Multifunctional optical thermometry based on the stark sublevels of Er3+ in CaO-Y2O3: Yb3+/Er3+

A conventional high temperature solid state method was utilized to prepare CaO-Y₂O₃, which is a potential candidate for manufacturing crucible material to melt titanium and titanium alloys with low cost. Meanwhile, Yb³⁺ ions and Er³⁺ ions were selected as the sensitizers and activators respectively to dope into CaO-Y₂O₃, aimed at providing real-time optical thermometry during the preparation process of titanium alloys realized using fluorescence intensity ratio (FIR) technology. The results reveal that a high measurement precision can be acquired by using the Stark sublevels of Er^{3+ 4}F_9/2 to measure the temperature with a maximum absolute error of only about 3 K. In addition, by analyzing the dependence of ⁴I_13/2 → ⁴I_15/2 transition on pump power of 980 nm excitation wavelength, it was found that the laser-induced thermal effect has almost no influence on the temperature measurement conducted by using the FIR of the Stark sublevels of Er^{3+ 4}I_13/2, which means that a high excitation pump power can be used to obtain strong NIR emission and good signal-to-noise ratio for optical thermometry without the influence of the laser-induced thermal effect. All the results reveal that CaO-Y₂O₃: Yb³⁺/Er³⁺ is an excellent temperature sensing material with high measurement precision.     

Dual-mode optical thermometry and multicolor anti-counterfeiting based on Bi3+/Er3+ co-activated BaGd2O4 phosphor

Here, Bi³⁺, Er³⁺ co-activated gadolinium phosphors with multimode emission properties are prepared, which can emits blue, green, and orange light under the excitation of ultraviolet, 980 and 1550 nm, respectively. Moreover, BaGd₂O₄:Bi³⁺, Er³⁺ can show multicolor luminescence under different excitation conditions, such as pump light source, ambient temperature, working current, and other factors. Based on the dynamic luminescence characteristics, the dynamic anti-counterfeiting experiments are designed based on the phosphor. At the same time, the material also shows multimode temperature sensing characteristics. Under the excitation of 980 nm laser, three strong up-conversion signals Er³⁺ ions are generated at 528 nm (²H_11/2), 555 nm (⁴S_3/2), and 668 nm (⁴F_9/2), which have different temperature dependences. Based on the fluorescence intensity ratio between thermal-coupled energy levels (²H_11/2/⁴S_3/2) and nonthermal-coupled energy levels (²H_11/2/⁴F_9/2) of Er³⁺ ions, respectively, the dual-mode temperature thermometer was constructed with high-temperature sensitivity. In addition, the fluorescence lifetime of Bi³⁺ ions also has a strong temperature dependence, which can be used as another temperature detection signal, greatly improving the stability of thermometers under harsh conditions. Therefore, the material has a bright prospect in the field of anti-counterfeiting and 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.     

Broad-scope dual-mode modulation thermometry based on up-conversion phosphor GaNbO4: Yb3+/Er3+

Fluorescence temperature measurement technology has set off another upsurge in non-contact temperature measurement, but still suffers from the large error for single-mode thermometry. Herein, in a broad temperature range of 93–633 K, a dual-mode modulation thermometry based on up-conversion phosphor of GaNbO₄:Yb³⁺/Er³⁺ is realized with the maximum relative sensitivity (S_r) of 11.7% K⁻¹ (93 K) and 13.1% K⁻¹ (123 K), respectively. GaNbO₄:Yb³⁺/Er³⁺ phosphors were synthesized by high temperature solid-state method. The structure, surface morphology and the optical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL). The fluorescence intensity ratio (FIR) readout method based on Er³⁺ thermal-coupled energy level (TCL) and non-thermal-coupled energy level (NTCL) was used to achieve the dual-mode temperature measurement with high temperature resolution and good repeatability in GaNbO₄:5 mol% Yb³⁺ and 5 mol% Er³⁺ phosphors. All the results show that GaNbO₄:Yb³⁺/Er³⁺ phosphors have great application potential in high sensitivity broadband thermometry.     

Dual-activator luminescence of LuAG:Mn4+/Tb3+ phosphor for optical thermometry

Mn⁴⁺ and Tb³⁺ singly doped and Mn⁴⁺/Tb³⁺ codoped lutetium aluminum garnet (Lu₃Al₅O₁₂, or simply LuAG) phosphors were synthesized and investigated for the application of optical thermometry. X-ray powder diffraction and luminescence spectroscopy measurements were performed on all samples to analyze their crystal phases and optical properties. In particular, temperature-dependent luminescence of the LuAG:Mn⁴⁺/Tb³⁺ sample was measured at the temperature range of 270–420 K. The results showed that the luminescence intensity of Mn⁴⁺ has gone through a remarkable decline while the luminescence of Tb³⁺ has an only insignificant change with the rise of temperature which leads to a dramatic decrease in the fluorescence intensity ratio (FIR) between the two activator Mn⁴⁺ and Tb³⁺. Further analysis showed that the LuAG:Mn⁴⁺/Tb³⁺ sample used for temperature sensing has a high relative sensitivity with maximum value of 4.3% K⁻¹ at 333 K. Our research indicated that this LuAG:Mn⁴⁺/Tb³⁺ material is a promising candidate for FIR-type optical temperature sensing.     

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.     

Effect of Gd3+/Ga3+ on Yb3+ emission in mixed YAG at cryogenic temperature

We investigated the effect of Gd³⁺ and Ga³⁺ on Yb:YAG emission at cryogenic temperatures by preparing ceramic pellets by solid state reaction method with different Gd³⁺ and Ga³⁺ content. Incorporation of Gd³⁺ shows only a small effect on spectral broadening whereas incorporation of Ga³⁺ in Yb:YAG results in significant broadening. Such an inhomogeneous broadening is due to the replacement of larger Ga³⁺ ion in two different cationic sites of Al³⁺ which causes a change in local crystal field on the Yb³⁺ site.     

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.     

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.     

Fabrication and optical thermometry of transparent glass-ceramics containing Ag@NaGdF4: Er3+ core-shell nanocrystals

Novel transparent glass-ceramics containing Ag@NaGdF₄:Er³⁺ core-shell nanocrystals were fabricated successfully by a melt-quenching method and subsequent heating. X-ray diffraction and transmission electron microscope images show that precious metal Ag is successfully encapsulated by the NaGdF₄:Er³⁺ nanoparticles to form an Ag@NaGdF₄:Er³⁺ core-shell structure in glass matrix. Compared with the NaGdF₄:Er³⁺ glass-ceramics, Ag@NaGdF₄:Er³⁺ core-shell glass-ceramics shows the great enhancement of emission intensity. The thermometric parameters such as fluorescence emission intensity, fluorescence intensity ratios of thermally coupled levels (²H_11/2/⁴S_3/2), and temperature sensitivity can be effectively controlled by changing the Ag concentration. When 0.15 mol% Ag is co-doped, the sensitivity of S_R in Ag@NaGdF₄:Er³⁺ core-shell glass-ceramics reaches a maximum value. This work presents a new method to enhance emission intensity and optical thermometry ability of NaGdF₄:Er³⁺ through constructing Ag@NaGdF₄:Er³⁺ core-shell structure.     

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.     

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.     

Temperature dependent upconversion properties of Yb3+:Ho3+ co-doped Gd2O3 nanoparticles prepared by pulsed laser ablation in water

Yb³⁺:Ho³⁺ co-doped Gd₂O₃ nanoparticles were successfully synthesized by pulsed laser ablation in water under different laser energy. The phase structure, morphology, crystallization and upconversion photoluminescence properties of obtained samples were investigated using X-Ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and photoluminescence spectra. The mechanism of the upconversion process was discussed based on the energy level diagram and power dependent upconversion emission. Upconversion mechanisms and thermal effects caused by absorption of excitation laser were discussed. Temperature dependent green and red emissions of Yb³⁺:Ho³⁺ co-doped Gd₂O₃ nanoparticles under the excitation of 980 nm were investigated in the low temperature range of 130 K–280 K. Non-radiative decay rate theory was used to explain the difference of quenching rates of green and red emissions. A further study on temperature sensing properties based on fluorescence intensity ratio (FIR) of green and red emissions was carried out. The FIR as a function of temperature can be well fitted by the model based on the thermal quenching theory. The relative sensitivity reaches its maximum value of 0.804% K⁻¹ at 216 K.     

Enhanced up-conversion luminescence and optical thermometry characteristics of Er3+/Yb3+ co-doped Sr10(PO4)6O transparent glass-ceramics

In this paper, the Yb³⁺/Er³⁺ co-doped parent glass (PG) with composition (in mol%) of 30P₂O₅-10B₂O₃-38SrO-22K₂O and transparent glass-ceramics (GCs) containing hexagonal Sr₁₀(PO₄)₆O nanocrystals (NCs) were synthesized for the first time by melt-quenching method and subsequent heating treatment in air. Under 980 nm laser prompting, the GCs samples showed intense red and green up-conversion emissions compared to those characteristics for the PG sample. The emission intensities varied with Er³⁺ concentration and heat treatment conditions. Furthermore, in Yb³⁺/Er³⁺ co-doped GCs specimens, the optical thermometry was researched by means of fluorescence intensity ratio (FIR) of ⁴S_3/2 and ²H_11/2 levels. The GC sample heated at 620°C for 5 hours possessed a high relative temperature sensitivity (S_r) of 0.769% K⁻¹ at 303 K and the maximal absolute temperature sensitivity (S_a) of 5.951 × 10⁻³ K⁻¹ at 663 K, respectively. It is expected that the as-fabricated GC materials with Sr₁₀(PO₄)₆O NCs are promising efficient up-conversion materials for optical temperature sensor.     

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.     

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.     

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.     

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.     

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.     

Optical properties of the CaEuAl3O7 phosphor with dual-activator Eu2+/Eu3+ for multifunctional applications

At present, most blue-red composite LED light sources are widely used in the field of plant lighting. However, their full-width at half-maximum of blue light is too small to meet the requirements of plants for photosynthesis. Herein, a dual-emitting single-phase self-luminescent phosphor CaEuAl₃O₇ (CEAO) is reported in this study, which provides broadband blue emission of Eu²⁺ ions and red emissions of Eu³⁺ ions. According to the optical properties of Eu²⁺ and Eu³⁺ ions in the CEAO phosphor, it can be found that all emissions are consistent with the absorption of chlorophylls and pigment carotenoids. In addition, the temperature sensing based on the fluorescence intensity ratio (FIR) in the CEAO phosphor is also studied and the maximum sensitivity (S) can reach as high as 6.90% K⁻¹ at 313 K. The results indicate that the single-component phosphor CEAO with blue and red double-color emission possesses an outstanding potential in plant growth lamps and optical thermometry applications.