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.     

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.     

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.     

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.     

Preparation and luminescent properties of CaF2:Ln3+ (Ln:Er,Er/Yb)/Nafion composite films

In this work, CaF_2:Ln~(3+)(Ln:Er,Er/Yb)/Nafion composite films were prepared using Nafion as modifications and matrices by dripping method. The composite films were characterized by Fourier transform infrared spectroscopy(FT-IR), X-ray diffraction(XRD) and scanning electron microscopy(SEM). Composite films are transparent and CaF_2:Ln~(3+)(Ln:Er,Er/Yb) nanoparticles are well dispersed in Nafion films.The thicknesses of CaF_2:Er~(3+)/Nafion and CaF_2:Er~(3+),Yb~(3+)/Nafion composite film are about 77 and 73 μm,respectively. The nanoparticles in composite film possess cubic phase. CaF_2:Er~(3+),Yb~(3+)/Nafion composite film has stronger characteristic emission of Er~(3+) around 1530 nm with full width at half-maximum(FWHM) of 73 nm and longer luminescence lifetimes of 22.04 μs(25.03%) and 100.77 μs(74.97%).     

Luminescent properties of Ce3+, Er3+ co-doped La3Si6N11

In order to obtain near-infrared phosphor pumped by blue chip with high luminous efficiency, a novel near-infrared phosphor Ce³⁺/Er³⁺ doped La₃Si₆N₁₁ was designed and firstly prepared via conventional solid-state reactions. The structure and morphology of Ce³⁺/Er³⁺ doped La₃Si₆N₁₁ were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Compared with Er³⁺ doped La₃Si₆N₁₁, the emission intensity of the Ce³⁺, Er³⁺ co-doped phosphor can be increased more than 5 times. Meanwhile, the mechanism of energy transfer from Ce³⁺ to Er³⁺ is confirmed according to the excitation, emission spectra and decay lifetimes curve. Above results suggest that La₃Si₆N₁₁:Ce³⁺,Er³⁺ is a promising near-infrared phosphor for blue pumped LEDs (light-emitting diodes).     

Flexible double narrowband near-infrared photodetector based on PMMA/core-shell upconversion nanoparticle composites

Flexible narrowband near infrared(NIR)photodetectors(PDs)are urgently in demand in the fastdeveloping era of flexible electronics,due to their crucial roles in various innovative applications.Hence,we designed and synthesized the core-shell structured NaYF4:Yb³⁺,Er³⁺@NaYF4:Nd³⁺upconversion nanoparticles(UCNPs),which can be pumped by the 808 and 980 nm lights.The upconversion luminescence(UCL)are significantly enhanced after being assembled with the opal photonic crystals(OPCs)due to the photonic crystal effect,with 55 and 48 folds of enhancement factors under illuminations of 808 and 980 nm lights,respectively.Based on this hybrid,the flexible narrowband PDs were successfully fabricated on the PET substrate with the structure of OPCs/NaYF4:Yb³⁺,Er³⁺@Nd³⁺/MAPbl3,which displays excellent detection performance to double narrowband NIR light(808 and 980 nm)benefiting from the amplified UCL,with responsivity of 8.79 and 7.39 A/W,detectivity of 3.01×10¹¹and2.68×10¹¹cm·Hz^1/2/W for 808 and 980 nm lights detection respectively,along with short response time in the range of 120-160 ms.Furthermore,the OPCs/NaYF4:Yb³⁺,Er³⁺@NaYF4:Nd³⁺/MAPbI3 double narrowband PDs display low photodetection power threshold(0.05 W/cm2),outstanding flexibility,prominent moisture resistance,and good long-time stability.This work displays a new concept of narrowband NIR PDs,which open a new field for specific NIR light detections.     

Size dependence of up-conversion luminescence of NaYF4:Yb3+/Tm3+

Tm³⁺/Yb³⁺ codoped NaYF₄ microcrystals were synthesized using a hydrothermal method. The bright upconversion light was observed under 980 nm excitation. The upconversion luminescence was systematically investigated at different Yb³⁺ concentrations and different reaction temperatures and time. The sample with 60% Yb³⁺ concentration and reacting at 180 °C for 24 h possessed the highest luminescent efficiency. The higher luminescent efficiency was contributed to a large surface area. The large surface area induced the large vibration mode by absorbed H₂O and CO₂. The larger vibration mode could enhance the energy transfer efficiency from the excited Yb³⁺ to Tm³⁺ by the process of phonon assisted energy transfer.     

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.     

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...     

Decorating rare-earth fluoride upconversion nanoparticles on AuNRs@Ag core-shell structure for NIR light-mediated photothermal therapy and bioimaging

Photothermal therapy(PTT)has presented its inherent application value in cancer treatment.Nevertheless,single-functional photothermal materials cannot meet the precise diagnosis and treatment of cance r.Therefo re,it is important to design a nanocomposite that has both high therapeutic efficiency and multimodal imaging capabilities.In our work,a new nanostructure of gold nanorods(AuNRs)with silver shells decorated by BaGdF5:Yb³⁺,Er³⁺nanoparticle was synthesized by a simple way.The biostability of AuNRs is increased by coating with silver shells,and the AuNR@Ag nanoparticles can be used as excellent surface enhanced Raman scattering(SERS)probe.Moreover,the modification of BaGdF5:Yb³⁺,Er³⁺nanoparticles provides the possibility of real-time optical imaging of the tumor area.Under the irradiation of NIR laser,the AuNR@Ag/BaGdF5:Yb³⁺,Er³⁺nanocomposites(NCs)have strong upconversion emission and excellent photothermal conversion efficiency.Meanwhile,the NCs show low cytotoxicity and good biocompatibility in MTT cytotoxicity test.Moreover,the NCs are also exceptional contrast agents for CT imaging.For in vitro photothermal therapy test,NCs show excellent killing efficiency on tumor cells.Therefore,the multifaceted research of AuNR@Ag/BaGdF5:Yb³⁺,Er³⁺multifunctional nanomaterials provides a break for high-efficiency tumor photothermal therapy and multimodal imaging.     

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...     

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.     

Upconversion luminescence of KGd（MoO_4）_2：Er~（3＋）,Yb~（3＋） powder prepared by Pechini method

Er3+ doped potassium gadolinium molybdate (KGM) phosphor with sensitizer Yb3+ ion was synthesized by the Pechini method using citric acid and ethylene glycol. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential scanning calorimetry (TG-DSC), which indicated that ultrafine uniform crystallites of KGM:Er,Yb were obtained by sintering the precursors at above 650 ℃ for 5 h. Upconversion luminescence (UL) spectra of the samples ...     

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.     

One-step synthesis of hollow PEI-NaBiF_4:Yb~(3+)/Er~(3+) upconversion nanoparticles for water-responsive luminescent probe

Novel PEI-modified NaBiF_4:Yb~(3+)/Er~(3+)upconversion nanoparticles(UCNPs) with hollow structure were prepared by a surface modification free one-step solvothermal method and applied as a luminescent probe to determinate water content in organic solvents.XRD,SEM and HRTEM results demonstrate that the obtained PEI-NaBiF_4:Yb~(3+)/Er~(3+) UCNPs are pure hexagonal phase with uniform size.The successful modification of PEI on the UCNPs surface was evidenced by ζ-potential test,XPS and TG analysis.These synthesized UCNPs are disintegrated into smaller nanoparticles in the presence of water and thus result in a surface quenching effect,which show the features of 0-100% wide range water response in various organic solvents.The sensing performance towards real samples was validated by the water content determination in beer,rum and white spirit.Furthermore,the luminescence intensity variation of the PEI-modified NaBiF_4:Yb~(3+)/Er~(3+) enable the test visualization and ease of portability.     

Zirconium metal organic framework for design of tetragonal rare earth-doped zirconia nanoparticles

Zirconium metal–organic frameworks ZrOBDC (where BDC = C₆H₄(COOH)₂, terephthalic acid) doped and co-doped with rare earth ions Ln (ZrOBDC:Ln³⁺, where Ln³⁺ = Eu³⁺ and Tb³⁺ as well as Er³⁺ and Yb³⁺) were used as precursors for the design of tetragonal rare earth doped zirconia nanoparticles (t-ZrO₂:Ln³⁺ NPs) through annealing process. Preparation, characterization and luminescence properties of ZrOBDC:Ln³⁺ and ZrO₂:Ln³⁺ NPs were investigated. The as-obtained t-ZrO₂:Ln³⁺ NPs have high purity with an average size of 20–30 nm. The luminescence spectra of ZrOBDC:Tb³⁺ and ZrOBDC:Eu³⁺ display strong green and red emission at around 544 and 611 nm which correspond to ⁵D₄ → ⁷F₅ and ⁵D₀ → ⁷F₂ transitions of Tb³⁺ and Eu³⁺ ions, respectively. The green and red up-conversion emissions of ZrO₂:Er³⁺,Yb³⁺ NPs due to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions are observed under 976 nm laser excitation.     

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.     

Preparation and characterization of Er3＋-Yb3＋-Ce3＋ co-doped transparent glass ceramic containing nano Cas（PO4）3F crystals

A transparent glass ceramic tri-doped with Ce3+/Er3+/Yb3+ was fabricated by the high-temperature melting technique and following heat-treatment.X-ray diffraction and transmission electron microscope results demonstrated that Ca5(PO4)3F(FAP) nanocrystals,possessed with preferable emission performances for the 1.54 m transition for doping Er3+,were homogeneously precipitated among the glass matrix with a mean size of 30 nm.Addition of Ce3+ greatly enhanced 1.54 m fluorescence of Er3+ by the cross relaxation energy transfer between Er3+ and Ce3+.Meanwhile,incorporation of Ce3+ dramatically decreased the visible upconversion emission intensity of glass ceramic than that of glass,suggesting that Ce3+ might incorporate into the FAP nanocrystals.The properties of this transparent glass ceramic showed the potential application as an efficient 980 nm pumped infrared laser medium.     

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.