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.     

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.     

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 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.     

Up-conversion emission in triply-doped Ho/Yb/Tm KGd(WO4)2 single crystals

Detailed spectroscopic studies of the triply doped KGd(WO₄)₂:Ho³⁺/Yb³⁺/Tm³⁺ single crystals (which exhibit multicolor up-conversion fluorescence) are reported for the first time. The absorption spectra of crystals were measured at 10 and 300 K; the room temperature luminescence spectra were excited at 980 nm wavelength. The dependence of the intensity of luminescence on the excitation power for three different concentration of Ho³⁺, Yb³⁺ and Tm³⁺ ions was investigated. Efficient green and red up-converted luminescence of Ho³⁺ ions and weak blue up-conversion luminescence of Tm³⁺ ions were observed in spectra. The red emission of Ho³⁺ ions is more intensive than their green emission. Dependence of the up-conversion luminescence intensity on the excitation power and impurities concentration was also studied; the number of phonon needed for efficient up-conversion was determined for each case. All possible energy transfer processes between different pairs of the impurity ions' energy levels are also discussed.     

Tm3+/Yb3+共掺氟氧硅铝酸盐玻璃陶瓷蓝色上转换发光研究

按摩尔百分比制备了组分为30SiO₂-(20-x-y)Al₂O₃-40PbF₂-10CdF₂-xTm₂O₃-yYb₂O₃的两组Tm³⁺/Yb³⁺共掺杂氟氧硅铝酸盐上转换蓝色发光玻璃陶瓷材料,测量了其在980nm激 关键词： 玻璃陶瓷 上转换发光 3+/Yb³⁺掺杂')" href="#">Tm³⁺/Yb³⁺掺杂 掺杂浓度     

Blue upconversion luminescence of CaMoO4:Li+/Yb3+/Tm3+ phosphors prepared by complex citrate method

Li⁺/Tm³⁺/Yb³⁺ co-doped CaMoO₄ upconversion (UC) phosphor was prepared by complex citrate-gel method and UC luminescence properties were investigated. Li⁺/Tm³⁺/Yb³⁺ co-doped CaMoO₄ has intense blue emission induced by ¹G₄??³H₆ transition at 476?nm that is improved 10 times more than that of Li⁺ undoped sample and weak red emission at 647 nm generated by ³F₂??³H₆ transition under excitation at 980?nm. The optimum doping concentration of Li⁺ ions was investigated and UC mechanism of Li⁺/Tm³⁺/Yb³⁺ co-doped CaMoO₄ was discussed in detail.     

High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

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⁺     

Enhancing up conversion luminescence effect of β-NaYF<Subscript>4</Subscript>: Yb<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> by Li<Superscript>+</Superscript> ion doped approach

Up-conversion (UC) is a photoluminescence process which converts few low energy photons to a higher energy photon. This process has more potential usages in many different fields like bioimaging, solar spectrum tuning, and security encoding. Nowadays, researches about UC mostly focusing on biomedical signory and synthesis of nanoparticles. The synthesis of NaYF₄ nanoparticles executed under series of pH value condition results in different morphology and photoluminescence effect. Samples in low pH value created better consequent and quality than the specimen which had higher pH value. In addition, we observed NaYF₄ samples of doping Li⁺, realizing that the action of distorting in the local symmetry around rare-earth ions is caused by Li⁺ doping. The NaYF₄ microparticles which doped higher concentration of Li⁺ has strong fluorescence properties and intensities compared with their corresponding group of Li⁺-free, the blue emission 479 nm luminescence intensities and 454 nm luminescence intensities in NaYF₄:Yb³⁺, Tm³⁺ microparticles doped 20 mol% Li⁺ are enhanced 3 and 8 times, separately. And violet emission luminescence intensities around 345 and 360 nm are about 10 and 7 times, respectively. The result indicated that the improved UC luminescence of NaYF₄:Yb³⁺. Tm³⁺ microparticles with Li⁺ doping have potentially applications.     

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.     

Intense visible luminescence from Nd-doped yttrium oxysulfide

We report on a novel luminescent phenomenon in Y₂O₂S doped with Nd³⁺. After irradiation by a 261 nm ultraviolet (UV) light into the Y₂O₂S host lattice, the Nd³⁺-doped Y₂O₂S phosphor emits intense blue luminescence in the visible light region. Moreover, this blue luminescence can also be obtained by exciting directly into the Nd³⁺ energy absorption itself. XRD, photoluminescence, and fluorescence decay curve are used to characterize the synthesized phosphor. The spectroscopic data indicate that all the visible emission peaks are originated from the electrical transitions of Nd³⁺, and the strong luminescence of the Nd³⁺ is considered to be due to an efficient energy transfer from the Y₂O₂S host lattice to the Nd³⁺ in Y₂O₂S:Nd³⁺. The optimum concentration for the luminescence Nd³⁺ is determined to be 1 mol% of Y³⁺ in Y₂O₂S host. The critical energy transfer distance has been calculated by the concentration quenching and the possible luminescent process of this blue luminescence-emitting phosphor is also investigated.     

Efficient blue upconversion emission due to confined radiative energy transfer in Tm-Nd co-doped Ta2O5 waveguides under infrared-laser excitation

Intense blue upconversion emission at 480 nm has been obtained at room temperature in Tm³⁺-Nd³⁺ co-doped Ta₂O₅ channel waveguides fabricated on a Si substrate, when the sample is excited with an infrared laser at 793 nm. The upconversion mechanism is based on the radiative relaxation of the Nd³⁺ ions (⁴F_3/2 → ⁴I_11/2) at about 1064 nm followed by the absorption of the emitted photons by Tm³⁺ ions in the ³H₄ excited state. A coefficient of energy transfer rate as high as 3 × 10⁻¹⁶ cm³/s has been deduced using a rate equation analysis, which is the highest reported for Tm-Nd co-doped systems. The confinement of the 1064 nm emitted radiation in the waveguide structure is the main reason of the high energy transfer probability between Nd³⁺ and Tm³⁺ ions.     

Enhanced Up-Conversion Emission in Al<Superscript>3+</Superscript> Co-Doped ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript>,Tm<Superscript>3+</Superscript> Powder Phosphors

Yb³⁺-Tm³⁺ co-doped up-conversion powder phosphors using Zn(Al_xGa_1-x)₂O₄ (ZAGO) as the host materials were synthesized via solid-state reaction successfully. In addition, the morphology, structural characterization and up-conversion luminescent properties were all investigated by scanning electron microscope (SEM), x-ray diffraction (XRD) and fluorescence spectrophotometer (F-7000), respectively. Under the excitation of a 980 nm laser, all as-prepared powders can carry out blue emission at about 477 nm (corresponding to ¹G₄ → ³H₆ transition of Tm³⁺ ions), and red emission at about 691 nm (attributed to ³F₃ → ³H₆ transition of Tm³⁺ ions). Also, the influence of doping Al³⁺ ions were investigated. In brief, the doping of Al³⁺ ions has no effect on the position of emission peak. Howbeit the up-conversion efficiency and intensity of ZAGO:Yb,Tm phosphors are stronger than ZGO:Yb,Tm and ZAO:Yb,Tm phosphors, while the crystallinity is the opposite. More particularly, all as-prepared powder phosphors emit strong luminescence, which is observable by the naked eye, demonstrating the potential applications in luminous paint, luminescent dye, etc.     

Enhancement of blue emission in β-NaYbF4:Tm3+/Nd3+ nanophosphors synthesized by nonclosed hydrothermal synthesis method

An improved nonclosed hydrothermal synthetic processing is used to synthesize Tm³⁺ and Nd³⁺ doped β-NaYbF₄ nanophosphors at 85°C in the air without any high-temperature and high-pressure treatments as a final step. The particles have average crystallite size around 40 nm as obtained by TEM and calculation in terms of the XRD data. Intense 475 nm blue upconversion emission originated from the ¹G₄→³H₆ transition of Tm³⁺ is observed under 808 nm excitation, and its intensity can be enhanced onefold by introducing Nd³⁺ ion. The dominant populating mechanisms for the β-NaYbF₄:Tm³⁺ and β-NaYbF₄:Tm³⁺/Nd³⁺ are thought as Tm³⁺→Yb³⁺→Tm³⁺ and Nd³⁺→Yb³⁺→Tm³⁺ energy transfer processes, respectively. The concentration quenching processes for blue and red emissions are discussed.     

VUV-UV-visible luminescence of Nd3+, Er3+ and Tm3+ in LiLuF4 single crystal host

An overlook of absorption and luminescence characteristics of Nd³⁺, Er³⁺ and Tm³⁺ centers in LiLuF₄ single crystal is provided. Single crystal doped with the mentioned RE ions were prepared by micro-pulling-down technique in the form of few cm long rods with the diameter of about 2 mm. Excitation and emission spectra and fast decay kinetics in VUV spectral region were measured at SUPERLUMI station at synchrotron DESY, Hamburg and characterization was further completed in UV-visible region at conventional spectrophotometers. Observed absorption and emission peaks are ascribed to the 5d–4f and 4f–4f optical transitions in the doped rare earth ions. Concentration dependence of the decay kinetics is discussed.     

Manifestation of up-conversion in Yb3+/Tm3+ doped Li2O–Y2O3–SiO2 glass system

In this study, we have investigated the principal role of Y₂O₃ on the emission features of Tm³⁺ ion and up-conversion phenomenon in Tm³⁺ and Yb³⁺ co-doped Li₂O–Y₂O₃–SiO₂ glass system. The concentration of Y₂O₃ is varied from 0 to 5 mol% while that of Yb³⁺ and Tm³⁺ is fixed. When the glasses are doped with Tm³⁺ ions, the intense blue and red emissions were observed, whereas Yb³⁺ doped glasses exhibited NIR emission at about 980 nm. When the glasses are co-doped with Tm³⁺ and Yb³⁺ ions and excited at 900 nm, the blue and red emission lines were observed to be reinforced and strengthened with increase in the concentration of Y₂O₃. The IR emission band detected at about 1.8 μm due to ³F₄ → ³H₆ transition of Tm³⁺ ions is also observed to be strengthened due to co-doping. The reasons for enhancement in the intensity of various emission bands due to co-doping have been identified and discussed with the help of rate equations for various emission transitions.     

Fabrication, photoluminescence, and potential application in white light emitting diode of Dy3+–Tm3+ doped transparent glass ceramics containing GdSr2F7 nanocrystals

Dy³⁺–Tm³⁺ doped transparent glass ceramics containing GdSr₂F₇ nanocrystals were fabricated successfully by a melt-quenching method and subsequent heating. X-ray diffraction and transmission electron microscopy analyses show that tetragonal GdSr₂F₇ nanocrystals are homogeneously precipitated among the borosilicate glass matrix. If excited with 354 nm UV light, the photoluminescence spectrum of Dy³⁺ single-doped transparent glass ceramics shows white-light emission. With doping of Tm³⁺, the overall emission color of Tm³⁺–Dy³⁺ co-doped transparent glass ceramics can be tuned from white to blue through energy transfer between Dy³⁺ and Tm³⁺. CIE chromaticity and color temperature measurements show that the resulting TGCS may be a candidate as a white LED material pumped by a UV InGaN chip.     

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.     

Photoluminescence and energy transfer of Tm doped LiIn (WO4)2 blue phosphors

Room temperature steady and time resolved emission spectra of LiIn_1−xTm_x(WO4)2 (where thulium concentration is 0, 0.5, 1, 5 and 10 at%) blue phosphors, under UV excitation energy have been investigated. The concentration quenching effect on the blue emission, due to the (WO₄)⁻² groups and ¹G₄→³H₆ emission transition of Tm³⁺ were studied. Two energy transfer mechanisms are shown. The first takes place between excited (WO₄)⁻² groups and the ¹G₄ energy level of Tm³⁺, and is mainly analyzed by phonon-assisted energy transfer. The second mechanism is due to an energy transfer from the excited Tm³⁺ ions to the surrounding ground state Tm³⁺ ions. The non-exponential decay curves of the ¹G₄ level observed for higher concentrations are analyzed by the Inokuti–Hirayama model. We think that the quenching effect between Tm³⁺ ions is mainly linked to the dipole–dipole interactions.