Experimental investigation on the upconversion mechanism of 754 nm NIR luminescence of Ho/Yb:Y2O3, Gd2O3 under 976 nm diode laserexcitation

Upconversion (UC) spectra of Ho³⁺/Yb³⁺ codoped Y₂O₃, Gd₂O₃ bulk ceramics were obtained under the excitation of a 976 nm diode laser. Systematic experimental studies, including power dependence, luminescence lifetime, and the intensity ratio σ for the green to NIR emissions, were carried out in order to confirm the UC mechanism of Ho³⁺ ions. Our results demonstrated that the NIR emission was associated with the ⁵F₄/⁵S₂→⁵I₇ transition of Ho³⁺ ions without the contribution of the ⁵I₄→⁵I₈ transition for Ho³⁺/Yb³⁺ codoped Y₂O₃ and Gd₂O₃ bulk ceramics. Additionally, population saturation in the ⁵I₇ energy level had been observed in Ho³⁺/Yb³⁺ codoped Y₂O₃, Gd₂O₃ bulk ceramics. All experimental observations can be well explained by the steady-state rate equations.     

High Quantum Yield Single‐Band Green Upconversion in La2O3:Yb3+, Ho3+ Microcrystals for Anticounterfeiting and Plastic Recycling

Single‐band green upconversion (UC) with high green purity and color stability is urgently required for plastic recycling and anticounterfeiting. However, it is very difficult to obtain single‐band green emission for benchmark Yb³⁺/Er³⁺ activated UC materials (such as NaYF₄:Yb³⁺,Er³⁺) due to the strong accompanying red UC. Herein, highly efficient and stable single‐band green UC is reported in La₂O₃:Yb³⁺/Ho³⁺ (LYH) microcrystals with record high absolute UC quantum yield (UCQY) of 2.6% for single‐band green UC. LYH yields pure green UC with large and stable intensity ratio, I_Green/I_Red ≈ 18. LYH presents not only higher UCQY for a single‐band green UC but also much more pure and stable green UC than the benchmark UC materials such as NaYF₄:Yb³⁺,Er³⁺ and Gd₂O₂S:Yb³⁺,Er³⁺. These results suggest that the newly developed LYH can, in principle, be promising for anticounterfeiting and plastic recycling. Its proof‐of‐concept is demonstrated as a security label based on a transparent institute logo.     

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.     

Effect of Yb3+ concentration on photoluminescence properties of cubic Gd2O3 phosphor

Yb³⁺ doped phosphor of Gd₂O₃ (Gd₂O₃:Yb³⁺) have been prepared by solid state reaction method. The structure and the particle size have been determined by X-ray powder diffraction measurements. The average particle size of the phosphor is in between 35 and 50 nm. The particle size and structure of the phosphor was further confirmed by TEM analysis. The visible and NIR luminescence spectra were recorded under the 980 nm laser excitation. The visible upconversion luminescence of Yb³⁺ ion was due to cooperative luminescence and the presence of rare earth impurity ions. The cooperative upconversion and NIR luminescence spectra as a function of Yb³⁺ ion concentration were measured and the emission intensity variation with Yb³⁺ ion concentration was discussed. Yb³⁺ energy migration quenched the cooperative luminescence of Gd₂O₃:Yb³⁺ phosphor with doping level over 5%, while the NIR emission luminescence continuously increases with increasing Yb³⁺ ion concentration.     

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.     

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.     

Synthesis, characterization and upconversion emission properties of the nanocrystals of Yb/Er-codoped YF3-YOF-Y2O3 system

Nanocrystalline Yb³⁺, Er³⁺-codoped fluoride (YF₃), oxyfluoride (YOF), and oxide (Y₂O₃) phosphors have been synthesized by a facile pyrolysis of a yttrium trifluoroacetate precursor. YF₃, YOF and Y₂O₃ nanoparticles were demonstrated to be good host materials for lanthanides. Varied hosts led to different optical properties. Red, green, and blue up-conversion (UC) was observed upon excitation in the NIR spectral range in all synthesized compounds. The UC mechanisms were also analyzed.     

A study of energy transfer phenomenon leading to photon up-conversion in Ho3+:Yb3+:CaF2 crystalline powders and its temperature sensing properties

When Ho³⁺:Yb³⁺:CaF₂ crystalline powders prepared by combustion synthesis were exposed to near-infrared (λ ～ 975 nm) radiation, intense photon up-conversion (UC) was observed at the visible with emission bands peaked at ～ 545, ～650 and ～750 nm identified as 4f-4f transitions from higher levels (⁵F₄, ⁵S₂) and ⁵F₅ to lower levels ⁵I₈ and ⁵I₇ of Ho³⁺. The emission bands at the green and red, in particular, have been demonstrated to be useful for temperature sensing based on luminescence intensity ratio technique. However, no model is available in literature to explain the change of the electronic populations of states (⁵F₄, ⁵S₂) and ⁵F₅ with temperature. The UC phenomenon was studied from both theoretical and experimental points of view. A rate equation model with temperature dependent parameters for Ho³⁺ and Yb³⁺ electronic populations considering a high sensitization of Ho³⁺ ions by Yb³⁺ ions was used. High Yb³⁺ → Ho³⁺ energy transfer efficiency was found (～88% at room temperature). The change with temperature predicted by the model for the luminescence intensity ratio of the UC green and red emission lines agrees well with the experimental data.     

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.     

Diode laser pumped Gd2O3:Er3+/Yb3+ phosphor as optical nano-heater

An intense green upconversion (UC) emission (λ _exc=976 nm) followed by the heating effect in Yb³⁺/Er³⁺ co-doped Gd₂O₃ nanoparticles has been detected. A temperature rise up to 504 K has been observed (on a noteworthy low laser excitation of 290 mW) using fluorescence intensity ratio (FIR) method of the thermalized UC luminescence bands ²H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 of Er³⁺ ion. The reported controlled optical heating of nanoparticles and its nano-volume has potential applications in biomedicines and in the creation of holes in soft materials.     

Upconversion white-light emission in Ho3+/Yb3+/Tm3+ codoped LiNbO3 polycrystals

Ho³⁺/Yb³⁺/Tm³⁺ codoped LiNbO₃ polycrystals exhibiting upconversion white-light under 980 nm excitation have been successfully fabricated by the high temperature solid-state reaction method. CIE coordinate of the Ho³⁺/Yb³⁺/Tm³⁺/LiNbO₃ polycrystal is (0.34, 0.35), which is very close to the standard equal energy white-light illuminate (0.33, 0.33). Efficient green, red, and blue upconversion emissions have been observed. The luminescent decay dynamics are studied, and rate equations for the blue, green, and red emissions are set up to analyze the upconversion luminescence mechanism. The present results demonstrate that the competition between the linear decay and the upconversion process for the depletion of the intermediate excited states plays an important role in upconversion mechanism. The LiNbO₃ with upconversion white-light will be a promising luminous material.     

White upconversion emission and color tunability of Y2O3:R(R=Yb3+, Er3+, Tm3+) nanophosphors

The Y₂O₃:R(R = Yb³⁺, Er³⁺, Tm³⁺) nanophosphors were synthesized by a solvothermal method and the temperature dependence of the white upconversion emission was studied using a 975 nm LD. The upconversion emission spectra in 1 mol% Er³⁺/5 mol% Yb³⁺/xTm³⁺ tri-doped Y₂O₃ nanophosphors were sintered at 1000 ^°C with x from 0 to 0.5 mol%. The blue emission intensity increases increasing Tm³⁺ concentration from 0 to 0.5 mol%, because the Tm³⁺ state can be easily reached due to the ²F_7/2 → ²F_5/2 transition of Yb³⁺ near 10,000 cm⁻¹. The Y₂O₃: Er³⁺/Yb³⁺/Tm³⁺ nanophosphors exhibit upconversion emission from white to green with increasing sintering temperature. The calculated CIE coordinates are located in the white region at a pump power of 700 mW at 1000 °C, and the color coordinates were very similar to the standard white light emission. Their upconversion process was described through energy level diagrams and results of upconversion emission spectra and pump power dependence.     

Improving monochromaticity of upconversion luminescence by codoping Eu ions in Y2O3:Ho, Yb nanocrystals

Upconversion (UC) luminescence of Y₂O₃:Ho³⁺, Yb³⁺ nanocrystals codoped with different concentrations of Eu³⁺ ions were investigated to improve the monochromaticity of the UC emission. The results show that the monochromaticity, quantified by a parameter SR, increases as the concentration of Eu³⁺ ions becomes higher, which is due to the energy transfer between ⁵I₇ (Ho³⁺) and ⁷F₆ (Eu³⁺). The energy transfer accelerates the relaxation of Ho³⁺ ions from the ⁵I₇ to ⁵I₈ state and then quenches the red emission. The influence of the Eu³⁺ concentration on the pump power dependence of the red UC fluorescence in Y₂O₃:Ho³⁺, Yb³⁺, Eu³⁺ nanocrystals is verified using the steady-state rate equation theory.     

Conversion of infrared radiation into visible emission in NaGd(WO4)2:Yb3+, Ho3+ crystals

NaGd(WO₄)₂:Yb³⁺, Ho³⁺ single crystals have been grown by the Czochralski technique along the (0 0 1) orientation. Conversion of the infrared (IR) radiation at 980 nm into the visible emission in NaGd(WO₄)₂ crystals containing several different concentrations of Yb³⁺ and Ho³⁺ has been investigated. The NaGd(WO₄)₂: 8 at. % Yb³⁺, 4 at. % Ho³⁺ system exhibits intense red upconverted emission originating from the ⁵F₅ level. The upconversion mechanism in a Ho³⁺-Yb³⁺ system under near infrared excitation is discussed. It is concluded that the green emission is excited by energy transfers from Yb³⁺ to Ho³⁺, whereas excited state absorption is involved in the excitation of red emission. The emission cross-section of the ⁵F₅→⁵I₈ transition at about 660 nm was estimated by using the Füchtbauer–Ladengurg formula. PACS 78.55.Hx; 78.20.-e     

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.     

Sensitizer-dependent up-conversion of Ho<Superscript>3+</Superscript> in nanocrystalline Y<Subscript>2</Subscript>O<Subscript>3</Subscript>

Ho³⁺–Yb³⁺ co-doped Y₂O₃ nanocrystals were synthesized by firing hydroxy carbonate precursors. Yb³⁺-concentration-dependent up-conversion properties of Ho³⁺ in Y₂O₃ nanocrystals have been investigated. The relative intensity of up-converted red emission increases more quickly than that of the green and the near-infrared ones with the enhancement of the concentration of Yb³⁺. It is believed that the energy process ⁵ S ₂ (⁵F₄) (Ho) + ⁵ I ₇ (Ho) →⁵ I ₆ (Ho)+⁵ F ₅ (Ho) plays an important role in the population of the ⁵ F ₅ level of Ho³⁺. The result indicates that the intensity ratio of the green emission to the red one can be tuned by changing the sensitizer concentration. PACS 78.55.-m     

Photoluminescence in Gd2O3: Er3+, Yb3+ upconversion inverse opal

Photoluminescence properties of Gd₂O₃: Er³⁺, Yb³⁺ upconversion inverse opal photonic crystals were investigated. The photoluminescence spectra of the inverse opal show strong dependence on upconversion emission intensity and the corresponding photonic band-gaps of the inverse opal. Significant suppression of the green or red upconversion emission was observed if the photonic band-gap overlaps with the Er³⁺ ions emission band. The color purity of the red or green emission was improved in the inverse opal by the suppression of green or red UC emission. We believe that the present work will be valuable for not only the foundational study of upconversion emission modification but also new optical devices in upconversion lighting and display.     

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.     

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