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.     

Violet and visible up-conversion emission in Yb-Ho co-doped germanium-borate glasses

The up-conversion emission properties of Yb³⁺-Ho³⁺ co-doped germanium-borate glasses have been investigated with 980 nm excitation. The violet, blue, green and red emission bands at about 350, 485, 544 and 653 nm can be identified, respectively. Experimental results indicated that the relative intensity ratios of the peaks I_Red/I_Green increased with increasing B₂O₃ concentration, which led to changing color of up-conversion emission from green at x=0 to yellow at x=40, to red at x=60. The violet emission at 350 nm was first reported in germanium-borate glass host and up-conversion mechanisms of the emissions were discussed. The Yb³⁺-Ho³⁺ co-doped germanium-borate glasses could be an alternative for the generation of violet and primary colors for application in solid-state displays.     

GENERATION OF MULTI-WAVELENGTH VISIBLE LIGHT IN Er3+-DOPED AND Er3+/Yb3+-DOPED SINGLE-MODE OPTICAL FIBER PUMPED AT 1313 nm

We report the generation of multi-wavelength visible light through amplified spontaneous emission (ASE) in Er³⁺-doped and Er³⁺/Yb³⁺-doped germanosilicate single-mode optical fiber pumped by a Nd:YLF laser at 1313nm. In the Er³⁺-doped fiber, the intense multi-wavelength blue emission hnes around 463-510nm corre-spond to transitions born ²G_7/2 etc. excited states to the metastable ⁴I_13/2 state, and their pumping mechanists is aecomphshed by a stepwise four-photon absorption. Some emission hnes in this wavelength region are attributed to the three-wave sum-frequency process of 1313 and 1530nm (corresponds to ⁴I_13/2 -⁴I_15/2). The intense green emission hnes at 525 and 540 nm are also observed in the Er³⁺-doped fiber. In the Er³⁺/Yb³⁺-doped fiber the blue and green lines are very weak compared with those in the Er³⁺-doped fiber.     

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.     

Y2O3:Yb3+,Tm3+纳米材料的可见及紫外上转换发光

通过燃烧法制备了Yb³⁺-Tm³⁺共掺的Y₂O₃纳米粉体,并对样品在980 nm激光照射下的上转换发光特性进行了研究.实验发现,样品在可见光区域能够产生强烈的蓝色发光(476 nm和487 nm)和较弱的红色发光(约650 nm),而且同时观察到了两个紫外发光峰¹I₆→³H₆ (~297 nm)和^{1关键词： 2O₃:Yb3+')" href="#">Y₂O₃:Yb3+ 3+}')" href="#">Tm³⁺ 上转换光谱 敏化 紫外发光     

Yb3+ site occupation and host sensitization luminescence of a novel near‐infrared emitting Sr2CaMoO6:Yb3+ phosphor

The host sensitized near‐infrared (NIR) emitting phosphor Sr₂CaMoO₆:Yb³⁺ was fabricated by the solid state reaction method. The structural refinement and Raman spectra elucidate that Yb³⁺ ions preferentially occupy Ca²⁺ sites. The phosphor can harvest ultraviolet (UV)–blue photons and exhibits intense NIR emission at around 1012 nm with full‐width‐at‐half‐maximum of 1635 cm^–1. Moreover, the absolute NIR photoluminesence quantum yield (PLQY) is estimated to be about 9%. The Sr₂CaMoO₆:Yb³⁺ phosphor may be a promising luminescence downshifting material for improving the spectral response of solar cells in the UV region. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Variation in luminescence behavior of Yb3+ doped GdAlO3 phosphor with gradual increase in Yb3+ concentration

The present paper reports the combustion synthesis of Yb³⁺ doped GdAlO₃ phosphors. The structural characterization and luminescence spectra of Yb³⁺ doped GdAlO₃ phosphors have been discussed. The effects of variable concentration of Yb³⁺ on Photoluminescence (PL) behavior were studied. The structural characterization was done by X-ray diffraction (XRD) and Transmission electron microscope technique (TEM). The good connectivity with grains and the semi-sphere line structure was found by TEM. The functional group analysis was carried out by Fourier transform infrared (FTIR) spectroscopic techniques. The prepared phosphor gives emission spectra in visible as well as NIR region. Both emissions were studied as a function of Yb³⁺ concentration. The emission intensity variation with Yb³⁺ ion concentration for visible and NIR region were discussed separately. The NIR emission luminescence of GdAlO₃:Yb³⁺ phosphor luminescence continuously increases with increasing Yb³⁺ ion concentration.     

The fluorescence properties of Yb3+ and Er3+ Co-doped YAl3(BO3)4 powders prepared by sol-gel method

Yb³⁺ and Er³⁺ co-doped YAB powders were prepared by sol-gel method. The structure and fluorescence properties were investigated. XRD pattern indicated that the single phase was obtained at 1150°C and the structure belonged to rhombohedral. Under 379 nm excitation, two emissions around 983 nm and 1531 nm were observed and the effect of Yb³⁺ ion concentration on the emission intensity was discussed. The energy transfer was observed under 930 nm excitation and the energy transfer efficiencies for all samples were calculated. The lifetimes of ² F _5/2 level of Yb³⁺ ion and ⁴ I _13/2 level of Er³⁺ ion were measured and the effect of Yb³⁺ ion concentration on the lifetime was also discussed. The results indicated that there was an additional mechanism for the decay of ⁴ I _13/2 level in powder samples. The Yb³⁺ and Er³⁺ co-doped YAB powders should be a potential candidate for ceramic laser materials.     

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.     

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 character of Er/Yb co-doped P2O5-CaO-Na2O-Al2O3-AgO phosphate glass

The up-conversion (UC) and near infrared (NIR) luminescence of Er³⁺/Yb³⁺ co-doped phosphate glass are investigated. In the UC emission range, the 523 nm, 546 nm green emissions and the 659 nm red emission are observed. With the increasing pump power, the intensity ratios of I₅₂₃/I₆₅₉, I₅₄₆/I₆₅₉ and I₅₂₃/I₅₄₆ increase gradually. The phenomenon is reasonably interpreted by theoretical analysis based on steady state rate equations. The emission cross section of the infrared emission at 1546 nm is larger (about 6.7 × 10^− 21 cm²), which is suitable for making fiber amplifier.     

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.     

Green and red up-conversion emissions of Er-Yb-codoped Al2O3 powders prepared by the nonaqueous sol-gel method

The 1 mol% Er³⁺- and 0-20 mol% Yb³⁺-codoped Al₂O₃ powders have been prepared by the nonaqueous sol-gel process using aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium and ytterbium nitrate as dopant under isopropanol environment. The two crystalline types of doped Al₂O₃, γ and θ, and a stoichiometric compound, (Yb,Er)₃Al₅O₁₂, were obtained for all the Er³⁺-Yb³⁺-codoped Al₂O₃ powders at the sintering temperature of 1000 °C. The maximal intensity of both the green and red up-conversion emissions centered at about 523, 545, and 660 nm was observed for the 1 mol% Er³⁺- and 10 mol% Yb³⁺-codoped Al₂O₃ powders. The intensity ratio of the red to green up-conversion emission (I_red/I_green) increased with increasing the Yb³⁺ doping concentration for the Er³⁺-Yb³⁺-codoped Al₂O₃ powders. Furthermore, the intensity ratio of the green up-conversion emission at about 523 to 545 nm (I₅₂₃/I₅₄₅) was proportional to the Yb³⁺ doping concentration and pump electric current, which was associated with the elevated temperature of powders.     

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.     

Upconversion studies in rare earth ions-doped lanthanide materials

In the present work, results of upconversion emission in various powder samples have been discussed. The powder upconversion phosphors such as La₂O₃:Er³⁺/Yb³⁺, LaF₃:Er³⁺/Yb³⁺, CeO₂:Er³⁺/Yb³⁺, CeF₃:Er³⁺/Yb³⁺ were prepared and their upconversion emission, using 976 nm wavelength excitation, was investigated in depth. These phosphors have shown good upconversion emission in the visible region except for the CeF₃:Er³⁺/Yb³⁺ phosphor. Two intense bands around 525 and 550 nm due to the ² H _11/2 →⁴ I _15/2 and ⁴ S _3/2 →⁴ I _15/2 transitions, respectively, are found to be in a thermally coupled state in these samples. The intensity ratio of these two bands permitted us to estimate the temperature of the environment. The pump power studies of the emission bands of these samples are also made to understand the dynamics of the upconversion emission.     

Noninvasive Temperature Measurement in Dental Materials Using Nd3+, Yb3+ Doped Nanoparticles Emitting in the Near Infrared Region

In this work, the application of near infrared (NIR)-emitting NaYbF₄:1%Tm³⁺@NaLuF₄:30%Nd³⁺ core–shell nanoparticles is reported for noninvasive probing and monitoring the temperature during photopolymerization of dental materials. When excited at 808 nm, the synthesized nanoparticles emit NIR photoluminescence (PL) with two distinctive peaks at 865 and 980 nm which correspond to radiative transitions from the doped Nd³⁺ and Yb³⁺ ions, respectively. Luminescence intensity ratio between these two bands is found to vary with temperature due to temperature-dependent electronic excitation energy transfer between Nd³⁺ and Yb³⁺ ions at the core/shell interface. This finding allows luminescence ratiometric evaluation of the in situ temperature during photopolymerization of resin cement (doped with nanoparticles) in a veneer placement procedure. In addition, the NIR emission also enables PL imaging of the distribution of the adhesive under the veneer. The results highlight that rare-earth ions–doped nanoparticles with both excitation and emission in the NIR spectral range are advantageous for both PL-based nanothermometry and imaging due to the reduced attenuation of NIR light by dental ceramics.     

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⁺     

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.     

Ultraviolet and visible upconversion emission in Tb3+/Yb3+ co-doped fluorophosphate glasses

Ultraviolet and visible upconversion emissions in Tb³⁺/Yb³⁺ co-doped YF₃–BaF₂–Ba(PO₃)₂ glasses were observed under 980-nm laser diode excitation. The dependence of the emission intensities of Tb³⁺ on the pump power reveals that two-photon processes account for blue cooperative emission of Yb³⁺ at 476 nm and green upconversion emission of Tb³⁺ at 543 nm, and three-photon processes for ultraviolet emission of Tb³⁺ in the wavelength range of 379–435 nm. The effects of Tb³⁺ concentration on the emission intensity and the lifetime of Tb³⁺ and Yb³⁺ are investigated in detail. It is found that the cooperative energy transfer from a pair of excited Yb³⁺ ions to a ground Tb³⁺ ion is responsible for the appearance of blue and green upconversion emissions due to the ⁵D₄→⁷F _J (J=6,5,4,3) transitions of Tb³⁺, and the resonance energy transfer from Yb³⁺ to Tb³⁺ accounts for the population on the ⁵D₃,⁵G₆ level and ultraviolet upconversion emission.     

Visible and NIR luminescence of nanocrystalline β-Ga2O3:Er prepared by solution combustion synthesis

In this paper we report on facile solution combustion synthesis of erbium doped β-Ga₂O₃ with urea as fuel. The product was characterized using powder X-ray diffraction and transmission electron microscopy (TEM). X-ray diffraction and TEM showed that the material is nanostructured. Luminescence properties of β-Ga₂O₃:Er are studied with excitation in near infrared (Nd:YAG laser at 1064 nm) and visible (argon laser at 514.5 nm). A strong NIR emission of Er³⁺ in the window of minimal optical loss in silica based optical fibers, due to the ⁴I_13/2→⁴I_15/2 transition at 1.55 μm has been observed. Codoping with Yb³⁺ significantly increases the intensity of that important emission.