Controlled synthesis of β-NaYF4:Yb3+/Er3+ microstructures with morphology- and size-dependent upconversion luminescence

Hexagonal NaYF₄ microcrystals with controllable morphologies and tunable sizes have been successfully synthesized by a facile hydrothermal method. The influences of the molar ratios of trisodium citrate (Cit³⁻) to Y³⁺ and pH values on the phase and morphology evolution were investigated and discussed in detail. It is found that trisodium citrate and pH value as two significant external factors play key roles in the formation of the anisotropic architectures of β-NaYF₄ microcrystals. Taking hexagonal β-NaYF₄ microprisms as a candidate, the possible formation mechanism has been proposed on the basis of time-dependent experiments. In addition, the upconversion (UC) luminescence properties of β-NaYF₄:Yb³⁺/Er³⁺ samples were systematically studied and discussed. The results reveal that the UC luminescence properties are strongly dependent on their morphologies and sizes. This study not only provides important information for shape-controlled synthesis of other complex rare earth fluoride compounds, but also gives a reference for exploration of morphology- and size-dependent UC luminescence properties.     

Infrared luminescence in Er3+:Yb3Al5O12 bulk ceramics prepared by sol–gel method

Erbium doped and pure ytterbium aluminium garnet (YbAG, Yb₃Al₅O₁₂) bulk ceramics were successfully prepared by a chelating sol–gel route based on the polyesterification of ethylenediaminetetraacetic acid (EDTA) with triethanolamine (TEA). The gel decomposition and phase formation in precursor powders were studied using XRD and TG/DTA. Amorphous precursor was directly converted to YbAG phase after calcinations at 800 °C. The influence of intermediate grinding on microstructure and luminescent properties was investigated. The discrete luminescence bands of the ⁴I_13/2 → ⁴I_15/2 transition were observed in the infrared emission spectra of erbium doped samples. The lifetime of luminescence at 1530 nm was 2.82 ms and 1.82 ms for the doped samples. This may be attributed to the different efficiency of surface recombination channel, caused by different grain size distribution. Prepared samples are suitable as a standard for photoluminescence measuring of Er-doped YbAG thin films.     

Ultraviolet and visible upconversion in Yb/Er-CaSiO3 β-wollastonite phosphors

Wollastonite (CaSiO₃) is a well-known rock-forming mineral and an important constituent in ceramics and cement industries due to its outstanding mechanical, chemical, and thermal stabilities. Despite technological importance, functional properties such as photon upconversion in CaSiO₃ wollastonite ceramics have not been studied. In this contribution, Yb- and Er-doped CaSiO₃ (Yb/Er–CaSiO₃) wollastonite ceramics were synthesized via microwave hydrothermal technique followed up by heat-treatment in an air environment. X-ray diffraction and transmission electron microscopy studies confirmed the β-wollastonite (2M) phase in the synthesized samples heat-treated at 1050 °C. X-ray photoelectron spectroscopy analysis has shown that the binding energy of Ca 2p orbitals decreases after doping, indicating a change in the crystal environment of Ca in the CaSiO₃ and hence a successful incorporation of Yb³⁺ and Er³⁺ ions in the lattice. The 980 nm excitation resulted in ultraviolet, violet and strong green and red upconversion emissions as well as downshifting infrared emissions due to the energy transfer between Yb³⁺ and Er³⁺ ions. An absolute upconversion quantum yield in the 400–800 nm range is 0.04%. The most intense phonon band was observed at 969 cm^?1 in the Yb/Er–CaSiO₃ system. This study demonstrates that the β-wollastonite can be developed as a new kind of efficient upconversion phosphor material.     

Intense 2.85 μm mid-infrared emissions in Yb3+/Ho3+ codoped and Yb3+/Er3+/Ho3+ tridoped TBLL fluorotellurite glasses and their energy transfer mechanism

Yb³⁺/Ho³⁺ codoped and Yb³⁺/Er³⁺/Ho³⁺ tridoped TeO₂–BaF₂–LaF₃–La₂O₃ (TBLL) fluorotellurite glasses with low OH^? absorption (0.026 cm^-1), high glass transition temperature (434 °C) and low phonon energy (784 cm^-1) were prepared. Their mid-infrared fluorescence properties and related energy transfer (ET) mechanism were studied under 980 nm excitation. A strong emission at 2.85 μm was realized in Yb³⁺/Ho³⁺ codoped tellurite glass, which was attributed to the high-efficiency ET from Yb³⁺ ions to Ho³⁺, and the ET efficiency was 91.1%. Further introduction of Er³⁺ ions induced stronger 2.85 μm emission, and the ET efficiency was improved to 96.2%, ascribed to the establishment of more ET channels and Er³⁺ ions playing the role of ET bridge between Yb³⁺ and Ho³⁺ ions. These results indicate that the Yb³⁺/Er³⁺/Ho³⁺ tridoped tellurite glass could be a hopeful gain medium material for the ～3 μm fiber laser.     

Er3+:Yb3+:Y3Al5O12单晶中Er3+离子光谱参数的计算

采用提拉法生长出光学质量的Er3 :Yb3 :Y3Al5O12(YAG)单晶,测定了晶体的吸收光谱和上转换荧光光谱,根据Judd-Ofelt理论,计算出Er3 在YAG晶体中的强度参数Ω2=1.074 1×10-20cm2,Ω4=1.295 3×1020cm2,Ω6=0.923 8×1020cm2.由此得到部分波段跃迁的荧光分支比、辐射寿命和积分发射截面积.提出将679 nm波段的4F9/2→4I15/2跃迁作为激光输出进一步研究的新通道.     

YVO4:Er3+/Yb3+纳米纤维的静电纺丝制备及表征

实验采用静电纺丝技术和高温煅烧法结合制备YVO_4∶Er~(3+)/Yb~(3+)纳米纤维,利用X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)对其物相结构、尺寸与形貌进行了基本的表征。并系统地研究了YVO_4∶Er~(3+)/Yb~(3+)纳米纤维的上转换发光性能。结果表明,YVO_4∶Er~(3+)/Yb~(3+)纳米纤维的红色发射与绿色发射,均随激光工作电流强度的增大而增大,都随着温度的升高呈现单调下降趋势。     

Variation of crystal structure and defect luminescence in Ca3−xSrxAl2O6 phosphors

Ca_3−xSr_xAl₂O₆(x=0, 1.07, 1.88, 1.98, 3) phosphors were prepared through solid state reaction route under different atmospheres and two kinds of oxygen-defects were identified in Ca_3−xSr_xAl₂O₆ by means of X-ray photoelectron and electron spin-resonance spectra. Their defect luminescence behavior was discussed based on photoluminescence spectra as well as the calculation of bond volume polarizability of chemical bonds. Interstitials oxygen O_i is easily formed by the lattice oxygen (O1) with increasing Sr²⁺ content and air atmosphere may also provide O_i(O_i=1/2O₂). Besides, emission intensities of samples regularly changed by accommodating more O_i in air. By selecting proper excitation energy (276/355 nm), emission occurred from different O_i defect centers, with Spectral regions from 350 nm to 600 nm. Analysis suggested that the tunable emission characteristic at different excitation energies was linked with abnormal O_i, which was located in the interior of [AlO₄] six-member rings and the capacity of accommodating O_i is related to the size of six-member rings. Based on the theoretical and experimental results, a model was proposed to explain the mechanisms related to emission tunability accordingly. This research may help elucidate emission induced by an oxygen defects system.     

Pore and microstructure change induced by SiC whiskers and particles in porous TiB2–TiC–Ti3SiC2 composites

TiB₂–TiC–Ti₃SiC₂ porous composites were prepared through a plasma heating reaction using powder mixtures of Ti, B₄C SiC whiskers (SiC_w) and SiC particles (SiC_p). The effects of the SiC_w and SiC_p content on pore structures, phase constituents, microstructure, and crystal morphology of TiC were studied. The results show that TiC, TiB, Ti₃B₄ phases are formed within the 5Ti+B₄C system. With the addition of SiC_w and SiC_p, the TiB and Ti₃B₄ phases are reduced, sometimes even disappeared. Interestingly, the content of TiB₂ and TiC increased, resulting in Ti₃SiC₂ and TiSi₂ being formed. The porosity of composites increases notably with the addition of SiC_w. However, with the increase of SiC_p, the porosity of the composites first decreases, followed by an increase. After adding the specified amount of SiC_w/SiC_p, the compressive strength of composites are improved significantly. Additionally, the pore size of the composites are decreased significantly with the addition of SiC_w/SiC_p. During the plasma heating process, some Si atoms will diffuse into the TiC lattice, which in turn made the cubic TiC grains into hexagonal lamellar TiC or Ti₃SiC₂ grains.     

Crystal structure and luminescence properties of green-emitting Sr1−xAl12O19:xEu2+ phosphors

In this paper, a series of novel luminescent Sr_1−xAl₁₂O₁₉:xEu²⁺ phosphors were synthesized by a high temperature solid-state reaction. The phase structure, photoluminescence (PL) properties, as well as the decay curves were investigated. The quenching concentration of Eu²⁺ in SrAl₁₂O₁₉ was about 0.15 (mol). Upon excitation at 378 nm, the composition-optimized Sr_0.85Al₁₂O₁₉:0.15Eu²⁺ exhibited strong broad-band green emission at 530 nm with the CIE chromaticity (0.2917, 0.5736). The results indicate that Sr_1−xAl₁₂O₁₉:xEu²⁺ phosphors have potential applications as green-emitting phosphors for UV-pumped white-light LEDs.     

Upconversion thermal enhancement of 2H11/2→4I15/2 of Er3+ and blue emission of impurity Tm3+ in Sr3(PO4)2:Er3+/Yb3+

A series of Sr_2.99-x(PO₄)₂:.01Er³⁺/xYb³⁺ (x = .02, .04, .06, .08, .10) phosphors in the presence of impurity Tm³⁺ were synthesized by high temperature solid-state method, and X-ray diffraction results show that these samples are pure R-3 m(166) space group phase. The upconversion luminescence (UCL) of Er³⁺ and impurity Tm³⁺ under 980-nm laser excitation were investigated, and the results show that the intense blue UCL of impurity Tm³⁺ and thermal enhancement of ²H_11/2→⁴I_15/2 of Er³⁺ simultaneously exist. When Er³⁺ doping concentration is kept at .01, both the blue UCL intensity of impurity Tm³⁺ and green and red UCL intensity of Er³⁺ reach the maximum at Yb³⁺ doping concentration of .08. The thermal enhancement effect of ²H_11/2→⁴I_15/2 of Er³⁺ was observed as high as 3.27 times from 303 to 723 K, which is because of lattice distortion and phonon-assisted transition. In addition, the optical temperature performance of Sr_2.91(PO₄)₂:.01Er³⁺/.08Yb³⁺ sample was studied, and the maximum absolute temperature sensitivity was calculated as .00623 K⁻¹ at 538 K. This study suggests that Sr₃(PO₄)₂:Er³⁺/Yb³⁺ phosphors in the presence of impurity Tm³⁺ have a promising application prospect as optical temperature sensor at high temperature.     

Cation and polyhedron substitution strategies: Effects on local crystal structure and on Bi3+ and Eu3+ co-doped inverse garnet phosphors’ luminescence property

Following the rapid growth of lightning technology, the development of red-emitting phosphors is effective for improving color temperature and color rendering index for w-LEDs devices. Herein, a single phased garnet phosphor with cation and polyhedron substitution modification was firstly prepared. For Mg₃Gd₂Ge₃O₁₂: Bi³⁺, Eu³⁺, the intensity has been remarkably improved by about 16% compared to the one without Bi³⁺ sensitization. The energy transfer mechanism is identified in this work. Based on cation and polyhedron substitution strategies, novel phosphors with different compositions were obtained and further modified the PL properties. With Lu³⁺ substitution, the bond lengths between Bi³⁺ ion and anion ligands are decreased and the site symmetry has been strengthened, which leads to a 21 nm blue shift when Lu³⁺ totally replaced Gd³⁺ ions. In addition, Lu³⁺ and [SiO₄] substitution strategies both effectively increased symmetric rigid structure, which leads to a significant improvement in thermal stability, indicating the samples own great potential in optical applications This work provides a new insight to synthesis red-emitting phosphors for warm white-LEDs.     

Glass-forming regions and enhanced 2.7 μm emission by Er3+ heavily doping in TeO2–Ga2O3–R2O (or MO) glasses

Er³⁺-doped fiber lasers operating at 2.7 μm have attracted increasing interest because of their various important applications; however, the intrinsic self-terminating effect of Er³⁺ and the reliability of glass hosts hindered the development of Er³⁺-doped fiber lasers. Herein, the glass-forming regions of a series TeO₂–Ga₂O₃–R₂O (or MO) (R = Li, Na, and Rb; M = Mg, Sr, Ba, Pb, and Zn) glasses are predicted by the thermodynamic calculation method. On this basis, the physical and optical properties of TeO₂–Ga₂O₃–ZnO (TGZ) glass are investigated in detail as an example. Under the excitation of 980 nm laser diode, the fluorescence intensity at 2.7 μm reaches a maximum in the heavily Er³⁺-doped TGZ glass. By contrast, the accompanying near-infrared fluorescence at 1.5 μm and upconversion green emissions at 528 nm and 546 nm are all effectively weaken. Furthermore, the lifetime gap between the ⁴I_11/2 upper laser level and ⁴I_13/2 lower laser level is sharply narrowed from 2.81 ms to 0.59 ms, which is beneficial to overcome the population conversion bottleneck. All results demonstrate that these newly developed ternary tellurite glass systems are promising candidates for near-/mid-infrared laser glass fiber, fiber amplifiers, and fiber lasers.     

Enhanced broadband NIR emission in glass–ceramic fibers containing Nd3+/Yb3+ co-doped YCa4O(BO3)3 disordered nanocrystal

Demands are increasing for ultrashort pulse laser in industrial applications, where the gain bandwidth of most optical fiber material is not wide enough, and developing a wide bandwidth gain medium is challenging. Glass–ceramic fibers containing Nd³⁺/Yb³⁺ co-doped YCa₄O(BO₃)₃ nanocrystals were fabricated by the molten core method and successive heat treatment. After a careful heat treatment, Nd³⁺/Yb³⁺ co-doped YCa₄O(BO₃)₃ nanocrystals were precipitated in the fiber core. Enhanced broadband near-infrared (NIR) emission from 850 to 1150 nm (bandwidth: ∼252 nm) was obtained in the glass–ceramic fiber compared to that of precursor fiber. These results suggest that the Nd³⁺/Yb³⁺ glass–ceramic fibers are promising for broadband NIR optical amplifications and lasers.     

Intense emission at 2.9 μm from Yb3+/Ho3+ co-doped TeO2–Ga2O3–ZnO tellurite glasses

Mid-infrared lasers have important applications in infrared countermeasures, sensing, environmental monitoring, biomedicine, and many military and civilian fields. In this work, an intense emission at 2.9 μm from Yb³⁺/Ho³⁺ co-doped TeO₂-Ga₂O₃-ZnO (TGZ) glass was reported. The 2 μm, 1.2 μm and visible emissions were also performed to understand the competitive luminescent mechanism. With the increase in Yb³⁺ concentration, all the emissions of Ho³⁺ increased, whereas the emission of Yb³⁺ decreased due to the phonon-assisted energy transfer from Yb³⁺ to Ho³⁺. The lifetimes of optimized 3 mol% Yb₂O₃ and 1 mol% Ho₂O₃ co-doped TGZ glass, which has the maximum emission intensity, are 548 μs and 1.7 ms at 2.9 and 2 μm, respectively. The Judd–Ofelt intensity parameters, absorption, and emission cross sections were calculated to evaluate the mid-infrared fluorescence properties of this new glass matrix material. The gain coefficients show that the 2 and 2.9 μm laser gain can be realized by small pump energy, indicating that this glass is a promising medium for the mid-infrared optical fiber laser.     

Preparation of Er3+/Yb3+ co-doped citrate microstructure fiber of large mode field and its 3.0 μm laser performance

The double-cladding Er³⁺/Yb³⁺ co-doped bismuth germanium gallate microstructure fiber of large mode, with the core diameter of 30.6 μm, the inner cladding air pore diameter of about 3.06 μm and a lattice constant of 10.2 μm is prepared by a bundle-drawing method. The spectral characteristics at 975 nm wavelength were studied and the results show that the maximum fluorescence intensity and the high gain quality factor of the fiber core glass can be obtained when the molar ratio of Er³⁺ to Yb³⁺ is 0.5%:2% and its emission cross section is up to 10.9 × 10⁻²¹ cm². A stable laser output with a maximum power of 51.16 mW and a wavelength of 2710 nm was obtained in a microstructure optical fiber with a length of 160 mm employing a independently constructed fiber laser with a cascade structure, whose pump light power was 561 mW, the slope efficiency was 6.89%, the effective mode field area is about 576 μm² and the beam quality factor M² < 1.02. The double-cladding Er³⁺/Yb³⁺ co-doped bismuth germanium gallate microstructure fiber of large mode has excellent laser properties and is an ideal optical fiber material for the development of the 3.0 μm laser.     

Structure and upconversion analyses of Er3+-doped Ba6Ti2Nb8O30–Sr6Ti2Nb8O30 solid solutions

Er³⁺-doped filled tungsten bronze Ba₆Ti₂Nb₈O₃₀–Sr₆Ti₂Nb₈O₃₀ solid solutions with different Ba₆Ti₂Nb₈O₃₀/Sr₆Ti₂Nb₈O₃₀ ratios (SBTNx) have been prepared by a high temperature solid-state reaction. The crystal structure has been investigated simultaneously by the Rietveld structural refinement and upconversion photoluminescence (UC-PL) spectra. It is found that the crystal structure of SBTNx changes from TE-FTB symmetry (0≤x≤3, space group P4bm) to OR-FTB symmetry (3.5≤x≤5.91, space group Pba2) with x increasing. More interestingly, the structure transition of SBTNx system is also revealed by the UC-PL spectra which indicate the intimate correlation between the UC-PL spectra and the structure transition. Furthermore, the underlying origin concerning the variation of UC-PL spectra has been studied from crystal structure aspect which suggests UC-PL spectra can be explored as a structure probe for present filled tungsten bronze solid solutions.     

Multifunctional α-NaYbF4:Tm3+ nanocrystals with intense ultraviolet self-sensitized upconversion luminescence and highly efficient optical heating

Lanthanide-doped upconversion photoluminescent nanoparticles with unique anti-Stokes spectroscopic properties excel in many fields of application. Ytterbium-based self-sensitized fluorides with rich Yb³⁺ possess higher absorption efficiency of incident near infrared laser, and are more favorable for photoluminescence or optical heating applications. In this work, α-NaYbF₄:Tm³⁺ crystalline nanoparticles are synthesized, which exhibit intense ultraviolet self-sensitized upconversion photoluminescence and highly efficient optical heating capability under 980 nm laser excitation. NaYbF₄:Tm³⁺ nanocrystals emit multi-band luminescence with emission peaks located in the ultraviolet, blue and red spectral regions. The energy transfer mechanism and electronic transition pathways for the Upconversion luminescence are investigated based on the energy level scheme, and are further confirmed by luminescent dynamic analysis. Due to cross-relaxations between Tm³⁺ and energy back transfer from Tm³⁺ to Yb³⁺ processes, the NaYbF₄: 1 mol% Tm³⁺ nanoparticles possess the highest luminescence intensity. The luminescent dynamic characteristics, such as decay time and rise time, vary with Tm³⁺ doping concentrations. Highly efficient optical heating effect is observed in the NaYbF₄:Tm³⁺ nanoparticles with slope efficiency of photothermal conversion for 10 s laser irradiation is as high as 100.48 °C/W.     

Structural-phase state and lasing of 5–15 at% Yb3+:Y3Al5O12 optical ceramics

Yttrium aluminum garnet (Yb³⁺:Y₃Al₅O₁₂) laser ceramics doped by 5, 10 and 15 at% of ytterbium ions were obtained by reactive sintering. Optimal sintering temperature range for the formation of highly-dense transparent Yb³⁺:Y₃Al₅O₁₂ ceramics under normal recrystallization conditions was found to be T = 1750–1800 °C. The influence of Yb³⁺ ions on structural-phase state, phase composition, microstructure, optical and luminescent properties of sintered samples was experimentally investigated. It was shown that lattice parameter a of Yb³⁺:Y₃Al₅O₁₂ ceramics decreases linearly with increasing of Yb³⁺ concentration in a good agreement with L. Vegard’s rule, that indicates to the formation of (Y_1−xYb_x)₃Al₅O₁₂ (х = 0.05–0.15) substitutional solid solutions. No concentration quenching of Yb³⁺ luminescence was observed in Yb³⁺:Y₃Al₅O₁₂ within the 5–15 at% doping range. Quasi-CW lasing of Yb³⁺:Y₃Al₅O₁₂ ceramics was studied under diode-pumping at 970 nm. A highest slope efficiency of about 50% was obtained for 15 at%-doped Yb³⁺:Y₃Al₅O₁₂ ceramics sintered at T = 1800 °C for 10 h.