Synthesis and luminescence properties of Tb3+/Eu3+ co-doped GdAlO3 phosphors with enhanced red emission

The(Gd_(0.97-x)Eu_xTb_(0.03))AIO_3(x= 0.005-0.07) phosphors were synthesized by the co-precipitation method,using ammonium bicarbonate as a precipitant.The combined technologies of FT-IR,XRD,FESEM,PLE/PL and photo luminescence decay analysis were used to study the phase evolution,morphologies and luminescent properties.The phosphors with good dispersion exhibit strong vivid red emission located at 617 nm(~5 D_0-~7 F_2 transition of Eu~(3+)) under the optimal excitation wavelength of 275 nm(~4 f~8-4 f~75 d~1 transition of Tb~(3+),~8 S_(7/2)→6~I_J transition of Gd~(3+)).The presence of Gd~(3+) and Tb~(3+) excitation bands on the PLE spectra monitoring the Eu~(3+) emission directly gives an evidence of Tb~(3+) → Eu~(3+) and Gd~(3+) → Eu~(~(3+)) energy transfer,The emission intensity varies with the Eu~(3+) amount,and the quenching concentration is ～5 at% which is close to the calculated value.The quenching mechanism is determined to be the exchange reaction between Eu~(3+).The temperature-dependent PL analysis indicates that the best(Gd_(0.92)Eu_(0.05)Tb_(0.03))AlO_3 sample possesses good thermally stable properties.All the(Gd_(0.97-x)Eu_xTb_(0.03))AIO_3 phosphors in this work have similar CIE chromaticity coordinates and color temperatures,which are(0.65 ± 0.02,0.35 ± 0.02) and ～2558 K,respectively.Fluorescence decay analysis shows that the lifetime for～617 nm emission decreases with the content of Eu~(3+) and temperature increasing.Owing to the Tb~(3+)→ Eu~(3+) energy transfer,the luminescent properties of the(Gd_(0.92)Eu_(0.05)Tb_(0.03))AlO_3 phosphors are superior to the single Eu~(~(3+)) doped sample(Gd_(0.95)Eu_(0.05))AlO_3.As a result,the prepared phosphors may be widely used in solid-state display and light emitting devices.     

Effects of Bi3+ on down-/up-conversion luminescence,temperature sensing and optical transition properties of Bi3+/Er3+ co-doped YNbO4 phosphors

A series of YNbO₄:Bi³⁺ and YNbO₄:Bi³⁺/Er³⁺ phosphors were prepared by a conventional high temperature solid–state reaction method. The results of XRD and Rietveld refinement confirm that monoclinic phase YNbO₄ samples are achieved. The down-/up-conversion luminescence of Er³⁺ ions was investigated under the excitation of ultraviolet light (327 nm) and near infrared light (980 nm). Under 327 nm excitation, broad visible emission band from Bi³⁺ ions and characteristic green emission peaks from Er³⁺ ions are simultaneously observed, while only strong green emissions from Er³⁺ ions are detected upon excitation of 980 nm. Remarkable emission enhancement is observed in down-/up-conversion luminescence processes by introducing Bi³⁺ ions into Er³⁺-doped YNbO₄ phosphors. Pumped current versus up-conversion emission intensity study shows that two-photon processes are responsible for both the green and the red up-conversion emissions of Er³⁺ ion. Through the study of the temperature sensing property of Er³⁺ ion, it is affirmed that the temperature sensitivity is sensitive to the doping concentration of Bi³⁺ ions. By comparing the experimental values of the radiative transition rate ratio of the two green emission levels of Er³⁺ ions and the theoretical values calculated by Judd-Ofelt (J-O) theory, it is concluded that the temperature sensing property of Er³⁺ ions is greatly affected by the energy level splitting.     

Cr3+/Y3+ co-doped persistent luminescence nanoparticles with biological window activation for in vivo repeatable imaging

The near-infrared(NIR) persistent luminescence materials(PLMs) can remain long-lasting luminescence after removal of the excitation light,which permits bioimaging with high sensitivity owing to the absence of background fluorescence interference from in situ excitation.Recently,the NIR PLMs have aroused intensive research interest in bioimaging.However,the optimal excitation wavelength of current NIR PLMs is located in the ultraviolet region with shallow tissue penetration,making it difficult to...     

Thermally stable photoluminescence and long persistent luminescence of Ca3Ga4O9:Tb3+/Zn2+

A green long persistent luminescence (LPL) phosphor Ca₃Ga₄O₉:Tb³⁺/Zn²⁺ was prepared. Ca₃Ga₄O₉ matrix exhibits blue self-activated LPL due to the creation of intrinsic traps. When Tb³⁺ is doped, the photoluminescence (PL) and LPL colors change from blue to green with their intensities significantly enhanced. The doping of Zn²⁺ evidently improves the PL and LPL performances of the Ca₃Ga₄O₉ matrix and Ca₃Ga₄O₉:Tb³⁺. The thermoluminescence (TL) spectra show that a successive trap distribution is formed by multiple intrinsic traps with different depths in the Ca₃Ga₄O₉ matrix, and the incorporation of Tb³⁺ and Zn²⁺ effectively increases the densities of these intrinsic traps. The existence of a successive trap distribution makes the Ca₃Ga₄O₉:Tb³⁺/Zn²⁺ phosphor exhibit thermally stable PL and LPL. It is indicated that this phosphor shows great promise for the application such as high-temperature LPL phosphor.     

Upconversion multicolor tuning of NaY(WO4)2:Tb3+ with Eu3+ doping

A series of Tb~(3+) and Eu~(3+) co-doped NaY(WO_4)_2 phosphors were synthesized by hydrothermal reactions.The crystal structure,morphology,upconversion luminescent properties,the energy transfer from Tb~(3+) to Eu~(3+)ions and the ~5 D_4→ ~7 F_5 transition of the Tb~(3+) ion in NaY(WO_4)_2:Tb~(3+),Eu~(3+) phosphors were investigated in details.The results indicate that all the synthesized samples are of pure tetragonal phase NaY(WO_4)2.Furthermore,the micrometer-sized needle spheres and excellent dispersion of the particles are obtained by adding polyethylene glycol(PEG-2000) as the surfactant.Phosphors of NaY(WO_4)_2:Tb~(3+),Eu~(3+) exhibit the492 nm blue emission peak,546 nm green emission peak,595 nm orange emission peak and 616 nm red emission peak under 790 nm excitation.The energy transfer from Tb~(3+) to Eu~(3+) is a resonant transfer,in which electric dipole-dipole interaction plays a leading role.By adjusting the doping concentration of Eu~(3+) in NaY(WO_4)_2: 1.0 mol%Tb~(3+),xmol%Eu~(3+) phosphors,the emitting color of UC phosphors can be tuned from green to red.     

Fabrication and long persistent luminescence of Ce3+-Cr3+ co-doped yttrium aluminum gallium garnet transparent ceramics

Persistent luminescence (PersL) materials are widely used in safety indication, traffic and transportation signs, architectural decoration and other fields. In this paper, (Y_1?xCe_x)₃(Al_0.9995Cr_0.0005)₂Ga₃O₁₂ (x = 0.001, 0.002, 0.003, 0.005) transparent ceramics were successfully prepared by solid-state reaction method in air followed by HIP post-treatment. With the increase of Ce³⁺ doping concentration, the optical quality of the as-prepared ceramics is improved and the morphology is denser. Luminescent quenching occurs when the Ce³⁺ concentration is more than 0.2%. The as-prepared transparent ceramics were annealed in different atmospheres. From the PersL decay curves, the transparent ceramics after air annealing show the best PersL performance: luminance with 4424.0 mcd/m² and PersL duration over 865 min after ceasing 365 nm excitation, respectively. The effects of Ce³⁺ doping concentration and annealing atmospheres are also discussed in detail.     

Effect of BaF2 addition on luminescence properties of Er3+/Yb3+ co-doped phosphate glasses

Er~(3+)/Yb~(3+) co-doped phosphate glasses(P_2O_5-Al_2O_3-BaO-BaF_2-K_2O-Er_2O_3-Yb_2O_3) with varying BaF_2 content,were prepared by a conventional melt quenching technique and their spectroscopic properties were examined through the Raman, absorption, emission and decay measurements. Raman spectra(350-1400 cm~(-1)) of the Er~(3+)/Yb~(3+) co-doped phosphate glasses with varying BaF_2 content, were recorded upon laser excitation at 785 nm. Near infrared luminescence spectra were measured in the1400-1600 nm region under 970 nm diode laser excitation and characteristic band was observed at1533 nm corresponding to ~4Ⅰ_(13/2)→~4Ⅰ_(15/2) transition of Er~(3+) ion. The decay curves for the ~4Ⅰ_(13/2) level of Er~(3+)ion, were measured and the lifetime is found to decrease from 7.94 to 7.70 ms when BaF_2 content increases from 0 to 8 mol% and then increases up to 7.83 ms with further increase in BaF_2 content(12 mol%). The emission cross-section.lifetime and figure of merit for the ~4Ⅰ_(13/2)→~4Ⅰ_(15/2) transition of Er~(3+) ion were evaluated and compared to the other host matrices. The upconversion luminescence was measured and intense red emission was observed for all the studied samples.     

Multicolor luminescence of hexagonal NaYF4:Yb3+/Ho3+/Ce3+ microcrystals with tunable morphology under 940 nm excitation for temperature-responsive anti-counterfeiting

In this study, the hexagonal NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ microcrystals were synthesized controllably, and upconversion luminescence excited at 940 nm and its application in temperature-responsive anti-counterfeiting are reported. It is clarified that the Ln³⁺ (Ln = Y + Yb + Ho + Ce) density ratio of bottom plane to side plane in the unit cell can be regulated by Ce³⁺ doping. It is also proved that the energy transfer of Yb³⁺ to Ho³⁺ is responsible for the activation of Ho³⁺ under 940 nm excitation, while the cross relaxation between Ho³⁺ and Ce³⁺ participates in the redistribution of electron population of ⁵S₂/⁵F₄ and ⁵F₅ levels. Both theory and experiment confirm that the intensity ratio of red to green emission (I_R/I_G) as a function of temperature as an independent variable has good linear characteristics in the temperature range of 300–500 K. Due to the good responsiveness of multicolor luminescence to temperature, the hexagonal NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ with tunable morphology is a promising candidate for advanced temperature-responsive upconversion anti-counterfeiting. Our results provide a new pathway for the controllable synthesis of hexagonal NaYF₄ microcrystals as well as the regulation of upconversion luminescence that is excited by wavelengths other than 980 nm and its application in anti-counterfeiting.     

Up-conversion luminescence of Tm3+/Yb3+ co-doped oxy-fluoride glasses

The oxy-fluorosilicate glasses co-doped with Yb3+/Tm3+ were prepared.The absorption spectra were recorded.The Tm3+ ion showed two absorption bands,with one at 774 nm due to 1G4→3H6 transition and the other at 667 nm due to 1G4→3F4 transition.The energy transfer between Tm3+ ion and Yb3+ ion and the up-conversion fluorescence of Tm3+ ion were investigated using 980 nm LD excitation.The results showed that the blue and red emissions were three-photon absorption processes corresponding with 1G4→3H6 and 1G4→3F4...     

Nd~(3+)/Yb~(3+) co-doped mid-infrared luminescence fluorobromide glass with energy transfer and zero-thermal-quenching IR emission

Nd~(3+)/Yb~(3+) co-doped fluorobromide glass samples were prepared by melt quenching.The mid-infrared(MIR) luminescence of the Nd~(3+)/Yb~(3+) co-doped fluorobromide glass was investigated by Br-doping reduces the phonon state density of the matrix.The 3.9 μm MIR luminescence of the samples excited at 793 and 980 nm pump excitation was investigated in detail.There is an effective mutual energy transfer process between Nd~(3+) and Yb~(3+).It is proved under 793 nm excitation that the luminescence of Nd~(3+)at 3.9 μm is reduced by effective energy transfer from,Nd~(3+):~2 H_(11/2)→Yb~(3+):~2 F_(5/2),At the same time,it is proved that the effective energy transfer from Yb~(3+):~2 F_(5/2)→Nd~(3+):2 H_(11/2) under the excitation of 980 nm enhances the luminescence of Nd~(3+) at 3.9 μm.In addition,it is found that the samples still have good infrared(IR) luminescent properties when the temperature changes.The emission cross-sectional area and the absorption cross-sectional area are σ_(em)(3.87 × 10~(-20) cm~2) and σ_(abs)(4.25×10~(-20) cm~2).The fluorescence decay characteristics of the sample at 3.9 μm at the ~2 H_(11/2) level were investigated and the fluorescence lifetime was calculated.The gain performance of the sample was calculated and analyzed,which can reach 4.25 × 10~(-20) cm~2.Those results prove that Nd~(3+)/Yb~(3+)co-doped fluorobromide glass is the potential mid-infrared laser gain material.     

Upconversion luminescence of Gd2O3:Er3+ and Gd2O3:Er3+/silica nanophosphors fabricated by EDTA combustion method

Gd_2O_3:Er~(3+) nanophosphors were fabricated by the combustion method in presence of Na_2 ethylene diamine tetra acetic acid(EDTA-Na_2) as fuel at not high temperature(≤350℃) within a very short time of 5 min.The added concentration of Er~(3+)ions in Gd_2O_3 matrix was changed from 0.5 mol% to 5.0 mol%.The X-ray diffraction pattern of samples indicates the monoclinic structure of Gd_2O_3:Er3+.The morphology and chemical composition analysis of the Gd_2O_3:Er~(3+) samples are characterized by a field emission scanning electron microscope(FESEM) and a Fourier-transform infrared spectrometer(FTIR).The photoluminescence(PL),photo luminescence excitation(PLE) and upconversion(UC) at room temperature of the prepared materials with different concentrations of Er~(3+) were investigated.The PL of Gd_2O_3:Er~(3+)nanomaterials are shown in visible at 545,594,623,648,688 nm under excitation at 275 nm.The emission bands from transitions of Er~(3+) from ~2P_(3/2) to ~4F_(9/2) are observed,UC luminescent spectra of the Gd_2O_3:Er~(3+)/silica nanocomposites under 976 nm excitation show the bands at 548 and 670 nm.The influence of excitation power at 980 nm for transitions were measured and calculated.The results indicate that the upconversion process of Gd_2O_3:Er~(3+)/silica is two photons absorption mechanism.The low temperature dependence of UC luminescent intensities of the main bands of Gd_2O_3:Er~(3+)was investigated towards development of a nanotemperature sensor in the range of 10-300 K.     

A NIR to NIR rechargeable long persistent luminescence phosphor Ca2Ga2GeO7:Yb3+,Tb3+

Near infrared to near infrared (NIR–NIR) photo-stimulated persistent luminescence (PSPL) has shown excellent potential in high-resolution bioimaging for deep tissues. However, the PSPL in NIR-Ⅱ region (900–1700 nm) is still lacking. In this work, Ca₂Ga₂GeO₇:Yb³⁺,Tb³⁺ (CGGYT) phosphor with unique low-dimensional crystal structure was synthesized by high-temperature solid–state reaction. Thanks to the carriers transferring from deep traps to shallow ones induced by low energy light, the 978 nm PSPL originating from ²F_5/2 to ²F_7/2 transition of Yb³⁺ induced by multimode stimulating (980 nm or WLED) is successfully realized after pre-excited by UV lamp. The NIR PSPL of the specimen can be repeatedly stimulated after placed in dark for 12 h. Moreover, the results indicate that codoping with Tb³⁺ can significantly enhance the NIR-II PSPL owing to the quantum cutting persistent energy transfer (QC PET) from Tb³⁺ to Yb³⁺. Our study points to a new direction for the future development of multimode PSPL materials for bioimaging or multimode optical storage applications.     

Improving luminescence and thermometric performance of Ba2CaWO6:Er3+ by tri-doping with Yb3+ and Na+

The Er³⁺doped double perovskite Ba₂ CaWO₆ crystal is a promising ratiometric thermometer based on the fluorescence intensity ratio(FIR) of transitions from ² H_11/2 and ⁴ S_3/2to the lowered ⁴ I_15/2 level.However,the Ca²⁺vacancy defect caused by the charge difference between rare-earth ions and the substituted alkaline-earth ions gives rise to the non-radiative probability and limits the t...     

Color-tunable Ca10Na(PO4)7:Ce3+/Tb3+/Mn2+ phosphor via energy transfer

A series of Ca_(10)Na(PO_4)_7:Ce~(3+)/Tb~(3+)/Mn~(2+)(CNPO:Ce~(3+)/Tb~(3+)/Mn~(2+)) phosphors with high brightness were synthesized by high-temperature solid-state method. X-ray diffraction(XRD), scanning electron microscopy(SEM), diffuse reflectance spectra(DRS), photo luminescence(PL) spectra, luminescence decay curves and thermally stability were performed to characterize the as-prepared samples. For Ce~(3+)-doped samples, an intense and broad band emission is present under 265 nm excitation. When Ce~(3+) and Tb~(3+)are codoped, energy transfer(ET) process from Ce3+ to Tb3+ is demonstrated with electric dipole-dipole interaction. The internal and external quantum efficiencies(QEs) of CNPO:0.15 Ce~(3+), 0.04 Tb~(3+), 0.005 Mn~(2+)are measured to 76.79% and 54.11% under 265 nm excitation and temperature-dependent PL intensity can remain 51.78% at 150 ℃ of its initial intensity at 25 ℃. It is indicated that single-phased white lightemitting CNPO:Ce~(3+)/Tb~(3+)/Mn~(2+) phosphor can serve as a promising phosphor for illumination devices.     

Effect of Eu3+ doping on luminescence properties of a KAlSiO4:Sm3+ phosphor

This study presents the photoluminescence characteristic analysis of a series of red phosphors of KAlSiO₄:1.5 mol%Sm³⁺,x mol%Eu³⁺ (x = 2, 3, 4, 5, 6, 7) prepared via high-temperature solid-phase reaction. The results show that the X-ray diffraction (XRD) refinement results are reliable. The unit cell parameters and volume gradually decrease as the Eu³⁺ concentration increases, resulting in a grain size reduction of 10.22%. When x = 6, the emission peaks of Sm³⁺ at 564, 601, and 651 nm disappear completely, and the corresponding full width at half maximum becomes 0. At 610 nm, the emission peak intensity of Eu³⁺ is increased by a factor of 4.8. The resonant non-radiative energy transfer effect is greater than the co-excitation effect. A maximum energy transfer efficiency of 97.8% is achieved. The integral area at 610 nm is as high as 85%. The color purity of the phosphor is as high as 92.97%, and the internal quantum yield gradually changes from 32% to 51%. Ultimately, these results confirm that the silicate phosphor is suitable for the red component in the three primary color phosphors of white light-emitting diodes.     

Down- and up-conversion processes in Nd3+/Yb3+ co-doped sodium calcium silicate glasses with concomitant Yb2+ assessment

Novel Nd³⁺/Yb³⁺ co-doped sodium calcium silicate glasses were prepared by melting quenching method:Spectroscopic study was carried out as a function of doping content by fixing sensitizer(Nd³⁺) concentration to 0.2 mol% and adjusting activator(Yb³⁺) from 0 to 1.0 mol%.The energy transfer(ET)mechanisms between Nd³⁺and Yb³⁺ are discussed based on their energy levels and excitation powerdependence emission intensity.Results show that...     

Preparation,structure, luminescence properties of europium doped zinc spinel structure green-emitting phosphor ZnAl2O4:Eu2+

The Zn_(1-x)Al_2 O_4:xEu~(2+) phosphor powders were synthesized by the solid-state reaction method.The synthesis temperature for ZnAl_2 O_4 was optimized,whereas the phase structure,TEM images,photoluminescence(PL) properties,the concentration quenching mechanism,the fluorescence decay curves,as well as the CIE chromaticity coordinates of the samples were investigated in details.Under the excitation at 379 nm,the phosphor exhibits an asymmetric broad-band green emission with a peak at 532 nm,which is ascribed to the 5 d-4 f transition of Eu2+.When the doping concentration of Eu2+ ions is 0.01,the luminescence intensity of the sample reaches the maximum value.It is further proved that the exchange interaction results in the concentration quenching of Eu2+ in the Zn_(1-x)Al_2 O_4:xEu~(2+) phosphor powders.The thermal quenching property of ZnAl_2 O_4:Eu~(2+)phosphor was investigated and the quantum efficiency(QE) values of the selected Zn_(0.99)Al_2 O_4:0.01 Eu~(2+) phosphor was measured and determined as 54.85%.The lifetime of the optimized sample Zn_(0.99)Al_2 O_4:0.01 Eu~(2+) is 3.0852 μs and the CIE coordinate of the sample was calculated as(0.3323,0.5538) with high-color-purity green emission.All properties indicate that the green-emitting ZnAl_2 O_4:Eu~(2+) phosphor powder has potential application in white LEDs.     

An optical thermometer with high sensitivity and superior signal discriminability based on dual-emitting Ce3+/Eu2+ co-doped La5Si2BO13 thermochromic phosphor

A novel non-contact optical thermometer, qualified with high sensitivity and temperature resolution, is urgently needed for temperature measuring of micro devices, moving objects and specific severe environments. Hence, a series of dual-emitting La₅Si₂BO₁₃:Ce³⁺,Eu²⁺ phosphors were synthesized. The two ions show diverse responses with the changing in temperature. The variational emissions of Ce³⁺ and Eu²⁺ can be converted to FIR (fluorescence intensity ratio) signals. The maximal absolute sensitivity S_a and relative sensitivity S_r reach up to 0.07526%/K and 3.2241%/K, respectively. It is worthy noting that the S_a and S_r possess the same variation tendency and both have high values in the low temperature region (293–373 K), showing the great temperature measuring property especially in low temperature region. The temperature sensing characteristics are superior to the results of most previous reports. The energy transfer (ET) process is certified to occur from Ce³⁺ to Eu²⁺ ions. These studies indicate that La₅Si₂BO₁₃: Ce³⁺,Eu²⁺ phosphor could have a good prospect for optical thermometry.     

Tunable luminescence in co-doped Zn3Al2Ge2O10:Cr3+ by controlling crystal field splitting and nephelauxetic effect

Ce³⁺/Dy³⁺/Tb³⁺/Eu³⁺/Mn²⁺and Cr³⁺ ions co-doped Zn₃ Al₂ Ge₂ O₁₀ phosphor were prepared by a hightemperature solid-state method.X-ray diffraction patterns prove the cubic phase structure of prepared Zn₃ Al₂ Ge2 O₁₀ phosphor,Emission,excitation spectra and decay curves confirm the tunable luminescence.Different degrees of the decrease of emission FWHM in Zn<...     

Tracing mechanism of optically and thermally stimulated luminescence in Lu_2O_3:Tb,M(M=Hf,Zr,Ti)ceramic storage phosphors

A series of energy storage phosphors,Lu_2O_3:Tb,M(M=Hf,Zr,Ti),were investigated by means of photoand thermoluminescence techniques to compare the effect of the co-dopant from the same group of periodic table of elements on charge carriers trapping capability and trap parameters.Most of the investigated processes were tracked individually for the Tb~(3+) in the two different metal sites offered by the Lu_2O_3 host-noncentrosymmetric C_2 and centrosymmetric C_(3i).It is proved that both Tb~(3+)ions participate in hole trapping and electrons are immobilized in traps whose depths are defined by the codopant.Deepest traps,～1.79 eV,appear upon Ti addition,while Zr and Hf generate traps of very similar,～1.40-1.44 eV,depths.The stored energy may be released not only by means of thermal stimulation but also upon the impact of optical photons.Light from the 390-430 nm range of wavelengths was found the most efficient in the latter process.Also deep red radiation of 780 nm releases most of the trapped electrons in Zr/Hf co-doped ceramics but is much less effective in the case of Tb,Ti material.Consistent scheme of electronic levels engaged in charge carriers trapping and subsequent generation of thermoand optically stimulated luminescence was constructed.