermogravimetric analysis (TGA), energy-dispersive X-ray spectra (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-formed products via the hydrothermal process could transform to cubic Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ with the same morphology and slight shrinking in size after a postannealing process. Both Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods exhibit strong green emission corresponding to ⁵D₄ → ⁷F₅ transition (542 nm) of Tb³⁺ under UV light excitation (307 and 258 nm, respectively), and low-voltage electron beam excitation (1.5 → 3.5 kV), which have potential applications in fluorescent lamps and field emission displays.     

Synthesis and photochromic properties of EDTA-induced MoO3 powder

In this study, the photochromic MoO₃ powder with novel morphology has been synthesized via hydrothermal method, using ethylene diamine tetraacetice acid (EDTA) as organic inducing agent. The influence of EDTA on the morphology, structure and photochromic properties of MoO₃ powder has been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), as well as ultraviolet and visible spectroscopy (UV-vis) and color difference meter. When the molar ratio of EDTA/Mo⁶⁺ is 0.05:1, the EDTA-induced MoO₃ powder is found to have 3D flower-like morphologies and excellent photochromic properties. Furthermore, the possible growth mechanism of the flower-like structure and the photochromic mechanism of MoO₃ powder are also discussed in detail.     

Facile synthesis of water-soluble YF3 and YF3: Ln nanocrystals

Water-soluble lanthanide-doped YF₃ nanocrystals with cubic structure were successfully synthesized for the first time using a simple solvothermal method with ethanol as solvent at 160 °C for 12 h. SEM and TEM results demonstrated that the obtained nanocrystals have an irregular shape and an average size of below 30 nm. Tb³⁺, Tb³⁺/Ce³⁺ co-doped YF₃ nanocrystals were also prepared and their photoluminescence properties were investigated. The luminescent intensity of the Tb³⁺ for the Tb³⁺/Ce³⁺ co-doped YF₃ nanocrystals is about ten times higher than that of the Tb³⁺ doped YF₃ nanocrystals. The products were characterized by XRD, SEM and TEM. Owing to their water-soluble properties and high processability, extensive applications may be found.     

RE3+ (RE = Ce3+, Tb3+) doped BaGdF5 nanocrystals: Synthesis,optical and magnetic properties,and energy transfer

Through a citric acid assisted hydrothermal method, the RE³⁺ (RE³⁺ = Ce³⁺, Tb³⁺) doped cubic phase BaGdF₅ nanocrystals with a sphere-like morphology and an average size of 30 nm have been synthesized. The samples show paramagnetic properties at 300 K. The photoluminescence spectra of the obtained samples suggest that the existence of Ce³⁺ can dramatically enhance the emission intensity of Tb³⁺ due to an efficient energy transfer from Ce³⁺ to Tb³⁺. The energy transfer efficiency from Ce³⁺ to Tb³⁺, the critical energy transfer distance between Ce³⁺ and Tb³⁺, and the energy transfer mechanism of Ce³⁺–Tb³⁺ are discussed based on the experimental data and the theoretical analysis.     

Organic additive assisted hydrothermal synthesis and photoluminescence properties of CeF<Subscript>3</Subscript>:Tb<Superscript>3+</Superscript> and NaCeF<Subscript>4</Subscript>:Tb<Superscript>3+</Superscript> nanoparticles

A series of Tb³⁺ doped CeF₃ and NaCeF₄ nanoparticles with different morphology and dimension were synthesized via hydrothermal method. Different organic additives, including sodium dodecyl sulfonate (SDS), polyvinylpyrrolidone (PVP), cetyltrimethyl ammonium bromide (CTAB), oleic acid (OA), polyethylene glycol (PEG), trisodium citrate (Cit) were introduced to control the crystallite size and morphology. Powder X-ray diffraction (PXRD), fourier transform infra-red spectra (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and down-conversion (DC) photoluminescence spectra were used to characterize the samples. The emission peaks of all the prepared samples centered at 490, 545, 585 and 621 nm which can be ascribed to the ⁵D₄→⁷F_J (J?=?6, 5, 4, 3) transitions respectively of Tb³⁺ ion. However, emission intensities are strongly controlled by morphology and particle sizes which are influenced by different organic additives used in synthesis. Moreover, the crystal growth process was monitored through a series of time-dependent experiments and a possible formation mechanism has been proposed.     

Morphology-tailored synthesis of flower-like Y2O3:Eu3+ microspheres

Flower-like Y₂O₃:Eu³⁺ microspheres with strong red photoluminescent emission were successfully synthesized through a controlled solvothermal approach followed by a subsequent heat treatment. The experimental results showed that the flower-like microspheres were composed of nanopetals with the thickness of about 50 nm, and the solvent properties as well as the characteristics of the reactants were very crucial for the morphology-controlled process. Meanwhile, the formation mechanism study revealed a possible assembly and etching process. In addition, their photoluminescence property investigation indicated that the flower-like products exhibited the strongest red emission corresponding to ⁵D₀ → ⁷F₂ transition (609 nm) among the synthesized samples, implying better photoluminescence property provided by the assembled spheres with higher crystallinity and better size-distribution and suggesting their potential application in optoelectronics.     

Luminescence properties and energy transfer of a novel bluish-green tunable NaBa4(BO3)3:Ce3+, Tb3+ phosphor

A series of single-phased emission tunable NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors were synthesized by solid-state reaction. The crystal structure, photoluminescence properties, concentration quenching and energy transfer of NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ were systematically investigated. The wavelength-tunable bluish-green light can be realized by coupling the emission bands centered at 425 and 543 nm ascribed to the contribution from Ce³⁺ and Tb³⁺, respectively. The energy transfer from Ce³⁺ to Tb³⁺ in NaBa₄(BO₃)₃ host was studied and demonstrated to be a resonant type via a dipole–dipole interaction mechanism. The energy transfer efficiency (Ce³⁺ → Tb³⁺) obtained by decay curves was consistent with the result calculated by the emission intensity, which gradually increased from 0% to 84.5% by increasing the Tb³⁺ doping content from 0 to 0.45. The results indicate that the NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors have potential applications as an ultraviolet-convertible phosphor due to its effective excitation in the ultraviolet rang.     

Properties of Gd2O3:Eu, Tb nanopowders obtained by sol-gel process

A significant practical application for nanostructured materials is X-ray medical imagery, because it is necessary to use dense materials in order to enable absorption of high energy photons. An important requirement of these materials is UV-vis range emission produced by X-ray excitation, which can be influenced by the particle size. Europium doped gadolinium oxide is a well known red phosphor. Moreover, nanophosphors of Gd₂O₃ codoped with Tb³⁺, Eu³⁺ increase their light yield by energy transfer between Tb³⁺ and Eu³⁺. In this study, Gd₂O₃ nanopowders codoped with Eu³⁺ and Tb³⁺ (2.5 at.% Eu³⁺, and 0.005 and 0.01 at.% Tb³⁺) were obtained via a sol-gel process using gadolinium pentanedionate as precursor and europium and terbium nitrates as doping sources. In this paper, we report the influence of annealing temperature on the structure, morphology and luminescent properties of Gd₂O₃:Eu³⁺, Tb³⁺ by means of TGA, XRD, TEM and X-ray emission measurements.     

Hydrothermal synthesis of LaPO4:Ce,Tb@LaPO4 core/shell nanostructures with enhanced thermal stability

LaPO₄:Ce³⁺,Tb³⁺ (LAP) nanorods were prepared by hydrothermal method, and LaPO₄:Ce³⁺,Tb³⁺@LaPO₄ core/shell nanostructures were formed by hydrothermal growth of LaPO₄ nanocoating onto the LAP nanorods. Oxidation behavior of the LAP nanorods and core/shell nanostructures was systematically presented by investigating change of their photoluminescence intensities with different durations of exposure to air at different temperatures. The results revealed that the LAP nanorods had severe loss of photoluminescence due to the oxidation of Ce³⁺ and Tb³⁺ to their respective tetravalent ions. In contrast, the photoluminescence properties of the core/shell nanostructures are more stable than those of the LAP nanorods with regard to thermal stress under aerobic conditions due to the surface protection from the LaPO₄ nanocoating. Therefore, formation of core/shell nanostructure may be a alternative route for photoluminescence stable LAP nanophosphors.     

Hydrothermal synthesis and luminescence of MWO4:Tb3+ (M = Ca,Sr, Ba) microsphere phosphors

Spherical MWO₄:Tb³⁺ (M = Ca, Sr, Ba) particles were synthesized by a hydrothermal route at 180 °C for 10 h. The synthesized MWO₄:Tb³⁺ particles were characterized by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and luminescence spectroscopy. The XRD and FT-IR results show that MWO₄:Tb³⁺ particles with a scheelite-type crystal structure were synthesized successfully. The SEM and TEM results show that uniform spherical particles in the range of hundreds of nanometers were obtained. The possible growth mechanism may be attributed to a typical Ostwald ripening process. The excitation spectra of MWO₄:Tb³⁺ phosphors show a strong absorption band of the WO₄ ^2? group and some weak absorption bands of Tb³⁺ ions. The emission spectra of MWO₄:Tb³⁺ phosphors show the characteristic emission bands of Tb³⁺ ions. CaWO₄:Tb³⁺ sample has the highest excitation and emission intensity.     

Hydrothermal synthesis and photoluminescence of novel green-emitting phosphor Y1−xBO3:xTb3+

Y_1−xBO₃:xTb³⁺ phosphors were first synthesized by hydrothermal reaction, and the samples were characterized by X-ray powder diffractometry, infrared absorption, nuclear magnetic resonance, scanning electron microscopy and photoluminescence. The results show that single phase is obtained with Tb concentration up to 0.28 and all the samples exhibit flake-like morphology. The sample was determined to be vaterite-type orthoborate and the boron is both four-coordinated (chief) and three-coordinated (few). The Y_1−xBO₃:xTb³⁺ phosphors showed intense green emission at 550 nm and the intensity of the emission increases with Tb³⁺ substitution up to 0.22 and then decreases for higher Tb³⁺ content. In the phosphors prepared by the hydrothermal method the concentration quenching is higher than in the phosphors prepared by solid-state reaction; the intensity of emission is stronger in the former than that of the latter. Y_1−xBO₃:xTb3⁺ is a promising phosphor for plasma display panels and hydrargyrum-free lamps.     

Fabrication and luminescence of YF3:Tb3+ hollow nanofibers

YF₃:Tb³⁺ hollow nanofibers were successfully fabricated via fluorination of the relevant Y₂O₃:Tb³⁺ hollow nanofibers which were obtained by calcining the electrospun PVP/[Y(NO₃)₃ + Tb(NO₃)₃] composite nanofibers. The morphology and properties of the products were investigated in detail by X-ray diffraction, scanning electron microscope, transmission electron microscope, and fluorescence spectrometer. YF₃:Tb³⁺ hollow nanofibers were pure orthorhombic phase with space group Pnma and were hollow-centered structure with the mean diameter of 148 ± 23 nm. Fluorescence emission peaks of Tb³⁺ in the YF₃:Tb³⁺ hollow nanofibers were observed and assigned to the energy levels transitions of ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) (490, 543, 588, and 620 nm) of Tb³⁺ ions, and the ⁵D₄ → ⁷F₅ hypersensitive transition at 543 nm was the dominant emission peak. Moreover, the emitting colors of YF₃:Tb³⁺ hollow nanofibers were located in the green region in CIE chromaticity coordinates diagram. The luminescent intensity of YF₃:Tb³⁺ hollow nanofibers was increased remarkably with the increasing doping concentration of Tb³⁺ ions and reached a maximum at 7 mol% of Tb³⁺. The possible formation mechanism of YF₃:Tb³⁺ hollow nanofibers was also discussed. This preparation technique could be applied to prepare other rare earth fluoride hollow nanofibers.     

Luminescence of SrGdGa3O7:RE(RE = Eu, Tb) phosphors and energy transfer from Gd to RE

Eu³⁺- and Tb³⁺-activated SrGdGa₃O₇ phosphors were synthesized by the solid-state reaction and their luminescence properties were investigated. Sr(Gd_1 − xEu_x)Ga₃O₇ and Sr(Gd_1 − xTb_x)Ga₃O₇ formed continuous solid solution in the range of x = 0-1.0. Unactivated SrGdGa₃O₇ exhibited a typical characteristic excitation and emission of Gd ion. The SrGdGa₃O₇:xEu³⁺ and SrGdGa₃O₇:xTb³⁺ phosphors also showed the well-known Eu³⁺ and Tb³⁺ excitation and emission. The energy transfer from Gd³⁺ to Eu³⁺ and Tb³⁺ were verified by photoluminescence spectra. The dependence of photoluminescence intensity on Eu³⁺ and Tb³⁺ concentration were also studied in detail and the photoluminescence (PL) intensity of SrGdGa₃O₇:Eu and SrGdGa₃O₇:Tb were compared with commercial phosphors, Y₂O₃:Eu and LaPO₄:Ce,Tb. The luminescence decay measurements showed that the lifetimes of Eu³⁺ and Tb³⁺ were in the range of microsecond. The energy transfer from Gd³⁺ to Tb³⁺ was also observed in decay curve.     

Luminescence properties and energy transfer of co-doped Ba<Subscript>3</Subscript>GdNa(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F:Ce<Superscript>3+</Superscript>,Tb<Superscript>3+</Superscript> green-emitting phosphors

Phase pure Ce³⁺ and Tb³⁺ singly doped and Ce³⁺/Tb³⁺ co-doped Ba₃GdNa(PO₄)₃F samples have been synthesized via the high temperature solid-state reaction. The crystal structures, photoluminescence properties, fluorescence lifetimes, thermal properties and energy transfer of Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ were systematically investigated. Rietveld structure refinement indicates that Ba₃GdNa(PO₄)₃F crystallizes in a hexagonal crystal system with the space group P-6. For the co-doped Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ samples, the emission color can be tuned from blue to green by varying the doping concentration of the Tb³⁺ ions. The intense green emission was realized in the Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ phosphors on the basis of the highly efficient energy transfer from Ce³⁺ to Tb³⁺. Also the energy transfer mechanism has been confirmed to be quadrupole–quadrupole interaction, which can be validated via the agreement of critical distances obtained from the concentration quenching (13.84 Å). These results show that the developed phosphors may possess potential applications in near-ultraviolet pumped white light-emitting diodes.     

Enhanced luminescence properties of YBO3:Eu phosphors by Li-doping

Different concentrations of Li-doped YBO₃:Eu³⁺ phosphors have been prepared by the conventional solid state reaction method and were characterized by X-ray diffraction, field emission scanning electron microscopy, photoluminescence excitation and emission measurements. An intense reddish orange emission is observed under UV excitation and the emitted radiation was dominated by an orange peak at 594 nm resulted from the ⁵D₀ → ⁷F₁ transitions of Eu³⁺ ions. The brightness of the YBO₃:Eu³⁺ phosphor was found greatly improved with Li-doping accompanied by slight improvement in the purity of the color which might be attributed to improvement in crystallinity, grain sizes and creation of oxygen vacancies with Li-doping. The observed results have been discussed in comparison with similar reported works.     

Hydrothermal synthesis and photoluminescence properties of Gd2Zr2O7:Tb phosphors

This paper presents hydrothermal synthesis, characterization, and photoluminescence (PL) properties of novel green-emitting phosphors, Gd₂Zr₂O₇:Tb³⁺. Their crystal structure, morphology and photoluminescence properties were investigated by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM) and fluorescence spectrophotometer. The results revealed that one-dimensional Gd₂Zr₂O₇:Tb³⁺ nanorods with diameter of about 30 nm and length of 150-300 nm were formed, and the products exhibited a fluorite-type structure. PL study revealed that Gd₂Zr₂O₇:Tb³⁺ phosphors presented dominant green emission luminescence, which was attributed to the transitions from ⁵D₄ excited states to ⁷F_J (J = 3-6) ground states of Tb³⁺. The luminescence intensity of Gd₂Zr₂O₇:Tb³⁺ with different Tb³⁺ concentration was also investigated and reported, and an obvious concentration quenching was observed when Tb³⁺ ion concentration was 5 at.%.     

Factors for determining photoluminescence properties of YBO3:Ce phosphor prepared by hydrothermal method

YBO₃:Ce³⁺ blue-emitting phosphors were prepared from boric acid and nitrates of yttrium and cerium(III) by hydrothermal method. An excess amount of boric acid, prolonged aging, high temperature, and a high pH value promote the formation of crystalline YBO₃. The higher crystallinity results in the higher photoluminescence (PL) intensity corresponding to the 5d-4f transition of Ce³⁺ under the irradiation of near-UV light. The PL intensity also depends on the pH value of precursor suspension and the nominal Ce³⁺ concentration, where the sample prepared at pH = 8 and Ce/(Y + Ce) = 0.25-0.5 at% shows the maximum PL intensity. In addition, the hydrothermally prepared sample shows the characteristic photobleaching behavior under the continuous irradiation of near-UV light. These results suggest that the crystallinity of the host YBO₃ crystal and the homogeneity of substituted Ce³⁺ ions play significant roles in the PL properties.