Near-infrared luminescence of OH and Cl doped Bi4Ge3O12 crystals

OH⁻ and Cl⁻ doped Bi₄Ge₃O₁₂ (BGO) single crystals had been grown by Vertical Bridgman (VB) method. The structure of these crystals was determined by XRD, the transmittance and emission spectra in near infrared region (NIR) were measured at room temperature. 5% OH⁻ doped BGO shows a significant emission band peaking around 1181 nm under 808 nm laser diodes (LDs) excitation, and the 5% Cl⁻ doped BGO exhibits a relatively weak emission band as well. 100% and 5% OH⁻ doped BGO show noticeable emission band centered at about 1346 nm under 980 nm LDs excitation.     

Spectroscopic properties of OH doped and Bi-rich Bi4Ge3O12 crystals by vertical Bridgman method

OH⁻ doped and Bi-rich Bi₄Ge₃O₁₂ (BGO) single crystals were grown by Vertical Bridgman (VB) method. The structure of these crystals was determined by XRD, and the emission spectra in visible and near infrared region (NIR) were measured at room temperature. The emission spectrum of Bi-rich BGO has extra peaks at 385, 367 and 357 nm, Bi-rich BGO after annealing in Ar at 500 °C for 5 h shows a significant emission band peaking around 1170 nm under 808 nm laser diodes (LDs) excitation, and OH⁻ doped BGO shows a noticeable emission band centered at about 1346 nm under 980 nm LDs excitation. A brief discussion is presented.     

Up-conversion emission in triply-doped Ho/Yb/Tm KGd(WO4)2 single crystals

Detailed spectroscopic studies of the triply doped KGd(WO₄)₂:Ho³⁺/Yb³⁺/Tm³⁺ single crystals (which exhibit multicolor up-conversion fluorescence) are reported for the first time. The absorption spectra of crystals were measured at 10 and 300 K; the room temperature luminescence spectra were excited at 980 nm wavelength. The dependence of the intensity of luminescence on the excitation power for three different concentration of Ho³⁺, Yb³⁺ and Tm³⁺ ions was investigated. Efficient green and red up-converted luminescence of Ho³⁺ ions and weak blue up-conversion luminescence of Tm³⁺ ions were observed in spectra. The red emission of Ho³⁺ ions is more intensive than their green emission. Dependence of the up-conversion luminescence intensity on the excitation power and impurities concentration was also studied; the number of phonon needed for efficient up-conversion was determined for each case. All possible energy transfer processes between different pairs of the impurity ions' energy levels are also discussed.     

VUV spectroscopy of pure and Tm-doped LicaAlF6 crystals

Nominally pure and Tm³⁺-doped LiCaAlF₆ crystals were grown by the Czochralski technique in a reducing atmosphere. The optical properties of transparent single crystals were studied using absorption and time-resolved luminescence spectroscopy in the VUV spectral range (330-100 nm). The strongest VUV emission peaking at 60 800 cm⁻¹ with a decay time of 5.6 μs (7 μs) at 300 K (7.4 K) was assigned to the spin-forbidden 4f¹¹5d-4f¹² transition of Tm³⁺. The fine structure observed in the VUV emission and corresponding excitation spectra indicate intermediate strength of electron-phonon coupling in this system. The efficient excitation of f-f emissions above 72 000 cm⁻¹, higher than the onset of f-d absorption at 63 000 cm⁻¹, is mainly caused by the F⁻ to Tm³⁺ charge transfer absorption. The nature of various host-related excitation processes in the energy transfer to the Tm³⁺ ions is discussed.     

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.     

Emission analysis of Pr and Tm: Ca2Gd2W3O14 phosphors

5 mol% of Pr³⁺ and Tm³⁺ ions activated calcium gadolinium tungstate (Ca₂Gd₂W₃O₁₄₎ phosphors were synthesized by traditional solid state reaction method. Crystalline phase structure was identified from the X-ray diffraction (XRD) profiles. From the scanning electron microscopy (SEM) images, we have observed the agglomeration of the particles, and average grain size is around 40-300 nm. Using the energy dispersive X-ray analysis (EDAX) and Fourier transform infrared (FTIR) spectra, identified the elements and functional groups present in the prepared phosphors. The emission spectrum of Pr³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown an intense red emission at 615 nm with the excitation wavelength λ_exci=450 nm and thus these red color emitting powder phosphors are used as one of the components in the preparation of WLEDs. The excitation spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ powder phosphor has shown a ligand to metal charge transfer (W-O) band (LMCT) within the WO₄²⁻ group. Emission spectrum of Tm³⁺: Ca₂Gd₂W₃O₁₄ phosphors have shown blue emissions at 453 nm (¹D₂→³F₄).     

Optical spectroscopy of heavily Ho-doped BaY2F8 crystals

The ultraviolet, visible, and near IR (0.8-2.4 μm) luminescence spectra of BaY₂F₈ single crystals heavily doped with Ho³⁺ ions (10 and 30 mol%) have been investigated at room temperature and 12 K, together with the luminescence decay curves (up to 300 μs) of the visible emission. Excitation in the visible region gives rise to very strong emission bands originating from the first ⁵I₇ level and located around 2070 nm. However the ⁵I₇ emission is not observed upon excitation at wavelengths shorter than 300 nm. The inter-ionic processes are found to shorten the decay times of the levels emitting in the visible region with respect to the corresponding radiative lifetimes.     

Investigation of crystallographic sites of Eu in La2BaZnO5 by site-selective laser-excitation spectroscopy

La₂BaZnO₅:Eu³⁺ (0.05 mol%) was prepared by a solid-state reaction at high temperature. X-ray powder diffraction analysis confirmed the formation of single phase La₂BaZnO₅. Luminescence properties of La₂BaZnO₅:Eu³⁺ are investigated by site-selective laser-excitation and emission spectroscopy at 18 K. Two different crystallographic sites for Eu³⁺ corresponding to the La³⁺ and Ba²⁺ sites are identified from the ⁷F₀→⁵D₀ excitation spectra obtained by monitoring the ⁵D₀→⁷F_J (J=1, 2, …, 6) emissions. It is found that Eu³⁺ substituted for the Ba²⁺ ion experiences stronger crystal-field strength than Eu³⁺ substituted for the La³⁺ ion. Energy transfer between the two crystallographic Eu³⁺ centers is investigated by luminescence decay curves at 18 K.     

Conversion of infrared radiation into visible emission in NaY(WO4)2:Yb, Ho crystal

The spectroscopic characteristics and fluorescence dynamics for Yb³⁺/Ho³⁺:NaY(WO₄)₂ crystal were investigated. The parameters of oscillator strengths, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and the stimulated emission cross sections have been calculated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The energy transfer efficiency from Yb³⁺ to Ho³⁺ was 65.85%. The green emission (530-570 nm) corresponding to (⁵F₄, ⁵S₂)→⁵I₈ transition, red emission (640-670 nm) due to ⁵F₅→⁵I₈ transition and NIR emission (740-770 nm) attributed to (⁵F₄, ⁵S₂)→⁵I₇ transition were observed on 974 nm excitation at room temperature. Under low pump power, the intensity of green light emission is weaker than that of the red light, while under high pump power, the case is on the contrary. The upconversion is based on the two-photon process either the energy transfer from Yb³⁺ ions or by the excited state absorption. The proposed mechanisms of upconversion emissions were provided.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

Combustion synthesis and luminescence properties of NaY1−xEux(WO4)2 phosphors

The red phosphors NaY_1−xEu_x(WO₄)₂ with different concentrations of Eu³⁺ were synthesized via the combustion synthesis method. As a comparison, NaEu(WO₄)₂ was prepared by the solid-state reaction method. The phase composition and optical properties of as-synthesized samples were studied by X-ray powder diffraction and photoluminescence spectra. The results show that the red light emission intensity of the combustion synthesized samples under 394 nm excitation increases with increase in Eu³⁺ concentrations and calcination temperatures. Without Y ions doping, the emission spectra intensity of the NaEu(WO₄)₂ phosphor prepared by the combustion method fired at 900 °C is higher than that prepared by the solid-state reaction at 1100 °C. NaEu(WO₄)₂ phosphor synthesized by the combustion method at 1100 °C exhibits the strongest red emission under 394 nm excitation and appropriate CIE chromaticity coordinates (x=0.64, y=0.33) close to the NTSC standard value. Thus, its excellent luminescence properties make it a promising phosphor for near UV InGaN chip-based red-emitting LED application.     

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.     

Luminescence properties of Y2WO6:Eu incorporated with Mo or Bi ions as red phosphors for light-emitting diode applications

In this study, the red phosphors, Y₂W_1−xMo_xO₆:Eu³⁺ and Y₂WO₆:Eu³⁺,Bi³⁺, have been investigated for light-emitting diode (LED) applications. In Y₂WO₆:Eu³⁺, the excitation band edge shifts to longer wavelength with the incorporation of Mo⁶⁺ or Bi³⁺ ions. The emission spectra exhibit ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ ion at 588, 593, and 610 nm, respectively. Moreover, the bluish-green luminescence of the WO₆⁶⁻ at about 460 nm is observed to decrease with the incorporation of Mo⁶⁺, which results in pure red color. Thus, this study shows that the red phosphor, Y₂WO₆:Eu³⁺, incorporated with Mo⁶⁺ or Bi³⁺ ions is advantageous for LEDs applications.     

Tm3+离子掺杂的钨酸钇钠晶体中浓度猝灭效应的研究

测量了Tm³⁺离子不同浓度(0.5at.%, 3 at.%, 5 at.%)掺杂的NaY(WO₄)₂晶体在800nm激光二极管激发下的上转换发射光谱.结合吸收谱、荧光谱和由Judd-Ofelt理论计算的光谱参数，详细分析了Tm³⁺:NaY(WO₄)₂晶体中上转换能量传递机理和离子浓度对上转换发射的影响.讨论了四种影响上转换发光效率的离子间相互作用机理：³H₅+¹G₄→³H₆+¹D₂，³H₅+³H₅→³H₆+³F₃，¹G₄+³H₆→³F₄+³F₃，¹G₄+³H₆→³F₃+³F₄，并根据Miyakawa-Dexter理论定量计算了各过程的发生概率.论证了交叉弛豫和共协上转换等浓度猝灭效应是影响Tm³⁺离子蓝色上转换荧光发射效率的主要因素. 关键词： 3+离子')" href="#">Tm³⁺离子 4)₂晶体')" href="#">NaY(WO₄)₂晶体 上转换 浓度猝灭     

Luminescence in trivalent rare earth activated Sr4Al2O7 phosphor

In this paper we report the combustion synthesis of trivalent rare-earth (RE³⁺ = Dy, Eu and Ce) activated Sr₄Al₂O₇ phosphor. The prepared phosphors were characterized by the X-ray powder diffraction (XRD) and photoluminescence (PL) techniques. Photoluminescence emission peaks of Sr₄Al₂O₇:Dy³⁺ phosphor at 474 nm and 578 nm in the blue and yellow region of the spectrum. The prepared Eu³⁺ doped phosphors were excited by 395 nm then we found that the characteristics emission of europium ions at 615 nm (⁵D₀?⁷F₂) and 592 nm (⁵D₀?⁷F₁). Photoluminescence (PL) peaks situated at wavelengths of 363 and 378 nm in the UV region under excitation at around 326 nm in the Sr₄Al₂O₇:Ce³⁺ phosphor.     

Low-temperature vibrational properties of KGd(WO4)2: (Er, Yb) single crystals studied by Raman spectroscopy

Temperature-dependent polarized Raman spectra of KGd(WO₄)₂: (Er, Yb) single crystals have been analyzed over the 77-292 K temperature range. The A_g and B_g spectra obtained are discussed in terms of factor group analysis. The spectra have been found to reveal the bands related to internal and external vibrations of WO₄²⁻, WOW and WOOW molecular groups. Strong depolarization of the majority of the Raman bands has been observed in the whole temperature range. Some anomalies in the spectral parameters of selected Raman bands below 175 K have been discussed in terms of the local distortion of WO₄²⁻ ions in KGd(WO₄)₂: (Er, Yb) crystals.     

Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

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.     

Sol-gel growth of Gd2MoO6:Eu nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6:Eu) and their luminescent properties

SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors. The XRD results demonstrate that the Gd₂MoO₆:Eu³⁺ layers on the SiO₂ spheres begin to crystallize after annealing at 600 °C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd₂MoO₆:Eu³⁺ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀-⁷F₂ red emission at 613 nm) under the excitation of 307 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles.     

Optical characterization of fourfold (Td)- and sixfold (Oh)-transition-metal species in MgAl2O4:Co by time-resolved spectroscopy

This work investigates the origin of novel visible photoluminescence (PL) bands observed in the spinel MgAl₂O₄:Co²⁺. Besides the well-known fourfold-coordinated Co²⁺(T_d) PL at 670 nm [N.V. Kuleshov, V.P. Mikhailov, V.G. Scherbitsky, P.V. Prokoshin and K.V. Yumashev, J. Lumin. 55 (1993) 265.], a rich structured PL band at 686 nm was also observed that we associate with uncontrolled impurities of sixfold coordinated Cr³⁺(O_h) by time-resolved spectroscopy and lifetime measurements and their variation with temperature. We also show that the lifetime of the Co²⁺(T_d) emission at 670 nm varies from τ=6.7 μs to 780 ns on passing from T=10 to 290 K. This unexpected behaviour for T_d systems is related to the excited-state crossover (⁴T₁↔²E), making the emission band to transform from a narrow-like emission from ²E at low temperature to a broad structureless band from ⁴T₁ at room temperature.