Visible green upconversion luminescence of Er3+/Yb3+/Li+ co-doped CaWO4 particles

The upconversion (UC) luminescence of Li⁺/Er³⁺/Yb³⁺ co-doped CaWO₄ phosphors is investigated in detail. Single crystallized CaWO₄:Li⁺/Er³⁺/Yb³⁺ phosphor can be obtained, co-doped up to 25.0/5.0/20.0 mol% (Li⁺/Er³⁺/Yb³⁺) by solid-state reaction. Under 980 nm excitation, CaWO₄:Li⁺/Er³⁺/Yb³⁺ phosphor exhibited strong green UC emissions visible to the naked eye at 530 and 550 nm induced by the intra-4f transitions of Er³⁺ (²H_11/2,⁴S_3/2→⁴I_15/2). The optimum doping concentrations of Yb³⁺/Li⁺ for the highest UC luminescence were verified to be 10/15 mol%, and a possible UC mechanism that depends on the pumping power is discussed in detail.     

Power dependent upconversion in Er3+/Yb3+ co-doped BiNbO4 phosphors

In the present article, optical properties and energy upconversion in Er³⁺/Yb³⁺ co-doped BiNbO₄ matrix were investigated. The BiNbO₄ matrix was prepared using the solid-state reaction method. X-ray diffraction of the matrix shows that the crystal structure is consistent with ICSD code 74338. The grain distribution and the behavior of doping with Er³⁺ and Yb³⁺ on the sample surface were obtained by scanning electron microscope. Raman spectral characterization was carried out to examine the behavior of the vibrational modes of the samples. Upconversion emissions in the visible region at 484.5, 522, 541.5 and 670.5 nm in the matrices BiNbO₄:Er,Yb and BiNbO₄:Er were observed and analyzed as a function of 980 nm laser excitation power and rare-earth doping concentration. The results show that BiNbO₄ is a promising host material for efficient upconversion phosphors.     

Efficient near-infrared to visible and ultraviolet upconversion in polycrystalline BiOCl:Er3+/Yb3+ synthesized at low temperature

Er³⁺/Yb³⁺ co-doped BiOCl poly-crystals were synthesized by the conventional solid state method at 500 °C, which exhibited good crystalline and low phonon energy. Under 980 nm excitation, the samples showed intense red upconversion (UC) luminescence (Er³⁺: ⁴F_9/2→⁴I_15/2) as well as other four UC emission bands, including ultraviolet (UV) emission at 380 nm, violet emission at 411 nm, green UC emissions at 525 and 545 nm and near-infrared (NIR) emission between 800 and 850 nm, corresponding to the transitions of ⁴G_11/2, ²H_9/2, ²H_11/2, ⁴S_3/2 and ⁴I_9/2→⁴I_15/2 of Er³⁺, respectively. Interestingly, including the violet and green UC emissions, the red one originated a nearly three-photon process in this system, and a possible UC mechanism was proposed for the enhanced red emission.     

The upconverted luminescence and chemical stability of morphologically controllable La2O3:Yb3+/Er3+ nanoparticles

Morphology and size controls are critical for the research of luminescent nanomaterials. In this work, La₂O₃:18%Yb³⁺/2%Er³⁺ nanoparticles were synthesized by a urea-assisted coprecipitation process, where the morphology and size of nanoparticles could be precisely controlled by adjusting the doping concentration, urea dosage and reaction time. With increasing Yb³⁺ doping concentration and reaction time, morphological evolution processes from nanosheets to nanospheres to nanofibers were observed. The experimental results revealed that the nanospheres could only be synthesized when 18%Yb³⁺ and 2%Er³⁺ were doped into the La₂O₃ host, where the size of the nanospheres could be precisely controlled by adjusting the urea dosage. The effects of the particle morphology and size on the upconversion luminescence of La₂O₃:18%Yb³⁺/2%Er³⁺ nanoparticles were investigated. In addition, the chemical stability of La₂O₃:18%Yb³⁺/2%Er³⁺ nanospheres in air was investigated by recording XRD and upconversion luminescence spectra after exposure to air for different periods. The experimental conclusions were useful for further probing the effects of the particle morphology and size on the upconversion emission of Er³⁺.     

Concentration effects on the upconversion luminescence in Ho3+/Yb3+ co-doped NaGdTiO4 phosphor

Ho³⁺/Yb³⁺ co-doped NaGdTiO₄ phosphors were synthesized by a solid-state reaction method. The upconversion (UC) luminescence characteristics excited by 980 nm laser diode were systematically investigated. Bright green UC emission centered at 551 nm accompanied with weak red and near infrared (NIR) UC emissions centered at 652 and 761 nm were observed. The dependence of UC emission intensity on excitation power density showed that all of green, red and NIR UC emissions are involved in two-photon process. The UC emission mechanisms were discussed in detail. Concentration dependence studies indicated that Ho³⁺ and Yb³⁺ concentrations had significant influences on UC luminescence intensity and the intensity ratio of the red UC emission to that of the green one. Rate equations were established based on the possible UC mechanisms and a theoretical formula was proposed to describe the concentration dependent UC emission. The UC luminescence properties of the presented material was evaluated by comparing with commercial NaYF₄:Er³⁺, Yb³⁺ phosphor, and our sample showed a high luminescence efficiency and good color performance, implying potential applications in a variety of fields.     

Effect of ligand field symmetry on upconversion luminescence in heat‐treated LaBGeO5:Yb3+, Er3+ glass

In this paper, we report upconversion (UC) luminescence enhancement in LaBGeO₅:Yb³⁺, Er³⁺ glass‐ceramics (GCs), surface crystallized glass‐ceramics (SCGCs) and ceramics compared with the as‐melt glass fabricated by the conventional melt‐quenching technique. Based on structural investigations, we find that the nucleation and crystallization of trigonal stillwellite LaBGeO₅:Yb³⁺, Er³⁺ nanocrystals occur first at the glass surface before the following volume crystallization. The local site symmetry around rare earth (RE) ions which was evaluated using the Eu³⁺ ions as a probe together with Judd‐Ofelt theory calculations exhibits a clear increase with the devitrification of the glass. Consequently, complete crystallization of the glass leads to largest enhancement in the UC emissions of the LaBGeO₅:Yb³⁺, Er³⁺ ceramics. We ascribe the enhancement of UC luminescence in the LaBGeO₅:Yb³⁺, Er³⁺ GCs, SCGCs, and ceramics to the structural ordering and the improvement of site symmetry surrounding RE ions that minimizes the rate of nonradiative relaxation process.     

Optimization of sensitizer concentration for upconversion photoluminescence of Yb3+/Er3+: La10W22O81 nanophosphor rods

Yb³⁺/Er³⁺codoped La₁₀W₂₂O₈₁ (LWO) nanophosphor rods have been successfully synthesized by a facile hydrothermal assisted solid state reaction method, and their upconversion photoluminescence properties were systematically studied. X-ray diffraction patterns revealed that the nanophosphors have an orthorhombic structure with space group Pbcn (60). A microflowers-like morphology with irregular hexagonal nanorods was observed using field emission scanning electron microscopy for the Yb³⁺(2 mol%)/Er³⁺(2 mol%):LWO nanophosphor. The shape and size of the nanophosphor and the elements along with their ionic states in the material were confirmed by TEM and XPS studies, respectively. A green upconversion emission was observed in the Er³⁺: LWO nanophosphors under 980 nm laser excitation. A significant improvement in upconversion emission has been observed in the Er³⁺: LWO nanophosphors by increasing the Er³⁺ ion concentration. A decrease in the upconversion emission occurred due to concentration quenching when the doping concentration of Er³⁺ ions was greater than 2 mol%. An optimized Er³⁺(2 mol%): LWO nanophosphor exhibited a strong near infrared emission at 1.53 μm by 980 nm excitation. The green upconversion emission of Er³⁺(2 mol%): LWO was remarkably enhanced by co-doping with Yb³⁺ ions under 980 nm excitation because of energy transfer from Yb³⁺ to Er³⁺. The naked eye observed this upconversion emission when co-doping with 2 mol% Yb³⁺. In order to obtain the high upconversion green emission, the optimized sensitizer concentration of Yb³⁺ ions was found to be 2 mol%. The upconversion emission trends were studied as a function of stimulating laser power for an optimized sample. Moreover, the NIR emission intensity has also been enhanced by co-doping with Yb³⁺ ions due to energy transfer from Yb³⁺ to Er³⁺. The energy transfer dynamics were systematically elucidated by energy level scheme. Colorimetric coordinates were determined for Er³⁺ and Yb³⁺/Er³⁺: LWO nanophosphors. The energy transfer mechanism was well explained and substantiated by several fluorescence dynamics of upconversion emission spectra and CIE coordinates. The results demonstrated that the co-doped Yb³⁺(2 mol%)/Er³⁺(2 mol%): LWO nanophosphor material is found to be a suitable candidate for the novel upconversion photonic devices.     

Phase evolution in Bi2O3:Yb3+/Er3+ nanoparticles with nearly single-band red upconversion luminescence

Bi₂O₃:Yb³⁺/Er³⁺ nanoparticles with flower-like morphology were easily synthesized by urea-assisted coprecipitation reactions. The influences of calcination temperature and doping concentration on the crystal phase structures of Bi₂O₃ and Bi₂O₃:x%Yb³⁺/2%Er³⁺ (x = 0–30) were systematically investigated by XRD analysis. The experimental results revealed that lanthanide doping could effectively improve the thermal stability of Bi₂O₂CO₃ samples, and the monoclinic-to-tetragonal-to-cubic phase transitions of Bi₂O₃ were implemented by controlling calcination temperatures and introducing smaller lanthanide ions (Ln³⁺) into the host lattices. Based on the analysis of TG and DSC curves, we found that the fundamental reason for this phase transition was the different stabilities of each crystalline phase under different doping conditions. Upon 980 nm laser excitation, Bi₂O₃:x%Yb³⁺/2%Er³⁺ samples presented near single-band red upconversion emission owing to the efficient energy reabsorption of the Bi₂O₃ host to Er³⁺ emission.     

Yb3+/Er3+共掺碲钨酸盐玻璃的能量传递与频率上转换发光

在970nm LD激发和Er^3 离子浓度几乎不变情况下,研究了Yb^3 ／Er^3 共掺碲钨酸盐玻璃中的能量传递和其上转换发光特性。结果表明：随掺Yb^3 浓度的增加,Yb^3 ／Er^3 间能量传递效率也增加,其值在0．52到0．60之间。在Yb^3 ／Er^3 共掺碲钨酸盐玻璃中观察到峰值分别位于533,547nm和668nm的上转换绿光和红光,它们分别来源于Er^3 离子^2H11/2→^4I15／2(533nm),^4S3／2→^4I15／2(547nm)和^4F9/2→^4I15／2(668nm)辐射跃迁。上转换红光和绿光均为双光子过程,且随Yb^3 离子掺杂浓度的增加,上转换红绿光强度和其强度比值Ic／Ig也增加,这被认为是与激发态Er^3 与激发态Yb^3 之间的能量传递过程有关。     

High sensitive Ln3+/Tm3+/Yb3+ (Ln3+ = Ho3+, Er3+) tri-doped Ba3Y4O9 upconverting optical thermometric materials based on diverse thermal response from non-thermally coupled energy levels

Upconversion (UC) optical thermometers using the fluorescence intensity ratio (FIR) technique arising from the thermally coupled energy levels (TCLs) are still suffering from low sensitivity owing to the restriction of small energy gap. In the present study, a strategy to strive for superior temperature sensitivity and signal discriminability is employed with the help of non-thermally coupled energy levels (NTCLs). A novel tri-doped Ba₃Y₄O₉: Ho³⁺/Tm³⁺/Yb³⁺ phosphor with rhombohedral symmetry was successfully prepared via a solid-state reaction method, and the temperature sensing performance was evaluated by analyzing temperature-dependent upconversion emission spectra. The emission intensities of both Ho³⁺ and Tm³⁺ activators can be almost completely restored to their original values when the temperature of the sample is cooled to room temperature. The temperature-dependent FIR between NTCLs can be fitted well by a derived three-term equation with the correlation coefficient above 99.6%, and the FIR of NTCLs exhibits high temperature sensitivity over a wide temperature range owing to the different temperature responses of the NTCLs. The maximum absolute sensitivity S_A and relative sensitivity S_R values reaches as high as 0.0552?K^?1 and 1.49% K^?1, respectively, which are much higher than those of the previously reported bulk UC optical temperature sensing materials. Moreover, the emission bands of NTCLs are well separated, which endows the material a good signal discriminability for temperature detection. Excellent temperature sensing performance is also demonstrated in Er³⁺/Tm³⁺/Yb³⁺ tri-doped Ba₃Y₄O₉, evidencing the validity of this strategy. These results indicate that the present UC materials can be potential candidates for optical temperature sensors, and the present strategy will provide a thought for developing other innovative UC temperature sensing materials.     

Wide‐range thermometry based on green up‐conversion luminescence of K3LuF6:Yb3+/Er3+ bulk oxyfluoride glass ceramics

Yb³⁺/Er³⁺ ions codoped bulk glass ceramics (GC) with embedded monoclinic K₃LuF₆ nanocrystals are reported for potential temperature‐sensing application by using the fluorescence intensity ratio method. Such GC with good transparency and enhanced up‐conversion were prepared by the simple conversional melt‐quenching method and subsequent annealing process. Optical, structural, and temperature‐sensing up‐conversion properties were characterized systematically. Optical spectroscopy analysis confirms the incorporation of Yb³⁺/Er³⁺ into the K₃LuF₆ crystalline lattice, resulting in enhanced up‐conversion luminescence. Compared to other Er³⁺‐doped typical systems, Er³⁺ ions in K₃LuF₆ GC present large energy gap (870 cm^?1) and high relative sensitivity (37.6 × 10^?4 K^?1 at 625 K), revealing that K₃LuF₆:Yb³⁺/Er³⁺ GC can be excellent candidates for optical thermometers.     

Enhanced green upconversion luminescence properties of Er3+/Yb3+ co-doped strontium gadolinium silicate oxyapatite phosphor

Upconversion Sr₂(Gd_.98-xEr_.02Yb_x)₈Si₆O₂₆ (SGSO:2Er³⁺/xYb³⁺) phosphor materials were synthesized using a citrate sol-gel process. X-ray diffraction patterns confirmed their hexagonal structure. Field emission scanning electron microscopy images of SGSO:2Er³⁺/xYb³⁺ phosphors depicted submicron particles. The enhanced upconversion luminescence properties of SGSO:2Er³⁺/xYb³⁺ phosphors were analysed as a function of Yb³⁺ ion concentration and laser power. The energy transfer induced enhanced emission of the Er³⁺/ Yb³⁺ ions co-doped SGSO phosphors was ascribed to multi-phonon relaxation. The calculated chromaticity coordinates of the SGSO:2Er³⁺/xYb³⁺ phosphors showed emissions could be tuned by changing Yb³⁺ ion concentration. Optimized sample exhibited the chromaticity coordinate values near to the ultra-high definition television standard green emission coordinates.     

Bi3+ as an enhancer for down- and upconversion luminescence in ternary vanadate structures

A series of dual-mode nanomaterials based on Ba₂LaV₃O₁₁:Yb³⁺, Er³⁺, Bi³⁺, with different bismuth content were synthesized using the hydrothermal method. Various analytical methods, such as x-ray diffraction (XRD) with additional detailed Rietveld analysis, transmission electron microscopy (TEM), inductively coupled plasma mass spectroscopy (ICP-MS) and laser spectroscopy have confirmed that with increasing Bi³⁺ content, phase purity, optical absorption and luminescence intensity significantly increased. Moreover, a slight luminescence color tunability was observed along with the gradual introduction of bismuth into the host structure since, among the others, the local crystal field around emitting Er³⁺ ions was changing. The use of ultraviolet and near-infrared excitation wavelengths allowed to obtain a dual mode luminescence, which extended the emission range and demonstrated the possibility of using the studied materials, e.g. in solar cells.     

Intense upconversion luminescence and energy‐transfer mechanism of Ho3+/Yb3+ co‐doped SrLu2O4 phosphor

A series of novel SrLu₂O₄: x Ho³⁺, y Yb³⁺ phosphors (x=0.005‐0.05, y=0.1‐0.6) were synthesized by a simple solid‐state reaction method. The phase purity, morphology, and upconversion luminescence were measured by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The doping concentrations and sintering temperature were optimized to be x=0.01, y=0.5 and T=1400°C to obtain the strongest emission intensity. Under 980 nm laser diode excitation, the SrLu₂O₄:Ho³⁺, Yb³⁺ phosphors exhibit intense green upconversion (UC) emission band centered at 541 nm (⁵F₄,⁵S₂→⁵I₈) and weak red emission peaked at 673 nm (⁵F₅→⁵I₈). Under different pump‐power excitation, the UC luminescence can be finely tuned from yellow‐green to green light region to some extent. Based on energy level diagram, the energy‐transfer mechanisms are investigated in detail according to the analysis of pump‐power dependence and luminescence decay curves. The energy‐transfer mechanisms for green and red UC emissions can be determined to be two‐photon absorption processes. Compared with commercial NaYF₄:Er³⁺, Yb³⁺ and common Y₂O₃:Ho³⁺, Yb³⁺ phosphors, the SrLu_1.49Ho_0.01Yb_0.5O₄ sample shows good color monochromaticity and relatively high UC luminescence intensity. The results imply that SrLu₂O₄:Ho³⁺, Yb³⁺ can be a good candidate for green UC material in display fields.     

Effect of Ce dopant on upconversion and temperature sensing performances in homogeneous ultrasmall Y2O3:Yb3+/Ho3+ nanoparticles through flame aerosol synthesis

Flame aerosol synthesis (FAS) is an excellent strategy for continuous, fast, and mass production of small-size upconversion nanoparticles (UCNPs), which have high potential applications in fields like biological imaging, colour display and optical temperature sensing. However, flame-made UCNPs have received less attention, and relevant studies are limited. Herein, for the first time, we successfully fabricated cerium (Ce)-doped homogeneous ultrasmall Y₂O₃:Yb³⁺/Ho³⁺ UCNPs using a liquid-fed FAS method. Ce was doped to improve the upconversion luminescence (UCL) of the Y₂O₃:Yb³⁺/Ho³⁺ UCNPs. The overall UCL intensity was enhanced ～77.9-fold for an optimal concentration of 20 mol% Ce-doped UCNPs, compared with the UCNPs without Ce doping with a relatively homogeneous ultrasmall size of 8–10 nm. Further studies confirmed that both trivalent (Ce³⁺) and tetravalent (Ce⁴⁺) simultaneously exist in the Y₂O₃ hosts and are critical in enhancing the UCL properties. In addition, the fluorescence intensity ratio (FIR) method was used to evaluate the thermal properties of the fabricated UCNPs. Ce doping significantly improved the thermal sensitivity of Y₂O₃:Yb³⁺/Ho³⁺ UCNPs. An excellent relative sensitivity (S_R) of 0.622% K^?1 at 598 K was obtained for flame-made UCNPs doped with 20 mol% Ce.     

Comprehensive study of tellurium based glass ceramics for thermoelectric application

Tellurium based glasses have interesting thermoelectric characteristics. However, their high electrical resistivity is still an obstacle to considering them for thermoelectric applications. In this work, the (Te₈₅Se₁₅)_60???0.6xAs_40???0.4xCu_x glass system was studied. This revealed that Cu can act as glass former and increase both glass thermal stability and electrical conductivity. The best candidate, (Te₈₅Se₁₅)₄₅As₃₀Cu₂₅, was chosen to prepare composites with Bi_0.5Sb_1.5Te₃ using spark plasma sintering. These glass ceramic samples exhibited a much better thermoelectric performance. Glass ceramics with 50?mol. % of Bi_0.5Sb_1.5Te₃ show a maximum ZT value equal to 0.37 at 413?K. Meanwhile, the advantages of glass including low sintering temperature and high formability are well maintained.     

Energy transfer and up-conversion luminescence in Er/Yb co-doped transparent glass ceramic containing YF3 nano-crystals

Transparent glass ceramics containing YF₃ nano-crystals were fabricated by heat treatment of the SiO₂–Al₂O₃–NaF–YF₃–LnF₃ (Ln = Er, Yb) glasses. X-ray diffraction and transmission electron microscopy analyses evidenced the homogeneous distribution of spherical YF₃ nano-crystals sized 25–30 nm among the glassy matrix. Energy dispersive X-ray spectroscopy measurement, combined with the Stark splitting of the absorption and emission bands, verified the incorporation of Er³⁺ and Yb³⁺ ions into YF₃ nano-crystals. The infrared to visible up-conversion emission of Er³⁺ intensified with the increasing of Yb³⁺ concentration, ascribing to the increase of the efficiency of non-radiative energy transfer from Yb³⁺ to Er³⁺ which exceeded 45% for the 0.5Er³⁺/1.0Yb³⁺ co-doped sample. The up-conversion luminescence at 545 and 660 nm were affirmed coming from two-photon excitation process.     

Transmission electron microscopic and optical spectroscopic studies of Ni2+/Yb3+/Er3+/Tm3+ doped dual‐phase glass‐ceramics

Ni²⁺/Yb³⁺/Er³⁺/Tm³⁺ codoped transparent glass‐ceramics (GCs) containing both hexagonal β‐YF₃ and spinel‐like γ‐Ga₂O₃ dual‐phase nanoparticles (NCs) are synthesized by melt‐quenching and subsequent heating procedures. Two techniques of transmission electron microscopy (TEM) nanoanalytics and optical spectroscopy are conjugated to understand the distribution of the rare‐earth ions (REs) and transition metals (TMs) in the nanostructured GCs. It is found that the REs are located predominantly in β‐YF₃, whereas the TMs in γ‐Ga₂O₃ NCs. As a result, energy transfer (ET) between the REs and TMs is considerably suppressed due to the large spatial separation (> 3 nm), but it is enhanced between the REs partitioned in the β‐YF₃ NCs. This has important implications for intended and demanding photoluminescence functions. For example, an ultrabroadband near‐infrared (NIR) emission in the wavelength region of 1000‐2000 nm covering the entire telecommunications window is observed for the first time. Meanwhile, intense upconversion (UC) emissions covering the 3 primary colors and locating in the first biological window can be also recorded under excitation by a single pump source at 980 nm.     

Ho3+/Yb3+掺杂铋镓酸盐光学玻璃的上转换发光

制备了高折射率Ho3 /Yb3 掺杂铋镓酸盐玻璃,用Brewster原理测量玻璃的折射率为2.296.用倒易法计算Yb3 的发射截面面积为2.109×10-20 cm2.在室温,用974nm激光器激发玻璃样品,观察并记录到强烈的双光子上转换荧光.分析认为:铋镓酸盐玻璃中Yb3 直接敏化Ho3 的上转换发光的激发机理是Yb3 到Ho3 的高效能量传递.上转换过程中红光相对强度较强的原因为:玻璃声子能量特性、最大能量声子密度降低和玻璃绿光区强吸收3方面因素增加了5F5能级上的粒子数布居,使5F5→5I8能级的跃迁几率升高,导致红光强度大于绿光强度.     

Lu3+/Yb3+ and Lu3+/Er3+ co-doped antimony selenide nanomaterials: synthesis,characterization, and electrical,thermoelectrical, and optical properties

Lu³⁺/Yb³⁺ and Lu³⁺/Er³⁺ co-doped Sb₂Se₃ nanomaterials were synthesized by co-reduction method in hydrothermal condition. Powder X-ray diffraction patterns indicate that the Ln_xLn^′_xSb_2−2xSe₃ Ln: Lu³⁺/Yb³⁺ and Lu³⁺/Er³⁺ crystals (x = 0.00 − 0.04) are isostructural with Sb₂Se₃. The cell parameters were increased for compounds upon increasing the dopant content (x). Scanning electron microscopy and transmission electron microscopy images show that co-doping of Lu³⁺/Yb³⁺ ions in the lattice of Sb₂Se₃ produces nanorods, while that in Lu³⁺/Er³⁺ produces nanoparticles, respectively. The electrical conductivity of co-doped Sb₂Se₃ is higher than that of the pure Sb₂Se₃ and increases with temperature. By increasing the concentration of Ln³⁺ions, the absorption spectrum of Sb₂Se₃ shows red shifts and some intensity changes. In addition to the characteristic red emission peaks of Sb₂Se₃, emission spectra of co-doped materials show other emission bands originating from f-f transitions of the Yb³⁺ ions.