Photoluminescence properties and pump-saturation effect of Er3+/Yb3+ co-doped Y2Ti2O7 nanocrystals

The Er³⁺/Yb³⁺ co-doped Y₂Ti₂O₇ phosphors were synthesized by the sol–gel method. XRD, TEM, and photoluminescence spectra of samples were measured and studied. The results demonstrate that the Y₂Ti₂O₇ would transform from the amorphous to nanocrystalline at about 750 °C. The mechanism of both upconversion and near infrared (NIR) photoluminescence and their changes with annealing temperature were analyzed. What is more, the pump-saturation effect of NIR emission and the anomalous slopes of the fitted straight line in the double-logarithmic plots for upconversion emissions were found in the nanocrystalline samples, which can be ascribed to domination of upconversion over linear decay for the ⁴I_11/2 and ⁴I_13/2 state and the saturation of ⁴I_13/2 state in Er³⁺ ions largely owing to the energy back-transfer process. They are induced by high pump power and Yb³⁺ ions concentration.     

Infrared-to-visible upconversion emission of Er3+/Yb3+-codoped SrMoO4 phosphors as wide-range temperature sensor

Er³⁺/Yb³⁺-codoped SrMoO₄ phosphors were prepared by a high-temperature solid-state reaction method. At room temperature, all the as-prepared samples exhibited strong upconversion properties and the emission intensity increased dramatically with the increase of Yb³⁺ ion concentration, reaching its maximum value when the concentration was 5 mol%. The dependence of emission intensity on the pump power suggested that the upconversion emission was a two-photon process. Furthermore, the optical temperature sensing properties based on green upconversion emissions of the SrMoO₄:0.01Er³⁺/0.05Yb³⁺ phosphor were studied. It is found that the SrMoO₄:0.01Er³⁺/0.05Yb³⁺ phosphor can be operated over a very wide temperature range of 93–773 K with a maximum sensitivity of ∼0.0128 K⁻¹, indicating that low- and high-temperature thermometry can be simultaneously realized in this phosphor.     

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.     

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.     

NIR to visible frequency upconversion in Er3+ and Yb3+ codoped ZrO2 phosphor

The ZrO₂:Er³⁺ codoped with Yb³⁺ phosphor powders have been prepared by the urea combustion route. Formation of the compounds ZrO₂:Er³⁺ and ZrO₂:Er³⁺, Yb³⁺ was confirmed by XRD. The frequency upconversion emissions in the green and red regions upon excitation with a CW diode laser at ～978 nm are reported. Codoping with Yb³⁺ enhances the emission intensities of the triply ionized erbium in the green and red spectral regions by about ～130 and ～820 times respectively. The emission properties of the ZrO₂:Er³⁺ phosphor powders are discussed on the basis of excited state absorption, energy transfer, and cross-relaxation energy transfer mechanisms.     

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.     

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.     

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.     

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.     

Yb3+敏化的Er3+/Ho3+共掺碲酸盐玻璃的上转换发光研究

用高温熔融法制备了系列Er³⁺/Yb³⁺共掺，Ho³⁺/Yb³⁺共掺，和Er³⁺/Yb³⁺/Ho³⁺三掺碲酸盐玻璃，在975nm激光抽运下三种掺杂玻璃中都出现了较强的绿光和红光上转换.研究了Yb³⁺离子对Er³⁺和Ho³⁺离子上转换发光强度的影响以及Yb³⁺→Er关键词： 3+/Yb³⁺/Ho³⁺共掺')" href="#">Er³⁺/Yb³⁺/Ho³⁺共掺 碲酸盐玻璃 光谱性质 上转换     

Upconversion properties of Er^3＋/Yb^3＋ co-doped TeO2-Nb2O5-Li2O glasses

The Er^3＋/Yb^3＋ co-doped TeO2-Nb2O5-Li2O glass is prepared by conventional melting method, and its upconversion spectra are measured. The intense green upconversion luminescence upon excitation with a 976 nm laser diode is observed with the naked eyes. The dependence of luminescence intensity on the ratio of Yb^3＋/Er^3＋ is discussed in detail, and the relationship between the ratio of green luminescence intensity to red luminescence intensity and the ratio of Yb^3＋/Er^3＋ is also studied, The luminescence intensity increases with the ratio of Yb^3＋/Er^3＋ increasing. The ratio of Yb^3＋/Er^3＋ plays a more important role than the concentration of Er^3＋ in determining the upconversion luminescence intensity. The ratio of green luminescence intensity to red luminescence intensity reaches a maximum when ratio of Yb^3＋/Er^3＋ is 3. Thus the glass could be one of the potential candidates for LD pumping solid-state lasers.     

Ce3+对Er3+/Yb3+共掺氟磷酸盐玻璃光谱性质的影响

研究了能量接受离子Ce³⁺对Er³⁺上转换发光强度以及Er³⁺在1.5μm附近波段发光性能参数的影响，并从能量匹配及能级结构角度出发对Er³⁺/Ce³⁺间的能量转移机制进行了分析.分析认为，⁴I_11/2能级的Er³⁺通过无辐射能量转移把能量传递给²F_5/2能级的Ce³⁺关键词： 氟磷酸盐玻璃 光谱性质 光纤放大器 3+和Ce³⁺')" href="#">Er³⁺和Ce³⁺     

Analysis of Upconversion Fluorescence Dynamics in NaYF4 Codoped with Er3+ and Yb3+

The efficiency of upconversion fluorescence for Er³⁺ and Yb³⁺ codoped into NaYF₄ powder crystals is investigated. The dependence of Er³⁺ green (540 nm) and red (660 nm) upconversion fluorescence intensities on laser excitation intensity and the ratio of the green and red fluorescence intensities respectively under 355‐nm and 936‐nm excitations have been measured and analyzed in terms of radiative and nonradiative relaxation mechanisms. It is shown that the intensity of both the green and red upconversion fluorescence bands is affected at high pumping intensities by a low‐lying state acting as a bottleneck, with the red fluorescence less affected than the green. In addition to two‐photon, two‐step excitation and energy transfer processes, nonlinear optical coupling mechanisms of avalanche processes appear responsible for reducing the bottleneck saturation of the red upconversion fluorescence.     

Ce3+对Er3+/Yb3+共掺TeO2-WO3-ZnO玻璃发光性能的影响

在Er³⁺/Yb³⁺共掺TeO₂-WO₃-ZnO玻璃中引入Ce³⁺，研究了Ce³⁺对Er³⁺1.5μm发射性能及其上转换发光性能的影响。结果表明，随Ce³⁺浓度的增加Er³⁺1.5μm波段的荧光强度先增强后降低，优化的Ce³⁺掺杂浓度在2.07×10²⁰/cm³左右；1.5μm波段的荧光寿命则随Ce³⁺浓度的增加有轻微降低，从3.4ms降到3.0ms，但Ce³⁺浓度的增加对1.5μm波段的荧光半高宽基本无影响；Er³⁺/Ce³⁺间的交叉弛豫Er³⁺(⁴I_11/2)+Ce³⁺(²F_5/2)→Er³⁺(⁴I_13/2)+Ce³⁺(²F_7/2)使玻璃的上转换发光强度大大降低，但在过高的Ce³⁺浓度下，Er³⁺/Ce³⁺间的另一交叉弛豫Er³⁺(⁴I_13/2)+Ce³⁺(²F_5/2)→Er³⁺(⁴I_15/2)+Ce³⁺(²F_7/2)则使Er³⁺⁴I_13/2能级粒子数减少，导致1.5μm波段荧光强度和荧光寿命降低. 关键词： 碲钨酸盐玻璃 发光性能 3+离子')" href="#">Er³⁺离子 3+离子')" href="#">Ce³⁺离子 交叉弛豫     

Vaaisible upconversion emission of Er3+-doped and Er3+/Yb3+-codoped LiInO2

Lithium-indium oxide is a high-density (5.9 g·cm⁻³), wide band-gap semiconductor with promising applications for scintillating detection of solar neutrinos as well as for efficient phosphorescence when doped with Er³⁺ or Sm³⁺ ions. In this report, we demonstrate visible upconversion emission of Er³⁺-doped LiInO₂ synthesized by a simple solid-state chemistry procedure and discuss mechanisms responsible for pumping the Er³⁺ ions to upper levels. Intense upconversion emission is observed in the green and red spectral regions under near-infrared excitation, and it is greatly enhanced by co-doping with Yb³⁺ ions. We also examined the upconversion intensity change as a function of temperature, and, consequently, possible applications of this material as a low-temperature sensor.     

Visible upconversion emission and non-radiative direct Yb to Er energy transfer processes in nanocrystalline ZrO2:Yb,Er

Wide band gap Yb³⁺ and Er³⁺ codoped ZrO₂ nanocrystals have been synthesized by a modified sol-gel method. Under 967 nm excitation strong green and red upconversion emission is observed for several Er³⁺ to Yb³⁺ ions concentration ratios. A simple microscopic rate equation model is used to study the effects of non-radiative direct Yb³⁺ to Er³⁺ energy transfer processes on the visible and near infrared fluorescence decay trends of both Er³⁺ and Yb³⁺ ions. The microscopic rate equation model takes into account the crystalline phase as well as the size of nanocrystals. Nanocrystals phase and size were estimated from XRD patterns. The rate equation model succeeds to fit simultaneously all visible and near infrared fluorescence decay profiles. The dipole-dipole interaction parameters that drive the non-radiative energy transfer processes depend on doping concentration due to crystallite phase changes. In addition the non-radiative relaxation rate (⁴I_11/2→⁴I_13/2) is found to be greater than that estimated by the Judd-Ofelt parameters due to the action of surface impurities. Results suggest that non-radiative direct Yb³⁺ to Er³⁺ energy transfer processes in ZrO₂:Yb,Er are extremely efficient.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO₂-ZnO-Na₂O的Tm³⁺离子单掺和Tm³⁺/Yb³⁺共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ω_t(t=2, 4, 6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τ_rad等光谱参量,测量得到了不同Yb³⁺离子掺杂浓度下玻璃样品的Tm³⁺离子上转换发光谱.结果显示,在980 nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm³⁺离子上转换发光分析表明,强烈的Tm³⁺离子近红外上转换发光主要来自于Yb³⁺/Yb³⁺离子间的共振能量传递以及基于单声子和双声子辅助的Yb³⁺/Tm³⁺离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm³⁺:³F₄→³H₆能级间跃迁的1.8 μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb³⁺/Tm³⁺共掺TeO₂-ZnO-Na₂O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

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.     

Thermal effect on multiphonon-assisted anti-Stokes excited upconversion fluorescence emission in Yb3+-sensitized Er3+-doped optical fiber

The temperature effect upon infrared-to-visible frequency upconversion fluorescence emission in Yb³⁺-sensitized Er³⁺-doped germanosilicate optical fibers excited with cw radiation at 1.064 μm is investigated. The experimental results revealed an eightfold enhancement in the visible upconversion emission intensity as the fiber temperature was increased from 17 °C to 180 °C. The fluorescence emission enhancement is attributed to the temperature-dependent multiphonon-assisted anti-Stokes excitation process of the ytterbium sensitizer. A theoretical approach that takes into account a sensitizer absorption cross-section, which depends on the phonon occupation number, has proven to agree very well with the experimental data Received: 6 April 1999 / Revised version: 27 August 1999 / Published online: 27 January 2000     

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.