Effect of Li+ ion concentration on upconversion emission and temperature sensing behavior of La2O3:Er3+ phosphors

The effects of Li~+ co-doping concentration on the structure, upconversion luminescence and temperature sensing behavior of Er~(3+):La_2O_3 phosphors were investigated. X-ray diffraction and scanning electron microscopy observations reveal that Li~+ ion co-doping can change the lattice parameter of La_2O_3 host and increase the particle size of the samples. The optical investigation shows that co-doping of Li~+ ions can enhance the upconversion emission of Er~(3+) ions in La_2O_3 matrix effectively. Most importantly, the temperature sensing sensitivity of the samples is found to be dependent on Li~+ co-doping concentration,when the emission intensity ratio of the(~2H_(11/2)→~4 I_(15/2)) and(~4 S_(3/2)→~4 I_(15/2)) transitions of Er~(3+) is chosen as the thermometric index. Both of the optimum upconversion luminescence and temperature sensing sensitivity are obtained for 7 mol% Li~+ co-doped sample. When the Li~+ concentration is beyond 7 mol%,both the quenching in upconversion intensity and the degradation of temperature sensitivity are observed, which may be due to the serious distortion in local crystal field around Er~(3+) ions caused by the excess Li~+ ions.     

Enhancing upconversion of Nd3+ through Yb3+-mediated energy cycling towards temperature sensing

Photon upconversion of lanthanides has been a powerful means to convert low-energy photons into high-energy ones. However, in contrast to the mostly investigated lanthanide ions, it has remained a challenge for the efficient upconversion of Nd³⁺ due to the deleterious concentration quenching effect. Here we report an efficient strategy to enhance the upconversion of Nd³⁺ through the Yb³⁺-mediated energy cycling in a core-shell-shell nanostructure. Both Nd³⁺ and Yb³⁺ are confined in the interlayer, and the presence of Yb³⁺ in the Nd-sublattice provides a more matched energy for the upconversion transitions occurring at the intermediate state of Nd³⁺ towards much better population at its emissive levels. Moreover, this design also minimizes the possible cross-relaxation processes at both intermediate level and the emissive levels of Nd³⁺ which are the primary factors limiting the upconversion performance for the Nd³⁺-doped materials. Such energy cycling-enhanced upconversion shows promise in temperature sensing.     

Synthesis,upconversion luminescence and optical heating of hexagonal NaGdF4:Yb3+,Er3+

An optical heater based on hexagonal NaGdF_4:Yb~(3+)/Er~(3+) is reported. XRD, SEM and EDS characterization results show that F~-/Ln~(3+) can not only control the phase composition, particle size and morphology, but also affect the effective doping concentration of Yb~(3+) and Er~(3+).When F~-/Ln~(3+) is 12/1, the strongest upconversion luminescence is obtained. Based on the luminescent temperature sensing behavior of Er~(3+),the photo-thermal conversion performance was investigated. The results indicate that the temperature of irradiation spot is linearly dependent on the power density, and the photo-thermal responsivity is determined to be 3.3K·cm~2/W. Also, it is found that the photo-thermal conversion efficiency can be regulated by changing the Yb~(3+) doping concentration. Compared with the nano-gold, copper sulfide and carbon nanotubes, the NaGdF_4:Yb~(3+)/Er~(3+) has the triple functions of upconversion luminescence, temperature sensing, and photo-thermal conversion, and may therefore be a promising optical heater for photo-thermal therapy of tumors.     

Plasmonic enhancement of upconversion emission in Ag@NaYF4:Er3+/Yb3+ phosphor

In this article upconversion luminescence of silver nanoparticles(AgNPs) coated NaYF_4:Er~(3+)/Yb~(3+)phosphor nano-particles was investigated.The prepared samples were characterized through various techniques.The surface plasmon band is observed for prepared AgNPs by analyzing UV-vis measurements and is used to enhance the upconversion emission.From the upconversion measurement the emission bands are observed at 522,546,and 656 nm corresponding to the ~2 H_(11/2)→ 4~1_(15/2),~4 S_(3/2)→~4 I_(15/2)and ~4 F_(9/2)→~4 I_(15/2) levels,respectively.The upconversion emission intensity of the above bands is found to enhance for sample containing 1 mmol AgNPs.Decay time of ~4 S_(3/2) and 4~F_(9/2) levels is found to decrease on coating of AgNPs and hence intensity enhancement is assumed due to the surface plasmon resonance(SPR) effect.     

Er3+/Yb3+/Li+/Zn2+: Gd2(MoO4)3 upconverting nanophosphors in optical thermometry

Er~(3+)-Yb~(3+)-Li~+:Gd_2(MoO_4)_3 and Er~(3+)-Yb~(3+)-Zn~(2+):Gd_2(MoO_4)_3 nanophosphors, synthesized by chemical co-precipitation technique were characterized through XRD,FESEM,dynamic light scattering(DLS),diffuse reflectance, photoluminescence, photometric and decay time analysis. The enhancement of about～28, ～149 and ～351 times in the green upconversion emission band is observed for the optimized Er~(3+)-Yb~(3+),Er~(3+)-Yb~(3+)-Li~+ and Er~(3+)-Yb~(3+)-Zn~(2+):Gd_2(MoO_4)_3 nanophosphors in comparison to the singly Er~(3+) doped nanophosphors. The electric dipole-dipole interaction is found to be responsible for the concentration quenching. The temperature dependent behaviour of the two green thermally coupled levels of the Er~(3+) ions based on the fluorescence intensity ratio technique was studied. The maximum sensor sensitivity ～38.7 × 10~(-3) K~(-1) at 473 K for optimized Er~(3+)-Yb~(3+)-Zn~(2+) codoped Gd_2(MoO_4)_3 nanophosphors is reported with maximum population redistribution ability～88% among the ~2H_(11/2) and ~4S_(3/2) levels.     

Er~(3+)-Yb~(3+)-Na~+:ZnWO_4 phosphors for enhanced visible upconversion and temperature sensing applications

The crystal structure and surface morphology of the Er³⁺/Yb³⁺/Na+:ZnWO₄ phosphors synthesized by solid state reaction method were analyzed by X-ray diffraction(XRD) and field emission scanning electron microscopy(FESEM) analysis.The frequency upconversion(UC) emission study in the developed phosphors was investigated by using 980 nm laser diode excitation.The effect of codoping in the Er³⁺:ZnWO₄ phosphors on the UC emission intensity was studied.The UC emission bands that are exhibited in the blue(490 nm),green(530,552 nm),red(668 nm) and NIR(800 nm) region correspond to the ⁴F_7/2→⁴I_15/2.²H_11/2,⁴S_3/2→⁴I_15/2,⁴F_9/2→⁴I_15/2 and ⁴I9/2→⁴I_15/2 transitions,respectively.The temperature sensing performance of the Er³⁺-Yb³⁺-Na+:ZnWO₄ phosphors was investigated based on the 2 H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 thermally coupled transitions of the Er³⁺ions.The photometric study was also carried out for the developed phosphors.     

Enhanced ultraviolet upconversion in YF3：Yb^3＋/Tm^3＋ nanocrystals

Unusual intense infrared-to-ultraviolet upconversion luminescence was observed in YF3:Yb3+(20%)/Tm3+(1%) nanocrystals under 980 nm excitation. The intense ultraviolet emissions (1I6→3H6, 1I6→3F4, and 1D2→3H6) were affirmed arising from the excitation processes of five-photon and four-photon. In comparison with the bulk sample with the same chemical compositions, ultraviolet upconversion lumi-nescence of the nanocrystals was markedly enhanced. Spectral analysis indicated that the enhancement was attributed to the decrease of Judd-Ofelt parameter Ω2, which precluded the transition rate from 3F2 to 3F4, enhanced the energy transfer process and populated the 1D2 level: 3F2→3H6 (Tm3+): 3H4→1D2 (Tm3+).     

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.     

White up-conversion luminescence and highly-sensitive optical temperature sensing in Na3La(VO4)2:Yb,Er,Tm,Ho phosphors

In this work,tunable white up-conversion luminescence was achieved in the Yb³⁺,Er³⁺,Tm³⁺,Ho³⁺ codoped Na₃La(VO₄)₂ phosphors under 980 nm excitation.The emissions of three primary colors are mainly attributed to the ²H_11/2/⁴S_3/2→⁴I_15/2 transitions of Er³⁺,¹G₄→³H₆ transition of Tm³⁺,and_5...     

Cooperative energy transfer in Eu3+,Yb3+ codoped Y2O3 phosphor

Under 980 nm laser excitation,red emission(5D0-7FJ(J=0,1,2)) of Eu3+ was observed in cubic Y2O3 codoped with Eu3+ and Yb3+.The dependence of the upconverted emission on doping concentration and laser power was studied.Yb3+ emission around 1000 nm(2F5/2-2F7/2) was reported upon excitation of Eu3+ ions.The decay curves of 5DJ(J=0,2) emission of Eu3+ under excitation of 266 nm pulse laser were examined to investigate the Eu3+→Yb3+ energy transfer process.Cooperative energy transfer process was discussed as the possible mechanism for the visible up-conversion luminescence of Eu3+ and near-infrared down-conversion emission of Yb3+.     

Preparation and upconversion luminescence of YAG（Y3Al5O12）：Yb^3＋,Ho^3＋ nanocrystals

Cubic YAG: Yb3+, Ho3+ pure phase nanocrystals were synthesized by using coprecipition nitrate and ammonium hydrogen carbonate as raw materials. After calcining the precipitates at 800 ℃, the resultant YAG: Yb3+, Ho3+ nanocrystals were nearly spheric and the particle size was about 40 nm. Intense upconversion spectra were observed on the powder compact pumped by a 980 nm continuous wave diode laser, and green emission centered at 549 nm, red emission centered at 667 nm, and NIR centered at 760 nm were all due to two photons process, which originated from 5S2 (5F4)→5I8, 5F5→5I8, and 5S2 (5F4)→5I7 transitions, respectively.     

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.     

Colour modulation and enhancement of upconversion emissions in K2NaScF6:Yb/Ln (Ln = Er,Ho, Tm) nanocrystals

Effective colour modulation of upconversion emissions in lanthanide-doped nanomaterials becomes even more important for fundamental and applied research. Herein, on the one hand, by raising the content of doped Yb³⁺ from 10 mol% to 50 mol%, a significant increase of the red/green emission ratio from 4.0 to 68.2 is observed in K₂NaScF₆:Yb/Er nanocrystals. This yellow to red colour change is attributed to the increased cross relaxation between Er³⁺ and Yb³⁺ caused by the increased Yb³⁺ amount, ⁴S_3/2 (Er³⁺) + ²F_7/2 (Yb³⁺) → ⁴I_13/2 (Er³⁺) + ²F_5/2 (Yb³⁺). On the other hand, the upconversion green and red emission of K₂NaScF₆:Yb/Er (20/2 mol%) nanocrystals are intensified 10.6 and 8.8 folds, respectively, after an active shell (K₂NaScF₆:Yb) is epitaxially grown, which are more effective than the 7.4- and 6.4-fold enhancement from an inert shell (K₂NaScF₆) growth. Moreover, the shell thickness from 2.85 to 9.5 nm through controlling the molar ratio of shell-precursor to core from 1:2 to 3:1 can be easily realized. This study will provide more opportunities for the application of K₂NaScF₆:Yb/Ln nanoparticles in varied fields such as theranostics, photovoltaics, and photocatalysis.     

Promising light converting BaMoO4:Er3+-Tm3+-Yb3+ phosphors for display and optical temperature sensing

Er³⁺-Tm³⁺-Yb³⁺ tri-doped BaMoO₄ phosphors were synthesized by co-precipitation technique and characterized by X-ray diffraction analysis, absorption study and field emission scanning electron microscopy analysis. Upconversion as well as downconversion luminescence studies were performed by using near infrared (980 nm) and ultraviolet (380 nm) excitations. Energy level diagram, pump power dependence and colour coordinate study were utilized to describe the multicolor upconversion emission properties. Under single 980 nm diode laser excitation the dual mode sensing behaviour is realized via Stark sublevels and thermally coupled energy levels of the Tm³⁺ and Er³⁺ ions in the prepared tri-doped phosphors. A comparative fluorescence intensity ratio analysis for integrated emission intensities arising from the Stark sublevels {¹G_4(a) and ¹G_4(b)} and thermally coupled energy levels {²H_11/2 and ⁴S_3/2} of the Tm³⁺ and Er³⁺ ions, respectively was carried out in the prepared tri-doped BaMoO₄ phosphors. The maximum sensitivity for thermally coupled energy levels of the Er³⁺ and Stark sublevels of the Tm³⁺ ion was reported. The developed phosphors could be useful in the display devices and optical thermometric applications.     

Study on UV Excitation Properties of Eu^3＋ at S6 Site in Bulk and Nanocrystalline Cubic Y2O3

Increases of emission intensities for Eu^3 at the S6 site relative to that at the C2 site were observed as UV excitation wavelength decreases from 300 nm to 200 nm in both bulk and nanocrystalline cubic Y2O3:Eu^3 . Decomposition of excitation spectra shows that the charge transfer band of Eu^3 at the S6 site lies in the high-energy side of that at the C2 site, resulting in that the energy transfer from the host prefers to the S6 site. Detailed emission and excitation spectral characteristics were analyzed and discussed. In addition, spectral red-shift were found in both charge transfer bands in nanocrystalline Y2O3: Eu^3 compared to the bulk material. The number ratio of S6 sites to C2 sites is also smaller in nanocrystalline Y2O3:Eu^3 than that in the bulk one.     

Strong dependence of upconversion luminescence on doping concentration in holmium and ytterbium co-doped Y2O3 phosphor

Under the excitation of 980 nm diode laser, intense green emission (5F4+5S2-5I8) of Ho3+ was observed in Ho3+ and Yb3+ co-doped cubic Y2O3. The doping concentration and laser power dependence of the upconverted emission were studied. The decay curves of 5F4+5S2 emission of Ho3+ under the excitation of 355 nm pulse laser were measured to investigate the energy transfer process between Ho3+ and Yb3+. The results indicated that two-photon process was responsible for the upconversion (UC) emission. The Ho3+ con...     

Hydrothermal synthesis of SrF2：yb^3＋/Er^3＋ micro-/nanocrystals with multiform morphologies and upconversion properties

Micro-and nanocrystals cubic-phase SrF2:Yb3+/Er3+ upconversion luminescence phosphors were synthesized via a facile hydro-thermal route in the presence of different surfactants.The samples were characterized with X-ray diffraction (XRD),Fourier transform infra-red spectra (FT-IR),scanning electron microscopy (SEM),transmission electron microscopy (TEM),and upconversion emission spectra.As-prepared products showed a variety of morphologies,such as cubic-shaped microcrystal,hierarchical structure microspheres...     

溶胶-凝胶法制备Y2Zr2O7∶Tm3+及其发光性能研究

以柠檬酸为络合剂采用溶胶-凝胶法制备了（Y1-xTmx）2Zr2O7（x=0.005,0.01,0.03,0.05）荧光粉.采用X-射线衍射分析仪（XRD）、扫描电子显微镜（SEM）和荧光光谱仪分别检测了Y2Zr2O7∶Tm3+的晶体结构、颗粒形貌以及样品的荧光光谱.XRD图谱表明,所得到的产物Y2Zr2O7∶Tm3+为单一相的萤石结构,而且Tm3+的掺杂并没有改变其晶体结构.荧光光谱的测试表明,在359 nm波长的紫外光激发下,1000℃下烧结的（Y1-xTmx）2Zr2O7（x=0.01）样品的发光性能最好,发射峰对应于Tm3+的1D2→3F4跃迁和1G4→3H6跃迁,并对其发光机理进行了探讨.样品在454 nm处的发光强度随Tm3+离子掺杂浓度的增加先升高后降低,即出现了浓度猝灭的现象,当Tm3+掺杂浓度摩尔百分比为1%时,样品的发光强度达到最大.     

Synthesis and luminescent properties of Ba3Y3.88Gd0.12O9:Eu3+ phosphors with enhanced red emission

In this work, the Gd³⁺/Eu³⁺ activated Ba₃Y₄O₉ (BYO) phosphors were successfully synthesized via coprecipitation method at 1400 °C. The precursor composition, crystal structure stability, microscopic morphology, photoluminescence (PL)/photoluminescence excitation (PLE) spectra and fluorescence attenuation analysis of the phosphors are discussed in detail. The chemical composition of the precursor was determined by Fourier transform infrared spectroscopy (FT-IR) and thermogravimetry (TG) analysis; According to field emission-scanning electron microscopy (FE-SEM) analysis, it is found that the particle size of phosphor is uniform and the agglomeration is few. According to PL/PLE spectra analysis, Ba₃Y_3.28Eu_0.6Gd_0.12O₉ phosphors has the strongest excitation band at 260 nm and the strongest emission band at 614 nm, and the fluorescence intensity of Ba₃Y_3.28Eu_0.6Gd_0.12O₉ is higher than that of Ba₃Y_3.4Eu_0.6O₉. The quenching concentration of Eu³⁺ in Ba₃Y_3.88–4xEu_4xGd_0.12O₉ phosphors is x = 0.15 and the mechanism of quenching concentration of Eu³⁺ is electric dipole-quadrupole type interactions. The lifetime value of Ba₃Y_3.88–4xEu_4xGd_0.12O₉ (x = 0.15) phosphors is 0.686 ms and decreases with the increase of Eu³⁺ content. In addition, the CIE chromaticity diagram of Ba₃Y_3.28Eu_0.6Gd_0.12O₉ phosphors is (0.66, 0.34). Finally, the lamp beads assembled with Ba₃Y_3.28Eu_0.6Gd_0.12O₉ phosphors have an ideal luminous effect. Therefore, the Ba₃Y_3.88–4xEu_4xGd_0.12O₉ phosphors designed in this work may hopefully meet the requirements of various lighting and optical display applications.     

Green, orange, and red upconversion luminescence in Nd3+/Yb3+: Cs2NaGdCl6 powders under 785 nm laser excitation

Nd3+:Cs2NaGdCl6 and Nd3+, Yb3+:Cs2NaGdCl6 polycrystalline powder samples were prepared by Morss method E. Under 785 nm semiconductor laser pumping, the upconversion luminescence of Nd3+ ions in Cs2NaGdCl6 was investigated at room temperature, and three upconversion emissions near 538 nm (Green), 603 nm (Grange), and 675 nm (Red) were observed and assigned to 4G7/2→4I9/2, (4G7/2→4I11/2; 4G5/2→4I9/2), and (4G7/2→4I13/2; 4G5/2→4I11/2), respectively. The dependences of these upconverted emissions on laser power and Nd3+ ion con-eentration were investigated, to explore the upconversion mechanism. The effect of doping Yb3+ ions on the upconversion luminescence of Nd3+ in Cs2NaGdCl6 was also studied under 785 nm laser excitation. The energy transfer processes were discussed as the possible mecha-nism for the above upconversion emissions.