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.     

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.     

Up-conversion luminescence of Er/Yb/Nd-codoped tellurite glasses

Up-conversion luminescence and energy transfer (ET) processes in Nd³⁺-Yb³⁺-Er³⁺ triply doped TeO₂-ZnO-Na₂O glasses have been studied under 800 nm excitation. Intense green up-conversion emissions around 549 nm, which can be attributed to the Er³⁺: ⁴S_3/2→⁴I_15/2 transition, are observed in triply doped samples. In contrast, the green emissions are hardly observed in Er³⁺ singly doped and Er³⁺-Yb³⁺ codoped samples under the same condition. Up-conversion luminescence intensity exhibits dependence of Yb₂O₃-concentration and Nd₂O₃-concentration. Up-conversion mechanism in the triply doped glasses under 800 nm pump is discussed by analyzing the ET among Nd³⁺, Yb³⁺ and Er³⁺. And a possible up-conversion mechanism based on sequential ET from Nd³⁺ to Er³⁺ through Yb³⁺ is proposed for green and red up-conversion emission processes.     

Infrared-to-visible frequency upconversion in SrAl2O4 powders containing Er3+ and Yb3+

The phenomenon of frequency upconversion (UC) is observed in Er³⁺:Yb³⁺:SrAl₂O₄ powders prepared by combustion synthesis. Strong UC emission at the green (bands peaked at 521, 538, 547, and 562 nm) and weak UC emission at the red (bands peaked at 659 and 682 nm) corresponding to 4f–4f transitions of Er³⁺ were observed when the samples were irradiated with near-infrared laser excitation at ～980 nm. Saturation of UC emission is observed for concentrations of 1.5 wt.% of Er³⁺ and 1.5 wt.% of Yb³⁺. The green-to-red intensity ratio, on the other hand, increases linearly with Er³⁺ concentration (Er³⁺ concentration varying from 0.5 to 1.5 wt.%) while keeping Yb³⁺ concentration fixed (at 1.5 wt.%). The green UC decay time was measured and Er³⁺–Er³⁺ interaction was suggested as a possible mechanism to explain the luminescence quenching effect observed.     

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⁺.     

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.     

Synthesis and luminescence properties of Gd6MoO12:Yb3+, Er3+ phosphor with enhanced photoluminescence by Li+ doping

Yb³⁺/Er³⁺ co-doped Gd₆MoO₁₂ and Yb³⁺/Er³⁺/Li⁺ tri-doped Gd₆MoO₁₂ phosphors were prepared by adjusting the annealing temperature via the high temperature solid-state method. Under the excitation of 980 nm semiconductor, the upconversion luminescence properties were investigated and discussed. In the experimental process, we get the optimum Yb³⁺ concentration and the concentration quench effect will happen while the concentration extends the given region. According to the Yb³⁺ concentration quenching effects, the critical distance between Yb³⁺ ions had been calculated. The measured UC luminescence exhibited a strong red emission near 660 nm and green emission at 530 nm and 550 nm, which are due to the transitions of Er³⁺(⁴F_9/2, ²H_11/2, ⁴S_3/2) → Er³⁺(⁴I_15/2). Then the effect of excitation power density in different regions on the upconversion mechanisms was investigated and the calculated results demonstrate that the green and red upconversion is a two-photon process. A possible mechanism was discussed. After Li⁺ ions mixing, the upconversion emission enhanced largely, and the optimum Li⁺ concentration was obtained while fixed the Yb³⁺ and Er³⁺ on the above optimum concentration. This enhancement owns to the decrease of the local symmetry around Er³⁺ after Li⁺ ions doping into the system. This result indicates that Li⁺ is a promising candidate for improving luminescence in some case.     

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.     

Sensitized deep-ultraviolet up-conversion emissions of Gd3+ via Tm3+ and Yb3+ in hexagonal NaYF4 nanorods

Deep-ultraviolet (UV) up-conversion (UC) emissions in the region of 270～330 nm of Gd³⁺ under the excitation of a 980 nm laser diode in hexagonal Yb³⁺-Tm³⁺-Gd³⁺ triply doped NaYF₄ nanorods synthesized using a hydrothermal method are reported. Spectral analyses indicate that the UV UC emissions originate from highly efficient energy transfer from Yb³⁺ to Tm³⁺, then to Gd³⁺ions, and the intensity of the emission as well as the ratios of the emission peaks are strongly dependent on the doping concentrations and pump power. The materials are envisioned to have potential applications in anti-counterfeiting, optical and magnetic dual modal nanoprobes for biomedicine, solution-based scintillator materials and UV compact solid-state lasers.     

Preparation and upconversion properties of Ba2ErF7 and Ba2ErF7:Yb powders

Novel Ba₂ErF₇ and Yb³⁺-doped Ba₂ErF₇ powders were synthesized by a coprecipitation method. In Ba₂ErF₇ sample, abundant upconverted emission bands from violet to infrared region are observed under 980 nm excitation, whereas only green and red emissions are observed under 812 nm excitation. Under the two excitations, the luminescence decay curves of the green and red emissions are measured and the quenching behaviors of Yb³⁺ doping are also explored. It is found that a suitable Yb³⁺ concentration can efficiently enhance the intensity ratio of the blue and violet emissions to the green and red ones, which may be due to the competition between the energy transfer process from Er³⁺ to Yb³⁺ and the sensitizing process from Yb³⁺ to Er³⁺ in Ba₂ErF₇:Yb³⁺. This indicates that the Yb³⁺-doped Ba₂ErF₇ might be a good candidate for blue and violet upconversion phosphor.     

Color variety of up-conversion emission of Er3+/Yb3+ co-doped phosphate glass ceramics

The sample of Er³⁺/Yb³⁺ co-doped phosphate glass ceramic was prepared. At 975 nm laser diode (LD) excitation, the strong up-conversion (UC) emissions were observed, which were the UC green emission at 510–570 nm and the UC red emission at 636–692 nm, respectively. At low pump power (126 mW), the red emission is primary, and the color purity R_cp is 0.81. With the increasing of pump power, the emission color gradually varies from red to green. The intensity of the green emission is stronger compared to that of the red emission at high power (868 mW), and the color purity R_cp is 0.76. Thus, this material can be applied to fluorescence anti-counterfeiting by the color variety of UC emission under different pump power.     

Upconversion in Detail: Multicolor Emission of Yb/Er/Tm-Doped Nanoparticles under 800, 975, 1208, and 1532 nm Excitation Wavelengths

Spectroscopic properties of YPO₄ nanoparticles doped with Yb³⁺, Tm³⁺, and Er³⁺ ions have been studied in detail. These multiemitting materials are promising not only for photonic or electronic use but especially for anticounterfeiting applications. The nanopowders are synthesized by the facile coprecipitation method with annealing in the air atmosphere at 1000 °C. The structural and morphological studies reveal pure tetragonal nanocrystallites with an average size of 20–30 nm. Most interestingly, under NIR excitation, the samples exhibit intense upconversion (UC) luminescence where the color can be tuned by changing the laser source, switching the excitation wavelengths between 800, 975, 1208, and 1532 nm, double-wavelength excitation, and by changing laser power density. As a result, a very high color shift, being the result of intensity changes in the emission bands of Er³⁺ (green and red) and Tm³⁺ (blue and red) is obtained. The luminescence lifetimes, temporal evolution, and the pump power dependences are also measured to propose the mechanisms responsible for the observed UC emission.     

Energy Back Transfer Induced Color Controllable Upconversion Emissions in La2MoO6:Er3+/Yb3+ Nanocrystals for Versatile Applications

Color controllable Er³⁺/Yb³⁺‐codoped La₂MoO₆ upconverting nanocrystals are successfully synthesized via a facile sol‐gel method. Under the irradiation of 980 nm light, the entire samples exhibit dazzling upconversion (UC) emissions arising from the intra‐4f transitions of Er³⁺ ions and the UC emission intensity is strongly dependent on the Yb³⁺ ion concentration. Moreover, by controlling the Yb³⁺ ion concentration, the emission color is changed from green to yellow and finally to red as a result of the energy back transfer from Er³⁺ to Yb³⁺ ions, which is further verified by the theoretically discussion based on the steady‐state rate expressions. The optical thermometric properties of the prepared nanocrystals based on the (²H_11/2,⁴S_3/2) thermally coupled levels of Er³⁺ ions are systematically studied by analyzing the temperature‐dependent green UC emission spectra in the range of 303–663 K. The maximum sensor sensitivity of resultant nanocrystals is determined to be 0.0083 K⁻¹ at 510 K. Furthermore, the emitting color of the synthesized nanocrystals relies on the temperature. In addition, the heating effect induced by the excitation pump power is also investigated and the host lattice temperature is enhanced from 319 to 404 K with raising the pump power from 159 to 757 mW.     

SrAl4O7:Tm3+/Yb3+ nanocrystalline blue phosphor: structural, thermal and optical properties

Strontium aluminate (SrAl₄O₇) nanophosphor codoped with Tm³⁺–Yb³⁺ has been synthesized through the combustion route using urea as the reducing agent. Structural, thermal and optical characterizations have been carried out. Heat treatment of the samples shows a change in the crystallite phases and the relative luminescence intensities for the different bands. The nanocrystalline particles in the as-synthesized sample seem to arrange in rod like shapes of submicrometer length on annealing. A broad (350–550 nm) emission in the UV–green region is observed when 266 nm radiation is used for excitation. Intense upconversion (UC) emissions in blue, red and infrared are seen with excitation by 976 nm radiation. An emission at 364 nm not observed earlier and attributed to ¹D₂→³H₆ transition in Tm³⁺ is also seen. The blue emission from SrAl₄O₇:Tm³⁺/Yb³⁺ codoped nanophosphor (annealed at 1200°C) exhibits high color purity (89%) and is comparable to phosphors used commercially. The energy transfer mechanisms, responsible for these UC emissions, are proposed and discussed.     

Intense White Luminescence from Combustion Synthesized Ca<Subscript>12</Subscript>Al<Subscript>14</Subscript>O<Subscript>33</Subscript>: Yb<Superscript>3+</Superscript>/Yb<Superscript>2+</Superscript> Single Phase Phosphor

The Ca₁₂Al₁₄O₃₃: Yb³⁺/Yb²⁺ single phase nano-phosphor has been synthesized through combustion route and its luminescence and lifetime studies have been carried out up to 20 K using 976 and 266 nm excitations. The samples heated in open atmosphere have shown the presence of Yb in Yb³⁺ and Yb²⁺ states. The 976 nm excitation results a cooperative upconversion emission at 486 nm due to the Yb³⁺ state and a broad band in the blue region and has been assigned to arise from the defect centers. The 266 nm excitation on the other hand results a broad emission band even from as-synthesized phosphor without doping of Yb, the width of which increases in presence of Yb due to the emission from Yb²⁺ ions formed in heated samples. The white emission covers almost whole visible region with bandwidth 190 nm. The ions in Yb²⁺ state has been found to increase with the increase in heating temperature up to 1,273 K. A back conversion of Yb²⁺ to Yb³⁺ has been observed for higher temperatures. Effect of boric and phosphoric acids as flux on the emission properties of Yb³⁺ and Yb²⁺ states have been examined and discussed. Quantum yield of emission has also been determined for different samples.     

Green,blue, red,near-infrared up-conversion luminescence of Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript> co-doped YVO<Subscript>4</Subscript> nanoparticles

YVO₄:Yb³⁺,Er³⁺; YVO₄:Yb³⁺,Tm³⁺; and YVO₄:Yb³⁺,Er³⁺,Tm³⁺ were all synthesized via sol-gel method with a subsequent thermal treatment. Specifically, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ phosphors were prepared with different annealing temperatures to study the influence of temperature. The transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffractometer (XRD), and photoluminescent (PL) spectrofluorometer were used to investigate the morphology, crystal structure, and up-conversion luminescent properties of all samples. In summary, all samples were granular-like nanoparticles and well crystallized with the same tetragonal phase as YVO₄. Under the irradiation at 980 nm, YVO₄:Yb³⁺,Er³⁺ phosphors can generate green emission at 525 and 553 nm and red emission at 657 nm, while YVO₄:Yb³⁺,Tm³⁺ phosphors can generate blue emission at 476 nm, red emission at 648 nm, and near-infrared emission at 800 nm. Notably, YVO₄:Yb³⁺,Er³⁺,Tm³⁺ samples can exhibit green emission, blue emission, red emission, and near-infrared emission at the same time, which might endow the as-prepared samples with potential applications in many fields, such as luminous paint, infrared detection, and biological label.     

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.     

Er3+及Er3+/Yb3+掺杂ZrO2-Al2O3的制备及发光性质

采用共沉淀法制备了纳米晶ZrO₂-Al₂O₃∶Er³⁺发光粉体.所制备的粉体室温下具有Er3+离子特征荧光发射,主发射在绿光,其中位于547 nm、560 nm的绿光最强,并得出稀土离子与基质之间有能量传递.对不同煅烧温度下的样品研究表明:因不同温度下所制得的样品晶相不同.研究了纳米晶ZrO2-Al2O3∶Er3+及ZrO₂-Al₂O₃∶Er³⁺/Yb³⁺的上转换发光,并分析了上转换的跃迁机制.发现ZrO₂-Al₂O₃∶Er³⁺的绿光为双光子过程,而ZrO₂-Al₂O₃∶Er³⁺、Yb³⁺的上转换光谱中,红光和绿光也为双光子过程,而极弱的蓝光为三光子过程.讨论了Er³⁺的浓度猝灭现象.最适宜掺杂浓度的原子分数为2%（Er³⁺/Zr⁴⁺）.     

Er3+，Er3+/Yb3+掺杂氟化镧超微材料的光谱特性与上转换发光

采用共沉淀法制备了Er³⁺掺杂和Er³⁺/Yb³⁺共掺杂LaF₃超微材料,所制备的样品的颗粒呈球形,尺寸为250nm左右.计算得到Er³⁺单掺杂样品中对应着⁴S_3/2和⁴F_9/2能级的发光量子效率分别为67.0%和71.9%.研究发现,随着Yb³⁺离子浓度的增加 关键词： 3+')" href="#">Er³⁺ 3+')" href="#">Yb³⁺ 发光 能量传递     

Er-Yb Codoped Ferroelectrics for Controlling Visible Upconversion Emissions

Under a 980 nm laser pumping, quenching of green upconversion (UC) emission accompanied with enhancement of red UC emission observed was dominated by the energy back-transfer (EBT) process in Er³⁺ and Yb³⁺ co-doped PbTiO₃, BaTiO₃, and SrTiO₃ polycrystalline powders. The efficiency of the EBT process depends not only on Yb³⁺ concentration but also on level match of the doped Er³⁺ and Yb³⁺ ions caused by the crystal fields with different symmetries. Our UC emission spectra and X-ray diffraction confirm that the centrosymmetric crystal field arising from reducing tetragonality causes level match of transition of Er³⁺ and of Yb³⁺. This level match is responsible for enhancing red UC emission.