Upconversion white-light emission in Ho³⁺/Yb³⁺/Tm³⁺ tridoped LiNbO₃ single crystal

Ho³⁺/Yb³⁺/Tm³⁺ tridoped LiNbO₃ single crystal exhibiting intense upconversion white light under 980?nm excitation has been successfully fabricated by the Czochralski method. The tridoped LiNbO₃ single crystal offers power dependent color tuning properties by simply changing excitation power. Efficient three-photon blue upconversion emission and two-photon green and red upconversion emissions have been observed. In addition, the red emission of Ho³⁺ originates dominantly from the nonradiative decay of green emission. The LiNbO₃ with upconversion white light will be a potential laser candidate material.     

Upconversion and color tunability in Tm/Ho/Yb doped low phonon energy bismuth tellurite glasses

Low phonon energy Tm³⁺/Ho³⁺/Yb³⁺ triply doped bismuth tellurite glasses exhibiting multicolor upconversion fluorescences have been fabricated and characterized. The multicolor fluorescence composed of three primary colors green, red and blue upconversion emissions from Ho³⁺ and Tm³⁺ has been investigated. By adjusting the excitation power, the fluorescence colors can be tuned from multicolor to white color, and the dependence of color tunability on pump power has been presented in the CIE 1931 chromaticity diagram. With the increase in pumping power, the color coordinates move along the down-left direction and hit the equal energy point. The upconversion and color tunability via changing the pump power of infrared excitation in Tm³⁺/Ho³⁺/Yb³⁺ triply doped bismuth tellurite glasses will lead to new breakthrough in the field of three-dimensional solid-state displays and white-light emitting devices.     

应用于白光显示的Tm3+/Ho3+/Yb3+共掺碲酸盐玻璃上转换发光特性研究

用高温熔融法制备了Tm³⁺/Ho³⁺/Yb³⁺共掺碲酸盐玻璃(TeO₂-ZnO-La₂O₃)样品,测试了玻璃样品的吸收光谱和上转换发光光谱,分析了上转换发光机理.结果发现:在975 nm波长激光二极管(LD)激励下,制备的碲酸盐玻璃样品可以观察到强烈的红光(662 nm)、绿光(546 nm)和蓝光(480 nm)三基色上转换发光,红光对应于Tm³⁺离子 关键词： 碲酸盐玻璃 上转换发光 白光 3+/Ho³⁺/Yb³⁺共掺')" href="#">Tm³⁺/Ho³⁺/Yb³⁺共掺     

Infrared-to-visible up-conversion luminescence and energy transfer of RE3+/Yb3+(RE = Ho,Tm) co-doped SrIn2O4

Near-infrared excited up-conversion phosphors of RE³⁺/Yb³⁺(RE = Ho, Tm) co-doped SrIn₂O₄ were synthesized by a solid-state reaction method. X-ray diffraction analysis revealed the phase composition of those samples, and the up-conversion spectroscopic properties were studied in terms of up-conversion emission spectra. Under 980 nm near-infrared laser excitation, strong green emission with the peak at 546 nm was observed in SrIn₂O₄: Ho³⁺/Yb³⁺, which can be assigned to the characteristic ⁵S₂(⁵F₄) → ⁵I₈ transition of Ho³⁺. Furthermore, SrIn₂O₄: Tm³⁺/Yb³⁺ showed bright blue emission with the peak at 486 nm, which is associated with the ¹G₄ → ³H₆ transition of Tm³⁺. The UC power studies indicated that the luminescence of SrIn₂O₄: Ho³⁺/Yb³⁺ and SrIn₂O₄: Tm³⁺/Yb³⁺ are attributed to two-photon and three-photon process, respectively. The possible UC luminescence mechanism and energy transfer in SrIn₂O₄: RE³⁺/Yb³⁺ were discussed.     

Microwave sol-gel process of KGd(WO4)2:Ho3+/Yb3 phosphors and their upconversion photoluminescence properties

Double tungstate KGd_1−x(WO₄)₂:Ho³⁺/Yb³⁺ phosphors with doping concentrations of Ho³⁺ and Yb³⁺ (x=Ho³⁺+Yb³⁺, Ho³⁺=0.05, 0.1, 0.2 and Yb³⁺=0.2, 0.45) were successfully synthesized by the microwave sol–gel method, and the upconversion mechanisms were investigated in detail. The synthesized particles formed after heat-treatment at 900 °C for 16 h showed a well crystallized morphology with particle sizes of 2–5 μm. Under excitation at 980 nm, the UC intensities of KGd_0.7(WO₄)₂:Ho_0.1Yb_0.2 and KGd_0.5(WO₄)₂Ho_0.05Yb_0.45 particles exhibited yellow emissions based on a strong 550-nm emission band in the green region and a strong 655-nm emission band in the red region, which were assigned to the ⁵S₂/⁵F₄→⁵I₈ and ⁵F₅→⁵I₈ transitions, respectively. The Raman spectra of the doped particles indicated the presence of strong peaks at higher frequencies of 764, 812, 904, 984, 1050, 1106, 1250 and 1340 cm⁻¹ induced by the disorder of the [WO₄]²⁻ groups with the incorporation of the Ho³⁺ and Yb³⁺ elements into the crystal lattice or by a new phase formation.     

Upconversion luminescence in Tm3+/Yb3+co-doped lead tungstate tellurite glasses

This work reports the upconversion luminescence properties of Tm³⁺/Yb³⁺ ions in lead tungstate tellurite (LTT) glasses. Judd–Oflet intensity parameters have been obtained from the absorption band intensities of Tm³⁺ singly-doped and Tm³⁺/Yb³⁺ co-doped LTT glasses. The spontaneous emission probabilities, radiative lifetimes and branching ratios for ¹G₄ and ³H₄ emission levels of Tm³⁺ have been determined. Upconversion luminescence has been observed by exciting the samples at 980 nm (Yb³⁺:²F_7/2→²F_5/2) at room temperature. Four upconversion emission bands corresponding to the ¹G₄→³H₆ (477 nm), ¹G₄→³F₄ (651 nm), ¹G₄→³H₅ (702 nm) and ³H₄→³H₆ (810 nm) transitions have been identified. The relative variation in the intensities of upconversion bands, the different channels responsible for upconversion spectra and the effect of Yb³⁺ ions concentration on the upconversion luminescence of Tm³⁺ ions have also been discussed.     

Increase of the blue upconversion emission in YAG:Tm3+ nanopowders by codoping with Yb3+ ions

The YAG nanopowders were prepared by a co-precipitation method using nitrate and ammonium hydrogen carbonate as raw materials. To obtain homogenous precipitate, reverse-strike (adding salt solutions to the precipitant solution) technique was adopted. Therefore, single (Tm³⁺) and codoped (Tm³⁺–Yb³⁺) YAG nanopowders with a size between 40–90 nm have been obtained.Blue upconversion emission at around 480 nm has been found in YAG: Tm³⁺ nanopowders under excitation to the ³H₄ level of Tm³⁺ at around 800 nm. However, this upconversion emission in nanopowders codoped with Tm³⁺–Yb³⁺ ions is increased by a factor of about 10. The analysis of the temporal evolution of the involved levels and the dependence of the upconversion intensity on the pump power at 800 nm allowed to distinguish the upconversion mechanism. In YAG: Tm³⁺ nanopowders the upconversion mechanism is due to excited state absorption processes. However, in the codoped samples, Yb³⁺ ions acts as the sensitizers; in consequence, the blue upconversion is strongly increased.     

Hydrothermal synthesis and the enhanced blue upconversion luminescence of NaYF4:Nd3+,Tm3+,Yb3+

Nd³⁺, Tm³⁺ and Yb³⁺ co-doped NaYF₄ upconversion (UC) material was synthesized by the hydrothermal method. The structure of the sample was characterized by the X-ray diffraction, and its UC luminescence properties were investigated in detail. Under the 980 nm semiconductor laser excitation, its UC spectra exhibited distinct emission peaks at 451 nm, 475 nm and 646 nm respectively. On the basis of the comparison of UC spectra between NaYF₄:Nd³⁺,Tm³⁺,Yb³⁺ and NaYF₄:Tm³⁺,Yb³⁺, it was indicated that the existence of Nd³⁺ ion enhanced the blue emission intensity. The law of luminescence intensity versus pump power proved that the blue emission at 475 nm, and the red emission at 646 nm were the two-photon processes, while the blue emission at 451 nm was a three-photon process.     

Optical spectroscopy and laser parameters of Zn2+/Er3+/Yb3+-tridoped LiNbO3 crystal

The Zn/Er/Yb:LiNbO₃ and Er/Yb:LiNbO₃ crystals were grown by the Czochralski technique. The laser characteristics of 1.54 μm emission were predicted based on the Judd–Ofelt theory, and the intensity parameters Ω_t (Ω₂=7.23×10^?20 cm², Ω₄=3.15×10^?20 cm² and Ω₆=1.43×10^?20 cm²) were obtained. The stimulated emission cross sections (σ_em) at 1.54 μm emission in Zn/Er/Yb:LiNbO₃ were calculated based on the McCumber theory and the Füchtbauer–Ladenburg theory. The gain cross section spectrum of Zn/Er/Yb:LiNbO₃ crystal was also investigated. Under 980 nm excitation, a lenghthening lifetime of 1.54 μm emission and an enhancement of green upconversion emission were observed for Zn/Er/Yb:LiNbO₃ crystal. The studies on the power pump dependence and the upconversion mechanism suggested that both green and red upconversion emissions were populated via the three-photon process, and Zn²⁺ ion tridoping increases the probability of cross relaxation process between the two neighboring Er³⁺ ions.     

Spectroscopic properties of Tm3+/Ho3+ co-doped NaLa(WO4)2 single crystal

Tm³⁺/Ho³⁺ co-doped NaLa(WO₄)₂ single crystal was successfully grown by the Czochralski method. The crystal was characterized by room temperature absorption spectra, fluorescence spectra around 2 μm, up-conversion fluorescence and luminescence decay measurements. Spectroscopic properties related to the laser operation around 2 μm of Ho³⁺ ions have been evaluated. The energy level scheme and energy transfer processes of Tm³⁺ and Ho³⁺ were analyzed. The obtained spectroscopic results show the crystal is a potentially host for Ho³⁺ 2 μm infrared laser.     

Laser induced optical heating from Yb3+/Ho3+:Ca12Al14O33 and its applicability as a thermal probe

Yb³⁺/Ho³⁺ co-doped calcium aluminate phosphor has been synthesized using solution combustion process. Multicolored (blue, green and red) strong upconversion emission (λ_exc=980 nm) due to Ho³⁺ ion is observed which shows a color tunability (from green to red) with a variation in input laser power. The color tunability has been attributed to be due to the induced heating in the local volume of the sample and the temperature produced has been estimated using the fluorescence intensity ratio (FIR) method. The sample shows temperature sensing behavior and more importantly the temperature could be sensed through two pairs of thermally coupled levels, one lying in the green region (⁵F₄/⁵S₂→⁵I₈) and the other in the blue region (⁵G₄/⁵G₅→⁵I₈). The temperature sensing through the blue pair of levels is novel in itself. The material thus prepared serves as temperature sensor as well as a source for the production of heat in a localized volume.     

Blue upconversion luminescence in 12 CaO·7 Al2O3:Tm3 +/Yb3 + polycrystals

The effect of Yb^3 + concentration on the fluorescence of 12 CaO·7 Al₂O₃:Tm^3 +/Yb^3 + polycrystals is investigated. Under the excitation of 980 nm laser, the strong blue (477 nm) emission band is observed and attributed to ¹G₄ → ³H₆ of Tm^3 +. The ratio of blue to red emission increases with the increasing of Yb^3 + and remains constant at 10 mol% Yb^3 +. The pump dependence and upconversion mechanisms show that the two-photon cooperative upconversion process is responsible for the enhancement of the blue upconversion emission. The Commission Internationale de l'eclairage chromaticity coordinates (x, y) illustrate that the 12 CaO·7 Al₂O₃:1 mol% Tm^3 +/10 mol% Yb^3 + can emit high-purity blue light.     

Optical temperature sensor through infrared excited blue upconversion emission in Tm3 +/Yb3 + codoped Y2O3

An analysis of the intense blue upconversion emission at 476 and 488 nm in Tm^3 +/Yb^3 + codoped Y₂O₃ under excitation power density of 86.7 W/cm² available from a diode laser emitting at 976 nm, has been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive blue upconversion emission at 476 and 488 nm in this material was recorded in the temperature range from 303 to 753 K. The maximum sensitivity derived from the FIR technique of the blue upconversion emission is approximately 0.0035 K^? 1. The results imply that Tm^3 +/Yb^3 + codoped Y₂O₃ is a potential candidate for the optical temperature sensor.     

Towards efficient upconversion and downconversion of NaYF4:Ho3+,Yb3+ phosphors

NaYF₄ microcrystals co-doped with Ho³⁺ and Yb³⁺ were prepared by a facile hydrothermal synthesis. The products were characterized by X-ray diffractometer, scanning electron microscopy, and photoluminescence spectroscopy. Upon excitation with a 980 nm laser diode, the sample shows an intense green upconversion emission centered at 540 nm corresponding to the ⁵S₂→⁵I₈ transition of Ho³⁺. The quadratic dependence of the green emission intensity on the excitation power reveals a two-phonon upconversion process. On the contrary, upon excitation with 448 nm, both visible and near-infrared emissions peaked at 483, 540, 644, 749, and 978 nm are simultaneously observed, which could be assigned to the electronic transitions of Ho³⁺: ⁵F₃→⁵I₈, ⁵S₂→⁵I₈, ⁵F₅→⁵I₈, ⁵S₂→⁵I₇, and Yb³⁺: ²F_5/2→²F_7/2, respectively. The energy transfer processes between Ho³⁺ and Yb³⁺ ions and the involved mechanisms have been investigated and discussed.     

Synthesis and up-conversion luminescence properties of Ho3+, Yb3+ co-doped BaLa2ZnO5

Up-conversion phosphors BaLa₂ZnO₅ co-doped with Ho³⁺/Yb³⁺ were synthesized by high temperature solid-state reaction method. The phase composition of the phosphors was characterized by X-ray diffraction (XRD). The structure of BaLa₂ZnO₅: 0.75% Ho/15% Yb phosphor was refined by the Rietveld method and results showed the decreased unit cell parameters and cell volume after doping Ho³⁺ and Yb³⁺, indicating Ho³⁺ and Yb³⁺ have successfully replaced La³⁺. Under the excitation of 980 nm diode laser, the strong green and weak red up-conversion emissions centered at 548 nm, 664 nm and 758 nm were observed, which originating from ⁵S₂, ⁵F₂→⁵I₈, ⁵F₄→⁵I₈ and ⁵S₂, ⁵F₂→⁵I₇ transitions of Ho³⁺ ions, respectively. The optimum doping concentrations of Ho³⁺ and Yb³⁺ were determined to be 0.75% and 15%, and the corresponding Commission International de L'Eclairage (CIE) coordinates are calculated to be x=0.298 and y=0.692. The related UC mechanism of Ho³⁺/Yb³⁺ co-doped BaLa₂ZnO₅ depending on pump power was studied in detail. The results indicate that BaLa₂ZnO₅: Ho³⁺/Yb³⁺ can be an effective candidate for up-conversion yellowish-green light emitter.     

Highly efficient upconversion emission and luminescence switching from Yb3+/Tm3+ co-doped water-free low silica calcium aluminosilicate glass

We present highly efficient 480 and 800 nm upconversion emissions in Tm³⁺/Yb³⁺ co-doped water-free low silica calcium aluminosilicate glass under excitation at 976 nm. As a result of this efficient upconversion process, a luminescent switching with the excitation intensity has been observed. The switching is explained and discussed using rate equations analysis and saturation effects. By means of fitting of the experimental data point, it was possible to obtain the value of the energy transfer parameter related to the transition ²F_5/2, ³H₄→²F_7/2, ¹G₄. The value of this parameter is higher than that of materials like YLF. This switching mechanism could be used in the development of sensors and networks for optical processing and optical communications.     

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.     

Dopant occupancy and optical properties of Er3+ in Er/Zn-codoped lithium niobate crystal

The effect of Zn²⁺ ion on the dopant occupancy and optical characteristic of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal is reported. The intense 1.54 μm and relatively weak green upconversion emissions are observed for Er (1 mol%)/Zn (6 mol%):LiNbO₃ crystal. The OH^? absorption and the time-resolved spectra show that the Zn²⁺ codoping decreases the threshold concentration of Er³⁺ ion in Er/Zn-codoped LiNbO₃ crystal. The experimental results here imply that the potential application of Er³⁺-doped LiNbO₃ crystal can be designed and optimized on the basis of the theoretical investigations.     

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.     

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.