Y4GeO8:Er3+,Yb3+ up-conversion phosphors for optical temperature sensor based on FIR technique

Herein, we reported novel Y₄GeO₈:Er³⁺,Yb³⁺ phosphors elaborated via conventional solid-state reaction, and we further explored their properties as optical thermometer by using fluorescence intensity ratio (FIR) method complemented by detailed analysis on crystal structure, up-conversion luminescence and energy transfer from Yb³⁺ to Er³⁺. Upon 980 nm laser excitation, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors present 525, 547 and 659 nm emission bands assigned to the characteristic transitions of Er³⁺. Furthermore, Y₄GeO₈:Er³⁺,Yb³⁺ samples show outstanding temperature sensing performances. To be specific, the minimal temperature resolution is 0.03 K (303 K), and the relative sensitivity of FIR can be up to 1.152%/K (303 K). Hence, Y₄GeO₈:Er³⁺,Yb³⁺ phosphors can be possible candidates for thermometry devices.     

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.     

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...     

Up-conversion luminescence of Er~（3＋）-doped and Yb~（3＋）/Er~（3＋） co-doped 12CaO·7Al_2O_3 poly-crystals

The optical properties of Er3+-doped and Yb3+/Er3+ co-doped 12CaO·7Al2O3 (C12A7) poly-crystals, synthesized by high temperature solid state method, were investigated in detail. For Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals, two main emission bands centered around 530/550 nm (green) and 660 nm (red) were observed under 980 nm diode laser excitation via an up-conversion process. The intensity of green up-conversion emission had a strong increase in Er3+ (1.0 mol.%, 1.5 mol.%, 3.0 mol.%), and the intensity ratio of red to green up-conversion emission had an increase in Yb3+ (1.0 mol.%, 2.0 mol.%, 10. 0 mol.%)/Er3+ (fixed at 1.0 mol.%). This detailed study of the up-conversion processes allowed us to identify the dominant up-conversion mechanisms in Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals.     

Up-conversion luminescence properties of Yb^3＋ and Ho^3＋ co-doped Bi3.84W0.16O6.24 powder synthesized by hydrothermal method

Using polyethylene glycol (PEG) as the surfactant, Bi3.84W0.16O6.24 up-conversion luminescence nano-crystal co-doped with Yb3+ and Ho3+ ions was synthesized by the hydrothermal method. The structure and properties of luminescence powder were studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). It was of cubic system when the sample was synthesized at a low temperature and the particle size was about 30 nm. The results showed that adding surfactants was useful to improve the powder agglomeration and the grain crystal was spherical. The green emission peak at 546 nm and red emission peak at 655 nm, corresponding to the ( 5F4, 5S2)→ 5 I 8 and the 5 F 5 → 5 I 8 transitions of Ho 3+ , respectively, were simultaneously observed at room temperature under excitation of 980 nm semiconductor laser. The up-conversion luminescence intensity was the strongest when the concentration ratio of Yb3+ /Ho3+ was 6:1 and the concentration of Ho 3+ ion was 1.5 mol.%. The up-conversion mechanism was also studied. The green and red emission peaks were the two-photon absorption according to the relationship between the pump power and the luminescence intensity.     

Luminescent ionic lattice occupation and wide tunable emission spectra of La2MgZrO6:Bi3+,Eu3+ double perovskite phosphors for white light LED

La₂Mg_1-x/2Zr_1-x/2O₆:xBi³⁺(x=0.01-0.035,abbreviated as LMZ:Bi³⁺) and La_2-yMg_0.99Zr_0.99O₆:0.02Bi³⁺,yEu³⁺(y=0.1-0.11,abbreviated as LMZ:Bi³⁺,Eu³⁺) double-perovskite phosphors were prepared through high-temperature solid-phase method.The emission spectrum of LMZ:xBi³⁺(x=0.01-0.035)phosphors excited at 353 nm is asymmetric in the range be...     

Bi3+ assisted luminescence in SrMoO4:Sm3+ red phosphors

In this paper, we report synthesis of pure SrMoO₄, Sm³⁺ (1 at%–5 at%) doped SrMoO₄ and Bi³⁺ (1 at%–3 at%) co-doped in 4 at% Sm³⁺ doped SrMoO₄ (SrMoO₄:4Sm³⁺) phosphors by solution combustion method. The X-ray diffraction (XRD) analysis reveals the tetragonal phase of all samples, also Bi³⁺ co-doping supports crystallite size growth and reduces lattice strain. Absorption analysis of Sm³⁺ doped SrMoO₄ ascertains a decrease in band gap and Bi³⁺ co-doping confirms the emergence of an absorbance peak at around 308 nm attributed to Bi³⁺ energy levels. Photoluminescence (PL) analysis ascertains an increase in emission peaks for Sm³⁺ doped SrMoO₄ up to 4% concentration, which are attributed to an electron transition from ⁴G_5/2 to ⁶H_J (J = 5/2, 7/2, 9/2, and 11/2) energy levels of Sm³⁺ ions. We have explained the effects of Bi³⁺ co-doping on the luminescence of Sm³⁺ doped SrMoO₄. The reduced microstrain and increased crystallinity of the phosphors as a result of Bi³⁺ co-doping and their correlation with the luminescence of Sm³⁺ ions are discussed.     

Luminescence properties of Pr3+ and Bi3+ co-doped NaCaTiNbO6 phosphor for red-LEDs

This paper investigates the photoluminescence properties of NaCaTiNbO_6:Pr~(3+) and NaCaTiNbO_6:Pr~(3+),Bi~(3+) phosphors. NaCaTiNbO_6:Pr~(3+) and NaCaTiNbO_6:Pr~(3+),Bi~(3+) powder were synthesized successfully by solid state reaction method. Phase purity was checked using X-ray powder diffractometry(XRD). The excitation and emission spectra were recorded to elucidate the photoluminescence properties of NaCaTiNbO_6:Pr~(3+) and NaCaTiNbO_6:Pr~(3+),Bi~(3+). Furthermore,fluorescence lifetime measurements were performed. The excitation spectra of NaCaTiNbO_6:Pr~(3+) show a main band centered at around 357 nm.The luminescence spectra of NaCaTiNbO_6:Pr~(3+) exhibit a red emission peak at 615 nm from the ~1 D_2→~3 H_4 transition of Pr~(3+) ions. With the introduction of the Bi~(3+) ion into NaCaTiNbO_6:Pr~(3+), the luminescence intensity is enhanced nearly two times. Meanwhile,the absorption band edge of NaCaTiNbO_6:Pr~(3+) is shifted from 380 to 420 nm. Thus, this study shows that the red phosphor NaCaTiNbO_6:Pr~(3+) incorporated with Bi~(3+) is advantageous for light-emitting diode applications.     

Enhanced luminescence efficiency and thermal stability via introduction of non-rare earth Bi3+ in Gd5Si2BO13:Eu3+

A series of Gd₅Si₂BO₁₃:Eu³⁺ and non-rare earth Bi³⁺ ions doped Gd₅Si₂BO₁₃:Eu³⁺ phosphors was successfully synthesized via high-temperature solid-state method,and the as-obtained phosphors were studied on their phase structures,luminescence characteristics,thermal stability and luminescence lifetime.Transient fluorescence spectroscopy data show that the addition of Bi³⁺ can obviously enha...     

Color tunable and white light emitting via energy transfer in single-phase BiOCl:Er3+,Sm3+ phosphors for WLEDs

BiOCl crystal shows potential as efficient optical host due to its special layered structure. Here,the luminescence properties of the Er~(3+)/Sm~(3+) co-doped BiOCl phosphors as single-phase phosphors were reported. Upon near ultraviolet excitation(NUV, 380 nm corresponding the ~4 I_(15/2)→ ~4 G_(11/2) transition of Er~(3+) ions), the phosphors exhibit the efficient characteristic emissions of Er~(3+) and Sm~(3+) ions simultaneously. The energy transfer(ET) from Er~(3+) to Sm~(3+) ions in the layered crystals has been validated by the variation of emission intensities and decay lifetimes respectively, which is ascribed to be a dipoledipole interaction. By virtue of the ET behavior and increasing Sm~(3+) ion concentration, the enhancing emission intensity of Sm~(3+) and the tunability of emission color from yellowish-green(0.318, 0.420) to white(0.343, 0.347) are realized. The results of our work indicate that the Er~(3+)/Sm~(3+) co-doped BiOCI phosphor has a promising application serving as single component white emitting phosphors for NUV excited WLEDs.     

Synthesis and photoluminescence properties of Er3+ and Dy3+ doped Na2NbAlO5 phosphors

A series of Ln³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) ions doped Na₂NbAlO₅ (NNAO) phosphors were synthesized by solid-state method. The Er³⁺ and Dy³⁺ ions doped phosphors were characterized by XRD, photoluminescence (PL) and decay profiles. The Ln³⁺-doped samples are consistent with the pure NNAO phase which is analyzed by the X-ray diffraction result. The PL graphs show that the intensity of luminescence increases with the increasing doping concentrations up to their critical certain values and then decreases at higher concentrations due to the concentration quenching effect of Er³⁺/Dy³⁺ ions. The energy level diagrams containing the positions of 4f and 5d energy levels of Er³⁺ and Dy³⁺ ions have been established and studied. In addition, under the ultraviolet light, the prepared NNAO:xLn³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) phosphors show the characteristic green (Er³⁺), cyan (Dy³⁺) emission, respectively. Under the excitation of 365 nm, the quantum efficiencies of NNAO:0.01Er³⁺ and NNAO:0.03Dy³⁺ phosphors are measured to be 61.7% and 72.2%, respectively. The obtained results indicate that the new NNAO:xLn³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) phosphors are promising applications in white-light emitting diodes field.     

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.     

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.     

Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work,calcium niobium gallium garnet(Ca₃ Nb_1.6875Ga_3.1875O₁₂-CNGG) ceramic samples singledoped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method.The structural characterization of the samples was carried out by X-ray diffraction measurements.The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:...     

Synthesis of NaYF4:20% Yb3+,2% Er3+,2% Ce3+@NaYF4 nanorods and their size dependent uptake efficiency under flow condition

Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications. However, the low uptake efficiency of nanoparticles by cells has limited their applications. In this work, we demonstrate how the uptake efficiency is affected by the size of nanoparticles under flow conditions. Using the same size NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺ (the contents of rare earths elements are in molar fraction) nanoparticles as core, NaYF₄:20% Yb³⁺,2% Er³⁺,2% Ce³⁺@NaYF₄ core–shell structured nanorods (NRs) with different sizes of 60–224 nm were synthesized by thermal decomposition and hot injection method. Under excitation at 980 nm, a strong upconversion green emission (541 nm, ²H_11/2 → ⁴I_15/2 of Er³⁺) is observed for all samples. The emission intensity for each size nanorod was calibrated and is found to depend on the width of NRs. Under flow conditions, the nanorods with 96 nm show a maximum uptake efficiency by endothelial cells. This work demonstrates the importance of optimizing the size for improving the uptake efficiency of lanthanide-doped nanoparticles.     

Optical thermometry based on near-infrared luminescence from phosphors mixture

Luminescence ratiometric thermometry based on rare earth(RE)ions has attracted great interest for the potential applications in many fields.But the improvement of the measurement sensitivity and accuracy is significantly restricted due to the small energy gap between thermally coupled levels(TCL).Here,a strategy striving for good thermometric properties of luminescent materials was designed by using the phosphors mixture composed of NaY(WO₄)₂:Nd³⁺-Yb³⁺and NaY(WO₄)₂:Er³⁺,which were prepared by secondary sintering method.Under the excitation of 980 nm lase r,the near-infrared(NIR)emissions(710-920 nm)from Nd³⁺ions are effectively strengthened when the temperature increases from 304 to773 K,whereas Er³⁺NIR luminescence centered at around 1536 nm is thermally quenched.The remarkably different response of NIR emissions to the thermal variation allows us to map temperature through the ratiometric method.By optimizing the dopant concentration of rare earth(RE)ions,a maximum sensitivity of 5.14%/K together with a measurement uncertainty of about 0.1 K is acquired at304 K,which is superior to the previously reported RE luminescence-based temperature sensors,indicating that the approach developed here can pave the way for achieving optical thermometry with desired properties.     

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.     

Plasmon-enhanced broad-band quantum-cutting of NaBaPO4:Eu2+,Er3+ phosphors with silver nano-particles

NaBaPO₄:Eu²⁺,Er³⁺ phosphors and Ag nano-particles (NPs) were prepared by the solid-state reaction and chemical reduction method, respectively. The fluorescence spectra and decay curves demonstrate the effective energy transfer from Eu²⁺ to Er³⁺ and the existence of three-photon quantum-cutting through two-step cross-relaxation of Er³⁺. The quantum-cutting emission is peaked at 1534 nm with a broad excitation band centered at 352 nm. Plasmon-enhanced quantum-cutting of NaBaPO₄:Eu²⁺,Er³⁺ phosphors was realized by decorating Ag NPs. The largest enhancement factor is 1.395. It is hopeful to improve the photovoltaic conversion efficiency of Ge solar cells by using this phosphor.     

Upconversion luminescence of Y2O3：Er^3＋ ,Yb^3＋ nanoparticles prepared by a homogeneous precipitation method

Y2O3： Er^3＋, Yb^3＋ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3：Er^3＋,Yb^3＋ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to ^2H11/2,^4S3/2→^4I15/2 and ^4F9/2→^4I15/2 transitions of the ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

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.