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CERAMICS INTERNATIONAL · 2024 · IF 5.1

Energy transfer in dual-emission LiY6(BO3)3O5: Bi3+, Eu3+ phosphors for temperature sensing applications

Xiaoxuan Fan,Lirong Xu,Wen Liu,Feifei Yin,Jianbo Xu,Shuo Cao,Yadan Ding,Xia Hong,Tianya Tan,Kexin Wang,Jiwei Wang

In this work, a Bi 3+ and Eu 3+ co-doped borate oxide LiY 6 (BO 3 ) 3 O 5 (LYBO) phosphor was prepared using high temperature solid-state method. Eu 3+ can be well sensitized by Bi 3+ in the LYBO matrix under 305 nm excitation and produce well-separated emission bands with high intensity. The energy transfer from Bi 3+ to Eu 3+ results in the tunable multicolor emission from LYBO. The maximum energy transfer efficiency can reach 95.93 %. The Bi 3+ and Eu 3+ emissions exhibit the differentiated responses to thermal quenching. The fluorescence intensity ratios between 615 nm and 421 nm show a favorable linear relationship in the range of 123–483 K. It indicates the outstanding optical thermometry performance of LYBO: Bi 3+ , Eu 3+ . The maximum absolute sensitivity (S a ) and relative sensitivity (S r ) are determined to be 0.0087 K -1 and 3.84 % K −1 , respectively. The results exhibit that LYBO: Bi 3+ , Eu 3+ phosphor has a promising application as an optical thermometer in non-contact temperature measurement.

CAS / MDL: 554-13-2
研究领域: 材料科学 · 光学
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Chemosensors · 2022 ·Vol. 10 ·期 12 ·527 · IF 4.229

Microstructure and Photoluminescence of ZrTiO4:Eu3+ Phosphors: Host-Sensitized Energy Transfer and Optical Thermometry

Anheng Gu,Guo-Hui Pan,Huajun Wu,Liangliang Zhang,Ligong Zhang,Hao Wu,Jiahua Zhang

Orthorhombic ZrTiO4is an attractive dielectric material; its optical properties are, however, less known. In this paper, we reported on the microstructure and luminescence studies of pristine ZrTiO4and Eu3+-doped ZrTiO4phosphors. The results indicated that two types of TiO6octahedra, the isolated/ localized and coupled/delocalized, coexisted in host matrix. Eu3+doping could induce oxygen vacancy defect states located below the bottom of the conduction band. Pristine ZrTiO4showed bright yellow luminescence via STEs recombination at defects sites at low temperatures, but significant thermal quenching occurred due to STEs migration to quenching centers at elevated temperatures. Effective host sensitized energy transfer to Eu3+was observed in ZrTiO4:Eu3+phosphors and yielded the red characteristic emissions of Eu3+. Anomalous STEs luminescence enhancement and spectral blue-shift in the excitation spectra with higher Eu3 +concentration appeared and were explained by considering three factors: competitive absorption between electron transitions from the top of the valence band to the defect states and host conduction band, Eu3+doping driving the production of more isolated TiO6octahedra, and energy back-transfer from Eu3+activators to other titanate groups. On the basis of the dual-emitting combination strategy involving host STEs and Eu3+luminescence, ZrTiO4:Eu3+phosphors were demonstrated to be ratiometric self-referencing optical thermometric materials, with a working range of 153–313 K and a maxima of relative sensitivity to ~1.1% K−1at 243 K.

研究领域: 材料科学 · 光学
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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Enhancing thermometric performance via improving indicator signal in Bi3+-doped CaNb2O6:Ln3+ (Ln = Eu/Sm/Dy/Tb) phosphors

Hang Zhang,Hang Yang,Guogang Li,Shiqi Liu,Haoran Li,Yuming Gong,Yujun Liang,Yongjun Chen

Currently, phosphor materials play an important role in designing noncontact remote optical thermometers. Although many approaches have contributed to improve thermometric performance of optical thermometers including optimization of host materials, size of nanoparticles , dopant type and concentration as well as excitation density and phonon energy engineering, the development of highly sensitive optical thermometric materials is still a challenge. Hence, we developed novel CaNb 2 O 6 (CNO):Ln 3+ (Ln 3+  = Eu 3+ /Sm 3+ /Dy 3+ /Tb 3+ ) phosphors as highly thermometric materials and proposed a novel strategy for further enhancing its thermometric performance via adding the intensity of indicator signal by co-doping Bi 3+ ions in current phosphor system. Typically, the as-prepared CNO:Ln 3+ phosphors present a broad blue emission around 470 nm originated from NbO 6 octahedral groups and some respective emission lines derived from the characteristic f-f transitions of Ln 3+ ions. Based on the diverse thermal quenching performance between blue emission and Ln 3+ ions emission , the temperature sensitivities of CNO:Ln 3+ were investigated in detail. Among them, the maximum relative sensitivity of CNO:Eu 3+ sample reached 1.991% K −1 in the range of 298–448 K and remained 97% after five temperature cycles. Furthermore, an obvious discoloration was discovered during temperature cycle testing in CNO:Ln 3+ samples under 254 nm UV lamp. Through doping Bi 3+ ion, the strongest intensity of indicator signal is 24 folds that of CNO host. Correspondingly, the relative sensitivity of CNO:Bi 3+ , Eu 3+ sample is obviously improved to 3.793% K −1 in the range of 298–523 K, owing to a larger range of the FIR value and a wider drop range of indicator signal. This work opens up an effective pathway to improving thermometric performance of optical thermometers by enhancing the intensity of indicator signal of employed phosphor materials.

研究领域: 材料科学 · 光学工程
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JOURNAL OF ALLOYS AND COMPOUNDS · 2017 · IF 3.133

Sn2+/Mn2+ codoped strontium phosphate (Sr2P2O7) phosphor for high temperature optical thermometry

Yan Gao,Yao Cheng,Feng Huang,Hang Lin,Ju Xu,Yuansheng Wang

In this work, a new type of luminescent temperature sensor based on the Sn 2+ →Mn 2+ resonance energy transfer is designed, which shows great potential in high temperature optical thermometry. Using the micro-sized Sn 2+ /Mn 2+ :α-Sr 2 P 2 O 7 phosphor fabricated by carbon reduction method as optical thermometer, the sensitivity in the temperature range of 423 K–623 K is well superior to that for the other micro/nano luminescent temperature sensing materials reported previously, and the maximal absolute sensitivity reaches as high as 0.027 K −1  at 623 K. Analyses of the temperature-dependent photoluminescence spectra and configurational coordinate diagrams for Sn 2+ :α-Sr 2 P 2 O 7 and Mn 2+ :α-Sr 2 P 2 O 7 indicate that the temperature-sensitive variation in fluorescence intensity ratio of Sn 2+ to Mn 2+ is originated from the difference in thermal quenching activation energy for 3 P J (J = 0,1) levels of Sn 2+ (4053 cm −1 ) and 4 T 1 level of Mn 2+ (2464 cm −1 ). These results may provide useful inspiration for building highly sensitive self-referencing optical thermometers based on energy transfer induced sensitized luminescence.

研究领域: 材料科学 · 光学工程
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DALTON TRANSACTIONS · 2021 ·Vol. 50 ·期 40 ·14342-14351 · IF 4.39

A highly sensitive ratiometric optical cryothermometer using a new broadband emitting trivalent bismuth singly activated Ba2ZnSc(BO3)3 microcrystal

Shixiang Huang,Feng Zhang,Zhangyue Wu,Ying Fu,Chao Li

Motivated by the growing demand for noncontact temperature sensing in cryogenic environments, the development of a high performance low temperature optical thermometer has become more and more urgent. Herein, we demonstrate a new broadband emitting bismuth singly activated Ba2ZnSc(BO3)3 optical thermometric material that exhibits a remarkable temperature-dependent emission color variation and a good low temperature sensing performance. First, Bi3+ doped Ba2ZnSc(BO3)3 phosphors were successfully synthesized by a high-temperature solid-state reaction. Upon excitation at 320 nm, the emission spectra of Ba2ZnSc(BO3)3:Bi3+ cover almost the entire visible region from 350 to 720 nm because of the multiple crystallographic sites occupied by Bi3+ ions, which have been verified by structure analysis and time-resolved emission spectroscopy. Interestingly, the temperature dependent emission characteristics indicated that the thermal quenching phenomena of Bi3+ at different lattice sites were different, resulting in a very sensitive emission color variation from orange to cyan. Further analysis indicated that these Bi3+ doped luminescent materials showed a good performance in temperature sensing over a wide temperature range from 10 to 374 K, with a maximum relative sensitivity of 3.076% K−1 at 210 K. Finally, this study provides a new perspective for the design of superior thermosensitive phosphors, aimed toward non-rare earth ion doped thermosensitive phosphors for optical cryothermometry applications.

研究领域: 材料科学 · 光学工程
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OPTICAL MATERIALS · 2024 · IF 3.8

Investigation of Ca2Al2SiO7: Pr3+/Gd3+ UVB upconverting phosphor and its optical thermometric properties

Shanshan Zhao,Saima Kanwal,Weiwen Su,Hui Lin,Zhaoxia Han,Songlin Zhuang,Dechao Yu,Dawei Zhang

On basis of fluorescence intensity ratio (FIR) over certain narrow coupled levels of rare-earth ions, up-conversion of RE-doped materials perform excellent temperature-sensing abilities for thermometry applications. A series of Pr 3+ /Gd 3+ co-doped Ca 2 Al 2 SiO 7 phosphors (Ca 2 Al 2 SiO 7 :Pr 3+ /Gd 3+ ) were prepared by a conventional high-temperature solid-state reaction. Under excitation of blue ∼445 nm, the Ca 2 Al 2 SiO 7 :Pr 3+ /Gd 3+ phosphor yields intense photoluminescence (PL) bands around 489, 528, 537, 580, 604, 613, and 646 nm due to electronic transition of 3 P 0 → 3 H 4 , 3 P 0 → 3 H 5 , 3 P 1 → 3 H 5 , 3 P 1 → 3 H 6 , 1 D 2 → 3 H 4 , 3 P 0 → 3 H 6 , and 3 P 0 → 3 F 2 of Pr 3+ , respectively. Their relative intensities are sensitively determined by Pr 3+ contents, which, from 0.1 % to 5 %, tune the emission color from pink to warm white under excitation of 445 nm. It is of great interest that intense irradiation using a blue ∼445 laser does make efficient ultraviolet B (UVB) up-conversion at about 297, 306, and 313 nm, just stemming from the 6 P 3/2  →  8 S 7/2 , 6 P 5/2  →  8 S 7/2 , and 6 P 7/2  →  8 S 7/2 of Gd 3+ , respectively. A typical two-photon absorption process was proved to account for the UVB up-conversion, i.e. successive absorption of two blue ∼445 nm photons populating Pr 3+ 4f5d excited state, which further efficiently transfer its energy to the 6 I J / 6 P J states of Gd 3+ neighbor for UVB emission. Moreover, the thermally coupled levels (TCLs) of Gd 3+ : 6 P 3/2 - 6 P 7/2 , and Gd 3+ : 6 P 5/2 - 6 P 7/2 were thoroughly investigated for temperature sensing in 298–598 K. Maximum relative sensitivity of the 6 P 3/2 - 6 P 7/2 TCLs, i.e. S r (I 306 /I 313 ), is proved to be 0.96 % K −1 at 298 K, and that of the 6 P 5/2 - 6 P 7/2 TCLs, i.e. S r (I 297 /I 313 ), is 1 % K −1 at 373 K. The relevant thermal stabilities of the Ca 2 Al 2 SiO 7 :Pr 3+ /Gd 3+ thermometric candidate was well validated with 10 cycles of heating and cooling processes in 298–598 K. Such continuous explorations of Pr 3+ /Gd 3+ co-doping system will significantly promote the development of robust UVB up-converting phosphors as well as their practical applications in the field of high-resolution optical thermometry.

研究领域: 材料科学 · 光学 · 热测量技术
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INORGANIC CHEMISTRY · 2020 · IF 4.825

ZnGa2–yAlyO4:Mn2+,Mn4+ Thermochromic Phosphors: Valence State Control and Optical Temperature Sensing

Langping Dong,Liang Zhang,Yongchao Jia,Yonghui Xu,Shuwen Yin,Hongpeng You

Dual-emitting and thermochromic manganese ion single doped ZnGa2–yAlyO4 phosphors were prepared by solid-state reaction. The regulation of the valence state and the luminescent properties, especially the luminescent thermal stability of manganese ions in ZnGa2–yAlyO4, are discussed in detail. When excited by ultraviolet (UV) light, the emission spectra of ZnGa2O4:Mn2+,Mn4+ present an ultranarrow green emission band at 503 nm with a fwhm of 22 nm, which derives from the Mn2+ ions formed by the self-reduction of doped Mn4+, and a red emission band of the Mn4+ ions at 669 nm. In addition, a ZnGa2–yAlyO4:Mn2+,Mn4+ solid solution was designed and synthesized by Al3+ replacing Ga3+. The doping of Al3+ effectively inhibited the degree of Mn4+ self-reduction to Mn2+, thus realizing the regulation of valence state of manganese ions. Interestingly, the thermal stability of luminescence shows that the response of Mn2+ and Mn4+ to temperature is obviously different in ZnGa2–yAlyO4, implying the potential of the prepared phosphors as optical thermometers. Subsequently, three kinds of optical thermometers with superior color discrimination and high relative sensitivity (Sr) based on the fluorescence intensity ratio (FIR) technique were realized in 100–475 K. The Sr value of ZGO:0.005Mn/ZGA0.5O:0.005Mn/ZGAO:0.005Mn phosphors can be as high as 4.345%/4.001%/3.488% K–1 (at 350/325/400 K), reflecting the great potential of ZnGa2O4:Mn2+,Mn4+ for optical thermometry applications.

研究领域: 材料科学 · 光学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2020 · IF 4.65

Highly efficient Eu3+-activated Ca2Gd8Si6O26 red-emitting phosphors: A bifunctional platform towards white light-emitting diode and ratiometric optical thermometer applications

Jiangwei Du,Xiaoyan Pan,Zepeng Liu,Yetao Jing,Beicheng Wang,Laihui Luo,Jun Wang,Peng Du

To fulfill bifunctional applications of the white light-emitting diode (white-LED) and optical thermometry, Eu 3+ -activated Ca 2 Gd 8 Si 6 O 26 phosphors were prepared. Upon 394 nm excitation, dazzling red emission with admirable color purity of 93.8% was seen and the optimal doping content of the Eu 3+ ions in the Ca 2 Gd 8 Si 6 O 26 host was 30 mol%. The Ca 2 Gd 8 Si 6 O 26 :2.4Eu 3+ phosphors showed a high quantum efficiency of 53.9%. Via investigation of the relation between the dopant content and emission intensity, one knows that the concentration quenching mechanism was decided by electric dipole-dipole interaction. Though estimating the values of Ω 2 and Ω 4 based on the Judd-Ofelt theory, it was proved that the Eu 3+ ions took the low symmetry sites in the Ca 2 Gd 8 Si 6 O 26 host lattices. Furthermore, the temperature-dependent emission spectra manifested that the resultant compounds had splendid thermal stability with activation energy of 0.25 eV. Utilizing the prepared compounds as the red-emitting components, a white-LED was packaged and it can emit high quality white light with high color rendering index (84.8) and low correlated color temperature (4981 K). Additionally, through analyzing the temperature-dependent excitation spectrum, the optical thermometric behaviors of the designed phosphors were studied. The maximum absolute and relative sensitivities of the studied compounds were 0.0014 K -1 and 0.276% K −1 , respectively. These results provided a new insight into searching for novel bifunctional luminescent materials towards white-LED and ratiometric optical thermometer applications.

研究领域: 材料科学 · 光学工程
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DALTON TRANSACTIONS · 2023 ·Vol. 52 ·期 37 ·13304-13315 · IF 4

Luminescence and energy transfer performances of Tb3+/Mn4+ co-doped Sr2LuTaO6 double-perovskite phosphors for a highly sensitive optical thermometer

Yuhong Zhang,Bo Sun,Jian Liu,Ziyi Zhang,Hang Liu

A series of Tb3+/Mn4+ co-doped double-perovskite oxides Sr2LuTaO6 (SLT) phosphors are synthesized by a solid-state method. The results of structural characterization prove that the Tb3+ and Mn4+ ions are successfully doped into the SLT host. The photoluminescence excitation (PLE) and photoluminescence (PL) spectra of Sr2LuTaO6:Tb3+, Sr2LuTaO6:Mn4+ and Sr2LuTaO6:Tb3+/Mn4+ are illustrated in detail. Under ultraviolet (UV) excitation, bright green and red lights are obtained from the Sr2LuTaO6:Tb3+/Mn4+ phosphor. In particular, the emission intensity of Tb3+ ions in Sr2LuTaO6:Tb3+/Mn4+ is enhanced by the energy transfer (ET) process from Mn4+ to Tb3+. The thermal enhancement of Tb3+ ion radiation in Sr2LuTaO6:Tb3+/Mn4+ also proves the ET process (Mn4+ → Tb3+). In addition, the thermal enhancement of Tb3+ ion radiation and the thermal quenching of Mn4+ ion radiation in the Sr2LuTaO6:Tb3+/Mn4+ system can be applied to develop optical thermometry based on luminescence intensity ratio (LIR) technology. Therefore, the LIRs of Mn4+ (2Eg → 4A2g) and Tb3+ (5D4 → 7F5,4) are investigated in the temperature range from 313 to 573 K. The absolute sensitivity (Sa) and relative sensitivity (Sr) of the Sr2LuTaO6:Tb3+/Mn4+ phosphor are calculated. The maximum values of Sa and Sr are obtained from the LIR of Tb3+: 5D4 → 7F4 (570–599 nm) and Mn4+: 2Eg → 4A2g (625–705 nm). The maximum Sa is 10.18% K−1 at 543 K, and the maximum value of Sr reaches 1.98% K−1 at 543 K. These results confirm that the ET process from Mn4+ to Tb3+ contributes to increasing the temperature measuring sensitivity of the Sr2LuTaO6:Tb3+/Mn4+ phosphor. Therefore, the Sr2LuTaO6:Mn4+/Tb3+ phosphor has prospective potential in optical thermometry and provides advantageous guidance for designing high-sensitivity optical thermometers.

研究领域: 材料科学 · 光学
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INORGANIC CHEMISTRY · 2021 · IF 5.165

Realization of an Optical Thermometer via Structural Confinement and Energy Transfer

Quwei Ni,Zhibin Mei,Chunxia Li,Jieying Li,Jiachun Liu,Wanqiang Liu,Jiansheng Huo,Qianming Wang

The influence of temperature on a variety of physiological or chemical processes has generated considerable interest, and recently noninvasive lanthanide-incorporated optical thermometers have been considered as promising candidates for monitoring its changes at different scales. Herein, a novel Bi3+-activated Sr3–xGdxGaO4+xF1–x phosphor with tunable color has been constructed by a cooperative cation–anion substitution strategy with to the replacement of [Sr2+–F–] by [Gd3+–O2–]. When x = 0, the sample Sr3GaO4F/Bi3+ possesses a peak wavelength at 438 nm, and this value will shift to 470 nm if x is equal to 1 (Sr2GdGaO5/Bi3+). In addition, photoluminescence tuning from blue to red has been realized successfully by an efficient Bi3+ → Eu3+ energy migration model in Sr2.6Gd0.4GaO4.4F0.6 samples. The specific Bi3+ → Eu3+ energy transfer has been explained by dipole–dipole interactions derived from a model of the Dexter pathway. Intriguingly, the two dopants (a blue signal from Bi3+ and a red signal from Eu3+) possess different thermal responses to increasing temperature. Accordingly, the intensity ratio values are sensitive to the temperature changes. The energy level cross relaxation causes the quenching effect of Bi3+, and the multi-phonon de-excitation mode leads to the thermal quenching of Eu3+. At room temperature (298 K), the determined maximum relative sensitivity (Sr) is 1.27% K–1. Moreover, the absolute sensitivity (Sa) is 0.067 K–1 since the temperature is elevated to 523 K. The collected results are superior to most of the reported optical thermometry materials.

研究领域: 材料科学 · 光学 · 生物医学工程
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JOURNAL OF LUMINESCENCE · 2022 · IF 4.171

Luminescent properties of Eu3+-doped NaLaCaWO6 red phosphors and temperature sensing derived from the excited state of charge transfer band

Xianju Zhou,Shouchun Zhao,Siyu Li,Yongjie Wang,Li Li,Sha Jiang,Guotao Xiang,Chuan Jing,Jingfang Li,Lu Yao

In this study, a series of NaLaCaWO 6 : Eu 3+ phosphors were synthesized by traditional high-temperature solid-phase method. The doping concentration of Eu 3+ was explored when the phosphors had the best luminescence performance, and the quenching concentration of Eu 3+ could reach 30%. The mechanism of concentration quenching is due to electric dipole-electric dipole interaction . The CIE coordinates of the phosphor are (0.66, 0.34), which are close to the standard red region of National Television Standard Committee (NTSC). Therefore, the samples could be potentially used as red phosphors of white light emitting diodes . The optical thermometry properties of NaLaCaWO 6 :30%Eu 3+ phosphors in 298–523 K were studied through temperature-dependent excitation spectra. The results demonstrate negative thermal quenching at the edge of the charge transfer band (CTB) with a red shift of the center of this band as temperature arises. Derived from the excited state of CTB , an optical temperature sensing strategy is proposed, and the relative sensitivity achieves 2.23%/K −1 .

研究领域: 材料科学 · 光学
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Advanced Optical Materials · 2024 ·Vol. 13 ·期 6 ·2402556 · IF 8

Lanthanides-Induced Enhancement in Self-Trapped Excitons Emission and Anti-Thermal Quenching of Cs2KInCl6 for Highly Sensitive Optical Thermometry

Yihan Liu,Zhichao Zhang,Yingjie Mao,Kai Liu,Denghui Xu,Dan Liu,Xiong Li,Jun Zhou

Doping lanthanide ions in double perovskites (DPs) offers a promising approach to tailor optical and optoelectronic properties for versatile applications. However, achieving efficient and thermal stable DPs remains a significant challenge. In this paper, a series of Cs 2 KInCl 6 :Yb 3+ ,Er 3+ DPs with a negative thermal quenching behavior and high sensitivity are fabricated. The intrinsic luminescence properties of Cs 2 KInCl 6 are studied with a broad intrinsic self-trapped excitons (STEs) emission peak at 500 nm, which can be enhanced by doping Er 3+ ions accompanied with greater distortion of the [InCl 6 ] 3− octahedrons as well as multiple characteristic emission modes of Er 3+ under ultraviolet and near-infrared excitation. Notably, the addition of sensitizer Yb 3+ ions leads to the enhanced up-conversion emission of Er 3+ (up-conversion quantum yield up to 1.66%), anti-thermal quenching performance brought by the phonon-assisted energy transfer up-conversion process, as well as high sensitivity and reproducibility based on fluorescence intensity ratio technology. This work provides an effective strategy to enhance the STEs emission of DPs and achieve efficient optical temperature sensors through lanthanide ions doping.

研究领域: 材料科学 · 光学 · 物理学
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