Effect of Li+ Ions Doping on Microstructure and Upconversion Emission of Y2Ti2O7:Er3+/Yb3+ Nanophosphors Synthesized Via a Sol–Gel Method

Er³⁺/Yb³⁺/Li⁺‐tridoped Y₂Ti₂O₇ nanophosphors were synthesized via a facile sol–gel process. The samples were characterized by the inductively coupled plasma atomic emission spectrometer (ICP‐AES), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and infrared‐to‐visible upconversion (UC) luminescence spectra. XRD analysis showed that the crystallization temperature of pyrochore‐type Y₂Ti₂O₇ was reduced due to the flux effect of Li⁺ ions, whereas TEM measurements confirmed that the particles size of (Y_0.815Er_0.01Yb_0.075Li_0.10)₂Ti₂O₇ was about 30–40 nm when calcining at 800°C for 1.0 h. The calcining temperature and Li⁺ ion concentration dependence on UC luminescence spectra were investigated. It was found that, when incorporating 10.0 mol% Li⁺ ion, the UC red and green emission intensity was drastically increased by a factor of 18.6 and 8.3, respectively. The enhancement of UC emission may be mainly attributed to the modification of local symmetry around Er³⁺ ions by tridoping Li⁺ ions. And also, the pump power dependence of the emission intensity was investigated to understand the fundamental UC mechanism.     

A Novel Multifunctional Upconversion Phosphor: Yb3+/Er3+ Codoped La2S3

Yb³⁺/Er³⁺ codoped La₂S₃ upconversion (UC) phosphors have been synthesized using high‐temperature solid‐state method. Under 971‐nm excitation, the maximum luminescence power can reach 0.64 mW at the excitation power density of 16 W/cm² and an absolute power yield of 0.36% was determined by an absolute method at the excitation power density of 3 W/cm², and the quantum yield of La₂S₃:Yb³⁺, Er³⁺ (green ~0.18%, red ~0.03%, integration ~0.21) was comparable to that of NaYF₄:Yb³⁺, Er³⁺ nanocrystals (integration ~0.005–0.30). Frequency upconverted emissions from two thermally coupled excited states of Er³⁺ were recorded in the temperature range 100–900 K. The maximum sensitivity of temperature sensing is 0.0075 K^?1. As the excitation power density increases, the temperature of host materials rapidly rises and the top temperature can reach to 600 K. Given the intense UC emission, high sensitivity, as well as good photothermal stability, La₂S₃:Yb³⁺/Er³⁺ phosphor can become a promising composite material for photothermal ablation of cancer cells possessing the functions of temperature sensing and in vivo imaging.     

Fabrication and Upconversion Luminescent Properties of Er3+‐Doped and Er3+/Yb3+ Codoped La2O2CN2 Nanofibers

La₂O₂CN₂:Er³⁺and La₂O₂CN₂:Er³⁺/Yb³⁺ upconversion (UC) luminescence nanofibers were successfully fabricated via cyanamidation of the respective relevant La₂O₃:Er³⁺ and La₂O₃:Er³⁺/Yb³⁺ nanofibers which were obtained by calcining the electrospun composite nanofibers. The morphologies, structures, and properties of the nanofibers are investigated. The mean diameters of La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers are 179.46 ± 12.58 nm and 198.85 ± 17.07 nm, respectively. It is found that intense green and weak red emissions around 524, 542, and 658 nm corresponding to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_l5/2 energy levels transitions of Er³⁺ ions are observed for La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers under the excitation of a 980‐nm diode laser. Moreover, the emitting colors of La₂O₂CN₂:Er³⁺ and La₂O₂CN₂:Er³⁺/Yb³⁺ nanofibers are all located in the green region. The upconversion luminescent mechanism and formation mechanism of the nanofibers are also proposed.     

Preparation,Structure, and Up‐Conversion Luminescence of Yb3+/Er3+ Codoped SrIn2O4 Phosphors

SrIn₂O₄, which shows lower phonon energy than CaIn₂O₄, is not only a good photocatalyst but also can be an excellent up‐conversion (UC) host to exhibits UC luminescence. In this work, Yb³⁺ and/or Er³⁺ doped SrIn₂O₄ phosphors were synthesized, and their UC luminescence properties were studied and compared with those in the CaIn₂O₄ host. The structure of SrIn₂O₄: 0.01Er³⁺ and SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ samples were refined by the Rietveld method and found to that SrIn₂O₄: 0.1Yb³⁺/0.01Er³⁺ showed increasing unit cell parameters and cell volume, indicating In³⁺ sites were substituted successfully by Yb³⁺ and/or Er³⁺ ions. From the UC luminescence spectra and diffuse reflection spectra, Er³⁺‐doped SrIn₂O₄ showed very weak luminescence due to ground state absorption of Er³⁺; Yb³⁺/Er³⁺ codoped SrIn₂O₄ presented strong green (550 nm) and red (663 nm) UC emissions which were assigned to energy transfer from Yb³⁺ transition ²F_7/2→²F_5/2 to the Er³⁺ transition ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2. Comparing with CaIn₂O₄, Yb³⁺/Er³⁺ codoped SrIn₂O₄ showed obvious advantages with higher UC luminescent intensity. The pumping powers study showed that UC emissions in Yb³⁺/Er³⁺ codoped SrIn₂O₄ were attributed to energy transfer of Yb³⁺→Er³⁺ with a two‐photon process. The possible UC luminescent mechanism of Yb³⁺/Er³⁺‐doped SrIn₂O₄ was discussed.     

Bright red upconversion luminescence from Er3+ and Yb3+ co-doped ZnO-TiO2 composite phosphor powder

ZnO-TiO₂ composites co-doped with Er³⁺ and Yb³⁺ ions were successfully synthesized by powder-solution mixing method and their upconversion (UC) luminescence was evaluated. The effect of firing temperature, ZnO/TiO₂ mixing ratio, and dopant concentration ranges on structural and UC luminescence properties was investigated. The crystal structure of the product was studied and calculated in detail by means of X-ray diffraction (XRD). Also, the site preference of Er³⁺ and Yb³⁺ ions in the host material was considered and analyzed based on XRD results and UC luminescence characteristics. Brightest UC luminescence was observed in the ZnO-TiO₂:Er³⁺,Yb³⁺ phosphor fired at 1300 °C in which the system consisted of mixed phases; Zn₂TiO₄, TiO₂, RE₂Ti₂O₇ and RE₂TiO₅ (RE = Er³⁺ and/or Yb³⁺). Under the excitation of a 980 nm laser, the two emission bands were detected in the UC emission spectrum, weak green band centered at 544 and 559 nm, and strong red band centered at 657 and 675 nm wavelengths in accordance with ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ion, respectively. The simple chemical formula equations, for explaining the site preference of Er³⁺ and Yb³⁺ ions in host crystal matrix, were generated by considering the Zn₂TiO₄ crystal structure, its crystal properties, and the effect of Er³⁺ and Yb³⁺ ions to the host crystal matrix. The UC emission intensity of the products was changed by varying ZnO/TiO₂ mixing ratios, and Er³⁺ and Yb³⁺ concentrations. The best suitable condition for emitting the brightest UC emission was 1ZnO:1TiO₂ doped with 3 mol% Er³⁺, 9 mol% Yb³⁺ fired at 1300 °C for 1 h.     

Quantitative relationship between microstructure and optical properties of Er3+-Yb3+ co-doped glass-ceramics containing pyrochlore-type crystalline phases

Er³⁺-Yb³⁺ co-doped transparent glass-ceramics (GCs) containing Y₂Ti₂O₇ crystalline phase were prepared by the melting crystallization method. The qualitative relationship between light transmittance and three-dimensional structure parameters of glass-ceramic was studied according to the principle of stereology under different heat treatment conditions. As indicated by the research results, the light transmittance decreased with the increase in the equivalent spherical diameter (D_3S) and specific surface area per unit volume of the grains (S_V). However, the light transmittance increased linearly with the increase in the discrete grains (S_VP) and the mean free distance (λ). The up-conversion luminescence intensity was found to be most vigorous under Er³⁺ and Yb³⁺ doping concentrations of 0.5% and 0.9%, respectively, at 980 nm excitation. Considering the correlation between pump power and up-conversion emission intensity, the up-conversion luminescence mechanism was explored. As revealed by the results of color purity and chromaticity coordinates, Er³⁺-Yb³⁺ co-doped GCs containing Y₂Ti₂O₇ have promising applications in green up-conversion luminescence.     

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.     

Near-infrared photo-responsive Er3+-K+ co-doped Y2O3 phosphors with enhanced UC luminescence

Y₂O₃: x% Er³⁺ (x=5, 7, 10, 12, 15) and Y₂O₃: 10% Er³⁺，x% K⁺ (x=0, 1, 3, 5, 7, 10, 15) phosphors were successfully prepared by a low-temperature combustion method. The structure as well as the absorption/emission spectra of phosphors were investigated. The effect of doping concentration of K⁺ ions on the upconversion (UC) luminescence of Y₂O₃: 10% Er³⁺ phosphor was examined and the possible optical transitions were discussed. The results showed that K⁺ ion doping not only changed the microstructure and crystallinity of the phosphors, but also enhanced its UC luminescence intensity. The Y₂O₃: 10% Er³⁺, 7% K⁺ phosphor exhibit the strongest UC emission intensity. Compared with the Y₂O₃: 10% Er³⁺ phosphor, the UC luminescence intensity at 563 nm and 661 nm was enhanced by 67.8 and 27.3 times for the K-codoped samples, respectively. The phosphor with the optimal doping concentration was mixed with a polymer to form a composite film, which was employed for the fabrication of near-infrared (NIR) photo-responsive detection devices. The device exhibited strong photo-current response to NIR light at 980 nm, implying that our work could inspire new design strategy for the development of NIR photo-detection devices.     

Color‐Tunable Up‐Conversion Emission and Infrared Photoluminescence and Dielectric Relaxation of Er3+/Yb3+ Co‐Doped Bi2Ti2O7 Pyrochlore Thin Films

The color‐tunable up‐conversion (UC) emission and infrared photoluminescence and dielectric relaxation of Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ pyrochlore thin films prepared by a chemical solution deposition method have been investigated. The pyrochlore phase structure of Bi₂Ti₂O₇ can be stabilized by Er³⁺/Yb³⁺ co‐doping. Intense color‐tunable UC emission and infrared photoluminescence can be detected on the thin films excited by a 980 nm diode laser. Two UC emission bands centered at 548 and 660 nm in the spectra can be assigned to ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺ ions, respectively. A Stokes infrared emission centered at 1530 nm is due to ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ions. The dependence of UC emission intensity on pumping power indicates that the UC emission of the thin films is a two‐photon process. The thin films also exhibit a relatively high dielectric constant and a low dissipation factor as well as a good bias voltage stability. Temperature‐ and frequency‐dependent dielectric relaxation has been confirmed. This study suggests that Er³⁺/Yb³⁺ co‐doped Bi₂Ti₂O₇ thin films can be applied to new multifunctional photoluminescence dielectric thin‐film devices.     

Marked reduction in the thermal conductivity of (La0.2Gd0.2Y0.2Yb0.2Er0.2)2Zr2O7 high-entropy ceramics by substituting Zr4+ with Ti4+

The (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ (x = 0–0.5) high-entropy ceramics were successfully prepared by a solid state reaction method and their structures and thermo-physical properties were investigated. It was found that the high-entropy ceramics demonstrate pure pyrochlore phase with the composition of x = 0.1–0.5, while (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂Zr₂O₇ shows the defective fluorite structure. The sintered high-entropy ceramics are dense and the grain boundaries are clean. The grain size of high-entropy ceramics increases with the Ti⁴⁺ content. The average thermal expansion coefficients of the (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics range from 10.65 × 10^?6 K^?1 to 10.84 × 10^?6 K^?1. Importantly, the substitution of Zr⁴⁺ with Ti⁴⁺ resulted in a remarkable decrease in thermal conductivity of (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics. It reduced from 1.66 W m^?1 K^?1 to 1.20 W m^?1 K^?1, which should be ascribed to the synergistic effects of mass disorder, size disorder, mixed configuration entropy value and rattlers.     

Enhancing upconversion luminescence and thermal sensing properties of Er/Yb co-doped oxysulfide core-shell nanocrystals

The development of noncontact thermal probe based on stable inorganic materials of trivalent lanthanide (Ln³⁺) doped phosphors with nontoxicity is of vital importance for their promising applications in bio-medical fields. Here we explore the upconversion luminescence and thermal sensing properties of Er³⁺, Yb³⁺ co-doped oxysulfide in a broad temperature range of 300-583 K. It was found that constructing an active shell with an optimum concentration of sensitizers is an efficient way to improve both the luminescent intensities and thermal sensitivity. Compared with the core-only sample, the luminescent intensity of the Y₂O₂S: Er³⁺, Yb³⁺@ Y₂O₂S: 5%Yb³⁺ sample is significantly enhanced by 12-fold at excitation of 980 nm. While further increasing the Yb³⁺ concentration in the shell activates new quenching pathways of Er³⁺ → Yb³⁺ → quencher from the core to the shell. Similar quenching mechanisms are also observed at excitation of 1550 nm. These energy transfer processes and luminescence mechanisms are verified in the fluorescence decay measurements. Furthermore, coating the core sample with an active shell doped by 10% Yb³⁺ enhances the thermal sensitivity by 30%, holding a high and stable sensitivity more than 50 × 10⁻⁴ K⁻¹ in a broad temperature range of 423-573 K at 980 nm excitation. In addition, at the much safer excitation wavelength of 1550 nm, this sample achieved the maximum sensitivity of 45 × 10⁻⁴ K⁻¹ at 503 K. Our work contributes a feasible and versatile way to promote the luminescence and thermal sensing properties of Ln³⁺-based materials, combining with the nontoxic oxysulfide host, indicating their potential applications as safe fluorescent and temperature nano-probes in bio-field.     

Influence of Cr3+ on yellowish-green UC emission and energy transfer of Er3+/Cr3+/Yb3+ tri-doped zinc silicate glasses

In this paper, we study the influence of Cr³⁺ on yellowish-green upconversion (UC) emission and the energy transfer (ET) of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in SiO₂–ZnO–Na₂O–La₂O₃ (SZNL) zinc silicate glasses under excitation of the 980 nm laser diode (LD). The influence of Cr³⁺ on enhancing the red UC emission of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in SiO₂–ZnO–Na₂O–La₂O₃ zinc silicate glasses under the excitation of 980nm LD was also investigated. The ET processes between Yb³⁺, Cr^3+, and Er³⁺, together with the combination of Yb³⁺-Cr³⁺-Er³⁺, which led to the green UC emission intensity of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in SiO₂–ZnO–Na₂O–La₂O₃ zinc silicate glasses bands centered at ~546 nm have been significantly enhanced. By increasing the concentration of Cr³⁺ from 0 up to 5 mol.%, we can locate the Commission Internationale de l'éclairage (CIE) 1931 (x; y) chromaticity coordinates for UC emissions of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in the central position of the yellowish-green color region of CIE 1931 chromaticity diagram. Besides, the ET processes between the Yb³⁺, Cr³⁺, and Er³⁺ are also proposed and discussed.     

Yb3+ concentration on emission color,thermal sensing and optical heater behavior of Er3+ doped Y6O5F8 phosphor

Up-conversion phosphor is a potential candidate as non-contact temperature sensor because of its unjammable and unique detection abilities. In this work, we investigate the influence of Yb³⁺ concentration on the emission color, thermal sensing and optical heater behavior of Er³⁺ doped Y₆O₅F₈ phosphor. Our results show that the emission color of Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder changes from green to yellow with the Yb³⁺ concentration increasing. Importantly, the temperature sensing sensitivities of Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder reach 0.008, 0.009, 0.010 and 0.011 K⁻¹ as the sample doped with 2%, 5%, 8% and 11% Yb³⁺ at 476 K, respectively. Moreover, the temperature of high Yb³⁺ concentration sample shows preferable optical heating behavior, whose temperature is ascended by a large value of 94 K when the excitation pump power density changes from 1.0 to 13.1 W cm⁻². These results suggest Er³⁺ and Yb³⁺ co-doped Y₆O₅F₈ powder has great potential in colorful display, temperature sensing and optical heating.     

High-entropy rare earth titanates with low thermal conductivity designed by lattice distortion

High-entropy single-phase rare earth titanates (RE_0.2Gd_0.2Ho_0.2Er_0.2Yb_0.2)₂Ti₂O₇ (RE = Sm, Y, Lu) were designed and synthesized successfully, in which their lattice distortion was quantitatively described by mass disorder and size disorder. It is worth mentioning that (Y_0.2Gd_0.2Ho_0.2Er_0.2Yb_0.2)₂Ti₂O₇ could obtain the low thermal conductivity (1.51 W·m⁻¹·K⁻¹, 1500°C), high thermal expansion coefficient (average, 11.69×10⁻⁶ K⁻¹, RT ∼1500°C) and excellent high-temperature stability. In addition, the relationship between the microstructure and thermal transport behaviors has been studied at the atomic scale. Due to the disorder of A-site ions, severe lattice distortion occurred in specific crystal planes, and the large mass difference between Y³⁺ and other RE³⁺ further causes mass fluctuation and results in lower thermal conductivity. Compared with YSZ, the high-entropy rare earth titanate (Y_0.2Gd_0.2Ho_0.2Er_0.2Yb_0.2)₂Ti₂O₇ has lower thermal conductivity, higher thermal expansion coefficient, and excellent high-temperature stability, which has great potential for application in the thermal protection field.     

Optical temperature sensor based on upconversion luminescence of Er3+ doped GdTaO4 phosphors

For the development of optical temperature sensor, a series of GdTaO₄ phosphors with various Er³⁺-doping concentrations (0, 1, 5, 10, 25, 35, 50 mol%) were synthesized by a solid-state reaction method. The monoclinic crystalline structure of the prepared samples was determined by X-ray diffraction (XRD). Under excitations of 980 and 1550 nm lasers, the multi-photon-excited green and red upconversion (UC) luminescence emissions of Er³⁺ were studied, and the critical quenching concentration of Er³⁺-doped GdTaO₄ phosphor was derived to be 25 mol%. By changing the pump power of laser, it was found that the two-photon and three-photon population processes happened for the UC emissions of Er³⁺-doped GdTaO₄ phosphors excited by 980 and 1550 nm lasers, respectively. Furthermore, based on the change of thermo-responsive green UC luminescence intensity corresponding to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺ with temperature, the optical temperature sensing properties of Er³⁺-doped GdTaO₄ phosphor were investigated under excitations of 980 and 1550 nm lasers by using the fluorescence intensity ratio (FIR) technique. It was obtained that the maximum absolute sensitivity (S_A) and relative sensitivity (S_R) of Er³⁺-doped GdTaO₄ phosphors are as high as 0.0041 K⁻¹ at 475 K and 0.0112 K⁻¹ at 293 K, respectively. These significant results suggest that the Er³⁺-doped GdTaO₄ phosphors are a promising candidate for optical temperature sensor.     

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.     

Preparation,luminescence properties,and application of temperature sensing and anti-counterfeiting of La2MgTiO6:Yb3+/Ln3+/Mn4+

The doping of transition metal ions in the up-conversion (UC) luminescent material doped with Yb³⁺/Ln³⁺ is a facile way to increase their UC luminescence intensities and alter their colors. In this study, La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ (Ln³⁺ = Er³⁺, Ho³⁺, and Tm³⁺) phosphors showing excellent luminescence properties were prepared by a solid-state method. The sensitivity of the La₂MgTiO₆:Yb³⁺/Ln³⁺/Mn⁴⁺ phosphor was double that without Mn⁴⁺, because Mn⁴⁺ affects the UC emissions of Ln³⁺ via energy transfer between these ions. Moreover, Mn⁴⁺ also acts as a down-conversion activator, which can combine with UC ions to achieve multi-mode luminescence at different wavelengths. Under 980 nm excitation, these samples emit green light (from Er³⁺ and Ho³⁺) and blue light (from Tm³⁺). In contrast, under 365 nm excitation, they emit red light (from Mn⁴⁺). Further testing revealed that the La₂MgTiO₆:Yb³⁺/Mn⁴⁺/Ln³⁺ phosphors have potential applications in temperature sensing and anti-counterfeiting.     

BiLaWO6: Er3+/Tm3+/Yb3+ phosphor: Study of multiple fluorescence intensity ratiometric thermometry at cryogenic temperatures

Highly thermally stable Er³⁺/Tm³⁺/Yb³⁺ tri-doped bismuth lanthanum tungstate phosphors were prepared by high temperature solid-state reaction method. The structural and morphological properties of the prepared phosphors were analysed by X-ray diffraction (XRD), Raman spectroscopy and Scanning electron microscopy (SEM) coupled with energy dispersion spectrum (EDS). Visible upconversion (UC) luminescence was measured by exciting the phosphors with 980 nm laser radiation. The dependence of the UC intensity of each emission band of Er³⁺ and Tm³⁺ ions as a function of temperature in the range from 30 to 300 K was monitored. Fluorescence intensity ratios (FIR) of thermally coupled levels (TCL) and non-thermally coupled levels (NTCL) were analysed and verified with appropriate theoretical validation. The absolute (S_A) and relative sensitivities (S_R) were estimated and compared with the reported systems. In the present case of BiLaWO₆: Er³⁺/Tm³⁺/Yb³⁺, S_R (0.43 % K^?1) related to TCL of Er³⁺ UC is found to have maximum sensitivity compared to any of the NTCL combinations at 300 K. From this study we inferred that the S_R values estimated from NTCL are smaller than that of TCL involved in BLW: Er³⁺/Tm³⁺/Yb³⁺ phosphor. The temperature dependent CIE color coordinates were also evaluated in the cryogenic temperature region.     

Tuning stoichiometry of high-entropy oxides for tailorable thermal expansion coefficients and low thermal conductivity

Thermal barrier coating materials with proper thermal expansion coefficient (TEC), low thermal conductivity, and good high-temperature stability are of great significance for their applications in next-generation turbine engines. Herein, we report a new class of high-entropy (La_0.2Sm_0.2Er_0.2Yb_0.2Y_0.2)₂Ce_xO_3+2x with different Ce⁴⁺ contents synthesized by a solid-state reaction method. They exhibit different crystal structures at different Ce⁴⁺ content, including a bixbyite single phase without Ce⁴⁺ doping (x = 0), bixbyite-fluorite dual-phase in the RE₂O₃-rich region (0 < x < 2), and fluorite single phase in the stoichiometric (x = 2) and CeO₂-rich region (x > 2). The high-entropy (La_0.2Sm_0.2Er_0.2Yb_0.2Y_0.2)₂Ce_xO_3+2x exhibit tailorable TECs at a large range of 9.04 × 10^–6–13.12 × 10^–6 °C^–1 and engineered low thermal conductivity of 1.79–2.63 W·m^–1·K^–1. They also possess good sintering resistance and high-temperature phase stability. These results reveal that the high-entropy (La_0.2Sm_0.2Er_0.2Yb_0.2Y_0.2)₂Ce_xO_3+2x are promising candidates for thermal barrier coating materials as well as thermally insulating materials and refractories.     

Morphology control and temperature sensing properties of micro-rods NaLa(WO4)2:Yb3+,Er3+ phosphors

Uniform spindle-like micro-rods NaLa(WO₄)₂:Yb³⁺,Er³⁺ phosphors are prepared by the solvothermal method in the text. Controllable morphology of NaLa(WO₄)₂ crystal can be obtained by adjusting the prepared temperature, PH value, complexing agent content, and solvent ratio. Uniform NaLa(WO₄)₂:Yb³⁺,Er³⁺ micro-rods of 1.8 μm in length and 0.5 μm in width are synthesized at a low temperature of 120°C. The prepared NaLa(WO₄)₂:Yb³⁺,Er³⁺ phosphors present green upconversion luminescence under 980 nm excitation, luminescence intensity reaches to maximum at the Yb³⁺ and Er³⁺ concentration of 6 and 2 mol%. The temperature performance of the NaLa(WO₄)₂:Yb³⁺,Er³⁺ phosphors are evaluated based on thermal coupling technology. Temperature dependence of the two green emissions ratio of Er³⁺ ion is obtained, and the sensitivity of the sample can be calculated, the maximum sensitivity of NaLa(WO₄)₂:Yb³⁺,Er³⁺ is up to 0.019 K⁻¹ at the sample temperature of 564 K.