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.     

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.     

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.     

Thermal enhancement of up-conversion luminescence in Lu2W2.5Mo0.5O12: Er3+, Yb3+ phosphors

Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors were synthesized through high temperature solid state method. Under 980 nm laser excitation, the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ compounds show thermal enhancement of up-conversion luminescence (UCL), which is attributed to the lattice contraction and distortion from negative thermal expansion (NTE) of Lu₂W_2.5Mo_0.5O₁₂ host enhancing the energy transfer of Yb³⁺ to Er³⁺, eliminating the energy transfer of Er³⁺ to Er³⁺ through Er³⁺ single-doped Lu₂W_2.5Mo_0.5O₁₂ phosphors without thermal enhancement of UCL. The green luminescence intensities at 693 K of the Lu_1.98-xW_2.5Mo_0.5O₁₂: 0.02Er³⁺, xYb³⁺ (x = 0.2, 0.3, 0.4) samples are 4.6, 4.3 and 7.0 times as that of 302 K, respectively. And through fluorescence intensity ratio (FIR) technique, the corresponding maximum absolute sensitivities are 0.00741, 0.00744 and 0.00723, respectively. The green monochromaticity of UCL spectra in Er³⁺/Yb³⁺ co-doped samples increase with the increasing of temperature, and the possible UCL mechanism with temperature was discussed. The results indicate that the Lu₂W_2.5Mo_0.5O₁₂: Er³⁺/Yb³⁺ phosphors can be applied at a high temperature as optical thermometer with a good green monochromaticity.     

Temperature self-monitoring photothermal nano-particles of Er3+/Yb3+ Co-doped zircon-tetragonal BiVO4

Self-monitored photo-thermal therapy (PTT) still faces huge challenge in cancer treatment, which aims to realize the real-time temperature reading during the course of optical heating. Exploiting new-type photo-thermal therapeutic agent (PTA) with thermometric function is considered to be one of effective methods to fulfill self-monitored PTT. In this work, spindle-like zircon-tetragonal (z-t) phase BiVO₄:Yb³⁺/Er³⁺ up-conversion (UC) nano-particles as self-monitored PTAs were prepared through the combination of co-precipitation and hydrothermal method. Under 980 nm laser diode excitation, real-time thermometry was accomplished by monitoring thermo-responsive emission intensity ratio of Er³⁺ (²H_11/2/⁴S_3/2 → ⁴I_15/2) transitions. Meanwhile, the photo-thermal conversion effect associated with UC process was trigged via the non-radiative transition channels. Considering the balance between UC emission intensity and heat generation, the optimal sample composition was determined as BiVO₄:20%Yb³⁺/3%Er³⁺. Their maximum absolute sensitivity (S_a) reached 0.0125 K^-1 at 460 K as the thermometer and the ability of photo-thermal conversion up to 3.32 K cm²/W as PTAs. Their potential applications in controlled subcutaneous photo-thermal treatment were estimated through ex vivo experiments. Results provided a new choice for nano-materials to realize real-time temperature feedback in the single host material (z-t BiVO₄) during the course of PTT.     

Enhancement of up-conversion emission and emerging cool white light emission in co-doped Yb3+/ Er3+: Li2O-LiF-B2O3-ZnO glasses for photonic applications

A series of co-doped (Yb³⁺/Er³⁺): Li₂O-LiF-B₂O₃-ZnO glasses were prepared by standard melt quenching technique. Structural and morphological studies were carried out by XRD and FESEM. Phonon energy dynamics have been clearly elucidated by Laser Raman analysis. The pertinent absorption bands were observed in optical absorption spectra of singly doped and co-doped Yb³⁺/Er³⁺: LBZ glasses. We have been observed a strong up-conversion red emission pertaining to Er³⁺ ions at 1.0 mol% under the excitation of 980 nm. However, the up-conversion and down conversion (1.53 µm) emission intensities were remarkably enhanced with the addition of Yb³⁺ ions to Er³⁺: LBZ glasses due to energy transfer from Yb³⁺ to Er³⁺. Up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses exhibits three strong emissions at 480 nm, 541 nm and 610 nm which are assigned with corresponding electronic transitions of ²H_9/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 respectively. Consequently, the green to red ratio values (G/R) also supports the strong up-conversion emission. The Commission International de E′clairage coordinates and correlated color temperatures (CCT) were calculated from their up-conversion emission spectra of co-doped (Yb³⁺/Er³⁺): LBZ glasses. The obtained chromaticity coordinates for optimized glass (0.332, 0.337) with CCT value at 5520 K are very close to the standard white colorimetric point in cool white region. These results could be suggested that the obtained co-doped (Yb³⁺/Er³⁺): LBZ glasses are promising candidates for w-LEDs applications.     

Temperature-sensing characteristics of NaGd(MoO4)2: Sm3+, Tb3+ phosphors

In this study, Sm³⁺/Tb³⁺-co-doped NaGd(MoO₄)₂ phosphors were prepared via the hydrothermal method, with sodium citrate used as a chelator. X-ray diffraction confirmed the structure of the samples, and the test outcomes showed that the phosphors exhibited a body-centered tetragonal structure. Field-emission scanning electron microscopy results showed that the specimen morphology changed with the change in the Cit^3?/Re³⁺ molar ratio. Moreover, the measured temperature-dependent emission spectra showed that Sm³⁺ and Tb³⁺ had different quenching trends; thus, the fluorescence intensity ratio can be used to represent temperature. In addition, the outcome of this experiment revealed that the temperature-sensing sensitivity of the phosphors gradually increased with the increasing Cit^3?/Re³⁺ ratio, and the highest sensitivity value was 0.346 K^?1 (at 503 K, Cit^3?/Re³⁺ = 2). When the temperature was 298–369 K, the temperature-sensing relative sensitivity increased with increasing Cit^3?/Re³⁺, but in the range 374–503 K, the relative sensitivity decreased with increasing Cit^3?/Re³⁺. The highest relative sensitivity value of the sample was 2.7% K^?1 (404 K, Cit^3?/Re³⁺ = 0). Additionally, the Commission International del’Eclairage chromaticity coordinates displayed that the luminous colors of Sm³⁺/Tb³⁺-co-doped specimens continuously changed from green to red as the temperature changed.     

Enhanced up-conversion luminescence of Tb3+-Yb3+ doped glass ceramics by doping Li+

Tb³⁺-Yb³⁺ co-doped transparent glass ceramics (GCs) containing Y₂Ti₂O₇ crystal phases were synthesized by the melt crystallization. The light transmittance of GCs in the visible region reached 78%, and the average grain size was 278 nm under the optimal heat treatment conditions (720 °C/2 h). The GCs exhibited greater up-conversion luminescence intensity than precursor glass, and the reason for this result was explained in accordance with the Judd-Ofelt theory. Moreover, the introduction of Li⁺ did not change the crystalline phase of GCs. The emission intensity of the green light of the 8% Li ⁺ doped GCs was significantly enhanced by nearly 4.48 times under 980 nm excitation. The XRD refinement results suggest that the enhanced luminescence intensity is correlated with the change of the Y₂Ti₂O₇ crystal lattice caused by Li⁺ doping. The relevant luminescence mechanism was elucidated. The results suggest that Li⁺ doped transparent GCs open novel avenues for green UC applications.     

Sensitive temperature reading from intensity ratio of Cr3+ and defects’ emissions in MgTiO3:Cr3+

The luminescence thermometry based on the intensity ratio of Cr³⁺ and host emissions in the Cr³⁺ activated MgTiO₃ phosphor powder is demonstrated over the 100–350 K temperature range. Phosphor was prepared by a two-step procedure based on the sol-gel and molten salt methods. Rhombohedral crystal structure of the material is confirmed by X-ray diffraction analysis, and the mean crystallite size of the powder was calculated to be ~ 32 nm. Morphology was investigated using scanning electron microscopy showing ellipsoidal, densely packed grains with 100 nm–150 nm average size. Photoluminescence emission spectra recorded under 385 nm excitation showed the broad host emission centered at ~ 485 nm and the Cr³⁺ emission around ~ 700 nm. The temperature-dependent emission spectra showed that host-emission intensity is almost temperature invariant, while the intensity of the Cr³⁺ emission rapidly decreases from 200 K to 350 K. Such behavior theoretically modelled and further applied for the ratiometric luminescence temperature sensing showed the maximal relative sensitivity of ~ 2.6% K^-1, temperature resolution of 0.3 K, and excellent repeatability.     

Preparation and mid-infrared 2.7 µm luminescence property of high content Er3+-doped (Y0.9La0.1)2O3 transparent ceramics pumped at 980 nm

High content Er³⁺ doped (Y_0.9La_0.1)₂O₃ transparent ceramics have been prepared by conventional ceramic process. Absorption spectra, mid-infrared, up-conversion and near-infrared emission spectra of Er³⁺ pumped at 980 nm have been investigated. The mechanisms of energy transfer processes have been discussed. Large values of Judd–Ofelt parameter Ω₂ (5.73 × 10^–20 cm²) and spectral quality factor X (3.71) have been obtained. The greatly enhanced green up-conversion emission in the high Er³⁺ doped sample is considered important for the applications in up-converters. The much enhanced mid-infrared 2.7 µm and up-conversion emissions, as well as the depressed near-infrared 1.5 µm emission demonstrate the efficient population inversion of Er³⁺:⁴I_11/2 → ⁴I_13/2 in high Er³⁺-doped ceramics for the 2.7 µm emission. These results suggest that high Er³⁺-doped (Y_0.9La_0.1)₂O₃ transparent ceramics are promising host materials for the applications of mid-infrared lasers and infrared-to-visible up-converters.