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.     

Enhancement of upconversion luminescence in Tm/Er/Yb-codoped glass ceramic containing LiYF4 nanocrystals

A transparent Er³⁺–Tm³⁺–Yb³⁺ tri-doped oxyfluoride glass ceramics containing LiYF₄ nanocrystals were prepared. Under 980 nm laser diode (LD) pumping, intensive red, green and blue upconversion (UC) was obtained. The blue, green, and red UC radiations correspond to the transitions ¹G₄→³H₆ of Tm³⁺, ²H_11/2/⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2 of Er³⁺ ions, respectively. This is similar to that in Tm³⁺–Yb³⁺ and/or Er³⁺–Yb³⁺ co-doped glass ceramics. However, the blue UC radiations of the Er³⁺–Yb³⁺ co-doped glass ceramics is two-photon process due to cooperative energy transfer. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

Frequency upconversion properties of Ag: TeO<Subscript>2</Subscript>–ZnO nanocomposites codoped with Yb<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Yb³⁺–Tm³⁺ codoped tellurite glasses containing silver nanoparticles (NPs) were synthesized and characterized using transmission electron microscopy and optical techniques. The samples’ composition and the nucleation of NPs were investigated using electron diffraction and energy dispersive spectroscopy. For the optical experiments, the samples were excited using a diode laser operating at 980 nm, in resonance with the Yb³⁺ transition ²F_7/2→²F_5/2. Photoluminescence (PL) bands corresponding to Tm³⁺ transitions were observed at 480, 650, and 800 nm due to the Yb³⁺→ Tm³⁺ energy transfer. PL enhancement was achieved by heat-treatment of the samples at 325°C during different time intervals. The growth of the PL bands correlates with the increase of the silver NPs concentration. The relevant mechanisms contributing for the PL characteristics are discussed.     

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.     

Upconversion luminescence and magnetic properties of ligand-free monodisperse lanthanide doped BaGdF5 nanocrystals

Lanthanide (Ln=Yb³⁺, Er³⁺and Tm³⁺) doped monodisperse oleate-capped BaGdF₅ nanocrystals with a mean diameter of approximately 18 nm were prepared via liquid-solid-solution method. The cell parameter of the as-prepared cubic BaGdF₅ nanocrystals is 5.884 Å, which is different from the reported 6.023 Å (JCPDS 24-0098). When excited by a 980 nm laser, these Ln³⁺ doped nanocrystals exhibit multi-color up-conversion (UC) emissions including blue, yellow and white, by precisely adjusting the dopant concentration of Yb³⁺, Er³⁺ and Tm³⁺. The oleate ligands capped on the surface of the as-synthesized products, which can be conversed from hydrophobic to hydrophilic along with certain extent of weakening of UC intensity, can be moved by the acid treatment process. The measured field dependence of magnetization (M-H curves) of the BaGdF₅ nanocrystals shows excellent paramagnetism. At room temperature, the magnetization of BaGd_0.798Yb_0.2Tm_0.002F₅ nanocrystals is 0.9165 emu/g and the magnetic mass susceptibility reaches 6.11×10⁻⁵ emu g⁻¹ Oe⁻¹ at 15 kOe. Our results indicate that these bi-functional hydrophilic Ln³⁺ doped BaGdF₅ nanocrystals have potential applications in color displays, bioseparation and optical-magnetic dual modal nanoprobes in biomedical imaging.     

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.     

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⁺.     

Excitation power controlled luminescence switching in Yb-Tm co-doped hexagonal NaYF4 nanorods

Intense infrared-to-visible up-conversion (UC) emissions were obtained in hexagonal Yb³⁺-Tm³⁺ co-doped NaYF₄ nanorods under excitation at 980 nm. Especially, luminescent switching between different UC emission wavelengths at 800, 480 and 450 nm were observed by adjusting excitation powers. Based on power-dependent spectral analyses, it was found that the cooperative energy transfer between Yb³⁺-Yb³⁺ pairs and Tm³⁺ ions play a key role on the luminescent switching besides the saturation effect of Yb³⁺²F_5/2 and Tm³⁺¹G₄ excited states. Our results indicate that hexagonal NaYF₄ nanostructures have potential applications in miniaturized solid-state laser, optical processing sensors and fluorescent biolabels.     

FLUORESCENCE MECHANISMS OF Tm3+- AND Yb3+/Tm3+ DOPED AlF3-BASED FLUORIDE GLASS

A complete set of spectroscopic parameters, including Judd-Ofelt parameters, radiative transition probabilities, radiative lifetime, branching ratios and integrated absorption cross section, have been calculated for Tm³⁺- doped fluoroaluminate (AYF) glass, based on the measured absorption spectra. The mechanism of Tm³⁺→Tm³⁺ and Yb³⁺\Leftrightarrow Tm³⁺ energy transfers and fluorescence properties have been investigated in both Tm³⁺ single-doped and Yb³⁺/Tm³⁺ double-doped AYF glasses. The cross-relaxation process, ³F₄+³H₆→2³H₄, is proved, which makes the optimum Tm³⁺ concentration of 1.77μm fluorescence (³H₄→³H₆) much higher than 1.45μm fluorescence (³F₄→³3H₄) in Tm³⁺:AYF glasses. In Yb³⁺/Tm³⁺:AYF glasses, a stronger concentration quenching is found for the 476nm emission than that for the 797nm emission, and is discussed under the 970nm-excitation.     

Cr3+/Tm3+/Ho3+共掺氟磷酸盐玻璃的制备及性能表征

制备了不同 Al(PO₃)₃含量的掺铥系列氟磷酸盐玻璃,研究了其结构、热稳定性和光谱性质. 研究了不同摩尔百分数 Al(PO₃)₃掺杂下 Cr³⁺/Tm³⁺/Ho³⁺共掺氟磷酸盐玻璃在 2.0μm 处的发光特性. 并且用Judd-Ofelt理论计算了强度参量,并由此计算了激发能级的自发辐射跃迁速率、辐射寿命、荧光分支比等光谱参量. 结果表明,随着 Tm³⁺浓度增加,2.0μm 处发光的强度逐渐增强. 证明了Tm³⁺(³F₄) →Ho³⁺(⁵I₇)能量转移是非常有效的,并与掺杂浓度有关. 关键词： 氟磷酸盐玻璃 能量传递 荧光光谱 吸收光谱     

Er3+，Tm3+共掺的NaY(WO4)2晶体的光谱分析和上转换发光

在室温下，测量了Er:Tm:NaY(WO₄)₂晶体的吸收光谱、激发光谱、发射光谱以及上转换发光，并运用J-O理论对测量的结果进行了计算，得出了Er:Tm:NaY(WO₄)₂晶体的强度参数.报道了Tm，Er离子间特殊的能量传递和相关上转换，解释了离子间的能级跃迁过程.同时，对于Er增强Tm离子近红外发光的特性也作了充分研究. 关键词： 4)₂晶体')" href="#">Er:Tm:NaY(WO₄)₂晶体 吸收光谱 发射光谱 激发光谱 上转换     

Tm3+/Yb3+共掺氧卤碲酸盐玻璃上转换发光研究

研究了Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光光谱，分析了Tm₂O₃含量对Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃上转换发光的影响机理.结果表明：在Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光中，Tm³⁺存在较强的浓度猝灭效应.随Tm₂O₃含量增加，Tm³⁺的上转换蓝光和红光强度先增加，后降低，在0.1mol% Tm₂O₃达到最大.该结果有助于进一步提高Tm³⁺的上转换发光效率.     

Energy transfer between doubly doped Er, Tmand Ho rare earth ions in SiO2 nanoparticles

Preparation of Er³⁺, Ho³⁺ and Tm³⁺ ions co-doped SiO₂ nanoparticle phosphor powders by sol gel method is reported. The morphology and the particle size of the SiO₂ host matrix were confirmed by field emission scanning electron microscopy (FESEM). Ultraviolet, visible (UV/VIS) and cathodoluminescence measurements were carried out in order to investigate the optical properties of our powder phosphors. Green emissions at 520 nm from Er³⁺ and 544 nm from Ho³⁺, and red emissions at 665 nm from both Er³⁺ and Ho³⁺ ions are reported. Another emission peak in the near infra-red (NIR) region at 875 nm from Er³⁺ was also measured. Blue emission at 460 nm, red at 705 nm and a NIR peak in the region of 865 nm from Tm³⁺ were observed. Red, green and blue (RGB) colours were measured from both SiO₂:Er³⁺,Tm³⁺ and SiO₂:Ho³⁺,Tm³⁺ systems. The change in the intensities of the emission peaks in both the SiO₂:Ho³⁺,Tm³⁺ and SiO₂:Er³⁺,Tm³⁺ systems with the change in accelerating beam voltage is shown. Energy transfer from Tm³⁺ ions to Er³⁺ and Ho³⁺ ions was observed. A mechanism explaining the increase and decrease behaviour of the emission with accelerating beam voltage from both systems is reported.     

Tm3+/Ho3+共掺镓铋酸盐玻璃1.47μm发光特性和能量传递的研究

报道了Tm³⁺/Ho³⁺共掺的镓铋酸盐玻璃14Ga₂O₃-25Bi₂O₃-20GeO₂-31PbO-10PbF₂玻璃1.47μm(S波段)发光和能量传递特征，应用Judd-Ofelt理论计算了玻璃的强度参数Ω_t(t=2，4，6)，自发辐射概率A、荧光分支比β，荧光辐射寿命τ等各项光谱参数以及有效荧光线宽Δλ_eff和峰值发射截面σ^peak_e.通过测量荧光光谱和荧光寿命研究了Ho³⁺离子掺杂浓度对Tm³⁺离子1.47μm波段发光性能的影响，分析了Tm³⁺和Ho³⁺之间的能量传递过程.结果表明一定浓度内Ho³⁺的共掺迅速降低了Tm³⁺：³F₄能级的粒子数，而对³H₄能级粒子数影响不大，从而降低了³F₄和³H₄能级间布居数反转的难度，极大地提高了1.47μm发光效率.研究表明镓铋酸盐玻璃是适用于S波段光纤放大器的一种潜在基质材料，而掺杂一定浓度的Ho³⁺离子有利于提高Tm³⁺离子在1.47μm波段的发光效率. 关键词： 重金属氧化物玻璃 光谱性质 3+/Ho³⁺离子')" href="#">Tm³⁺/Ho³⁺离子 能量传递     

Blue upconversion emission from Tm<Superscript>3+</Superscript> sensitized by Nd<Superscript>3+</Superscript> in aluminum oxide crystalline ceramic powders

Upconversion (UC) emission in thulium (Tm³⁺) and neodymium (Nd³⁺) co-doped aluminum oxide ceramic powders prepared by combustion synthesis was investigated at room temperature using a continuous wave laser operating at 800 nm. Our sample containing Tm³⁺ (1 wt.%) did not show any UC emission but our sample co-doped with Tm³⁺ and Nd³⁺ in 1:2 wt.% proportion presented blue (∼480 nm) UC intensity more than one order of magnitude larger than our sample co-doped with Tm³⁺ and Nd³⁺ in 1:1 wt.% proportion. X-ray diffraction data showed the presence of α-Al₂O₃ and REAlO₃ (RE=Tm or Nd) crystalline phases in co-doped powders, while the singly doped powder has only α-Al₂O₃ phase. Our results show that the UC emission efficiency of Tm³⁺ and the host crystalline structure can be tailored by manipulating the Nd³⁺ doping concentration.     

Spectroscopic properties of Tm3+ in fluorophosphate glasses

The optical properties of Tm³⁺ in a fluorophosphate glass are reported. Oscillator strengths and Ω_λ parameters for Tm³⁺ were calculated. Energy transfer between Ce³⁺ → Tm³⁺, Tm³⁺ → Eu³⁺ and Tm³⁺ → Tb³⁺ were measured at room temperature and interpreted using the Yokota and Tanimoto scheme. Fluorescence decay results seem to support the hypothesis of a diffusion-limited relaxation. The effects of Tb³⁺ and especially Ce³⁺ on the fluorescence of Tm³⁺ ion point out the interest of these dopants for obtaining a better emission of Tm³⁺ at 450 nm.     

Preparation of highly crystalline blue emitting MVO4:Tm (M=Gd, Y) spherical nanoparticles: Effects of activator concentration and annealing temperature on luminescence, lifetime and quantum yield

Highly crystalline spherical nanoparticles of MVO₄:Tm³⁺ (M=Gd, Y) having a size of 20–45 nm were prepared using ethylene glycol as both capping agent and reaction medium. X-ray diffraction study shows linear decrease in the unit cell volume with an increase in Tm³⁺ concentrations in MVO₄ (M=Gd, Y; Tm³⁺=0, 2, 5, 7, 10, 15, 20, 40, 60, 80 and 100 at%), indicative of quantitative substitution of Gd³⁺/Y³⁺ lattice sites by Tm³⁺ ions in MVO₄. Blue light emission at 475 nm is observed after excitation at 310 nm due to energy transfer from VO₄³⁻ absorption band to Tm³⁺. Emission intensity and average decay lifetime increase with an increase in heat treatment from 500 to 900 °C. This has been attributed to an extent of reduction in non-radiative process arising from surface. The emission intensity of Tm³⁺ in GdVO₄ host is higher than that in YVO₄ and thus the former host is better. Quantum yield increases with increase in heat-treatment temperature. This material will be the alternative blue light emitter.     

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.     

Luminescence properties of Tm co-doped Sr2Si5N8:Eu red phosphor

The Sr₂Si₅N₈:Eu²⁺ phosphors, both undoped and doped with Tm³⁺, were synthesized by high temperature solid-state method. The XRD pattern shows that only Sr₂Si₅N₈ phase is formed whatever Tm³⁺ was doped or not. The peak positions of both phosphors are centered at 612 nm which is assigned to the 4f⁶5d→4f⁷ transition of Eu²⁺. It implies that the crystal field, which affects the 5d electron states of Eu²⁺, is not changed dramatically after the phosphor is doped with Tm³⁺. The afterglow time is about 10 min after Tm³⁺ ion is introduced into the phosphor. The concentration of Tm³⁺ has little influence on the afterglow time of the phosphor. The depths of trap energy level of the two phosphors were calculated based on the TL spectra. The depths of Sr₂Si₅N₈:Eu²⁺ and Sr₂Si₅N₈:Eu²⁺, Tm³⁺ are 1.75 and 1.01 eV, respectively.     

Study on up-conversion emissions of Yb/Tm co-doped GdF3 and NaGdF4

The Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were synthesized through a combination method of a co-precipitation and an argon atmosphere annealing procedures. X-ray diffraction analysis indicated that the Yb³⁺/Tm³⁺ co-doped GdF₃ sample crystallized well and was orthorhombic phase, and the Yb³⁺/Tm³⁺ co-doped NaGdF₄ sample was hexagonal phase. With a 980-nm semiconductor continuous wave laser diode as the excitation source, the up-conversion emission spectra of the two samples in the wavelength range of 240-510 nm were recorded. In the up-conversion emissions of the samples, Yb³⁺ transferred energies to Tm³⁺ resulting in their ultraviolet, violet, and blue up-conversion emissions. And, Tm³⁺ simultaneously transferred energies to Gd³⁺, which finally resulted in ultraviolet up-conversion emissions of Gd³⁺. The study on the excitation power dependence of up-conversion fluorescence intensity indicated that there were multi-photon (three-, four-, five-, and six-) processes in the up-conversion emissions of the samples. And the up-conversion emissions of Gd³⁺ and Tm³⁺ in the Yb³⁺/Tm³⁺ co-doped GdF₃ and NaGdF₄ samples were compared studied, too.