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%.     

Optical and luminescence properties of Dy3+ ions in K–Sr–Al phosphate glasses for yellow laser applications

Trivalent dysprosium (Dy³⁺)-doped K–Sr–Al phosphate glasses have been prepared and investigated for their optical and luminescence properties. Judd–Ofelt theory has been used to derive radiative properties for the ⁴F_9/2 level of Dy³⁺ ions. The luminescence spectrum of 1.0 mol% Dy₂O₃-doped glass shows intense yellow emission around 572 nm ascribed to ⁴F_9/2 → ⁶H_13/2 transition with 78 % branching ratio and emission cross section of the order of 2.48 × 10^?21 cm². Moreover, the quantum efficiency of the ⁴F_9/2 level has been found to be 76 %. The luminescence decay curves for the yellow emission (⁴F_9/2 → ⁶H_13/2) have been measured and analyzed as a function of Dy³⁺ ion concentration. The results revealed that Dy³⁺-doped phosphate glasses could be useful for yellow laser applications.     

The VUV–vis luminescent properties of NaYFPO4: Dy3+ phosphor

Dy³⁺-doped monoclinic NaYFPO₄ phosphor has been synthesized by solid-state reaction technique. Its photoluminescence in the vacuum ultraviolet (VUV)-visible region was investigated. The most intensity broadband emission centered at about 171 nm was the host-related absorption. Another broadband at 153 nm could be related to the O₂→Dy³⁺ charge transfer band (CTB) absorption. The excitation peaks located at 178 nm and 256 nm were the spin-allowed (SA) and spin-forbidden (SF) f–d transitions of Dy³⁺, respectively. Some sharp lines in the range of 280–500 nm were due to the f–f transitions of Dy³⁺ within its 4f⁹ configuration. Under the VUV–vis excitation, the Dy³⁺-doped NaYFPO₄ phosphor showed the characteristic emissions of Dy³⁺ (⁴F_9/2→⁶H_15/2 transitions and ⁴F_9/2→⁶H_13/2 transitions) with a stronger blue emission peaking at about 485 nm. All the chromaticity coordinates of the sample were in the near cold-white region. It can be predicted that this phosphor can be applied in both mercury-free luminescence lamps and white LED.     

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.     

Optical absorption and fluorescence studies of Dy3+-doped lead telluroborate glasses

Lead telluroborate (PTBDy) glasses doped with different Dy³⁺ ion concentrations were prepared by melt quenching technique and investigated through optical absorption, fluorescence and decay measurements. The Judd–Ofelt intensity parameters (Ω_λ) are obtained by a least square fit analysis. The small root mean square deviation of ±0.34×10^?6 shows a good fit between the experimental and calculated oscillator strengths. The radiative properties of the ⁴F_9/2→⁶H_13/2 emission transition of PTBDy10 glass are determined and compared to the other reported glasses. The variation of decay time of the ⁴F_9/2 emission state is attributed to the interaction among the excited Dy³⁺ ions at higher concentration. The PTBDy10 glass is found to be a suitable candidate for solid state laser materials to produce intense yellow (576 nm) luminescence through the ⁴F_9/2→⁶H_13/2 transition.     

Influence of γ-radiation on photoluminescence properties of YPO4:Eu3+,Ce3+ and YPO4:Dy3+,Ce3+ phosphors

Hexagonal YPO₄ phosphors doped with Eu³⁺/Dy³⁺ and co-doped with Ce³⁺ were synthesized by a hydrothermal route assisted using lauric acid as a capping agent. The prepared phosphors were characterized by transmission electron microscopy, infrared spectroscopy, powder X-ray diffraction and photoluminescence spectra. YPO₄: Eu³⁺ gives two red emission peaks at 587 and 610?nm corresponding to ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions, respectively. YPO₄: Dy³⁺ exhibits two emission peaks at 485?nm (blue) and 575?nm (yellow) corresponding to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions, respectively. Ce³⁺ ions enhanced the emission intensity as a co-dopant in both phosphors. Moreover, the effect of γ-radiation in the dose range 5–300?kGy on the photoluminescence behaviour of YPO₄:Eu³⁺,Ce³⁺ and YPO₄:Dy³⁺,Ce³⁺ was also investigated. Quenching of emission intensity, after irradiation at 5 and 300?kGy, was observed in both the phosphors due to loss of excess energy through a non-radiative relaxation process.     

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.     

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.     

Luminescent properties of Eu2+and Dy3+ ions in Ba4Al2O7 phosphor for solid state lighting

In this paper we report the combustion synthesis of rare earth (RE=Eu, Dy) doped Ba₄Al₂O₇ phosphors. Prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), CIE color co-ordinates and their photoluminescence (PL) properties were also investigated. In case of Ba₄Al₂O₇: Eu²⁺, the emission spectra show unique band centered at 495 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺, and PL emission spectra of Dy³⁺ ion under 348 nm excitation give two bands centered at 478 nm (blue) and 575 nm (yellow), which originate from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The results indicate that the Eu²⁺ and Dy³⁺ activated Ba₄Al₂O₇ phosphor could find application in solid state lighting.     

NIR to visible upconversion emission from Dy: ZBLYAN glasses

This paper reports on the near infrared (730-783 nm) to the visible upconversion emissions at 482 nm (⁴F_9/2→⁶H_15/2), 576 nm (⁴F_9/2→⁶H_13/2) and 662 nm (⁴F_9/2→⁶H_11/2) from the Dy³⁺doped 53ZrF₄-20BaF₂-2LaF₃-2YF₃-3AlF₃-19NaF-1DyF₃ glasses. We have also carried out a systematic study on the normal emission properties of these glasses in order to understand their performance both as a NIR upconverted visible luminescent and as normal visible fluorescent optical systems of technical importance. With an increase in Dy³⁺ concentration beyond a particular value (1 mol%), activator-activator interaction becomes a significant cause of concentration quenching in the luminescence properties. The dependence of the emission spectra on the excitation wavelengths has also been examined and 451 nm was found to be the ideal excitation wavelength in the measurement of normal fluorescence spectra. In the case of NIR upconverted visible emission, we have observed that the NIR excitation at 783 nm as the suitable pump wavelength in demonstrating prominent visible emission colours from these glasses. The relevance in undertaking these optical materials lies in their potential for upconversion laser application in the visible wavelength region. The NIR upconversion phenomenon has been explained in terms of energy level schemes due to excited state absorption (ESA) and energy transfer upconversion (ETU) processes.     

Concentration and temperature quenching mechanisms of Dy3+ luminescence in BaGd2ZnO5 phosphors

BaGd₂ZnO₅:Dy³⁺ phosphors were synthesized by a traditional solid-state reaction. The crystal structure of the phosphors was characterized by X-ray diffraction (XRD). The blue emission (456 nm) corresponding to ⁴H_15/2→⁶H_15/2 transition was observed at higher sample temperatures, and the population mechanism of ⁴H_15/2 level was assigned to the thermal excitation of ⁴F_9/2 level. The fluorescence concentration quenching of ⁴F_9/2 level was studied based on Van Uitert's model, and that the electric dipole–dipole interaction was confirmed to be the responsible mechanism for the energy transfer between Dy³⁺ ions. Finally, the fluorescence thermal quenching of ⁴F_9/2 level was studied, and the crossover effect was found to be the main physical mechanism for the fluorescence temperature quenching of Dy³⁺.     

Solvent effect in monoclinic to hexagonal phase transformation in LaPO4:RE (RE=Dy, Sm) nanoparticles: Photoluminescence study

Nanosized phosphor materials, LaPO₄:RE (RE=Dy³⁺, Sm³⁺) have been synthesized using water, dimethyl sulfoxide (DMSO), ethylene glycol (EG) and mixed solvents at a relatively low temperature of 150 °C. X-ray diffraction (XRD) study reveals that as-prepared nanoparticles prepared in DMSO and EG are well crystalline and correspond to monoclinic phase. In the mixed water-DMSO or water-EG solvents, XRD patterns are in good agreement with hexagonal phase, but transformed to monoclinic phase at higher temperature of 900 °C. TEM images show well-dispersed and rice-shaped nanoparticles of diameter 5-10 nm, length of 13-37 nm for Dy³⁺-doped LaPO₄ and diameter of 25-35 nm, length of 73-82 nm for Sm³⁺-doped LaPO₄. Dy³⁺-doped LaPO₄ shows two prominent emission peaks at 480 and 572 nm corresponding to ⁴F_9/2→⁶H_15/2 (magnetic dipole) and ⁴F_9/2→⁶H_13/2 (electric dipole) transitions, respectively. Similarly, for Sm³⁺-doped LaPO₄, three prominent emission peaks at 561, 597 and 641 nm were observed corresponding to ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2 (magnetic dipole) and ⁴G_5/2→⁶H_9/2 (electric dipole) transitions, respectively. The luminescence intensity of the sample prepared in EG is more than that of DMSO or mixed solvents. Enhancement of luminescence is also observed after heat-treatment at 900 °C due to removal of quencher such as water, organic moiety and surface defects/dangling bonds. The samples are re-dispersible in polar solvent and can be incorporated in polymer film.     

Synthesis and photoluminescence properties of Dy3+, Sm3+ activated Sr5SiO4Cl6 phosphor

Dy³⁺ and Sm³⁺ doped Sr₅SiO₄Cl₆ phosphors were prepared by the modified solid state method and their luminescent properties were studied. From a powder X-ray diffraction (XRD) analysis the formation of Sr₅SiO₄Cl₆ was confirmed. In the photoluminescence emission spectra, the Sr₅SiO₄Cl₆:Dy³⁺ phosphors show efficient blue and yellow band emissions, which originates from the ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺ ion, respectively. Photoluminescence properties of Sm³⁺ doped Sr₅SiO₄Cl₆ phosphor exhibited characteristic orange-red emission coming from the intra-4f-shell ⁴G_5/2 →⁶H_J electron transitions.     

Spectroscopic and photoluminescence characteristics of Dy ions in lead containing sodium fluoroborate glasses for laser materials

Lead containing calcium zinc sodium fluoroborate (LCZSFB) glasses doped with different concentrations of trivalent dysprosium ions were prepared and investigated by the XRD, FTIR, optical absorption, photoluminescence and decay curve analysis. The experimentally determined oscillator strengths have been determined by measuring the areas under the absorption peaks and the Judd–Ofelt (J–O) intensity parameters were calculated using the least squares fit method. From the evaluated J–O parameters the radiative transition probability rates, radiative lifetimes and branching ratios were calculated for ⁴F_9/2 excited level. Room temperature photoluminescence spectra for different concentrations of Dy³⁺-doped LCZSFB glasses were obtained by exciting the glass samples at 386 nm. The intensity of Dy³⁺ emission spectra increases with increasing concentration of 0.1, 0.25, 0.5 and 1.0 mol% and beyond 1.0 mol% the concentration quenching is observed. The measuring branching ratios are reasonably high for transitions ⁴F_9/2→⁶H_15/2 and ⁶H_13/2, suggesting that the emission at 484 and 576 nm, respectively, can give rise to lasing action in the visible region. From the visible emission spectra, yellow–blue (Y/B) intensity ratios and chromaticity color coordinates were also estimated. The lifetimes of ⁴F_9/2 metastable state for the samples with different concentrations were also measured and discussed.     

Upconversion luminescence in Tm3+/Yb3+co-doped lead tungstate tellurite glasses

This work reports the upconversion luminescence properties of Tm³⁺/Yb³⁺ ions in lead tungstate tellurite (LTT) glasses. Judd–Oflet intensity parameters have been obtained from the absorption band intensities of Tm³⁺ singly-doped and Tm³⁺/Yb³⁺ co-doped LTT glasses. The spontaneous emission probabilities, radiative lifetimes and branching ratios for ¹G₄ and ³H₄ emission levels of Tm³⁺ have been determined. Upconversion luminescence has been observed by exciting the samples at 980 nm (Yb³⁺:²F_7/2→²F_5/2) at room temperature. Four upconversion emission bands corresponding to the ¹G₄→³H₆ (477 nm), ¹G₄→³F₄ (651 nm), ¹G₄→³H₅ (702 nm) and ³H₄→³H₆ (810 nm) transitions have been identified. The relative variation in the intensities of upconversion bands, the different channels responsible for upconversion spectra and the effect of Yb³⁺ ions concentration on the upconversion luminescence of Tm³⁺ ions have also been discussed.     

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.     

PL Properties of Sr<Subscript>2</Subscript>CeO<Subscript>4</Subscript> With Eu<Superscript>3+</Superscript> and Dy<Superscript>3+</Superscript> for Solid State Lighting Prepared by Precipitation Method

Photoluminescence studies of pure and Dy³⁺, Eu³⁺ doped Sr₂CeO₄ compounds are presented by oxalate precipitation method for solid state lighting. The prepared samples also characterized by XRD, SEM (EDS) and FTIR spectroscopy. The pure Sr₂CeO₄ compound displays a broad band in its emission spectrum when excited with 280 nm wavelength, which peaks centered at 488 nm, which is due to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ions. Emission spectra of Sr₂CeO₄ with different concentration of Dy³⁺ ions under near UV radiation excitation, shows that intensity of luminescence spectra is found to be affected by Dy³⁺ ions, and it increases with adding some percentages of Dy³⁺ ions. The maximum doping concentration for quenching is found to be Dy³⁺?=?0.2 mol % to Sr²⁺ions. The observed broad spectrum from 400 to 560 nm is mainly due to CT transitions in Sr₂CeO₄ matrix and some fractional contribution of transitions between ⁴F_9/2 → ⁶H_15/2 of Dy³⁺ ions. Secondly the effect of Eu³⁺ doping at the Sr²⁺ site in Sr₂CeO₄, have been studied. The results obtained by doping Eu³⁺ concentrations (0.2 mol% to 1.5 mol%), the observed excitation and emission spectra reveal excellent energy transfer between Ce⁴⁺ and Eu³⁺. The phenomena of concentration quenching are explained on the basis of electron phonon coupling and multipolar interaction. This energy transfer generates white light with a color tuning from blue to red, the tuning being dependent on the Eu³⁺ concentration. The results establish that the compound Sr₂CeO₄ with Eu³⁺?=?1 mol% is an efficient “single host lattice” for the generation of white lights under near UV-LED and blue LED irradiation. The commission internationale de I’Eclairage (CIE) coordinates were calculated by Spectrophotometric method using the spectral energy distribution of prepared phosphors.     

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.     

红色LiMBO3 : Re3+(Re=Eu,Sm) 发光材料的特性

采用固相法制备了红色LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)发光材料,研究了材料的发光性能。研究发现LiM(M=Ca, Sr, Ba)BO₃ : Eu³⁺材料呈现多峰发射,最强发射分别位于610,615,613 nm处,分别监测这三个最强峰,所得激发光谱峰值位于369,400,470 nm。LiM(M=Ca, Sr, Ba)BO₃ : Sm³⁺材料也呈多峰发射,分别对应Sm³⁺的⁴G_5/2→⁶H_5/2、⁴G_5/2→⁶H_7/2和⁴G_5/2→⁶H_9/2跃迁发射;分别监测602,599,597 nm三个最强发射峰,所得激发光谱峰值位于374,405 nm。研究了激活剂浓度对材料发射强度的影响,结果随激活剂浓度的增大,发射强度先增强后减弱,即,存在浓度猝灭效应。实验表明,加入电荷补偿剂Li⁺、Na⁺或K⁺均可提高LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)材料的发射强度。