Ultra-high sensitivity of rhodamine B sensing based on NaGdF4:Yb3+,Er3+@NaGdF4 core-shell upconversion nanoparticles

A series of mono-dispersed hexagon NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 core-shell nanoparticles with different shell thickness were synthesized via a co-precipitation method. Nanoparticles with high upconversion fluorescent emissions result in large signal-to-noise ratio, which guarantees the accuracy of the sensitivity. Besides, the maximum sensitivity of these NPs as detection film increases first and then decreases with the shell thickness increasing. When the shell thickness is 2.3 nm(NaGdF_4-2), the maximum sensitivity(0.69959 ppm~(-1)) is reached. A large degree of overlap between the rhodamine B absorption band and the Er~(3+) green emission bands ensures that the NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 nanoparticles can be used as fluorescent probe to detect the concentration of rhodamine B based on fluorescent intensity ratio technology. The linear relationship between the rhodamine B concentration and the intensity ratio(R) of green and red emission intensity(I_(S+H) and I_F) were studied systematically. The result shows that the maximum sensitivity can be obtained in low concentration rhodamine B(4 ppm), which is lower than the reported minimum detection concentration. Thus, the ultra-high sensitivity detection by NaGdF_4:Yb~(3+),Er~(3+)@NaGdF_4 core-shell upconversion nanoparticles in low concentration can be realized,which provides promising applications in bio-detection filed.     

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.     

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.     

Tracing of dye molecules in living plants through NaGdF4:Yb3+,Er3+ fluorescent nanoprobes

In this paper, we demonstrated trace of dye molecules in living plants. The NaGdF₄:Yb³⁺,Er³⁺ nanoparticles probe was used to detect the rhodamine B (RhB) in bean sprout. It is found that the fluorescencedye can be efficiently imbibed during the growing process and the absorbance presented a position dependence effect, which was supported by the upconversion spectra and the fluorescent image characterization. In addition, the concentration of the residual RhB in bean sprout can be efficiently traced by the synthesized probe based on the fluorescent resonant energy transfer. Finally, the relation between the excitation power, concentration and the ratio of yellow to green emission are discussed in detail. These results can be helpful in understanding the RhB dye molecules absorbance process in vegetable growth and provide an efficient way to trace the residual dyes in vivo plant.     

Gd3+ ion induced UV upconversion emission and temperature sensing in Tm3+/Yb3+:Y2O3 phosphor

Cubic phase Tm³⁺/Yb³⁺:Y₂O₃ and Tm³⁺/Yb³⁺/Gd³⁺:Y₂O₃ phosphors were prepared by low temperature combustion technique for upconversion emission in UV-visible range.The 980 nm excitation has generated UV emission at 314 nm in tridoped phosphor due to the energy transfer from Tm³⁺ to Gd³⁺ion.Characteristic emission bands from Tm³⁺ are also observed in both the phosphors....     

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...     

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.     

Synthesis of NaYF_4:Yb,Er upconversion nanoparticle-based optomagnetic multifunctional composite for drug delivery system

Optomagnetic multifunctional composite has attracted much attention in recent years because of its promising application prospect in bioimaging,analysis,detection,disease diagnosis,and targeted drug delivery.To explore a dual-targeted therapy for cancer,a novel class of optomagnetic multifunctional composite(UCNP-Fe_3 O_4@MSNs-FA) was successfully synthesized by using upconversion nanoparticles(UCNPs) as nucleus,embedding Fe_3 O_4 nanoparticles into the SiO_2 coating layer,and modifying the surface with folic acid(FA) to strengthen its tumor targeting performance.The properties of the composite were extensively studied.The obtained composite possesses excellent upconversion fluorescence,good dispersion,high specific surface area(229.347 m~2/g),and saturation magnetization value(10.9 A m2/g).Its drug loading co ntent and encapsulation efficiency can reach as high as 14.2% and 47.3%,respectively,using doxorubicin hydrochloride(DOX) as model drug.The DOX-UCNP-Fe_3 O_4@MSNs-FA system shows excellent sustained drug release and strong pH-dependent performance,in which the drug release would be accelerated at the slightly acidic microenvironment in the tumor;thus,the system can realize the targeted treatment of cancers.The viability of L929 cells demonstrates the good biocompatibility of the composite.Furthermore,DOX-UCNP-Fe_3 O_4@MSNs-FA exhibits specific cytotoxicity to folate receptor(FR) positive tumor cells,whereas DOX has weak toxicity to FR-negative cells.Therefore,the as-prepared UCNP-Fe_3 O_4@MSNs-FA can potentially be used as an anti-cancer targeted drug delivery system and enhance the therapeutic efficacy against FR-positive tumor cells.     

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.     

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.     

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.     

Oxalate-assisted morphological effect of NaYF4:Yb3+,Er3+ on photoelectrochemical performance for dye-sensitized solar cells

In this study. we have employed a facile oxalate-assisted hydrothermal approach to tailor the morphology of β-NaYF_4:Er~(3+),Yb~(3+)(NYFEY) powders through the variation of the molar ratio of oxalate ions(Oxa~(2-)) and rare earth ions(RE~(3+)) in the range of 0.5:1.1:1.2:1, 5:1. and 10:1. The obtained results show that the crystallinity, particle size and upconversion luminescence intensity of the as-synthesized NYFEY particles are gradually decreased as the Oxa~(2-):RE~(3+) molar ratio increases from 0.5:1 to 10:1. For the purpose of photoelectrochemical performance evaluation,the as-synthesized NYFEY particles with different morphologies are incorporated into the nanocrystalline TiO2 films to form the multifunctional nano-and sub-micro meter composite photoanodes of dye-sensitized solar cells(DSSCs). A short-circuit current density(Jsc) of 14.26 mA/cm~2 and power conversion efficiency(PCE) of 7.31% are obtained for DSSCs prepared with hexagonal rod-like NYFEY crystals,evidencing an increase of 29.8% compared with DSSCs prepared with only TiO_2 nanoparticles. The demonstrated synthesis approach for tailoring the morphology and size of NYFEY particles and enhancing the performance of DSSCs can also be applied for other types of solar cells.     

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.     

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...     

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.     

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.     

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.     

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.     

Synthesis and upconversion luminescence properties of NaYF4：yb^3＋/Er^3＋ microspheres

Cubic NaYF4:yb3+(20%)/Er3+(1%) microspheres were synthesized by EDTA-assisted hydrothermal method. Under 980 nm exci-tation, ultraviolet (4G11/2→4I15/2), violet (2H9/2→4I15/2), grogn (4F7/2→4I15/2, 2H11/2→4I15/2, and 4S3/2→4I15/2), and red (4F9/2→4I15/2) upconversion fluorescence were observed. The number of laser photons absorbed in one upconversion excitation process, n, was determined to be 3.89, 1.61, 2.55, and 1.09 for the ultraviolet, violet, green, and red emissions, respectively. Obviously, n=3.89 indicated that a four-photon process was involved in populating the 4G11/2 state, and n=2.55 indicated that a three-photon process was involved in populating the 4F7/2/2H<11/2>4S3/2 levels. For the violet and red emissions, the population of the states 2H9/2 and 4F9/2 separately came from three-photon and two-photon proc-esses. The decrease of n was well explained by the mechanism of competition between linear decay and upconversion processes for the de-pletion of the intermediate excited states.