Enhanced luminescence of Ca3B2O6:Dy phosphors by Na-codoping for LED applications

The Ca_2.95−yDy_0.05B₂O₆:yNa⁺ (0≤y≤0.20) phosphors were synthesized at 1100 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), photoluminescence excitation (PLE), photoluminescence (PL) spectra and thermoluminescence (TL) spectra. The PLE spectra show the excitation peaks from 300 to 400 nm due to the 4f-4f transitions of Dy³⁺. This mercury-free excitation is useful for solid-state lighting and light-emitting diodes (LEDs). The emission of Dy³⁺ ions on 350 nm excitation was observed at 480 nm (blue) due to the ⁴F_9/2→⁶H_15/2 transitions, 575 nm (yellow) due to ⁴F_9/2→⁶H_13/2 transitions and 660 nm (red) due to weak ⁴F_9/2→⁶H_11/2 emissions. The PL results from the investigated Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors show that Dy³⁺ emissions increase with the increase of the Na⁺ codoping ions. The integral intensity of yellow to blue (Y/B) can be tuned by controlling Na⁺ content. By the simulation of white light, the optimal CIE value (0.328, 0.334) can be achieved when the content of Na⁺-codoping ions is y=0.2. The results imply that the Ca_2.95−yDy_0.05B₂O₆:yNa⁺ phosphors could be potentially used as white LEDs.     

Photoluminescence characterization of Ce and Dy doped Li2CaGeO4 phosphors

Ce³⁺ and Dy³⁺ activated Li₂CaGeO₄ phosphors were prepared by a solid-state reaction method, and characterized by XRD (X-ray diffraction) and photoluminescence techniques. The characteristic emission bands of Dy³⁺ due to ⁴F_9/2→⁶H_15/2 (blue) and ⁴F_9/2→⁶H_13/2 (yellow) transitions were detected in the emission spectra of Li₂CaGeO₄:Dy³⁺. Ce³⁺ broad band emission was observed in Li₂CaGeO₄:Ce³⁺ phosphors at 372 and 400 nm due to 5d→4f transition when excited at 353 nm. Co-doping of Ce³⁺ enhanced the luminescence of Dy³⁺ significantly and concentration quenching occurs when Dy³⁺ is beyond 0.04 mol%. White-light with different hues can be realized by tuning Dy³⁺ concentration in the phosphors.     

Sol-gel synthesis, structural and optical properties of rare earth ions (Sm or Dy) activated Ca3Ga2Si3O12 powder phosphors

Structural, morphological and optical properties of rare earth ions (RE³⁺=Sm³⁺ or Dy³⁺) activated Ca₃Ga₂Si₃O₁₂ (CaGaSi) phosphors synthesized by the sol-gel method are reported. XRD results confirmed the cubic phase structure of RE³⁺:CaGaSi phosphors. From the SEM images of RE³⁺:CaGaSi phosphors, it is observed that the particles are agglomerated. Photoluminescence spectra of Sm³⁺:CaGaSi phosphors have shown bright orange red emission at 598 nm (⁴G_5/2→⁶H_7/2) with an excitation wavelength of λ_exci=401 nm. In the case of Dy³⁺:CaGaSi phosphors bright yellow emission has been observed at 574 nm (⁴F_9/2→ ⁶H_13/2) with λ_exci=451 nm. From the PL spectral results, the rare earth ion concentration of CaGaSi phosphors is optimized.     

Optical properties of Dy ions in sodium gadolinium tungstates crystal

Dy³⁺-doped NaGd(WO₄)₂ crystal with sizes of about Φ20×40 mm² was grown by the Czochralski technique along the (0 0 1) orientation. Polarized absorption spectra, fluorescence spectra, and fluorescence decay curve of Dy³⁺-doped NaGd(WO₄)₂ have been recorded at room temperature. Based on the Judd-Ofelt (J-O) theory, the intensity parameters from the measured line strengths were evaluated. The J-O parameters were used to predict radiative transition probabilities, radiative lifetimes and branching ratios for various excited levels of Dy³⁺-doped NaGd(WO₄)₂ crystal. The luminescent quantum efficiency of the ⁴F_9/2 level was determined to be approximately 63% for this material. The emission cross-section of the ⁴F_9/2→⁶H_13/2 transition was estimated by using the Füchtbauer-Ladengurg method.     

SrAl_2B_2O_7:Dy~(3+)材料的制备及其发光性能

采用高温固相法制备了SrAl2B2O7:Dy3+发光材料.在350nm紫外光激发下,测得SrAl2B2O7:Dy3+材料的发射光谱为一个多峰宽谱,主峰分别为480,573和678nm;分别和Dy3+的4F9/2→6H15/2,4F9/2→6H13/2,4F9/2→6H11/2的跃迁发射相对应;监测573nm的发射峰,得到材料的激发光谱为一个多峰宽谱,主峰分别为295,325,350,365,400nm.研究了Dy3+掺杂浓度对SrAl2B2O7:Dy3+材料发射光谱的影响,随着Dy3+掺杂浓度的增大,SrAl2B2O7:Dy3+材料的Iy/Ib逐渐增大,根据Judd-Ofelt理论解释了其原因.随着Dy3+掺杂浓度的增大,Dy3+的4F9/2→6H13/2跃迁产生的573nm发射峰强度先增大,在4%时达到最大值,之后减小,其自身的浓度猝灭机理为电偶极-电偶极相互作用.不同的电荷补偿剂Li+,Na+,K+的引入均使发光强度得到提高,尤其以Li+最佳,发光强度提高了大约33%.     

Ionoluminescence studies of combustion synthesized Dy doped nano crystalline forsterite

Ionoluminescence (IL) of nano crystalline Mg₂SiO₄:Dy³⁺ pellet samples bombarded with 100 MeV Si⁺⁸ ions with fluences in the range (1.124–22.480) × 10¹² ions cm⁻² have been studied. Two prominent IL bands with peaks at ∼480 nm and ∼580 nm and a weak band with peak at ∼670 nm are recorded. The characteristic peaks are attributed to luminescence center activated by Dy³⁺ ions due to the transitions ⁴F_9/2→⁶H_15/2,⁶H_13/2 and ⁶H_11/2. It is found that IL intensity initially decreases rapidly and then continuous to decrease slowly with further increase in ion fluence. The reduction in the Ionoluminescence intensity with increase of ion fluence might be attributed to degradation of Si–O ( 2ν₃) bonds present on the surface of the sample and/or due to lattice disorder produced by dense electronic excitation under heavy ion irradiation.     

Optical properties of lithium magnesium borate glasses doped with Dy and Sm ions

Several studies showed the interesting properties of trivalent lanthanide ions when doped in various types of glasses. Optical and physical properties of lithium magnesium borate glasses doped with Dy³⁺ then with Sm³⁺ ions were determined by measuring their absorption and luminescence spectra in the visible region. The absorption spectra of Dy³⁺ showed eight absorption bands with hypersensitive transition at 1265 nm (⁶H_15/2→⁶F_11/2-⁶H_9/2) and three PL emission bands at 588 nm (⁴F_9/2→⁶H_15/2), 660 nm (⁴F_9/2→⁶H_13/2) and 775 nm (⁴F_9/2→⁶H_11/2). Regarding the Sm3⁺, nine absorption bands were observed with hypersensitive transition at 1237 nm (⁶H_5/2–⁶F_7/2); the PL spectrum showed four prominent peaks at ⁴G_5/2→⁶H_5/2 (yellow color), ⁴G_5/2→⁶H_7/2 (bright orange color), ⁴G_5/2→⁶H_9/2 (orange reddish color) and ⁴G_5/2→⁶H_11/2 (red color), respectively. Finally, a series of physical parameters such as the oscillator strengths, refractive index, ions concentration, Polaron radius and other parameters were calculated for each dopant.     

Enhanced luminescence of Dy in Y3Al5O12 by Bi co-doping

In the present paper, phosphors with the composition Y_3−x−yAl₅O₁₂:Bi³⁺_x, Dy³⁺_y were synthesized with solid state reactions. The luminescence properties of Bi³⁺ and Dy³⁺ in Y₃Al₅O₁₂(YAG) and the energy transfer from Bi³⁺ to Dy³⁺ were investigated in detail. Bi³⁺ in YAG emits one broad band peaking at 304 nm which can be ascribed to the transition from excited states ³P_{0, 1} to ground state ¹S₀. Dy³⁺ in YAG emits two groups of peaks around 484 and 583 nm, respectively, which can be ascribed to the transitions from excited state ⁴F_9/2 to ground states ⁶H_15/2 and ⁶H_13/2. The co-doping of Bi³⁺ enhances the luminescent intensity of Dy³⁺ by ∼7 times because Bi³⁺ can transfer the absorbed energy to Dy³⁺ efficiently. The mechanism of energy transfer was also discussed.     

Intense up-conversion emissions of Yb3+/Dy3+ co-doped Al2O3 nanopowders prepared by non-aqueous sol—gel method

Yb³⁺/Dy³⁺ co-doped Al₂O₃ nanopowders have been prepared by the non-aqueous sol-gel method and their up- conversion photoluminescence spectra are measured under excitation by 980-nm semiconductor laser. The results show that there are comparatively abundant spectra of up-conversion emissions centered at 378, 408, 527 and 543, and 663 nm, corresponding to ⁴G_9/2 → ⁶H_13/2, ⁴G_9/2 → ⁶H_11/2, ⁴I_15/2 → ⁶H_13/2, and ⁴F_9/2 → ⁶H_11/2 transitions of Dy³⁺, respectively. Two-photon and three-photon processes are involved in ultraviolet, violet, green, and red up-conversion emissions. The energy transition between Yb³⁺ and Dy³⁺ is discussed.     

Synthesis and photoluminescence properties of Sm-doped CaWO4 nanoparticles

The Sm³⁺-doped CaWO₄ nanoparticles were synthesized by hydrothermal method. The room temperature photoluminescence (PL) spectra of Sm³⁺-doped CaWO₄ nanoparticles doped with different Sm³⁺ concentrations under 405 nm excitation have been investigated. The PL spectra showed four strong emission peaks at 460, 571, 609, and 653 nm. The first emission peak at 460 nm could be due to a structural defect of the lattice, an oxygen-deficient WO₃ complex. The other three emissions at 571, 609, and 653 nm were due to the f-f forbidden transitions of the 4f electrons of Sm³⁺, corresponding to ⁴G_5/2→⁶H_5/2 (571 nm), ⁶H_7/2 (609 nm), and ⁶H_9/2 (653 nm), respectively. In addition, the optimum Sm³⁺ concentration in CaWO₄ nanoparticles for optical emission was determined to be 1.0%. The Sm³⁺⁴G_5/2→⁶H_7/2 (609 nm) emission intensity of Sm³⁺-doped CaWO₄ nanoparticles significantly increased with the increase of Sm³⁺ concentration, and showed a maximum when Sm³⁺ doping content was 1.0%. If Sm³⁺ concentration continued to increase, namely more than 1.0%, the Sm³⁺⁴G_5/2→⁶H_7/2 emission intensity would decrease. The present materials might be a promising phosphor for white-light LED applications.     

Preparation and luminescence property of Dy-doped YPO4 phosphors

The co-precipitation reaction soft chemistry method was employed to prepare fine YPO₄:Dy³⁺ phosphor particles calcined at 950 °C. Adjusting appropriate pH and introducing lithium may greatly affect the particle size of the product and further affect the luminescence intensity. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron micrograph (TEM) and photoluminescence (PL) spectroscopy. The obtained YPO₄ nanocrystals appeared to be spherical with some agglomeration and their sizes ranged from 20 to 40 nm. The characteristic transitions of Dy³⁺ due to ⁴F_9/2→⁶H_15/2 (blue) and ⁴F_9/2→⁶H_13/2 (yellow) were detected in the emission spectra.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.     

Spectral analysis of Pr-, Sm- and Dy-doped transparent GeO2-BaO-TiO2 glass ceramics

In this paper, we present the photoluminescence properties of Pr³⁺-, Sm³⁺- and Dy³⁺-doped germanate glasses and glass ceramics. From the X-ray diffraction measurement, the host glass structure was determined. These glasses have shown strong absorption bands in the near-infrared (NIR) region. Compared to Pr³⁺-, Sm³⁺- and Dy³⁺-doped glasses, their respective glass ceramics have shown stronger emissions due to the Ba₂TiGe₂O₈ crystalline phase. For Pr³⁺-doped glass and glass ceramic, emission bands centered at 530 nm (³P₀→³H₅), 614 nm (³P₀→³H₆), 647 nm (³P₀→³F₂) and 686 nm (³P₀→³F₃) have been observed with 485 nm (³H₄→³P₀) excitation wavelength. Of them, 647 nm (³P₀→³F₂) has shown bright red emission. Emission bands of ⁴G_5/2→⁶H_5/2 (565 nm), ⁴G_5/2→⁶H_7/2 (602 nm) and ⁴G_5/2→⁶H_9/2 (648 nm) for the Sm³⁺:glass and glass ceramic, with excitation at ⁶H_5/2→⁴F_7/2 (405 nm) have been recorded. Of them, ⁴G_5/2→⁶H_7/2 (602 nm) has shown a bright orange emission. With regard to the Dy³⁺:glass and glass ceramic, a bright fluorescent yellow emission at 577 nm (⁴F_9/2→⁶H_13/2) has been observed, apart from ⁴F_9/2→⁶H_11/2 (667 nm) emission transition with an excitation at 454 nm (⁶H_15/2→⁴I_15/2) wavelength. The stimulated emission cross-sections of all the emission bands of Pr³⁺, Sm³⁺ and Dy³⁺:glasses and glass ceramics have been computed based on their measured full-width at half-maxima (FWHM, Δλ) and lifetimes (τ_m).     

Luminescent properties of nanoparticles YPXV1−XO4:Dy phosphors

Phosphors of nanoparticles YP_XV_1−XO₄:Dy³⁺ (0?X?1) have been prepared by a citrate sol-gel method. X-ray diffraction, transmission electron microscope (TEM), scanning electron microscope (SEM) and photoluminescence excitation and emission spectra were utilized to characterize the phosphors. The results of XRD showed that a solid solution formed in YP_XV_1−XO₄:Dy³⁺ phosphor series from X=0 to X=1 with zircon structure. TEM and SEM studies revealed that the obtained YP_XV_1−XO₄:Dy³⁺ nanocrystals appeared to be spherical with some agglomeration and their sizes ranged from 30 to 80 nm. Upon short ultraviolet excitation, the optical properties of all the powder presented that the characteristic transitions of Dy³⁺ due to ⁴F_9/2-⁶H_15/2 (blue) and ⁴F_9/2-⁶H_13/2 (yellow) were detected. Besides this, in the system of YP_XV_1−XO₄:Dy³⁺, the yellow-to-blue intensity ratio (Y/B) depended on the value of P/V greatly, with the increasing of X value and the decreased Y/B value. The phosphor found to yield white light when the value of X in the range of X=0.775-0.85, the optimum concentration for Dy³⁺ is 1 mol% of Y in the host, and the emission intensity increased with the annealing temperature.     

Synthesis and white light emission of Dy3+ ions doped hexagonal structure YAlO3 nanocrystalline

A series of hexagonal YAlO₃ with various Dy³⁺ ions concentrations were synthesized via a facile sol–gel combustion method. The samples were characterized by XRD, TEM, FT-IR and PL measurements. Results show that the Dy³⁺-doped hexagonal YAlO₃ can commendably output white light, which consists of the blue 487 nm (⁴F_9/2→⁶H_15/2) and the yellow 578 nm (⁴F_9/2→⁶H_13/2) emissions. The high intensity of hypersensitive forced electric dipole transition (⁴F_9/2→⁶H_13/2) is due to the serious destruction of crystal field symmetry surrounding Dy³⁺ ions.     

Rare earth doped lithium titanate (Li2TiO3) for potential phosphor applications

Lithium titanate ceramics doped with three rare earth (RE) ions namely Eu³⁺, Dy³⁺ and Tb³⁺ were synthesized and their photoluminescence (PL) properties were investigated. PL spectra of Eu doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=0, 1, 2, 3 and 4) transitions under 230 nm excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in a highly asymmetric environment. Dy doped samples showed the Dy³⁺ emission characteristic due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions. Their relative intensity ratios also suggested the presence of asymmetric environment around the metal ion. In case of the Tb³⁺ doped sample blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions was seen. The fluorescence lifetimes of Eu³⁺, Dy³⁺ and Tb³⁺ ions were found to be 645, 900 and 740 μs, respectively. PL intensity of the individual rare earth doped samples was compared with commercial red and green phosphors. It was found that the emission from Eu doped titanate sample was 46% of the commercial red phosphor and in case of the Tb samples it was 30% when excited at 230 nm. However, the synthesized Eu doped titanate sample showed better color purity as compared to the commercial phosphor. The titanate host was doped with all the three rare earths to get white light emission from the system. The individual rare earth ion content was optimized so as to get a near white light emission. The color coordinates of the triple doped systems were evaluated and plotted on the CIE x–y diagram. Our results suggest that lithium titanate has enough potential to be a phosphor material.     

Comparison study of the luminescent properties of the white-light long afterglow phosphors: CaxMgSi2O5+x:Dy(x=1, 2, 3)

A series of Dy³⁺-doped calcium magnesium silicate phosphors: CaMgSi₂O₆:Dy³⁺, Ca₂MgSi₂O₇:Dy³⁺, and Ca₃MgSi₂O₈:Dy³⁺ with white long-lasting afterglow were prepared and investigated. The characteristic intra-configurational 4f emissions of Dy³⁺ were observed in the emission spectra as well as the afterglow spectra under ultraviolet excitation. The combination of the 480 nm blue emission corresponding to the ⁴F_9/2→⁶H_15/2 transition and the 575 nm yellow emission corresponding to the ⁴F_9/2→⁶H_13/2 transition yielded white-light emission. The white-coloured afterglow emission can last more than 1 h for most of the samples under study. The concentration dependence of the ratio of the yellow emission intensity with blue emission intensity was also examined and found to be varied for the different hosts. The thermoluminescence spectra above room temperature are employed for the discussion of the origin of the traps and the mechanism of the persistent luminescence.     

The effect of different gas atmospheres on luminescent properties of pulsed laser ablated SrAl2O4:Eu,Dy thinfilms

SrAl₂O₄:Eu²⁺,Dy³⁺ thin films were grown on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique to investigate the effect of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological, photoluminescence (PL) and cathodoluminescence (CL) properties of the films. The films were ablated using a 248 nm KrF excimer laser. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and fluorescence spectrophotometry were used to characterize the thin films. Auger electron spectroscopy (AES) combined with CL spectroscopy were employed for the surface characterization and electron-beam induced degradation of the films. Better PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres with respect to those prepared in vacuum. A stable green emission peak at 515 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions were obtained with less intense peaks at 619 nm, which were attributed to transitions in Eu³⁺. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The CL intensity increased under prolonged electron bombardment during the removal of C due to electron stimulated surface chemical reactions (ESSCRs) on the surface of the SrAl₂O₄:Eu²⁺, Dy³⁺ thin films. The CL stabilized and stayed constant thereafter.     

Luminescence and laser transition studies of Dy:K-Mg-Al fluorophosphate glasses

Dysprosium ion doped fluorophosphate glasses with compositions of PKMAFDy: (56−x/2) P₂O₅+17K₂O+8Al₂O₃+(15−x/2)MgO+4AlF₃+xDy₂O₃ (x=0.01, 0.05, 0.1, 1.0 and 2.0 mol%) have been prepared by melt quenching technique and are characterized by optical absorption, emission spectra and fluorescence lifetime measurements. The observed bands in the absorption spectrum are analysed by using free-ion Hamiltonian (H_FI) model. The Judd-Ofelt (JO) analysis has been performed and the intensity parameters (Ω_λ, λ=2, 4, 6) have been evaluated that are used to predict radiative properties. From emission spectra, the effective bandwidth (Δλ_eff) and the stimulated emission cross-section (σ(λ_p)) were evaluated. The fluorescence decay from the ⁴F_9/2 level of Dy³⁺ ions have been measured by monitoring the intense ⁴F_9/2→⁶H_13/2 transition (573 nm). The lifetimes (τ) are found to decrease with increasing concentration due to concentration quenching. The decay curves are single exponential for lower concentrations and gradually changes to non-exponential for higher concentrations. The non-exponential decay curves are well fitted to the Inokuti-Hirayama (IH) model for S=6 which indicates that the energy transfer between the donor and acceptor is of dipole-dipole type. The systematic analysis on decay measurements reveals that the energy transfer mechanism strongly depends on concentration as well as glass composition.     

Luminescence investigations on sulfate apatite Na6(SO4)2FCl:RE (RE=Dy, Ce or Eu) phosphors

A new phosphor in the Cl-F system doped with Dy, Ce and Eu has been reported. Characterization of this phosphor using XRD, PL and TL techniques is described. Polycrystalline Na₆(SO₄)₂FCl:Dy; Na₆(SO₄)₂FCl:Ce and Na₆(SO₄)₂FCl:Eu phosphors prepared by a solid state diffusion method have been studied for their X-ray diffraction, photoluminescence (PL) and thermoluminescence (TL)characteristics. The PL excitation and emission spectra of phosphors were obtained. Dy³⁺ emission in the host at 475 and 570 nm is observed due to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transition, respectively, whereas the PL emission spectra of Na₆(SO₄)₂FCl:Ce phosphor shows the Ce³⁺ emission at 322 nm due to 5d→4f transition of Ce³⁺ ion. In Na₆(SO₄)₂FCl:Eu lattice, Eu²⁺ as well as Eu³⁺ emissions are observed. The emission of europium ion in this compound exhibits the blue as well as red emission. The TL glow curves of the same compounds have the simple structure with a prominent peak at 150, 175 and 200 °C. TL response, fading, reusability and trapping parameters of the phosphors are also studied. The TL glow curves of γ-irradiated Na₆(SO₄)₂FCl sample show one glow peak indicating that only one set of traps is being activated within the particular temperature range each with its own value of activation energy (E) and frequency factor (s). The trapping parameters associated with the prominent glow peak are calculated using Chen’s half width method. The release of hole/electron from defect centers at the characteristic trap site initiates the luminescence process in these materials. The intensity of the TL glow peaks increases with increase of the added γ-ray dose to the samples.