Enhancing upconversion emission and temperature sensing modulation of the La2(MoO4)3: Er3+, Yb3+ phosphor by adding alkali metal ions

Trivalent Er³⁺-doped La₂(MoO₄)₃ upconversion phosphors with intense green emmision were synthesized at 800 °C by the solid-state reaction route, promoting the development of novel optical thermometry. The color emitted from the samples was minorly affected by the excitation power and doping concentration. Yb³⁺ is a better sensitizer for the La₂(MoO₄)₃: Er³⁺ phosphor and it can enhance the emission intensity when a certain amount is co-doping in the system. The up-conversion luminescent mechanism was investigated using the pump power-dependent UC emission spectra. Alkali metal doping increased the up-conversion emission intensities drastically, and Li⁺ ions can enhance the luminous intensity by more than 20 times. The fluorescence intensity ratio of the transition emission ²H_11/2-⁴I_15/2 and ⁴S_3/2-⁴I_15/2 was used to study upconversion optical temperature sensing. The sensitivity changes from doping with diverse alkali metal ions and their effects on the optimal temperature range are discussed in detail. Alkali metal ions doping extended the temperature range, indicating that this phosphor is a potential candidate for temperature-sensing probes.     

Color-tunable up-conversion emission in Y2O3:Yb3+, Er3+ nanoparticles prepared by polymer complex solution method

Abstract

Powders of Y₂O₃ co-doped with Yb³⁺ and Er³⁺ composed of well-crystallized nanoparticles (30 to 50 nm in diameter) with no adsorbed ligand species on their surface are prepared by polymer complex solution method. These powders exhibit up-conversion emission upon 978-nm excitation with a color that can be tuned from green to red by changing the Yb³⁺/Er³⁺ concentration ratio. The mechanism underlying up-conversion color changes is presented along with material structural and optical properties.

PACS

42.70.-a, 78.55.Hx, 78.60.-b     

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.     

稀土上转换发光材料NaYF4:Yb:Er的合成研究

在NaYF4基质中掺杂Y3 和Er3 ,合成了上转换材料NaYF4:Yb:Er,并对所得到的产物进行了表征.探讨了在合成NaYF4:Yb:Er过程中,Yb和Er的掺杂浓度、溶液的酸度、活化的温度等因素对形成六方相NaYF4:Yb:Er的影响.     

Composition effects on elastic,thermal and corrosion properties of multiple-RE silicate (Ho1/4Er1/4Yb1/4Lu1/4)2SiO5 as a promising thermal and environmental barrier coating material

(Ho_1/4Er_1/4Yb_1/4Lu_1/4)₂SiO₅ is synthesized and characterized for the application of a promising multifunctional thermal and environmental barrier coating (TEBC) material. X-ray diffraction and scanning electron microscopy analysis indicate that a X2-type multiple-RE silicate (4RE_1/4)₂SiO₅ is formed with homogeneous distribution of the four rare earth species. Dense bulk sample exhibits excellent phase stability up to 1400 °C. Key properties including Young’s modulus, thermal conductivity and thermal expansion coefficient show interesting composition effects. Specially, (Ho_1/4Er_1/4Yb_1/4Lu_1/4)₂SiO₅ demonstrates higher elastic stiffness, lower thermal conductivity, lower thermal expansion coefficient and good resistances to molten CMAS and water vapor corrosions. These results confirm the strategy of multiple-RE engineering that may provide optimal property of advanced TEBCs.     

Design and preparation of white light emission from up-conversion transitions in Er3+/Tm3+/Yb3+ co-doped cubic zirconia single crystals

High-quality cubic YSZ crystals were designed with various contents of Er³⁺, Tm³⁺ and Yb³⁺ to produce white light emission, and grown by the optical floating zone method. The up-conversion luminescence spectra of the crystals under 980 nm laser irradiation show three distinct groups of emission peaks at ∼473 nm (blue) generated by the Tm^{3+ 1}G₄→³H₆ transition, 531 and 547 nm (green) from the Er^{3+ 2}H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions, and 640 and 662 nm (red) from the Er^{3+ 4}F_9/2 → ⁴I_15/2 transition. The optical power curve obtained by plotting the up-conversion luminescence intensity against the laser power shows that the blue emission involves a three-photon process, whilst both the green and red emissions are the results of two-photon processes. Overall white light emission was observed with the crystal prepared with 0.05 mol% Er₂O₃, 0.5 mol% Tm₂O₃ and 2.0 mol% Yb₂O₃, and this crystal is suitable for use in highly efficient white light emission devices.     

Calcium-Magnesium-Aluminosilicate (CMAS) corrosion resistance of high entropy rare-earth phosphate (Lu0.2Yb0.2Er0.2Y0.2Gd0.2)PO4: A novel environmental barrier coating candidate

Single phase (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ was synthesized, and its thermal properties and CMAS resistance were investigated to explore its potential as an environmental barrier coating (EBC) candidate. The high entropy phosphate (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ displays a lower thermal conductivity (2.86 W m⁻¹ K⁻¹ at 1250 K) than all the single component xenotime phase rare-earth phosphates. Interaction of (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄ pellets with CMAS at 1300 °C led to the formation of a dense and uniformed Ca₈MgRE(PO₄)₇ reaction layer, which halted the CMAS penetration into the bulk pellet. At 1400 and 1500 °C the (Lu_0.2Yb_0.2Er_0.2Y_0.2Gd_0.2)PO₄-CMAS corrosion showed CMAS penetrating beyond the reaction layer into the bulk pellet via the grain boundaries, and SiO₂ precipitates remaining at the pellet surface. The effects of duration, temperature, and compositions on the resistance against CMAS corrosion are discussed within the context of optimizing materials design and performance of high entropy rare-earth phosphates as candidates for advanced EBC applications.     

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.     

Shape-controllable synthesis of hydrophilic NaLuF4:Yb,Er nanocrystals by a surfactant-assistant two-phase system

Water-soluble upconversion nanoparticles (UCNPs) were prepared by a one-pot procedure in a two-phase reacting system. Four kinds of surfactants were tested in the synthesis process as capping agent to tune size and morphology of nanocrystals. Nanoparticles (approximately 70 nm) and rods (400 nm and 2.5 μm) were synthesized, respectively. Then, Fourier transform infrared spectroscopy analysis confirmed the successful linking between UCNP surface and surfactant. Ionic liquids (ILs) and surfactants participated in synthesis process together, competing with each other to cap on UCNPs. ILs still led the competition of capping, while surfactants worked as cooperative assistants to develop functional surface. Further characterizations such as high-resolution transmission electron microscopy and X-ray diffraction indicated the changes in crystallization and phase transformation under the influence of surfactants. In addition, the growth mechanism of nanocrystals and upconversion fluorescence luminance was also investigated in detail. At last, the cytotoxicity of UCNPs was evaluated, which highly suggest that these surface-functionalized UCNPs are promising candidates for biomedical engineering.     

Excellent CMAS resistance of a newly developed equiatomic high entropy (Dy1/4Ho1/4Tm1/4Yb1/4)2Si2O7 ceramic pyrosilicate

In this work, novel equiatomic high entropy (Dy_1/4Ho_1/4Tm_1/4Yb_1/4)₂Si₂O₇ or (4RE_1/4)₂Si₂O₇ ceramic pyrosilicate was fabricated through a single solid solution method to use as environmental barrier coating. The SEM analysis of high entropy powders shows the homogenous mixing and XRD proves the formation of single β-phase after milling and sintering. The coefficient of thermal expansion was reported as (2.3–4.8 × 10⁻⁶ K⁻¹) from 400 K⁻¹ to 1723 K⁻¹. The ultra-low thermal diffusivity (0.4 mm² s⁻¹) and thermal conductivity (0.8 W/m°C) were reported at 1500 °C for this novel HE ceramic disilicate. The as fabricated (4RE_1/4)₂Si₂O₇ pyrosilicate shows an excellent CMAS resistant for even up to 48 h and negligible amount of Ca is able to penetrate in the substrate. Rare earth disilicate species with intermediate radii such as Tm³⁺ helps in maintaining phase stability along with passive element Yb³⁺ of smaller radii which also protect the interface from severe CMAS attack. However, the rare earth species with larger radii such as Dy³⁺ and Ho³⁺ actively take part in apatite formation leading to reduced corrosion activity of CMAS melt by changing its composition. This result confirms the application of (4RE_1/4)₂Si₂O₇ as a potential candidate to be used as protecting coating material in harsh combustion environments.     

Effect of lattice distortion in high-entropy RE2Si2O7 and RE2SiO5 (RE=Ho,Er, Y,Yb, and Sc) on their thermal conductivity: Experimental and molecular dynamic simulation study

High-entropy materials are considered to be born with lattice distortion, which is still lack of comprehensive investigation in rare earth silicates to date. In this paper, we confirmed the existence of lattice distortions in high-entropy rare-earth silicates via experiments and molecular dynamic simulations. The effects of the lattice distortion on the thermophysical properties are elucidated. Simulation results indicate the lattice distortion is present in both cation and anion sublattice, leading to the compressing and stretching of atomic bond as well as fluctuation of atomic bond strength. Accordingly, lattice distortion in the Si and O sublattice is also verified by the Raman spectra. Furthermore, the thermal conductivity of high-entropy rare earth silicates remarkably reduces and exhibits glass-like behavior, which is confirmed by experiments in cooperation with molecular dynamic simulations. Simulation also reveals that the lifetimes and group velocities of vibrational modes are significantly reduced by lattice distortion, which result in the reduction of overall thermal conductivity of high-entropy rare-earth silicates.     

Preparation of ordered TiO2 nanofibers/nanotubes by magnetic field assisted electrospinning and the study of their photocatalytic properties

Ordered-and-oriented TiO₂ nanofibers and nanotubes were prepared by magnetic field-assisted electrospinning, and photocatalytic properties of all samples were analyzed under UV–Vis shine. TiO₂ nanofibers/nanotubes prepared by magnetic field-assisted electrospinning showed better degradation effect on rhodamine B, reduced the band gap, increased the contact area of organic pollutants with the sample and higher photocatalytic activity than TiO₂ nanofibers/nanotubes prepared by classical electrospinning. The product obtained after high temperature annealing was a mixed phase of rutile phase and anatase phase and could be advantageous to the segregate of photogenic electron hole pairs and enhance the high dye absorption capacity; Surface roughness could increase more active sites and accelerate the reaction rate of photocatalytic activity; the addition of magnetic field regulated the morphology of TiO₂, and narrowed the band gap to favor photocatalytic performance. The magnetic field-assisted electrospinning study prepared in this paper was an easy-to-use and versatile method for the preparation of ordered TiO₂ nanomaterials, which could be easily extended to practical applications or other materials for photocatalysis and water cleavage.     

Luminescent properties of MgAl2O4 ceramics doped with rare earth ions fabricated by spark plasma sintering technique

MgAl₂O₄ ceramics doped with rare earth ions (Eu²⁺ and Ce³⁺ ions) were fabricated by spark plasma sintering technique. A complex characterization of the crystalline and defect structure of the ceramic by XRD was carried out. Absorption, excitation, photo- and cathodoluminescence spectra were studied. The photoluminescence spectrum shifts to the blue region with a maximum at λ_em =?475?nm for the MAS:0.1Ce ceramics. The nature of this luminescence can be caused by the radiative transitions in the cerium ion 5d–4f. The emission spectrum of MAS:0.1Eu has a “green” band emission in range of 400–700?nm centered around 500?nm, which can be ascribed to the allowed 4f⁶5d¹→4f⁷ (5d–4f) transition of Eu²⁺. In the millisecond time range, simultaneously with the emission of the complex host centers, the impurity luminescence bands of the chromium ion are recorded. It was shown that cathodoluminescence spectra in nanosecond time range can be decomposed into several emission bands at 2.72, 3.01, 3.37, 3.63–3.82?eV caused by F-type centers. It was demonstrated that the Eu²⁺ and Ce³⁺ ions lead to change the intensity ratio of the luminescence bands. The luminescence decay kinetics of synthesized spinel ceramics in nano- and millisecond time range were investigated in detail.     

Effects of Er3+ concentration on down-/up-conversion luminescence and temperature sensing properties in NaGdTiO4: Er3+/Yb3+ phosphors

Usually, Er³⁺ doping concentration effect on the temperature sensing properties of Er³⁺ containing materials is ignored. In this work, we demonstrated the influence of Er³⁺ concentration and excitation path on the spectral and temperature sensing properties in Er³⁺, Yb³⁺ co-doped NaGdTiO₄ system. The NaGdTiO₄: Er³⁺/Yb³⁺ phosphors were prepared by a high temperature solid state reaction method. Different spectral patterns for down- and up-conversion processes were observed and ascribed to the different excitation and population routes. The concentration quenching behaviors for down- and up-conversion processes were explained via cross relaxations between Er³⁺ ions. Most importantly, the Er³⁺ concentration dependent optical temperature sensing performance was observed and experimentally explained as a fact that the optical transition rate of Er³⁺ in different samples was changed with various Er³⁺ doping concentration.     

Au/NaYF4 : Yb,Er Binary Superparticles: Synthesis and Optical Properties

Colloidal superparticles (SPs) are nanoparticle (NP) assemblies in the form of colloidal particles. Assembling nanoscopic objects into mesoscopic or macroscopic composite architectures allows for the bottom-up fabrication of functional nanomaterials. In this study, a method for single-step self-assembly synthesis of Au/NaYF₄ : Yb,Er SPs was developed using oil-in-water (O/W) microemulsions to simultaneously encapsulate gold nanoparticles (AuNPs) and NaYF₄ : Yb,Er upconversion nanoparticles (UCNPs) via evaporation at room temperature. The synthesized Au/NaYF₄ : Yb,Er SPs possess good dispersibility and stability. When the number of AuNPs added is increased, the SPs exhibit decreased upconversion luminescence, which can be ascribed to the Förster resonance energy transfer (FRET) from the NaYF₄ : Yb,Er UCNPs to the AuNPs. Time-resolved measurements of the green emission further confirm the existence of a new decay route corresponding to the FRET process. Our research provides a facile and versatile strategy for the synthesis of novel multifunctional nanocomposites with tunable upconversion luminescence properties, which can be of great significance in biological applications.     

Enhanced piezoelectricity and non-contact optical temperature sensing performance in Er3+ ion modified (K,Na)NbO3-based multifunctional ceramics

Rare earth ions doped ferroelectrics have attracted wide attentions due to their multifunction characteristics with both ferroelectric/piezoelectric properties and intriguing photoluminescence performance, which show great prospects for future multifunctional devices. In this work, a novel rare earth Er³⁺ ion modified potassium-sodium niobate (KNN) based ceramics were elaborately designed and prepared by the conventional solid-state reaction. The microstructure, phase structure, electric properties and photoluminescence performance of the Er³⁺ ion modified KNN-based ceramics were systematically investigated. Enhanced piezoelectricity (a considerable d₃₃ of exceeding 300 pC/N and a large d₃₃* up to 500 p.m./V) was realized through optimizing the substitution of BaZrO₃ by (Er_0.5,Na_0.5)ZrO₃. Both down-conversion and up-conversion photoluminescence emissions were detected in the optimal composition. The temperature-dependent upconversion emissions of the optimal Er³⁺ modified ceramic sample in the temperature range of 303–573K were verified to be applicable for non-contact optical temperature sensing with a maximum sensitivity S_a of 0.0028 K^-1 and a peak relative sensitivity S_r of 0.96% K⁻¹. Moreover, low-temperature sensing performance with a maximum S_r of 16.7% K⁻¹ in the temperature range of 80–280K was also presented based on the temperature-dependent down-conversion emissions. With both decent electrical properties and intriguing photoluminescence performance, the Er³⁺-modified KNN-based ferroelectrics exhibit good application potential in the future multifunctional optoelectronic devices.     

Upconversion emission,cathodoluminescence and temperature sensing behaviors of Yb3+ ions sensitized NaY(WO4)2:Er3+ phosphors

A series of Yb³⁺ ions sensitized NaY(WO₄)₂:Er³⁺ phosphors were synthesized through a solid-sate reaction method. The X-ray diffraction (XRD), upconversion (UC) emission and cathodoluminescence (CL) measurments were applied to characterize the as-prepared samples. Under the excitation of 980 nm light, bright green UC emissions corresponding to (²H_11/2,⁴S_3/2)→⁴I_15/2 transitions of Er³⁺ ions were observed and the UC emission intensities showed an upward trend with increasing the Yb³⁺ ion concentration, achieving its optimum value at 25 mol%. Furthermore, the temperature sensing behavior based on the thermally coupled levels (²H_11/2,⁴S_3/2) of Er³⁺ ions was analyzed by a fluorescence intensity ratio technique. It was found that the obtained samples can be operated in a wide temperature range of 133–773 K with a maximum sensitivity of approximately 0.0112 K⁻¹ at 515 K. Ultimately, strong CL properties were observed in NaY(WO₄)₂:0.01Er³⁺/0.25Yb³⁺ phosphors and the CL emission intensity increased gradually with the increment of accelerating voltage and filament current.     

Simultaneous enhancement of emission and thermal sensitivity via phase transition in Gd2(MoO4)3:Yb3+/Er3+ crystals

The effects of site symmetric distortion induced by the phase transition on up-conversion emission and thermal sensing performance of Gd₂(MoO₄)₃:Yb³⁺/Er³⁺ (GMO) crystals were elaborately studied by minimizing interference from many factors. Monoclinic GMO showed a much stronger fluorescence intensity and larger fluorescence intensity ratio under the irradiation of 980 nm laser in comparison to the orthorhombic counterpart. These remarkable up-conversion properties stemmed from the low site symmetry with large site symmetric distortion in monoclinic GMO. Moreover, the thermal sensing property of the samples was assessed based on the fluorescence intensity ratio technique, where monoclinic GMO exhibited much higher maximum absolute sensitivity (S_a = 0.0257 K⁻¹ at 510 K) due to the site symmetric distortion, which was further explained by the Judd–Ofelt theory and polarizability of the chemical bond volume model. Results opened an efficient avenue for achieving highly sensitive thermometry in many daily scenarios via finely tailoring the local site symmetry.     

Highly porous (La1/5Nd1/5Sm1/5Gd1/5Yb1/5)2Zr2O7 ceramics with ultra-low thermal conductivity

The high-entropy rare earth zirconate (La_1/5Nd_1/5Sm_1/5Gd_1/5Yb_1/5)₂Zr₂O₇ porous ceramics ((5RE_1/5)₂Zr₂O₇ PCs) were prepared using a foam-gel casting-freeze drying method combined with segmented calcination process. The results of SEM, TEM, and XRD analyses of the (5RE_1/5)₂Zr₂O₇ PCs indicated the formation of a defective fluorite crystal structure, with the rare earth elements homogeneously distributed. Meanwhile, the as-prepared (5RE_1/5)₂Zr₂O₇ PCs exhibited high porosity, low bulk density, low thermal conductivity, and relatively high compressive strength. Moreover, the high-temperature thermal conductivity of the samples was evaluated, and the results showed that the (5RE_1/5)₂Zr₂O₇ PCs maintain a thermal conductivity of 0.150 ± 0.002 W m^?1 K^?1 even at 1000 °C. The strategy used in this paper can be extended to the synthesis of other high-entropy porous ceramics with high porosity and low thermal conductivity, which is suitable for applications as thermal insulation materials.     

Highly sensitive acetone-sensing properties of Pt-decorated CuFe2O4 nanotubes prepared by electrospinning

Pristine and Pt-decorated copper ferrite nanotubes (Pt-CuFe₂O₄ NTs, 0.1%, 0.5%, and 1.0%, mole percent) were prepared by a simple electrospinning method. The samples were characterized by X-ray diffraction, scanning electron microscope, and transmission electron microscope. Their gas-sensing properties were evaluated by a commercial CGS-4TPs system. Microscopic images showed that all samples consisted of well-defined nanotubes with diameter of 70?100 nm. Gas-sensing measurements revealed that the Pt-CuFe₂O₄ NTs had an improved acetone-sensing properties compared with pristine CuFe₂O₄ NTs. In particular, 0.5% Pt-CuFe₂O₄ NT-based sensor showed a high response (16.5 at 100 ppm), good selectivity, and long-term stability for acetone at 300 °C. In addition, more Pt dopants would have a greater effect on promoting the sensing properties of the CuFe₂O₄ NTs at high acetone concentrations. A gas-sensing enhancement mechanism of Pt-CuFe₂O₄ NT-based sensors was proposed, according to the catalytic oxidation process of acetone molecules, which could be due to the kinetic competition between Pt dopants and CuFe₂O₄ NTs.