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DALTON TRANSACTIONS · 2022 ·Vol. 51 ·期 12 ·4685-4694 · IF 4.569

Synergistic luminescent thermometer using co-doped Ca2GdSbO6:Mn4+/(Eu3+ or Sm3+) phosphors

Guixian Li,Yu Xue,Qinan Mao,Lang Pei,Hong He,Meijiao Liu,Liang Chu,Jiasong Zhong

Luminescent thermometers provide a non-contact method of probing temperature with high sensitivity and response speed at the nanoscale. Synergistic photoluminescence from different activators can realize high sensitivity for luminescent thermometers by finely selecting ions with specific crystallographic sites. Herein, the more temperature-sensitive Mn4+ and the less-sensitive Eu3+ (or Sm3+) activators are co-doped into a Ca2GdSbO6 matrix to form an effective thermometer, where Mn4+ and Eu3+ (or Sm3+) ions occupy the Sb5+ and Gd3+ sites, respectively. The co-doping of Eu3+ ions or Sm3+ ions leads to lattice expansion of Ca2GdSbO6 matrix and a tuned narrow emission from deep-red to orangish-red. According to the ratio of luminescence intensity, the maximal Sa and Sr values are 0.19 K−0 (347 K) and 1.38% K−( (420 K) for Ca2GdSbO6:Mn4+/Eu3+ probe and 0.26 K−p (363 K) and 1.55% K−( (430 K) for Ca2GdSbO6:Mn4+/Sm3+ probe thermometers, respectively. In addition, thermometers based on Mn4+ emission lifetimes can provide the highest relative sensitivity of 1.47% K−s at 425 K. Thus, the highly-temperature-sensitive Ca2GdSbO6:Mn4+/(Eu3+ or Sm3+) phosphor is a promising candidate for practical luminescence thermometers.

研究领域: 材料科学 · 无机化学 · 光学材料 · 纳米技术 · 生物传感
✓ 已验证 DOI 高影响因子
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ACS Applied Optical Materials · 2025 · IF 3.8

Multifunctional Cr3+ Ion-Activated Sr2Sc2B4O11 Broadband Near-Infrared Phosphor with High Luminescence Thermal Stability through the Deformation Constraint

Bo Gao,Xiao Zang,Xiuhui Yin,Baolei Qi,Jiahao Li,Zewen Dong,Xufeng Zhou,Wei Li,Yangbo Wang,Huaiyong Li

Broadband near-infrared (NIR) phosphors emitting in the 700–1000 nm range find extensive applications in night vision, medical image, and food analysis. High luminescence thermal stability of their spectra is crucial for maintaining consistent and reliable output under various thermal conditions. Microcrystalline powders of Sr2Sc2B4O11:Cr3+ are synthesized, and their photoluminescence (PL) properties are studied as functions of Cr3+ concentration, temperature, and excitation power. The energy band structure and phonon density of states of the Sr2Sc2B4O11 lattice are studied theoretically. It is revealed that Sr2Sc2B4O11 is an indirect bandgap material with a bandgap of 3.16 eV. Sr2Sc2B4O11:Cr3+ shows broadband NIR emission centered at 825 nm upon 455 nm excitation with lifetimes on the order of 100 μs from 80 to 600 K. The PL shows good luminescence thermal stability with a quenching temperature of 380 K. Notably, 57% of the room-temperature PL intensity is retained at 423 K. The high luminescence thermal stability of the PL may be attributed to the constraint on the deformation of ScO6 polyhedra through the formation of dimers. A luminescence thermometer based on the lifetime of Sr2Sc2B4O11:Cr3+ is proposed. It is determined that the relative sensitivity of the thermometer increases gradually from 80 to 600 K and exceeds 0.5% K–1 starting from 300 K.

研究领域: 材料科学 · 光学 · 无机化学 · 固体物理
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PROGRESS IN SOLID STATE CHEMISTRY · 2024 · IF 9.1

Novel Mn5+-activated Ba2TiO4 phosphor emitting in the second near-infrared biological window

Hang Zhao,Xin Xin,Liangsheng Tian,Theeranun Siritanon,Suwit Suthirakun,Wongsathorn Kaewraung,Menghang Qi,Ruoxiu Xiao,Jingyi Ren,Peng Jiang

In recent years, second near-infrared window emitting phosphors have gained widespread research interest due to their excellent tissue penetration and high imaging accuracy. In this work, a new type of Ba 2 Ti 1- x Mn x O 4+ x /2 (0.02 ≤ x  ≤ 0.10) phosphors were successfully prepared by high-temperature solid-phase method and their potential in luminescence thermometry is evaluated. PL and PLE spectral analysis prove that the optimal Mn doping concentration is x  = 0.03. The as-synthesized phosphors exhibit a broad excitation band of 550–1000 nm and a narrow emission band of 1170–1220 nm. The electronic structures of the original Ba 2 TiO 4 and Mn-doped Ba 2 TiO 4 were calculated and analyzed using the DFT + U method, which facilitates a better understanding of the impact of Mn doping on the luminescent properties of Ba 2 TiO 4 . The luminescence decay lifetime is measured to be 101.44 μs at room temperature, which is a giant enhancement compared to conventional nanosecond lifetime phosphor, indicating a progress in imaging accuracy. In addition, the as-synthesized phosphors maintain over 75 % of the maximum luminescence intensity within the physiological temperature range. The potential applications in luminescence temperature measurement were also analyzed by the LIR ratio method, and the relative sensitivity could reach 2.31 %K −1 at 283 K, which is a relatively high value in the second near-infrared window. Therefore, the as-synthesized Ba 2 Ti 1- x Mn x O 4+ x /2 (0.02 ≤ x  ≤ 0.10) phosphors demonstrate great potential in NIR applications such as biological imaging and luminescent thermometry.

研究领域: 材料科学 · 生物医学工程
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JOURNAL OF LUMINESCENCE · 2023 · IF 3.6

Upconversion of Yb3+/Ho3+ co-doped bismuth oxyfluoride and fluoride microcrystals for high-performance ratiometric luminescence thermometry

Runfa Liu,Yue Pan,Jia Zhang,Xincui Zhuang,Yangbo Wang,Xufeng Zhou,Shanshan Du,Huaiyong Li,Wei Li

Ratiometric luminescence thermometry is awfully applicable for non-contact temperature detection. Lanthanide luminescent materials available for high-performance ratiometric thermometry are still highly desirable until now. Herein, two novel upconversion phosphors, Yb 3+ /Ho 3+ co-doped BiOF and BiF 3 microcrystals , were synthesized and investigated systematically in terms of their crystalline structure, room temperature and temperature-dependent upconversion properties. Under 980 nm laser excitation, both microcrystals bring forth the characteristic emissions of Ho 3+ , with an identical overall luminescent color of green, while the intensity is much higher in BiF 3 :Yb/Ho microcrystals. When increasing temperature, the upconversion intensity at various wavelengths for both microcrystals is reduced, meanwhile fluorescence intensity ratios of both 545/656 nm and 752/656 nm decrease highly regularly, establishing a ratiometric thermometry therefore. BiF 3 :Yb/Ho microcrystals were demonstrated to have significantly superior thermometric performance than BiOF:Yb/Ho, and a high relative sensitivity up to 5.41% K −1 as well as a wide temperature sensing range of 298–673 K were obtained.

研究领域: 材料科学 · 光学
✓ 已验证 DOI 高影响因子
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JOURNAL OF LUMINESCENCE · 2022 · IF 4.171

Eu3+/Tb3+ bimetallic complex-doped siloxane-polyether hybrid film for luminescent thermometry

Guangmin Xie,Yuan Wang,Xinzhe Zhou,Liang He,Huanrong Li

Developing a contactless ratiometric luminescent thermometry with high sensitivity, widely available temperature range, and reliable performance is still a challenge in materials science. Herein, we adopted an in-situ formation strategy to synthesize luminescent lanthanide complexes in siloxane-polyether matrix by the reaction between 4′-(4-carboxyphenyl)- 2,2′:6′,2″- terpyridine (Hcptpy) ligand and lanthanide ions (Eu 3+ /Tb 3+ ) to realize a ratiometric luminescent thermometer. The unique energy cascade from Hcptpy → Tb 3+ → Eu 3+ in siloxane-polyether enables the luminescent films to be not only the multi-color emission, but also provide highly temperature-sensitive over the wide temperature range. The EuTb 15 @SP film for luminescent thermometry performance is fine-tuned to reach a maximum relative sensitivity of 7.26% K −1 at 397 K and shows repeated utilization without sensitivity loss. Furthermore, the multi-color emission ranging from red through yellow to green can be achieved by tuning the Eu 3+ /Tb 3+ molar ratio. Consequently, utilizing siloxane-polyether as matrix has been proven to be an effective strategy for constructing lanthanide-based hybrid films with temperature sensor properties. We believe that the reported strategies for preparing a bimetallic complex-doped siloxane-polyether hybrid film will broaden potential applications.

CAS / MDL: 24801-88-5
研究领域: 材料科学 · 光学
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Laser & Photonics Reviews · 2024 ·Vol. 18 ·期 11 ·2400151 · IF 9.8

Thermal Enhancement of Er3+ NIR-II Luminescence by Ho3+-Mediated Energy-Trapping in Negative Thermal Expansion Nanocrystals

Jiaoyin Zhao,Jiwen Chang,Nan Wang,Peihang Zhao,Mengyuan Zhu,Ying Liu,Dongxu Guo,Yu Wang,Panlai Li,Zhijun Wang,Hao Suo

Thermal quenching of luminescence materials poses a major obstacle to the technological application of luminescence thermometry. It still remains challenging to attain thermally enhanced light emissions, especially in the second near-infrared window (NIR-II). Herein, an anomalous thermal dependence of NIR-II luminescence in the negative thermal expansion (NTE) Sc 2 Mo 3 O 12 :Er 3+ /Ho 3+ nanocrystals is reported. Mechanistic investigations affirm that Ho 3+ ion can work as an energy reservoir and back-transfer to Er 3+ ion with the assistance of lattice phonon at elevated temperatures. Moreover, the Ho 3+ -mediated energy feedback is strengthened by the thermal contraction between dopant ions, thereby enabling a remarkable thermal enhancement of NIR-II emission over 11-fold. The opposite thermal response of Er 3+ and Ho 3+ emissions is harnessed for NIR-II ratiometric thermometry, registering exceptional performance in a high-temperature regime ( S r = 1.71% K −1 , δT = 0.2 K at 513 K). These findings may inspire new insights for addressing the thermal quenching of NIR-II luminescence, which also raises exciting opportunities for flexible thermometry in complex settings.

研究领域: 材料科学 · 光学材料 · 纳米科技 · 生物医学工程 · 分子成像 · 温度传感
✓ 已验证 DOI 高影响因子
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CERAMICS INTERNATIONAL · 2024 · IF 5.1

La3Sc2Ga3O12:Cr3+, Nd3+ near-infrared phosphor for nondestructive detection and luminescence thermometry

Xin Xie,Wanyin Ge,Ye Tian,Qian Zhang,Maohao Yang,Chenge Wu,Peng He,Honglei Yin

To develop continuous broadband emission near-infrared (NIR) phosphors compatible with blue LED chips, numerous Cr 3+ -Yb 3+ co-doped phosphors have been synthesized. However, the emission spectra of Cr 3+ vary significantly across different matrix materials, while Yb 3+ maintains a relatively stable emission spectrum. This variation leads to notable luminescence depressions between 850 and 900 nm in many Cr 3+ -Yb 3+ co-doped phosphors. To address this emission spectrum gap, we utilized Cr 3+ as a sensitizer and introduced Nd 3+ as the luminescence center within the La 3 Sc 2 Ga 3 O 12 matrix material, establishing a Cr 3+ -Nd 3+ energy transfer channel. Under 480 nm excitation, we tuned emission peaks at 800 nm (Cr 3+ ) and 881 nm (Nd 3+ ). The stable NIR emission of Nd 3+ effectively compensates for the missing spectrum in Cr 3+ -Yb 3+ co-doping. The Cr 3+ -Nd 3+ energy transfer process was thoroughly analyzed using diffuse reflection spectrum, excitation spectrum, and fluorescence decay curves. The LSGO:0.125Cr 3+ , 0.03Nd 3+ compound with the best optical performance was packaged with a 480 nm LED chip to create a NIR light source. At a working current of 10 mA, it achieved a photoelectric conversion efficiency of 9.45 %, demonstrating its potential for applications in non-destructive detection and luminescence thermometry. This work presents a novel strategy for tuning NIR spectral distribution and developing continuous broadband NIR phosphors.

研究领域: 材料科学 · 光学 · 光子学 · 光谱学
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ChemNanoMat · 2023 ·Vol. 9 ·期 4 ·e202200532 · IF 3.8

NIR-triggered Synergetic Photothermal and Chemotherapy Cancer Treatment Based on SiO2@Au@SiO2@QDs-DOX Composite Structural Particles

Xinbing Jiang,Lu Qiao,Huan Yang,Ben Q Li,Shujiang Ding

Graphical SiO 2 @Au@SiO 2 @QDs nanocomposite with dual-functionality of simultaneous heating and temperature sensing were prepared. The heating is activated by a NIR laser through SPR effect while thermal sensing is accomplished by QDs PL thermometry. These nanocomposites are used as a drug carrier for in vitro chemotherapy-photothermal co-treatment for malignant cells. This paper reports the synthesis of multi-layer SiO 2 @Au@SiO 2 @QDs nanoparticles with a dual-functionality of simultaneous heating and temperature sensing and their applications to in vitro chemo-thermal therapy. The heating is activated by a NIR-light through resonance excitation of surface plasma while in-situ thermal sensing is accomplished by the QDs photoluminescent (PL) effect. These dual function nanoparticles are used as a drug carrier for in vitro chemotherapy-photothermal co-treatment for malignant cells. A comparative study of drug release profiles was performed with and without 808 nm laser irradiation. The drug release rate was accelerated by a rise of temperature, which is induced by plasmonic heat generation associated with Au nanoshells; while the temperature change is monitored by the QD nanoparticles at the same time. The results showed that SiO 2 @Au@SiO 2 @QDs-DOX platform enabled the combination of local specific chemotherapy with external near-infrared (NIR) photothermal therapy and significantly improved the efficacy of cancer treatment. This combined treatment demonstrated synergistic chemotherapeutic-thermal effects compared to chemotherapy or photothermal therapy alone, resulting in higher efficacy.

CAS / MDL: 78-10-4
研究领域: 纳米技术 · 癌症治疗 · 材料科学 · 生物医学工程
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Journal of Materials Chemistry C · 2024 ·Vol. 12 ·期 33 ·12854-12861 · IF 5.7

Deconstructing excitation transitions in Dy3+-doped CaWO4 to develop a new ratiometric luminescent thermometry for achieving ultra-high sensing sensitivity

Qianrui Liu,Baosheng Cao,Miao Gao,Lulu Qiu,Yujie Weng,Yangyang He,Xiaoguang Han,Bin Dong

Investigating excitation transition behavior is crucial for elucidating the photoluminescence (PL) characteristics of lanthanide ion-doped phosphors. This investigation provides a basis for developing new ratiometric luminescent thermometry methods based on thermally influenced excitation processes. In this study, the excitation transition lines of trivalent dysprosium (Dy3+) and charger-transfer band (CTB) in Dy3+-doped CaWO4 (CaWO4:Dy) phosphors were effectively deconstructed using the Dy3+ concentration- and temperature-dependent PL excitation (PLE) spectra in the ultraviolet range of 280–340 nm. The phosphors exhibited a thermal-quenched PLE intensity for Dy3+ and a thermal-enhanced PLE intensity for CTB owing to energy transfer between the CaWO4 host and Dy3+. A new ratiometric thermometry strategy was introduced using the opposite thermal-dependent PLE intensity of CTB as the temperature probe and Dy3+ as the reference signal. This method was based on the excited-state absorption intensity ratio between CTB and Dy3+. This new thermometry method exhibited ultra-high performance, reaching maximum absolute and relative sensitivities of 1.72 K−1 at 575 K and 4.66% K−1 at 300 K, respectively. This study presents a novel approach for developing highly sensitive and stable optical thermometric Dy3+-based materials and provides guidance for constructing an effective ratiometric thermometry strategy based on the deconstructed PLE properties.

研究领域: 材料科学 · 光学传感 · 发光测温 · 光子学 · 稀土掺杂材料
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