Enhanced upconverted luminescence and the optical thermometry behavior of Er3+-doped BaYbF5 transparent glass ceramics

Transparent SiO₂ - Al₂O₃ - Na₂O - CaO - BaF₂ - YbF₃ glass ceramics (GC) doped with Er³⁺ ions were successfully fabricated by a melt-quenching technique with subsequent heat treatment. The formation of BaYbF₅ nano-crystalline phase was confirmed by X-ray diffraction and transmission electron microscopy. Compared to the precursor glass (PG), the clearer Stark splitting and greatly enhanced up-conversion (UC) emission in GC indicate that Er³⁺ ions mainly enter into BaYbF₅ nanocrystals with low phonon energy after crystallization. The temperature dependent on purple UC emission ratio (which is due to the Er^{3+ 4}G_11/2→⁴I_15/2 and ²H_9/2→⁴I_15/2 transitions) and common green UC emission ratio with low-power excitation in BaYbF₅ GC have been studied respectively. In addition, the UC mechanisms in PG and GC are illustrated and analyzed. The outstanding properties of Er³⁺-doped BaYbF₅ transparent GC may present potential applications in all-solid-state UC lasers and optical fiber temperature sensors.     

Transparent Sr0.84Lu0.16F2.16: Yb3+, Er3+ glass ceramics: Elaboration,structure, up-conversion properties and applications

The development of optical temperature sensors is of fundamental and industrial importance for various applications. Despite the great advance in optical temperature-sensing techniques, challenges remain to search for novel sensing materials with low cost, easy fabrication and high sensitivity. Here, transparent glass ceramics (GC) embedded with cubic Sr_0.84Lu_0.16F_2.16:Yb³⁺/Er³⁺ nano-crystals were prepared via thermal annealing on the parent glass. The optical and structural properties were investigated. The enhanced emission intensity, obvious Stark splitting and prolonged lifetimes of Er³⁺ confirm the enrichment of Er³⁺ ions into formed Sr_0.84Lu_0.16F_2.16 nano-crystals. The temperature sensing performance of Yb³⁺/Er³⁺ ions in Sr_0.84Lu_0.16F_2.16GC were investigated based on up-conversion intensity ratio (FIR) from thermally coupled emitting states of Er³⁺. High energy difference ($\Delta E$?=?839?cm^?1) and high absolute sensitivity (27.4?×?10^?4?K^?1 at 606?K) are obtained. Our results reveal Sr_0.84Lu_0.16F_2.16GC are excellent host for rare earth ions doping and potential candidate for optical thermometry.     

Transparent sol-gel glass ceramics containing β-NaYF4:Yb3+/Er3+ nanocrystals: Structure,upconversion luminescent properties and optical thermometry behavior

Transparent bulk glass ceramics (GCs) containing $\beta ?\mathit{NaY}{\mathrm{F}}_4:{\mathit{Yb}}^{3+}/{\mathit{Er}}^{3+}$ upconversion nanocrystals were successfully prepared via a new sol-gel route for the first time. The structure, composition and morphology of the as-fabricated glass ceramics are characterized by X-ray diffraction ($\mathit{XRD}$), scanning electron microscopy ($\mathit{SEM}$) and transmission electron microscopy ($\mathit{TEM}$), which confirm the segregation of β-NaYF₄ nanocrystals in silica glass matrix with the maintenance of their crystalline phase and microstructure. More significantly, intense upconversion (UC) emissions can be realized for ${\mathit{Yb}}^{3+}/{\mathit{Er}}^{3+}$ co-doped glass ceramics by profiting from low-phonon-energy environment of erbium ions in β-NaYF₄ nanophase. Furthermore, temperature-dependent UC emission performance of the present GC is systematacially investigated to explore their potential application in optical thermometry. Obviously, owing to intense UC emissions of $\beta ?\mathit{NaY}{\mathrm{F}}_4:{\mathit{Yb}}^{3+}/{\mathit{Er}}^{3+}$ nanocrystals and high transparency, superior chemical/mechanical stability of oxide glassy matrix, the as-fabricated GCs exhibit good temperature sensing performance and good thermostability for precise temperature detecting. It is expected that the preliminary research can give a reference for designing new transparent bulk GCs and may exploit a valid method for developing high-performance optical temperature sensors.     

Efficient sensitization of Tb3+ emission by Dy3+ in CaMoO4 phosphors: Energy transfer,tunable emission and optical thermometry

Dy³⁺/Tb³⁺ codoped CaMoO₄ phosphors were synthesized by a simple sol–gel method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy. The energy transfer process of Dy³⁺→Tb³⁺ was confirmed by excitation and emission spectra and luminescence decay curves, and the energy transfer efficiency was also estimated. The results verified that the efficient emission of Tb³⁺ was sensitized by Dy³⁺ under the excitation of 354 nm, realizing tunable emission in CaMoO₄ phosphors. Furthermore, optical thermometry was achieved by the fluorescence intensity ratio between Tb³⁺: ⁵D₄→⁷F₅ (~546 nm) and Dy³⁺: ⁴F_9/2→⁶H_13/2 (~575 nm). It is expected that the investigated CaMoO₄ nanograins doped with Dy³⁺/Tb³⁺ have prospective applications in display technology and optical thermometry.     

High thermal stability pyroxene type CaScAlSiO6:Tb3+/Sm3+ ceramics with excellent cryogenic optical thermometry performance

The lanthanide-doped fluorescence intensity ratio (FIR) temperature measurement technology for detecting inaccessible objects has attracted the attention of many scholars. In fact, FIR technology can achieve high-precision and non-contact temperature measurement, which is widely used in the biomedical and industrial fields, among others. In this study, novel pyroxene-type CaScAlSiO₆:Tb³⁺/Sm³⁺ ceramics (CSAC) were synthesized using the traditional high-temperature solid-phase method, with the crystal structure, energy transfer mechanism, and optical behavior of the ceramics subsequently studied in detail. The use of ⁵D₄→⁷F₅ and ⁴G_5/2 → ⁶H_7/2 (I_544nm/I_602nm) energy level transitions as an optical thermometer has great potential, with the maximum absolute and relative sensitivity of the sensor found to be 0.1403 K^?1 and 1.65%K^?1, respectively. In addition, the material was cycled three times in the temperature range of 77–287 K and demonstrated a particularly high degree of credibility, with the luminous intensity having a particularly small effect on the temperature changes. Overall, the results indicate that the green-light-emitting CSAC:0.08Tb³⁺/0.01Sm³⁺ ceramic has great potential for use in optical cryothermometers.     

Germanate-based oxyfluoride transparent glass-ceramic embedded with Tm3+:Ca2YbF7 nanocrystals for high-performance optical thermometer

Germanate-based oxyfluoride transparent glass-ceramic functionalized by Tm³⁺:Ca₂YbF₇ nanocrystals was newly developed. The tremendously enhanced upconversion emission of ³F_2,3 energy levels by in situ crystallization was extremely beneficial for constructing optical thermometry involving the indirect thermally coupled energy levels (¹G₄ and ³F_2,3) of Tm³⁺ ions. Utilizing the fluorescence intensity ratio technique, the thermometry potentials of PG and GC8 were systematically evaluated based on the emissions from ³F_2,3 and ¹G₄ energy levels. The relative and absolute sensitivities, thermometry resolutions, and repeatabilities were superior to many reported materials. This work provides an avenue for precipitating ternary fluoride nanocrystals containing rare earths in germanate-based oxyfluoride glass, and proposes a promising way to achieve high performance optical thermometry based on the emissions from widely spaced energy levels.     

Luminescence and optical thermometry strategy based on emission and excitation spectra of Pr3+ doped SrMoO4 phosphors

Recent developments of luminescence ratiometric thermometry have attracted much attention owing to its merits of fast response, non-invasiveness and high spatial resolution. In this work, the synthesis, crystal structure and luminescence properties has been carried out for Pr³⁺-activated SrMoO₄ phosphors as optical thermometry. The XRD results show that all the phosphors possess the scheelite type tetragonal structure with space group I4₁/a. The efficient luminescence of Pr³⁺ can be observed under intra-configurational (4f-4f) and charge transfer band (Mo–O) excitations, respectively. Upon different excitations, the quenching concentration of Pr³⁺ is diverse due to the multi-phonon relaxation and cross-relaxation processes occurring in different excited states of Pr³⁺ ions. The fluorescence intensity ratio (FIR) techniques based on emissions of ³P₀ and ¹D₂ excited states of Pr³⁺, and the FIR in the excitations of the charge transfer band (Mo–O) and 4f-4f transitions of Pr³⁺ were employed for the thermometric characterizations in the 298–498 K range. Both results show remarkable performance in temperature sensing with the maximum relative sensitivity of 0.45%K^?1@489 K and 0.98 %K^?1@298 K, respectively. Our study demonstrates that Pr³⁺-activated SrMoO₄ phosphors have a promising potential application in non-contact optical thermometry.     

Luminescence and optical thermometry based on silico-carnotite Ca3Y2Si3O12: Pr3+ phosphor

The photoluminescence and temperature sensitivities of Ca₃Y₂Si₃O₁₂:Pr³⁺ thermo-phosphors with silico-carnotite structure obtained by solid state reaction method were investigated. Pr³⁺ ions were accommodated in the A sites having coordination number of 9 in AB₂C₂(SiO₄)₃ to replace Y³⁺ ions. The typical sample consisted of microcrystals with an irregular structure and the surface of particles was smooth, which could enhance the luminescence due to reducing the scattering and non-radiation produced by rough surfaces. The band gap value of typical sample was about 4.01 eV. Dipole-dipole interaction could account for concentration quenching. The two thermometry strategies including normalized intensities from ³P₀→³H₄ transition and Fluorescence intensity ration (FIR) of ³P₀→³H₄/³P₁→³H₅ transitions were employed for temperature sensing in 298–573 K. The results revealed that Ca₃Y₂Si₃O₁₂:Pr³⁺ thermo-phosphors had good temperature sensitivity performance with maximum S_r of 0.59% K^?1@573 K and 0.762% K^?1@298 K in the above two methods, respectively. Hence, Ca₃Y₂Si₃O₁₂:Pr³⁺ would be a promising candidate in the field of optical thermometry.     

Yb/Er/Ho-α-SiAlON ceramics for high-temperature optical thermometry

Maximum operating temperature in optical thermometry is limited due to poor thermal stability of the sensing material at high temperatures. Here, Yb, Er and Ho-doped α-SiAlON (Yb/Er/Ho-α-SiAlON) ceramic prepared by hot press method has been studied for optical thermometry via upconversion under 980 nm excitation. The phase of the sintered ceramic has been confirmed by Rietveld refinement of the X-ray diffraction data. The temperature-dependent upconversion was studied in a wide temperature range of 298–1023 K and fluorescence intensity ratio technique was used for temperature sensing behavior. Excellent spectral/thermal stability over the investigated temperature range was observed for the Yb/Er/Ho-α-SiAlON as the sensing material. The maximum values of absolute and relative sensitivity based on the thermally coupled levels of Er³⁺ are 59.2 × 10^?4 K^?1 and 1.10 %.K^?1 at 298 K and that based on non-thermally coupled levels are 108 × 10^?4 K^?1 at 385 K and 0.345 %.K^?1 at 329 K, respectively.     

Characterization and modeling of microstructural stresses in alumina

Brittle failure is often influenced by difficult to measure and variable microstructure‐scale stresses. Recent advances in photoluminescence spectroscopy (PLS), including improved confocal laser measurement and rapid spectroscopic data collection have established the potential to map stresses with microscale spatial resolution (< 2 μm). Advanced PLS was successfully used to investigate both residual and externally applied stresses in polycrystalline alumina at the microstructure scale. The measured average stresses matched those estimated from beam theory to within one standard deviation, validating the technique. Modeling the residual stresses within the microstructure produced qualitative agreement in comparison with the experimentally measured results. Microstructure scale modeling is primed to take advantage of advanced PLS to enable its refinement and validation, eventually enabling microstructure modeling to become a predictive tool for brittle materials.     

Up-conversion luminescence and optical thermometry properties of transparent glass ceramics containing CaF2:Yb3+/Er3+ nanocrystals

A series of Yb³⁺/Er³⁺ codoped transparent oxyfluoride glass ceramics with various amounts of Yb³⁺ have been successfully fabricated and characterized. Under 980 nm laser prompting, the samples produce intense red, green and blue up-conversion emissions, and the emission intensities increase with Yb³⁺ concentration and heat treatment temperature. Before losing good transparency in the visible region, optimum emission intensities are obtained for the sample with 25 mol% of Yb³⁺ at a heat treatment temperature of 680 °C. A possible up-conversion mechanism is proposed from the dependence of emission intensities on pumping power. The fluorescence intensity ratio between the two thermally coupled levels ²H_11/2 versus ⁴S_3/2 was measured with the laser output power of 57 mW to avoid the possible laser induced heating effect. The fluorescence intensity ratio values in the temperature range from 295 K to 723 K can be well fitted with the equation: A exp (−∆E/k_BT), where A = 6.79 and ∆E=876 cm⁻¹. The relative temperature sensitivity at 300 K was evaluated to be 1.4% K⁻¹. All the results suggest that the Yb³⁺/Er³⁺ codoped CaF₂ glass ceramics is an efficient up-conversion material with potential in optical fiber temperature sensing.     

Bundle-shaped β-NaYF4 microrods: Hydrothermal synthesis,Gd-mediated downconversion luminescence and ratiometric temperature sensing

In this study, bundle-shaped β-NaYF₄ microrods with uniform morphology and good monodispersity were successfully synthesized via a facile, template-free and environmentally-friendly hydrothermal route. According to the time-dependent experimental results, the formation mechanism for the crystal phase and shape evolution process has been proposed via the Ostwald-ripening process. Under single wavelength irradiation at 250?nm, intense multi-color downconversion emissions can be obtained by co-doping Ce³⁺, Gd³⁺ and X³⁺ (X = Eu, Tb and Dy) into the as-synthesized β-NaYF₄ crystals, in which Gd³⁺ plays an intermediate role in transferring the excitation energy from sensitizer Ce³⁺ to activators X³⁺. Furthermore, the temperature-dependent emission behaviors of β-NaY_0.8Gd_0.2F₄:Ce³⁺/X³⁺ dual-emitting products have been systemically investigated to explore their possible application in self-calibrated optical thermometry. Impressively, the high temperature sensitivity, good signal discriminability and excellent thermal stability of the investigated dual-emitting phosphors making them a promising candidate for temperature sensing.     

Thermally enhanced near-infrared luminescence in CaSc2O4: Yb3+/Nd3+ nanorods for temperature sensing and photothermal conversion

Non-invasive photothermal therapy (PTT) is proposed as a powerful method for cancer treatment, in which a precise temperature monitoring is strongly recommended during the photothermal conversion process to prevent the damage of normal cells. Herein, ultra-sensitive optical thermometry with excellent resolution and outstanding light-to-heat conversion are simultaneously realized in CaSc₂O₄: Yb³⁺/Nd³⁺ nanorods. The temperature sensing of the nanorods is accomplished through fluorescence intensity ratio (FIR) technology based on the thermally coupled levels (TCLs) Nd³⁺: ⁴F_j (j = 7/2, 5/2, 3/2), of which the obtained absolute sensitivity is about 6.5 times larger than the optimal value of TCLs-based thermometers reported previously. Meanwhile, an intense thermal enhancement of Nd³⁺: ⁴F_j (j = 7/2, 5/2, 3/2) → ⁴I_9/2 transition is found due to the efficiency improvement of phonon-assisted energy transfer process between Yb³⁺ ions and Nd³⁺ ions. The penetrability of the near-infrared light emitting by Nd³⁺ ions is determined by a simple ex vivo experiment, indicating a penetration depth of 8 mm in the biological tissues with negligible effect on FIR values. Beyond that, the nanorods show remarkable photothermal conversion capacity under the excitation of 980 nm wavelength. The properties mentioned above show enormous potentiality of the present nanorods for PTT along with a real-time temperature sensing.     

Improved photoluminescence and multi-mode optical thermometry of Er3+/Yb3+ co-doped (Ba,Sr)3Lu4O9 phosphors

Contactless optical thermometers have attracted extensive attentions for applications in scientific research and technological fields due to their apparent advantages. Herein, a novel sequence of Ba_3-xSr_xLu₄O₉ (B_3-xS_xLO):Er³⁺/Yb³⁺ phosphors were successfully prepared to investigate the temperature sensing property. By establishing energy transfer from Yb³⁺ to Er³⁺ and regulating the local lattice environment, up-conversion luminescence of Er³⁺ is dramatically improved when excited by 980 nm laser. This can effectively promote signal-noise ratio and reduce the errors in temperature detection. Furthermore, a multi-mode optical thermometry, which includes the fluorescence intensity ratio (FIR) from two thermally coupled levels of ²H_11/2/⁴S_3/2, FIR based on non-thermally coupled system of ²H_11/2/⁴F_9/2 and fluorescence lifetime of ⁴S_3/2 state of Er³⁺, was explored systematically. The fabricated samples exhibit the superior temperature measurement performances containing wide temperature-sensing range, superior signal discriminability, high sensitivity and favorable repeatability, indicative of the enormous utilization prospects of B_3-xS_xLO:Er³⁺/Yb³⁺ for thermometry.