Solvothermal synthesis, cubic structure and multicolor upconversion emission of ultrasmall monodisperse lanthanide-doped BaYF5 nanocrystals

Lanthanide (Ln³⁺) doped BaYF₅ (Ln=Yb³⁺, Er³⁺, Tm³⁺) nanocrystals (NCs) with a mean size of approximately 10 nm are synthesized by a solvothermal method using oleic acid as a stabilizing agent at 210 °C. The size of BaYF₅ NCs can be controlled by simply tuning the reaction parameters such as reaction temperature, reaction time and the molar ratio of F⁻/Y³⁺. The detailed structure investigation reveals that the as-synthesized BaYF₅ NCs are in the cubic structure with space group Fm3¯m instead of the reported tetragonal structure. Ln³⁺ cations occupy crystal lattice positions with lower point symmetry, which may lead to high upconversion efficiency under the excitation of a 980 nm diode laser. By adjusting the dopant concentrations of Yb³⁺, Er³⁺ and Tm³⁺, intense near-infrared, blue, yellow and white upconversion emissions are readily realized, respectively. The desirable property of the ultrasmall monodisperse NCs makes it the promising material for the applications in miniaturized solid-state light sources, multicolor three-dimensional display devices and fluorescent labels for biomedicine imaging.     

Upconversion emission enhancement in Er/Yb-codoped BaTiO3 nanocrystals by tridoping with Li ions

Er³⁺/Yb³⁺/Li⁺-tridoped BaTiO₃ nanocrystals were prepared by a sol-gel method to improve the upconversion (UC) luminescence of rare-earth doped BaTiO₃ nanoparticles. Effects of Li⁺ ion on the UC emission properties of the Er³⁺/Yb³⁺/Li⁺-tridoped BaTiO₃ nanocrystals were investigated. The results indicated that tridoping with Li⁺ ion enhanced the visible green and red UC emissions of Er³⁺/Yb³⁺-codoped BaTiO₃ nanocrystals under the excitation of a 976 nm laser diode. X-ray diffraction and decay time of the UC luminescence were studied to explain the reasons of the enhancement of UC emission intensity. X-ray diffraction results gave evidence that tridoping with Li⁺ ion decreased the local symmetry of crystal field around Er³⁺, which increased the intra-4f transitions of Er³⁺ ion. Moreover, lifetimes in the intermediate ⁴ S_3/2 and ⁴I_11/2 (Er) states were enhanced by Li⁺ ion incorporation in the lattice. Therefore, it can be concluded that Li⁺ ion in rare-earth doped nanocrystals is effective in enhancing the UC emission intensity.     

Infrared-to-visible upconversion in Er and Er/Yb activated Sb2O4 nanopowders prepared by sol-gel route

We prepared Er³⁺ doped and Er³⁺/Yb³⁺ codoped Sb₂O₄ nanocrystals by the sol-gel method. The Raman, X-ray diffraction (XRD), transmission electron microscope (TEM), and photoluminescence spectra of the samples were studied. The phonon energy of the Sb₂O₄ nanocrystals is very low (the maximum value being 461 cm⁻¹). The upconversion (UC) red emission of the Er³⁺/Yb³⁺ codoped sample is very strong at 975 nm laser diode excitation. The Sb₂O₄ nanocrystals will be a promising luminous material.     

Single color upconversion emission in Ho/Yb and Tm/Yb doped P2O5-MgO2-Sb2O3-MnO2-AgO glasses

The Ho³⁺/Yb³⁺ and Tm³⁺/Yb³⁺ doped P₂O₅-MgO₂-Sb₂O₃-MnO₂-AgO glasses were prepared by high temperature melting method. Under a 975 nm laser diode (LD) excitation, the single red and single blue upconversion (UC) emissions were observed in Ho³⁺/Yb³⁺ and Tm³⁺/Yb³⁺ doped samples, respectively. By studying the spontaneous radiative and multiphonon relaxation probabilities, we find that the multiphonon relaxation probability of ⁵I₆ (Ho³⁺) state is very large (1.39 × 10⁶ s^− 1), which is helpful to the population of ⁵I₇ state. The multiphonon relaxation probability of ³H₅ and ³F_2,3 (Tm³⁺) is also very large, which results in lots of population in ³F₄ and ³H₄ states. The results are that the red UC emission of Ho³⁺ and the blue UC emission of Tm³⁺ are stronger.     

Facile synthesis of well-dispersed SrF2:Yb/Er upconversion nanocrystals in oleate complex systems

Well oil-dispersible SrF₂:Yb³⁺/Er³⁺ upconversion (UC) nanocrystals (NCs) were easily synthesized in the water-ethanol-oleic acid-sodium oleate complex systems. The as-prepared NCs all show size-uniformity, and their sizes, morphologies can be controlled by varying the solvent and reaction time, and rectangular SrF₂:Yb³⁺/Er³⁺ nanosheets with the sizes of 5-25 nm can be obtained. The possible mechanism on the nucleation and growth of nanocrystals occurred at the oleic acid/sodium oleate interface was also discussed. The size and morphology dependent UC luminescence behaviors have been observed in SrF₂:Yb³⁺/Er³⁺ NCs, and their UC luminescence transitions were proposed. The as-prepared UC nanocrystals are expected to fulfill the demand for biological applications.     

Preparation and characterization of upconversion luminescent LaF3:Yb,Er/LaF3 core/shell nanocrystals

LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals were successfully synthesized using solvothermal method. The crystal structure, morphology and photoluminescence properties of as-prepared nanocrystals were investigated in detail. XRD patterns show that the obtained LaF₃:Yb³⁺,Er³⁺ core and LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals exhibit hexagonal structure. The average particle size is about 9.3 nm and 11.4 nm for core and core/shell nanocrystals, respectively. Compared with LaF₃:Yb³⁺,Er³⁺ nanocrystals, both the upconversion emission intensity and the lifetime increase in LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals. The enhancement can be attributed to the LaF₃ shell which can eliminate the nonradiative centers on the surface of LaF₃:Yb³⁺,Er³⁺ nanocrystals.     

Synthesis and characterization of new LnxSb2−xSe3 (Ln: Yb, Er) nanoflowers and their physical properties

New Ln_xSb_2−xSe₃ (Ln: Yb³⁺, Er³) based nanomaterials were synthesized by a co-reduction method. Powder XRD patterns indicate that the Ln_xSb_2−xSe₃crystals (Ln=Yb³⁺, Er³⁺, x=0.00-0.12) are isostructural with Sb₂Se₃. The cell parameters b and c decrease for Ln=Er³⁺ and Yb³⁺ upon increasing the dopant content (x), while a increases. SEM images show that doping of the lanthanide ions in the lattice of Sb₂Se₃ generally results in nanoflowers. UV-vis absorption and emission spectroscopy reveals mainly electronic transitions of the Ln³⁺ ions in case of Yb³⁺ doped nanomaterials. Emission spectra of doped materials, in addition to the characteristic red emission peaks of Sb₂Se₃, show additional emission bands centered at 955 nm, originating from the ²F_7/2→²F_5/2 transition (f-f transitions) of the Yb³⁺ ions. DSC curves indicate that Sb₂Se₃ has the highest thermal stability. The temperature dependence of the electrical resistivity of doped-Sb₂Se₃ with Yb³⁺ and Er³⁺ was studied.     

Up-conversion white light of Tm/Er/Yb tri-doped CaF2 phosphors

Tm³⁺/Er³⁺/Yb³⁺ tri-doped CaF₂ phosphors were synthesized using a hydrothermal method. The phosphors were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and up-conversion (UC) emission spectra. After annealing, the phosphors emitted white light under a 980 nm continuous wave diode laser (CW LD 2 W) excitation. As the excitation power density changed in the range of 20-260 W/cm², the chromaticity coordinates of the UC light of the phosphor Ca_0.885Tm_0.005Er_0.01Yb_0.1F₂ fell well in the white region of the 1931 CIE diagram. For the proportion of red, green and blue (RGB) in white light is strict, key factors for achieving UC white light, such as host materials, rare earth ions doping concentrations, annealing temperatures, as well as the excitation power densities, were investigated and discussed.     

Optical thermometry through green and red upconversion emissions in Er/Yb/Li:ZrO2 nanocrystals

Variations of fluorescence intensity ratio of green (generated from Er^{3+ 2}H_11/2 and ⁴S_3/2 levels) and red (generated from the sublevels of Er^{3+ 4}F_9/2 level) upconversion emissions in Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals have been studied as a function of temperature under 976 nm laser diode excitation. In the temperature range of 323-673 K, the maximum sensitivities of about 0.0134 K^− 1 and 0.0104 K^− 1 are obtained by using green and red emission, respectively. Er³⁺/Yb³⁺/Li⁺:ZrO₂ nanocrystals show potential application value in nanoscale thermal sensor.     

共沉淀法制备Y2SiO5∶Er3+ ,Yb3+ ,Tm3+及其上转换发光性能研究

采用化学共沉淀法制备了系列Y_1.98-2xYb_2x Er_0.02SiO₅(0.00≤x≤0.15)以及Y_1.736Yb_0.24Er_0.02Tm_0.004SiO₅上转换发光材料,比较了室温下Y_1.98-2xYb_2x Er_0.02 SiO₅ (x=0.00,0.08)样品在400—1600 nm范围内的吸收光谱,测量了所有样品在976 nm OPO激光器激发下的上转换发射光谱,以及Er³⁺离子⁴S_3/2(⁴F_9/2)→⁴I_15/2,Tm³⁺离子¹G₄→³H₆荧光衰减曲线和不同激发功率下的上转换蓝光发射强度,从而分析讨论了Er³⁺,Tm³⁺在Y₂SiO₅中的上转换发光机理.研究结果表明:在1250 ℃相对较低的温度下合成了X2型单斜晶系Y₂SiO₅ ∶Ln³⁺(Ln³⁺=Er³⁺,Yb³⁺,Tm³⁺),Yb³⁺的敏化显著增强了样品在976 nm附近的吸收能力,并大幅度加宽了该处的吸收带.分析上转换发射光谱发现:上转换绿光和红光强度都随着Yb³⁺浓度的增加先增强后减弱,但红光的猝灭浓度较高,归因于Er³⁺→Yb³⁺反向能量传递ETU4和Yb³⁺→Er³⁺正向能量传递ETU3过程的发生;上转换蓝光发射是三光子吸收过程,是通过Yb³⁺,Tm³⁺之间三次声子辅助的能量转移方式实现的. 关键词： 上转换 共沉淀 2SiO₅∶Er³⁺')" href="#">Y₂SiO₅∶Er³⁺ 3+')" href="#">Yb³⁺ 3+')" href="#">Tm³⁺     

Spectroscopic investigations of Nd-, Er-, Er/Yb-, and Tm-ions doped SiO2-Al2O3-CaF2-GdF3 glasses

This paper reports on the absorption, visible and near-infrared luminescence properties of Nd³⁺, Er³⁺, Er³⁺/2Yb³⁺, and Tm³⁺ doped oxyfluoride aluminosilicate glasses. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. Decay lifetime curves were measured for the visible emissions of Er³⁺ (558 nm, green), and Tm³⁺ (650 and 795 nm), respectively. The near infrared emission spectrum of Nd³⁺ doped glass has shown full width at half maximum (FWHM) around 45 nm (for the ⁴F_3/2→⁴I_9/2 transition), 45 nm (for the ⁴F_3/2→⁴I_11/2 transition), and 60 nm (for the ⁴F_3/2→⁴I_13/2 transition), respectively, with 800 nm laser diode (LD) excitation. For Er³⁺, and Er³⁺/2Yb³⁺ co-doped glasses, the characteristic near infrared emission bands were spectrally centered at 1532 and 1544 nm, respectively, with 980 nm laser diode excitation, exhibiting full width at half maximum around 50 and 90 nm for the erbium ⁴I_13/2→⁴I_15/2 transition. The measured maximum decay times of ⁴I_13/2→⁴I_15/2 transition (at wavelength 1532 and 1544 nm) are about 5.280 and 5.719 ms for 1Er³⁺ and 1Er³⁺/2Yb³⁺ (mol%) co-doped glasses, respectively. The maximum stimulated emission cross sections for ⁴I_13/2→⁴I_15/2 transition of Er³⁺ and Er³⁺/Yb³⁺ are 10.81×10⁻²¹ and 5.723×10^-21 cm². These glasses with better thermal stability, bright visible emissions and broad near-infrared emissions should have potential applications in broadly tunable laser sources, interesting optical luminescent materials and broadband optical amplification at low-loss telecommunication windows.     

White up-conversion emission in Ho/Tm/Yb tri-doped glass ceramics embedding BaF2 nanocrystals

Ho³⁺/Tm³⁺/Yb³⁺ tri-doped glass ceramics with white light emitting have been developed and demonstrated. Pumped by 980 nm laser diode (LD), intensive red, green and blue up-conversions (UC) were obtained. The green emission is assigned to Ho³⁺ ion and the blue emission is assigned to Tm³⁺ ion, whereas the red emission is the combination contribution of the Ho³⁺ and Tm³⁺ ions. The RGB intensities could be adjusted by tuning the rare-earth ion concentration and pump power intensity. Thus, multicolor of the luminescence, including perfect white light with CIE-X=0.329 and CIE-Y=0.342 in the 1931 CIE chromaticity diagram can be obtained in 0.15 Ho³⁺/0.2Tm³⁺/3Yb³⁺ tri-doped glass ceramics embedding BaF₂ nanocrystals pumped by a single infrared laser diode source of 980 nm at 500 mW. The up-conversion luminescence mechanism of Yb³⁺ sensitize Ho³⁺ and Tm³⁺ ions and the energy transfer from Ho³⁺ to Tm³⁺ in oxy-fluoride silicate glass ceramics were analyzed.     

Survey and research on up-conversion emission character and energy transition of Yb/Er/Tm co-doped phosphate glass and glass ceramic

By conventional high-temperature melting method, Yb³⁺/Er³⁺/Tm³⁺ co-doped phosphate glass was synthesized. After annealing the precursor glass, the phosphate glass ceramic (GC) was obtained. By measuring the X-ray diffraction (XRD) spectrum, it is proved that the LiYbP₄O₁₂ and Li₆P₆O₁₈ nano-crystals have existed in the phosphate GC. The up-conversion (UC) emission intensity of the GC is obvious stronger compared to that of the glass. The reason is that the shorter distance between rare earth ions in the glass ceramic increases the energy transitions from the sensitized ions (Yb³⁺) to the luminous ions (Er³⁺ and Tm³⁺). By studying the dependence of UC emissions on the pump power, the 523 and 546 nm green emissions of Er³⁺ ions in the glass are two-photon processes. But in the glass ceramic, they are two/three-photon processes. The phenomenon implies that a three-photon process has participated in the population of the two green emissions. Using Dexter theory, we discuss the energy transitions of Er³⁺ and Tm³⁺. The results indicate the energy transition of Tm³⁺ to Er³⁺ is very strong in the GC, which changes the population mechanism of UC emissions of Er³⁺.     

Enhancement of upconversion luminescence in Tm/Er/Yb-codoped glass ceramic containing LiYF4 nanocrystals

A transparent Er³⁺–Tm³⁺–Yb³⁺ tri-doped oxyfluoride glass ceramics containing LiYF₄ nanocrystals were prepared. Under 980 nm laser diode (LD) pumping, intensive red, green and blue upconversion (UC) was obtained. The blue, green, and red UC radiations correspond to the transitions ¹G₄→³H₆ of Tm³⁺, ²H_11/2/⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2 of Er³⁺ ions, respectively. This is similar to that in Tm³⁺–Yb³⁺ and/or Er³⁺–Yb³⁺ co-doped glass ceramics. However, the blue UC radiations of the Er³⁺–Yb³⁺ co-doped glass ceramics is two-photon process due to cooperative energy transfer. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

Enhancing upconversion emissions of NaTm0.02YbxY0.98−xF4 nanocrystals through increasing Yb doping

By increasing the content of Yb³⁺ ions from 20% to 98% in NaTm_0.02Yb_xY_0.98−xF₄ (x=0.2−0.98) nanocrystals with size about 10 nm, the intensities of near infrared (800 nm) and blue (470 nm) upconversion (UC) luminescence can be enhanced by orders of 45 and 49 times, respectively, under 970 nm diode laser excitation. Pump power dependence illustrated that the 800 and 470 nm radiations are still two- and three-photon processes, respectively. TEM imaging showed that the enhancement is not from the change of the crystal size. Steady-state equation and the measured lifetimes indicated that the enhanced 800 nm radiations can induce the enhancement of the 470 nm emissions, which is in good agreement with the experimental data.     

Selective enhancement of green upconversion emissions of Er3+:Yb3Al5O12 nanocrystals by high excited state energy transfer with Yb3+–Mn2+ dimer sensitizing

An innovative upconversion (UC) emissions route of Er³⁺ by Yb³⁺–Mn²⁺ dimer sensitizing in Er³⁺–Mn²⁺:Yb₃Al₅O₁₂ (YbAG) nanocrystals is reported here, which resulted in the selective enhancement of green UC emission and suppression of red UC emission by a 976 nm laser diode excitation. By codoping of Mn²⁺, the green UC emission intensity increased about 260 times, while the red UC emission intensity decreased about 20 times than that of Er³⁺:YbAG nanocrystals. It indicates that the green enhancement and red suppression arise from the high excited state energy transfer with |²F_7/2, ⁴T_1g> (Yb³⁺–Mn²⁺ dimer) to the ⁴F_7/2 (Er³⁺), which partly decreases the nonradiative processes happened in the lower levels of Er³⁺. The proposed sensitizing route here may constitute a promising step to realize high-efficient UC emissions of rare-earth ions doped oxides and significantly extend their scope of applications.     

Role of Al2O3 in upconversion and NIR emission in Tm and Er codoped calcium fluoro phosphorous silicate glass system

In this study, the principal role of Al₂O₃ on the features of the photoluminescence spectra of Tm³⁺ ion and upconversion phenomenon in Tm³⁺ and Er³⁺ codoped CaF₂−Al₂O₃−P₂O₅−SiO₂ glass system has been investigated. The concentration of Al₂O₃ is varied from 2 to 10 mol% while that of Er³⁺ and Tm³⁺ is fixed. IR and Raman spectral studies have indicated that there is a gradual increase in the degree of disorder in the glass network with increase in the concentration of Al₂O₃ up to 6.0 mol%. This is attributed to the presence of Al³⁺ ions in octahedral positions in larger proportions. When the glasses are doped with Tm³⁺ ions, the blue and red emissions were observed, whereas in Er³⁺ doped glasses blue, green and red emissions were observed. When the glasses are codoped with Tm³⁺ and Er³⁺ ions and excited at 790 nm, all the three emission lines were observed to be reinforced, especially in the glasses mixed with 6.0 mol% of Al₂O₃. The IR emission band detected at about 1.8 μm due to ³F₄→³H₆ transition of Tm³⁺ ions is also observed to be strengthened due to codoping. The reasons for enhancement in the intensity of various emission bands due to codoping have been identified and discussed with the help of rate equations for various emission transitions.     

The up-conversion properties of Yb and Er doped Y4Al2O9 phosphors

Er³⁺ doped and Yb³⁺/Er³⁺ co-doped Y₄Al₂O₉ phosphors are prepared by the sol-gel method. The effect of dopant concentration on the structure and up-conversion properties is investigated by X-ray diffraction (XRD) and photoluminescence, respectively. XRD pattern indicates that the sample structure belongs to monoclinic. Under 980 nm excitation, the green and red up-conversion emissions are observed and the emission intensities depended on the Yb³⁺ ion concentration. The green up-conversion emissions decrease with the increase of Yb³⁺ concentration, while red emission increases as Yb³⁺ concentration increases from 0 to 8 at% and then decreases at high Yb³⁺ concentration. The mechanisms of the up-conversion emissions are discussed and results shows that in Er³⁺ and Yb³⁺/Er³⁺ co-doped system, cross-relaxation (CR) and energy transfer (ET) processes play an important role for the green and red up-conversion emissions.     

Excitation power controlled luminescence switching in Yb-Tm co-doped hexagonal NaYF4 nanorods

Intense infrared-to-visible up-conversion (UC) emissions were obtained in hexagonal Yb³⁺-Tm³⁺ co-doped NaYF₄ nanorods under excitation at 980 nm. Especially, luminescent switching between different UC emission wavelengths at 800, 480 and 450 nm were observed by adjusting excitation powers. Based on power-dependent spectral analyses, it was found that the cooperative energy transfer between Yb³⁺-Yb³⁺ pairs and Tm³⁺ ions play a key role on the luminescent switching besides the saturation effect of Yb³⁺²F_5/2 and Tm³⁺¹G₄ excited states. Our results indicate that hexagonal NaYF₄ nanostructures have potential applications in miniaturized solid-state laser, optical processing sensors and fluorescent biolabels.     

NIR luminescence from Er/Yb, Tm/Yb, Er/Tm and Nd ions-doped zincborotellurite glasses for optical amplification

In this paper, we report the near-infrared luminescence from the Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped TeO₂-ZnO-B₂O₃-Li₂O-Na₂O glasses for optical amplification. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) profiles of the host glass matrix have been carried out. From the DSC thermogram, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The near-infrared spectra of Er³⁺/Yb³⁺, Tm³⁺/Yb³⁺, Er³⁺/Tm³⁺ and Nd³⁺ ions-doped glasses have shown full-width at half-maxima (FWHM) around 58, 127, 87 and 35 nm, respectively. These glasses with better thermal stability and broad near-infrared emissions should have potential applications in broadly tunable laser sources and broadband optical amplification at low-loss telecommunication windows.