Yellow phosphors doping with Gd3 + , Tb3 + and Lu3 + in MTiO3 (M = Mg and Sr) luminescence properties

This paper reports Gd^3?+?, Tb^3?+? and Lu^3?+? doped MTiO₃ (M = Mg and Sr)-based phosphors which were synthesized by the conventional solid-state reaction method, their crystal structures and luminescence properties were investigated. X-ray diffraction patterns (XRD) showed that phosphors sintered at 1000 °C for 2 h were the pure SrTiO₃ and MgTiO₃ phases. The optimization of reaction conditions was carried out by thermogravimetry and differential thermal analysis (DTA/TG) methods. Surface and elemental analyses were performed by using SEM instrument. The excitation and emission spectra were recorded by a photoluminescence spectrophotometer (PL). The thermoluminescence (TL) properties of MgTiO₃:RE (RE = Gd^3?+?, Tb^3?+?, Lu^3?+?) and SrTiO₃:RE (RE = Gd^3?+?, Tb^3?+?, Lu^3?+?) were investigated.     

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.     

Luminescent properties of GdAl3(BO3)4:Ln3+ (Ln3+:Eu3+, Tb3+, Dy3+) nano-phosphors

GdAl₃(BO₃)₄:Ln³⁺ (Ln³⁺:Eu³⁺, Tb³⁺, Dy³⁺) nano-phosphors were prepared by sol–gel method. The structure properties of the phosphors are characterized by XRD, and GdAl₃(BO₃)₄:Ln³⁺ nano-phosphors have average sizes around 40 nm. The doping concentrations of Eu³⁺, Tb³⁺ and Dy³⁺ ions in GdAl₃(BO₃)₄ nano-phosphors are from 1 to 9 mol% for Eu³⁺ ions, from 2 to 12 mol% for Tb³⁺ ions and from 1 to 5 mol% for Dy³⁺ ions, respectively. The luminescent properties of rare-earth ions doped GdAl₃(BO₃)₄ nano-phosphors are analyzed by the photoluminescence spectra, which prime doping concentration of Eu³⁺, Tb³⁺, and Dy³⁺ ions are at 5, 12 and 3 mol%, respectively. The energy transfers in the luminescent processes of rare-earth ions doped GdAl₃(BO₃)₄ nano-phosphors are discussed.     

Solvothermal synthesis of SrMoO4:Ln (Ln = Eu, Tb, Dy) nanoparticles and its photoluminescence properties at room temperature

Rare-earth ions (Eu³⁺, Tb³⁺, Dy³⁺) doped SrMoO₄ nanoparticles were prepared by solvothermal route using oleic acid as surfactant to control the particle shape and size. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), photoluminescence spectra (PL) and the kinetic decay times were applied to characterize the obtained samples. The XRD patterns reveal that all the doped samples are assigned to the scheelite-type tetragonal structure of SrMoO₄ phase. In addition, the as-synthesized SrMoO₄:Ln (Ln = Eu³⁺, Tb³⁺, Dy³⁺) particles are high purity well crystallized and with the average size of 30-50 nm. The possible formation process of SrMoO₄:Ln (Ln = Eu³⁺, Tb³⁺, Dy³⁺) nanoparticles have been discussed as well. Upon excitation by ultraviolet radiation, the as-synthesized SrMoO₄:Ln (Ln = Eu³⁺, Tb³⁺, Dy³⁺) nanoparticles exhibit the characteristic emission lines of corresponding Eu³⁺, Tb³⁺, Dy³⁺, respectively.     

Polyspectral white light emission from Eu3+, Tb3+, Dy3+, Tm3+ co-doped GdAl3(BO3)4 phosphors obtained by combustion synthesis

Polycrystalline sub-micron-sized GdAl₃(BO₃)₄ phosphors co-doped with Eu³⁺, Tb³⁺, Dy³⁺ and Tm³⁺ have been prepared by combustion synthesis with urea. The phosphors have been characterised by X-ray diffraction, scanning electron microscopy, excitation and emission spectroscopy. The chromaticity co-ordinates and the colour temperatures of the fluorescence of the materials presented have been calculated and analysed with Commission Internationale l’Eclairage (CIE) programs and diagrams. Depending on the excitation wavelength, different colour temperatures of the light emitted can be achieved. Due to its polyspectral nature, the emitted light reveals a high colour rendering index.     

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.     

Conversion of green emission into white light in Gd2O3 nanophosphors

Gd₂O₃ nanophosphors were prepared by combustion synthesis with and without doping of Dy³⁺ ions. The X-ray powder diffraction patterns indicate that as-prepared Gd₂O₃ and 0.1 mol% Dy₂O₃ doped Gd₂O₃ nanophosphors have monoclinic structures. The transmission electron microscope (TEM) studies revealed that the as-prepared phosphors had an average crystallite sizes around 37 nm. The excitation and emission properties have been investigated for Dy³⁺ doped and undoped Gd₂O₃ nanophosphors. New emission bands were observed in the visible region for Gd₂O₃ nanophosphors without any rare earth ion doping under different excitations. A tentative mechanism for the origin of luminescence from Gd₂O₃ host was discussed. Emission properties also measured for 0.1 mol% Dy³⁺ doped Gd₂O₃ nanophosphors and found the characteristic Dy³⁺ visible emissions at 489 and 580 nm due to ⁴F_9/2 → ⁶H_15/2 and ⁴F_9/2 → ⁶H_13/2 transitions, respectively. The chromaticity coordinates were calculated based on the emission spectra of Dy³⁺ doped and undoped Gd₂O₃ nanophosphors and analyzed with Commission Internationale de l'Eclairage (CIE) chromaticity diagram. These nanophosphors exhibit green color in undoped Gd₂O₃ and white color after adding 0.1 mol% Dy₂O₃ to Gd₂O₃ nanophosphors under UV excitation. These phosphors could be a promising phosphor for applications in flat panel displays.     

Down-shifting by energy transfer in Dy-Tb co-doped YF3-based sol-gel nano-glass-ceramics for photovoltaic applications

Highly transparent sol-gel derived nano-glass-ceramics containing YF₃ nanocrystals doped with Dy³⁺ or Tb³⁺ and co-doped with Dy³⁺-Tb³⁺ have been successfully developed. A structural analysis and luminescence spectra features confirmed the incorporation of rare-earth ions into precipitated YF₃ nanocrystals, where efficient energy transfer from Dy³⁺ to Tb³⁺ takes place. Higher efficiency is obtained with increasing Tb³⁺ concentration, and no quenching effects are observed. Observed luminescence features leads the way to enhance solar cell spectral response by down-shifting of the incident solar spectrum, with an extended absorption range from 300 to 500 nm, yielding to a predominant green emission by co-doping with Dy³⁺ and Tb³⁺ ions.     

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.     

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.     

Comparative study of the Mn4+ 2E → 4A2 luminescence in isostructural RE2Sn2O7:Mn4+ pyrochlores (RE3+ = Y3+, Lu3+ or Gd3+)

Red emitting Mn⁴⁺-doped crystalline materials have potential for application in light emitting devices and therefore it is important to understand how the optical properties of Mn⁴⁺ are influenced by the host lattice the Mn⁴⁺ ions are situated in. In this work we investigate the effect of the host cations in the second coordination sphere on the Mn⁴⁺ emission by studying the luminescence of Mn⁴⁺ ions doped into three isostructural rare earth (RE) stannate RE₂Sn₂O₇ pyrochlores (RE³⁺ = Y³⁺, Lu³⁺ or Gd³⁺). It is found that the energies of the Mn^{4+ 4}T₁ and ⁴T₂ states significantly increase with decreasing Mn⁴⁺-O^2- distance, whereas the energy of the ²E level shows a small shift to higher energies from RE³⁺ = Gd³⁺ to Lu³⁺ to Y³⁺. The observed trend for the ²E level energy is not related to the size of the RE³⁺ ion and is not in line with theoretical calculations reported previously. Low temperature emission spectra of the RE₂Sn₂O₇:Mn⁴⁺ phosphors reveal that only asymmetrical vibronic modes couple to the ²E → ⁴A₂ transition and furthermore show there is significant and unexpected local disorder for Mn⁴⁺ in Gd₂Sn₂O₇ that is not observed for Mn⁴⁺ in the other hosts. Photoluminescence decay measurements demonstrate that the luminescence of RE₂Sn₂O₇:Mn⁴⁺ is strongly quenched below room temperature which is assigned to non-radiative relaxation via a low-lying O²⁻ → Mn⁴⁺ charge-transfer state.     

Synthesis of novel halloysite@YF3:Ce3+,Tb3+ nanocomposite for enhanced luminescent properties

A novel halloysite@YF₃: Ce³⁺, Tb³⁺ anocomposite with strong luminescent properties was designed and synthesized by a facile direct precipitation strategy. Owing to the halloysite as a support, it can significantly prevent the aggregation of YF₃:Ce³⁺,Tb³⁺ and the distribution of YF₃:Ce³⁺,Tb³⁺ on halloysite was highly uniform. Importantly, due to the unique surface-interface-dielectric multiple confinement (SIDMC) effects, the as-harvested halloysite@YF₃:Ce³⁺,Tb³⁺ nanocomposite exhibited excellent luminescent performance. Compared with YF₃:Ce³⁺,Tb³⁺, the luminescence intensity of halloysite@YF₃:Ce³⁺,Tb³⁺ nanocomposite is significantly enhanced by about 6 times under 255 nm excitation. However, the fluorescence lifetime of halloysite@YF₃:Ce³⁺,Tb³⁺ nanocomposite (7.21 ms) is shorter than that of YF₃:Ce³⁺,Tb³⁺ nanoparticles (8.34 ms). This finding indicated that halloysite can change the luminescent properties of YF₃:Ce³⁺,Tb³⁺ nanoparticles through an SIDMC effect. The combination of halloysite and YF₃:Ce³⁺,Tb³⁺ nanoparticles not only endowed halloysite with special properties, and effectively tuned the luminescent properties of YF₃:Ce³⁺,Tb³⁺ nanoparticles, thereby improving the utility of halloysite and YF₃:Ce³⁺,Tb³⁺ nanoparticles. The research supplies an insight on the development of natural mineral-based luminescent materials, and hopefully it could promote them application in many fields.     

Vacuum ultraviolet optical properties of (La,Gd)PO4:RE (RE=Eu, Tb)

Vacuum ultraviolet excitation spectra of phosphors (La,Gd)PO₄:RE³⁺ (RE=Eu or Tb) and X-ray photoelectron spectra of LaPO₄ and GdPO₄ are investigated. The vacuum ultraviolet excitation intensity of (La,Gd)PO₄:RE³⁺ is enhanced with the increasing of Gd³⁺ content, which implies that Gd³⁺ plays an intermediate role in energy transfer from host absorption band to RE³⁺. When Gd³⁺ is doped into LaPO₄:Eu³⁺, charge transfer band (CT band) begins to shift to higher energy region and the overlap degree of CT band and the host absorption band gets greater with more Gd³⁺ doped into LaPO₄. These results suggest that the dopant (Gd³⁺) gives an important influence on energy transfer efficiency. The top of LaPO₄ valance band is formed by the 2p level of O²⁻, whereas that of GdPO₄ valance band is formed by the 2p level of O²⁻ and the 4f level of Gd³⁺, showing the differences in band structures between LaPO₄ and GdPO₄.     

Synthesis,structural and optical studies of sol–gel Gd2O3:Eu3+, Tb3+ films

Eu³⁺ and Tb³⁺ co-doped Gd₂O₃ films were elaborated by sol–gel process and dip-coating technique. The films were synthesized by hydrolysis of gadolinium pentanedionate. A homogeneous and stable sol was obtained by the reaction with acetylacetone. Gd₂O₃:Eu³⁺, Tb³⁺ films were crystallized around 500 °C; at an increase of temperature up to 700 °C, oriented growth of (4 0 0) face was observed. The obtained transparent Gd₂O₃: 2.5 at.% Eu³+, 0.005 at.% Tb³⁺ waveguide films at 700 °C display significant optical properties. Different crystallographic properties can be obtained in Gd₂O₃:Eu³⁺, Tb³⁺ films with varying sintering temperatures.     

The VUV–vis spectroscopic properties of phosphors Ca3Gd2(1−x)Ln2x(BO3)4 (Ln3+ = Ce,Sm, Eu,Tb)

The spectroscopic properties in VUV–vis range for phosphors calcium and gadolinium double borate Ca₃Gd₂(BO₃)₄ doped with rare-earth ions Ce³⁺, Sm³⁺, Eu³⁺ and Tb³⁺ were investigated. The host-related absorption, the f–d transitions of Ce³⁺ and Tb³⁺, as well as the charge transfer transitions of Sm³⁺ and Eu³⁺ in the host lattice are assigned and discussed. The CIE chromaticity coordinates for Eu³⁺- and Tb³⁺-activated phosphors are calculated.     

Photoluminescence properties of RE-activated Na3GdP2O8 (RE = Tb, Dy, Eu, Sm) under VUV excitation

RE³⁺-activated monoclinic Na₃GdP₂O₈ (RE³⁺ = Tb³⁺, Dy³⁺, Eu³⁺, Sm³⁺) phosphors have been synthesized by a solid-state reaction method. Their photoluminescence properties in the vacuum ultraviolet (VUV) region were investigated. By analyzing their excitation spectra, the host-related absorption band was determined to be around 166 nm. The f-d transition bands and the charge transfer bands for Na₃GdP₂O₈:RE³⁺ (RE³⁺ = Tb³⁺, Dy³⁺, Eu³⁺, Sm³⁺) were assigned and corroborated. For the sample Na₃GdP₂O₈:5%Tb³⁺, the strong bands at around 202 and 221 nm are assigned to the 4f-5d spin-allowed transitions and the weak band at 266 nm is related to the spin-forbidden transition of Tb³⁺. For Na₃GdP₂O₈:5%Dy³⁺, the broad band at 176 nm could be related to the f-d transitions of Dy³⁺ and the O²⁻ → Dy³⁺ charge transfer band (CTB) besides the host-related absorption. In the excitation spectrum of Eu³⁺ doped sample, the O²⁻ → Eu³⁺ CTB is observed to be at 245 nm. For the Sm³⁺ doped sample, the O²⁻ → Sm³⁺ CTB is not distinguished obviously and is overlapped with the host-related absorption band.     

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.     

An efficient green-emitting luminescent material: Tb3+-activated monoclinic Gd2O3

Monoclinic gadolinium oxide activated with Tb³⁺ is an efficient green-emitting phosphor, even for low Tb³⁺ concentrations. Under X-ray excitation its efficiency is about 50% of that of Gd₂O₂S-Tb. The low amount of blue ⁵D₃ emission from Gd₂O₃-Tb is ascribed to the low-energy position of the 4f-5d band (~ 280 nm). The intensity ratio of the Gd³⁺ excitation lines in the photoluminescence excitation spectrum provides information on the location of the quenching sites (probably Tb⁴⁺).     

Single-component and white light-emitting phosphor BaAl2Si2O8: Dy3+, Eu3+ synthesis,luminescence, energy transfer,and tunable color

A series of Dy³⁺ - Eu³⁺ co-doped BaAl₂Si₂O₈ phosphors were prepared via the conventional solid-state reaction method. Their crystal structure, luminescent characteristic and lifetime were investigated. The optimum doping concentrations of Dy³⁺and Eu³⁺ are both 0.05 for Dy³⁺ or Eu³⁺ singly doped BaAl₂Si₂O₈. Furthermore, BaAl₂Si₂O₈: 0.05Dy³⁺ and BaAl₂Si₂O₈: 0.05Eu³⁺ emits yellow and red light. The emission color of BaAl₂Si₂O₈: Dy³⁺, Eu³⁺ could be tuned from yellow to white due to the energy transfer. This energy transfer from Dy³⁺ to Eu³⁺ was confirmed and investigated by photoluminescence spectra and the decay time of energy donor Dy³⁺ ions. With constantly increasing Eu³⁺ concentration, the energy transfer efficiency from Dy³⁺ to Eu³⁺ in BaAl₂Si₂O₈ host increased gradually and reached as high as 81%, the quantum yield was about 47.43%. BaAl₂Si₂O₈: Dy³⁺, Eu³⁺ phosphors can be effectively excited by UV (about 348 nm) light and emit visible light from yellow to white by altering the concentration ratio of Dy³⁺ and Eu³⁺, indicating that the phosphors have potential applications as a white light-emitting phosphor for display and lighting.     

Photoluminescence of TiO2 films co-doped with Tb/ Gdand energy transfer from TiO2/Gd to Tb ions

Nanometer TiO₂ thin films doped with different concentration of Tb were prepared by sol-gel method and characterized by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. XRD results show preferentially oriented (101) anatase films. TEM image indicates that the TiO₂ films consist of TiO₂ grains with diameter about 15 nm. Under room temperature, strong visible luminescence of Tb³⁺ ions due to intra-4f shell transitions are obtained and the PL intensity is found to have a well matching relation with the doping concentration of Tb³⁺ ions. Concentration quenching of PL occurs when Tb³⁺ concentration exceeds a certain value (9.2 mol%). Furthermore, the luminescence intensity is improved obviously after co-doping with Gd³⁺ ions because of the sensitization effects of Gd³⁺ ions to Tb³⁺ ions in TiO₂ system. The energy transfer mechanism from TiO₂ and Gd³⁺ ions to Tb³⁺ ions was proposed.