Intense upconversion luminescence of Er3+/Yb3+ codoped oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals

Er3+/Yb3+-codoped transparent oxyfluoride borosilicate glass ceramics containing Ba2GdF7 nanocrystals were prepared and spectroscopic properties of rare earth ions were investigated.Fluoride nanocrystals Ba2GdF7 were successfully precipitated in glass matrix,which was confirmed by X-ray diffraction(XRD)and transmission electron microscopy(TEM)results.In comparison with the as-made precursor,significant enhancement ofupconversion luminescence was observed in the Er3+/Yb3+codoped oxyfluoride glass ceramics,which may be due to the variation of coordination environment around Er3+and Yb3+ions after crystallization.The transition mechanisms of the green and red upconversion luminescence were ascribed to a two-photon process,and that of the blue upconversion luminescence was a three-photon process.     

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.     

Increased downconversion efficiency and improved near infrared emission by different charge compensations in CaMoO_4：Yb~（3＋） powders

All of the samples were synthesized by sol-gel methods.Two approaches to charge compensation,(i) 2Ca2+→Yb3++M+,where M+ is an alkali ion like Li+,Na+ and K+,and(ii) indirect charge compensation:3Ca2+→2Yb3++vacancy,were studied in detail.It was found that charge compensation would be very beneficial for the growth of the grains,especially in Li+ ions added samples.All the grains were homogeneously spherical with less boundaries;in addition,a great variety of the absorption ability in different charge compens...     

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.     

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).     

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.     

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.     

Site occupation and energy transfer in full color emitting phosphor Ba2Ca(BO3)2:Ce3+(K+),Eu2+,Mn2+

White light-emitting diodes (WLEDs) fabricated by single-phase full color emitting phosphor are an emerging solution for health lighting. The crystallographic site occupation of activators in a proper host lattice is crucial for sophisticated design of such phosphor. Here, we report a high quality white light-emitting phosphor Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ with spectral distribution covering whole visible region. Blue light emission originates from Ce³⁺ ions occupying preferentially Ba²⁺ site by controlling synthesis conditions. Green and red lights are obtained from Eu²⁺ occupying Ba²⁺ (and Ca²⁺) site and Mn²⁺ occupying Ca²⁺ site, respectively. In this triple-doped phosphor, strong red emission with a low concentration of Mn²⁺ is realized by the efficient energy transfer from Ce³⁺ and Eu²⁺ to Mn²⁺. Furthermore, high quality white light is accomplished by properly tuning the relative doping amount of Ce³⁺(K⁺)/Eu²⁺/Mn²⁺ based on efficient simultaneous energy transfer. The results indicate that Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ is a promising white light-emitting phosphor in WLEDs application.     

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.     

Structural studies of BaTiO3：Er3＋ and BaTiO3：Yb3＋ powders synthesized by hydrothermal method

Erbium and ytterbium doped barium titanate nanopowders were prepared using the hydrothermal method. A barium titanate structure doped with rare earth ions manifested new characteristics and improved the field of application of optical devices such as trichromatic tubes, LCD displays, lamps, and infrared lasers. In this work, BaTiO3：Er3＋ and BaTiO3：Yb3＋ were prepared using barium chloride [BaCl2], titanium butoxide [C16H36O4Ti], erbium chloride [ErCl3] and ytterbium chloride [YbCl3] as precursors. Anhydrous methanol was employed as a solvent. Metallic potassium was used to promote solubility in the system and increase the pH to 13. This method yielded the formation of a predominantly cubic structure in both Er3＋ and Yb3＋ doped BaTiO3 powders. Characteristic bondings of BaTiO3 were observed with FT-IR spectroscopy. The predominantly cubic structure was confirmed by X-ray diffraction and micro-Raman analyses. The particle size（～30 nm） was estimated using the Scherrer equation and X-ray diffraction data. The results were presented and discussed.     

Energy transfer processes from Yb3＋ to Ln3＋ （Ln=Er or Tm） in heavy metal glasses

Heavy metal glasses doubly doped with Yb3+ and Ln3+ ions(Ln=Er or Tm) were studied. Glass host matrices were limited to lead borate glass and lead germanate glass. Efficient resonant(Yb3+-Er3+) and non-resonant(Yb3+-Tm3+) energy transfer was observed for the studied systems. Near-infrared luminescence spectra at 1.53 μm(Er3+) and 1.9 μm(Tm3+) were detected under excitation of Yb3+ by 975 nm diode laser line. They corresponded to 4I13/2→4I15/2(Er3+) and 3F4→3H6(Tm3+) transitions of rare earth ions, respectively. The unusual large spectral linewidth nearly close to 110 nm for 4I13/2→4I15/2 transition of Er3+ ions in lead borate glass was obtained, whereas long-lived near-infrared luminescence at 1.53 μm was detected in lead germanate glass. Quite different situation was observed for Yb3+-Tm3+ doubly doped glasses. In contrast to lead borate glass, near-infrared(3F4→3H6) luminescence spectra were registered for Tm3+ ions in lead germanate glasses, only. These phenomena strongly depended on stretching vibrations of glass host, which was confirmed by FT-IR spectroscopy.     

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.     

Luminescence properties of calcium tungstate activated by lanthanide(Ⅲ) ions

Calcium tungstate phosphors activated by the Ln3+ ions(Ln=Pr, Nd, Tb, Yb) were synthesized by a traditional high-temperature solid-state method. The crystal structures and morphologies of the products were characterized by scanning electron microscopy(SEM), X-ray powders diffraction(XRD) and infrared spectra(FT-IR). The samples were found to show luminescence properties(down-conversion, DC, at excitation wavelength 254 nm and up-conversion, UC, at excitation wavelength 980 nm). CaWO4 doped with Tb3+/Yb3+ showed green DC and UC luminescence characteristic of Tb(III) ion in the range of 470–660 nm, corresponding to the 5D4→7F6,5,4,3,2 electronic transition. CaWO4 doped with Pr3+/Yb3+ showed week blue, green and red(DC and UC) luminescence of Pr(III) ion, in the wavelength region of 450–700 nm. Emission peaks were ascribed to the 3P1→3H4,5,6, 3P0→3H4,5,6, 3P1→3F2 and 3P0→3F2 transitions, respectively. CaWO4 doped with Nd3+/Yb3+ phosphor emitted orange UC luminescence at 450–690 nm(2P3/2→4I15/2, 4G7/2→4I9/2,11/2,13/2) and strong near-infrared UC luminescence at 720–900 nm(4F7/2+4S3/2→4I9/2, 4F5/2+2H3/2→4I9/2, 4F3/2→4I9/2) which is the characteristic of Nd(III) ion.     

Energy transfer and cross-relaxation induced multicolor upconversion emissions in Er~(3+)/Tm~(3+)/Yb~(3+) doped double perovskite La_2ZnTiO_6 phosphors

Investigation on the bright and stable upconversion(UC) phosphors with multicolor emissions is fundamental and significant for the frontier applications of display and tempe rature probe.He re,dive rse emitting colors with blue,cyan and yellowish green,which are caused by the energy transfer and crossrelaxation processes,are obtained by altering Er~(3+),Tm~(3+)and Yb~(3+) concentrations in Er~(3+)singly,Er~(3+)-Tm~(3+)-Yb~(3+)co-and tri-doped double perovskite La_2 ZnTiO_6(LZT) phosphors synthesized by a simple solid-state reaction.In addition,excellent infrared emission at 801 nm located at "first biological windo w" is collected in Tm~(3+)-Yb~(3+)co-doped phosphors.Meanwhile,the temperature sensing properties based on the thermally coupled levels(~2 H_(11/2)/~4S_(3/2)) of Er~(3+) ions were analyzed from 298 to 573 K of LZT:0.15 Er~(3+)/0.10 Yb~(3+)phosphor,demonstrating that the maximal sensitivity value is about56×10-4 K~(1-) at 448 K.All these results imply that this kind of UC material has potential applications in display,bioimaging and optical device.     

Solvent induced shape change in CePO4:Dy3+ nanophosphors and effect of metal ions:A photoluminescence study

The influence of different solvents and metal ions (Li+, Ba2+, Bi3+) on the crystallization behaviour, morphology and enhancement in photoluminescence intensity of Dy3+ doped CePO4 were investigated. Highly crystalline luminescent nanophosphors of CePO4:Dy3+ re-dispersible in polar solvents were successfully prepared via a simple polyol route at 140 ℃. As-prepared Dy3+ doped CePO4 nanophos-phors prepared in EG and DMF appeared to have crystalline monoclinic phase but exhibited hexagonal phase when prepared in water and water mixed solvents. The hexagonal phase transformed to monoclinic phase after heating at 900 ℃. TEM study revealed different shapes of the synthesized nanophosphors with change of solvents. The luminescence intensity of 4F9/2→6H15/2 at 478 nm (blue) was found to be more prominent than 4F9/2→6H13/2 at 572 nm (yellow). The introduction of metal ions (Li+, Ba2+ and Bi3+) in CePO4:Dy3+ led to considerable lumi-nescent enhancement. The nanophosphors were subsequently incorporated in polymer films of PVA which showed the characteristic emissions of Dy3+. It also served as an effective method to improve the performance of polymer materials and brought about novel properties in them.     

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.     

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:...     

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.     

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 ...     

Fine controllable blue emission and its mechanism in Ce3+-doped orthosilicate solid solution phosphors for different plant growths

The designed Ce~(3+)-doped alkaline-earth silicate phosphors Ca_mSr_(2-m-n)Ba_nSiO_4:Ce~(3+),Li~+(CSBS:Ce~(3+))were synthesized by a high temperature solid-state reaction. The crystal field splitting and the centroid shift from the free ion energy of 5 d configuration were approximated from the spectrum for Ca_2SiO_4,Sr_2SiO_4 and Ba_2SiO_4 phosphors. The single-phase purity was checked by means of X-ray diffraction. Here,when the doped concentration of Ca~(2+) is less than 80%(m ≤1.6), we report the structural phase transformation from monoclinic system β-Ca_2SiO_4 to orthorhombic system α-Ca_2SiO_4. The phosphors excited by near-ultraviolet(NUV) light at wavelengths ranging from 200 to 400 nm demonstrate a broad asymmetric blue emission band. The emission peak wavelength redshifts firstly from 417 nm of Ca_2SiO_4 to 438 nm of Sr_(0.3)Ca_(1.6)SiO_4, and then blueshifts to 411 nm of Sr_2SiO_4, and the end of 401 nm of Ba_2SiO_4.These results indicate that the tunable blue-emission of the phosphors can be realized through changing the solid solution components, which has a potential use as a blue component for fabricated precision modulation LEDs light sources and auxiliaries of SSC plastics films for different plant growths.We discuss in detail the possible mechanism and energy diagram of the tunable blue luminescence in Ca_mSr_(2-m-n)Ba_nSiO_4:Ce~(3+),Li~+ phosphors.