Dual-mode up/down-conversion optical thermometry of Pr3+-regulated Li0.9K0.1NbO3:Er3+ phosphors

Jia Chao-Yang; Yang Xue; Wang Zhi-Gang; Chai Rui-Peng; Pang Qing; Zhang Xiang-Yu; Gao Dang-Li

doi:10.7498/aps.72.20231170

Abstract

Photothermal sensing is crucial in developing smart wearable devices. However, designing and synthesizing luminescent materials with suitable multi-wavelength emission and constructing multiple sets of probes in a single material system is a huge challenge for constructing sensitive temperature sensors with a wide temperature range. In this paper, Pr³⁺, Er³⁺ single-doped and double-doped Li_0.9K_0.1NbO₃ phosphors are successfully prepared by high temperature solid phase method, and their structures, morphologies, excitation wavelengths and temperature-dependent fluorescence properties are characterized by XRD, SEM, fluorescence spectrometer and self-made heating device. Firstly, the photoluminescences of the synthesized series of samples are investigated. The results show that comparing with the single-doped Li_0.9K_0.1NbO₃: Er³⁺ sample, the up/down-conversion spectra of Pr³⁺, Er³⁺ co-doped phosphors under 808 nm/380 nm excitation show that the green fluorescence emission of Er³⁺ is enhanced. In addition, under 980 nm excitation, Pr³⁺ can effectively regulate the fluorescence energy level population pathway, so that the electrons are more effectively arranged in the ²H_11/2 and ⁴S_3/2 energy levels in the excitation process. The red emission is weakened and the green emission is enhanced, which improves the signal resolution of the fluorescent material and has a significant influence on the optical temperature measurement. Secondly, the up-conversion fluorescence property of Er³⁺ under 808 nm/980 nm laser excitation in Li_0.9K_0.1NbO₃:Er³⁺ and Li_0.9K_0.1NbO₃:Pr³⁺,Er³⁺ phosphors are investigated. The results show that the red and green fluorescence emissions of Er³⁺ are two-photon processes. Finally, the up/down-conversion dual-mode temperature sensing properties of Er³⁺ in Li_0.9K_0.1NbO₃:Er³⁺ and Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺ phosphors are investigated. It is found that both materials have good optical temperature measurement performances. The Pr³⁺ doping optimizes the dual-mode optical temperature measurement performances of Li_0.9K_0.1NbO₃:Er³⁺ phosphors derived from the thermal coupling energy level of Er³⁺ ions. In addition, the up/down-conversion fluorescence mechanism of Li_0.9K_0.1NbO₃:Er³⁺ and Li_0.9K_0.1NbO₃:Er³⁺, Pr³⁺ phosphors are proposed, and the enhanced green fluorescence by Pr³⁺ co-doping is attributed to the energy transfer from Pr³⁺ ions to Er³⁺ ions, leading to the increase of green fluorescence level population and the decrease of red fluorescence level population of the Er³⁺ ions. This new dual-mode optical temperature measurement material provides a material basis and optical temperature measurement technology for exploring other temperature measurement materials.

Keywords:

Authors and contacts

1.
College of Science, Xi’an University of Architecture and Technology, Xi’an 710055, China
2.
College of Science, Chang’an University, Xi’an 710064, China

Corresponding author: Gao Dang-Li, gaodangli@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11604253, 51672208), the Key Science and Technology Innovation Team of Shaanxi Province, China (Grant No. 2022TD-34), and the Fundamental Research Funds for the Central Universities, China (Grant No. 300102120101).

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References

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[3]	Wang X F, Liu Q, Bu Y Y, Liu C S, Liu T, Yan X H 2015 RSC Adv. 5 86219 Google Scholar
[4]	Chen Y H, Chen J, Tong Y, Zhang W N, Peng X S, Guo H, Huang D X 2021 J. Rare Earths 39 1512 Google Scholar
[5]	Tian Y, Tian B N, Cui C, Huang P, Wang L, Chen B J 2015 RSC Adv. 5 14123 Google Scholar
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Cited By

图 1 (a) Li_0.9K_0.1NbO₃:Ln³⁺系列样品的XRD图; (b) Li_0.9K_0.1NbO₃的晶体结构图

Figure 1. (a) XRD patterns of a series of Li_0.9K_0.1NbO₃:Ln³⁺ samples; (b) crystal structure of Li_0.9K_0.1NbO₃.

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图 2 Li_0.9K_0.1NbO₃:Ln³⁺样品的SEM图片及EDX元素谱　(a) Li_0.9K_0.1NbO₃:Er³⁺的SEM图片; (b) Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺的SEM图片; (c) Li_0.9K_0.1NbO₃:Er³⁺荧光粉的EDX元素分布图谱

Figure 2. SEM images and element mappings of Li_0.9K_0.1NbO₃:Ln³⁺ phosphors: (a) SEM image of Li_0.9K_0.1NbO₃:Er³⁺; (b) SEM image of Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺; (c) EDX elemental distribution spectra of Li_0.9K_0.1NbO₃:Er³⁺ phosphors.

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图 3 不同波长激发下, Li_0.9K_0.1NbO₃:Ln³⁺的上/下转换发射谱比较　(a) Pr³⁺和Er³⁺单掺样品及Pr³⁺, Er³⁺共掺样品的发射谱 (λ_ex = 280 nm/380 nm); (b) Pr³⁺, Er³⁺共掺样品的激发谱(λ_moni = 554 nm/620 nm); Er³⁺单掺及Pr³⁺, Er³⁺共掺样品在(c) λ_ex= 808 nm, (d) 980 nm激光激发下的上转换发射谱

Figure 3. Comparison of up-conversion and down-conversion emission spectra of rare earth doped Li_0.9K_0.1NbO₃:Ln³⁺ under different excitation wavelengths: (a) Emission spectra of Pr³⁺ and Er³⁺ single-doped samples and Pr³⁺, Er³⁺ co-doped samples (λ_ex = 280 nm/380 nm); (b) excitation spectra of Pr³⁺, Er³⁺ co-doped samples (λ_moni = 554 nm/620 nm); (c), (d) up-conversion emission spectra of Er³⁺ single doped and Pr³⁺, Er³⁺ co-doped samples under 808 and 980 nm excitations.

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图 4 激发功率依赖的Li_0.9K_0.1NbO₃:Er³⁺和Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺荧光粉的发射谱, 其中内插图为对应发光强度与入射激光的功率关系　(a), (b) Li_0.9K_0.1NbO₃:Er³⁺荧光粉的发射谱(λ_ex = 808 nm和λ_ex = 980 nm); (c), (d) Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺荧光粉的发射谱(λ_ex = 808 nm和λ_ex = 980 nm)

Figure 4. Excitation power-dependent emission spectra of Li_0.9K_0.1NbO₃:Er³⁺ and Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺ phosphors, where the insets are the relationships between luminescence intensity and incident laser power: (a), (b) Emission spectra of Li_0.9K_0.1NbO₃:Er³⁺ phosphors (λ_ex = 808 nm and λ_ex = 980 nm); (c), (d) emission spectra of Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺ phosphors (λ_ex = 808 nm and λ_ex = 980 nm).

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图 5 Li_0.9K_0.1NbO₃:Er³⁺荧光粉的上、下转换测温性能　(a)—(c) 分别在380, 808, 980 nm激发下的发射谱; (d)—(f) 相应于图(a)—(c)中的上/下转换发射谱的双峰绿色FIR与温度的关系; (g)—(i) 相应于图(d)—(f)中双峰荧光强度比率测温的灵敏度曲线

Figure 5. Up/down-conversion temperature measurement performance of Li_0.9K_0.1NbO₃:Er³⁺ phosphor: (a)–(c) The emission spectra excited at 380, 808 and 980 nm, respectively; (d)–(f) the relationship between the bimodal green FIR and temperature corresponding to the up/down-conversion emission spectra in panel (a)–(c); (g)–(i) the sensitivity curves of temperature measurement of bimodal FIR corresponding to panel (d)–(f).

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图 6 Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺荧光粉的上/下转换双模式光学测温性能　(a)—(c) 分别在380, 808, 980 nm激发下的发射谱; (d)—(f) 相应于图(a)—(c)中的上/下转换发射谱的双峰绿色FIR与温度的关系; (g)—(i) 相应于图(d)—(f)中双峰FIR测温的灵敏度曲线

Figure 6. Up/down-conversion temperature measurement performance of Li_0.9K_0.1NbO₃:Pr³⁺, Er³⁺ phosphor: (a)–(c) The emission spectra excited at 380, 808, and 980 nm, respectively; (d)–(f) the relationship between the bimodal green FIR and temperature corresponding to the up/down-conversion emission spectra in panel (a)–(c); (g)–(i) the sensitivity curves of temperature measurement of bimodal FIR corresponding to panel (d)–(f).

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图 7 源自于Li_0.9K_0.1NbO₃:Er³⁺和Li_0.9K_0.1NbO₃:Er³⁺, Pr³⁺荧光粉的上/下转换荧光机理图, 其中, VB表示价带, CB表示导带

Figure 7. Proposed mechanism of up/down-conversion fluorescence of Li_0.9K_0.1NbO₃:Er³⁺ and Li_0.9K_0.1NbO₃:Er³⁺, Pr³⁺ phosphors. Therein, VB and CB represent valence band and conduction band, respectively.

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表 1 基于FIR技术下不同基质中掺杂Er³⁺的温度传感材料光学参数

Table 1. Optical parameters of temperature sensing materials doped with Er³⁺ in different substrates based on FIR technology

Materials	Wavelength/nm	S_r-Max/(10^–2 K^–1)	S_a-Max/(10^–2 K^–1)	References
SrSnO₃:Er	975 nm	0.997(294 K)	0.791(368 K)	[30]
BaBiNb₂O₉:Er	980 nm	0.959(300 K)	0.996(483 K)	[36]
La₂CaZnO₅:Er	378 nm	1.454(300 K)	—	[31]
Sr₂Gd₈(SiO₄)₆O₂:Er	379 nm	—	0.34(463 K)	[32]
Ca₃Bi(PO₄)₃:Er	376 nm	1.21(300 K)	0.312(473 K)	[33]
La₂Mo₂O₉:Er	980 nm	1.16(293 K)	0.527(493 K)	[37]
(K, Na)NbO₃:Er	980 nm 375 nm	0.96(303 K) 16.17(80 K)	0.28(433 K) 0.37(280 K)	[38]
Cs₃Bi₂Cl₉:Er	808 nm 980 nm	1.4(303 K) 1.38(303 K)	0.62(573 K) 0.61(573 K)	[13]
Li_0.9K_0.1NbO₃:Er	380 nm 808 nm 980 nm	0.97(303 K) 1.286(297 K) 1.221(297 K)	0.44(463 K) 0.89(443 K) 0.81(443 K)	This work

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表 2 基于FIR技术下不同基质中掺杂Er³⁺-Ln³⁺的温度传感材料光学参数

Table 2. Optical parameters of temperature sensing materials doped with Er³⁺-Ln³⁺ in different substrates based on FIR technology.

Materials	Wavelength/nm	S_r-Max/(10^–2 K^–1)	S_a-Max/(10^–2 K^–1)	References
La₂MgGeO₆:Bi, Er	980 nm	1.23(293 K)	0.94(473 K)	[39]
K₃Gd(PO₄)₂:Yb, Er, Tm	980 nm	1.35(300 K)	0.456(608 K)	[40]
NaLuF₄:Er, Tm	1532 nm	1.265(293 K)	0.4(519 K)	[41]
BiVO₄:Er, Tm	980 nm	1.1(293 K)	0.7(473 K)	[42]
BiVO₄:Er, Tm	1550 nm	1.1(293 K)	0.56(453 K)	[42]
Y₂SiO₅:Er, Tm	808 nm	0.395(298 K)	—	[29]
KYb(MoO₄)₂:Er, Gd	980 nm	1.1(303 K)	0.97(513 K)	[25]
KYb(MoO₄)₂:Er, La		1.1(303 K)	0.95(513 K)
KYb(MoO₄)₂:Er, Y		1.11(303 K)	0.91(513 K)
Li_0.9K_0.1NbO₃:Pr, Er	380 nm	1.12(296 K)	0.54(434 K)	This work
	808 nm	1.284(296 K)	1.12(443 K)
	980 nm	1.106(296 K)	0.83(443 K)

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map

[1]	Abbas M T, Khan N Z, Mao J, Qiu L, Wei X, Chen Y, Khan S A 2022 Mater. Today Chem. 24 100903 Google Scholar
[2]	Hua Y B, Yu J S 2021 ACS Sustainable Chem. Eng. 9 5105 Google Scholar
[3]	Wang X F, Liu Q, Bu Y Y, Liu C S, Liu T, Yan X H 2015 RSC Adv. 5 86219 Google Scholar
[4]	Chen Y H, Chen J, Tong Y, Zhang W N, Peng X S, Guo H, Huang D X 2021 J. Rare Earths 39 1512 Google Scholar
[5]	Tian Y, Tian B N, Cui C, Huang P, Wang L, Chen B J 2015 RSC Adv. 5 14123 Google Scholar
[6]	Zhang J, Chen J J, Jin C 2020 J. Alloys Compd. 846 156397 Google Scholar
[7]	León-Luis S F, Rodríguez-Mendoza U R, Martín I R, Lalla E, Lavín V 2013 Sens. Actuators, B 176 1167 Google Scholar
[8]	Alencar M A, Maciel G S, de Araújo C B, Patra A 2004 Appl. Phys. Lett. 84 4753 Google Scholar
[9]	Suo H, Guo C F, Li T 2016 J. Phys. Chem. C 120 2914 Google Scholar
[10]	Zheng W, Sun B Y, Li Y M, Lei T, Wang R, Wu J Z 2020 ACS Sustainable Chem. Eng. 8 9578 Google Scholar
[11]	Yu D C, Li H Y, Zhang D W, Zhang Q Y, Meijerink A, Suta M 2021 Light-Sci. Appl. 10 236 Google Scholar
[12]	Singh A K, Singh S K, Gupta B K, Prakash R, Rai S B 2013 Dalton Trans. 42 1065 Google Scholar
[13]	Zhao C L, Gao Y, Zhou D C, Zhu F M, Chen J Y, Qiu J B 2023 J. Alloys Compd. 944 169134 Google Scholar
[14]	Wang Z Y, Zhang F H, Datsenko O I, Golovynskyi S, Sun Z H, Li B K, Wu H L 2023 J. Alloys Compd. 946 169350 Google Scholar
[15]	阿热帕提·夏克尔, 王林香, 李晴, 柏云凤, 穆妮热·买买提 2023 72 060701 Google Scholar Arepati X, Wang L X, Li Q, Bai Y F, Munire M 2023 Acta Phys. Sin. 72 060701 Google Scholar
[16]	Chen J, Guo J J, Chen Y H, Peng X S, Ashraf G A, Guo H 2021 J. Lumin. 238 118294 Google Scholar
[17]	Gao D L, Zhao D, Pan Y, Chai R P, Pang Q, Zhang X Y, Chen W 2021 Ceram. Int. 47 32000 Google Scholar
[18]	Li T, Guo C F, Zhou S H, Duan C K, Yin M 2015 J. Am. Ceram. Soc. 98 2812 Google Scholar
[19]	Wu Y F, Suo H, He D, Guo C F 2018 Mater. Res. Bull. 106 14 Google Scholar
[20]	Li X F, Guan L L, Li Y, Sun H Q, Zhang Q W, Hao X H 2020 J. Mater. Chem. C 8 15685 Google Scholar
[21]	Gao D L, Gao F, Wu J L, Kuang Q Q, Xing C, Chen W 2022 Appl. Surf. Sci. 587 152820 Google Scholar
[22]	Jilili S, Aierken P, Wang Q L, Tuerxun A, Wang L, Sidike A 2022 Ceram. Int. 48 15755 Google Scholar
[23]	Maurya A, Bahadur A, Dwivedi A, Choudhary A K, Yadav T P, Vishwakarma P K, Rai S B 2018 J. Phys. Chem. Solids 119 228 Google Scholar
[24]	Gao D L, Gao J, Zhao D, Pang Q, Xiao G Q, Wang L L, Ma K W 2020 J. Mater. Chem. C 8 17318 Google Scholar
[25]	Tan S Y, Wang X S, Zhao Y, Li Y X, Yao X 2023 J. Lumin. 257 119747 Google Scholar
[26]	Lu H Y, Lu Y, Zhu J, Li J X, Wang J Y, Zou H 2023 Phys. Status Solidi RRL 17 2200379 Google Scholar
[27]	Kolesnikov I E, Mamonova D V, Kurochkin M A, Medvedev V A, Bai G X, Ivanova T Y, Kolesnikov E Y 2022 Phys. Chem. Chem. Phys. 24 15349 Google Scholar
[28]	Liu Y, Bai G X, Pan E, Hua Y J, Chen L, Xu S Q 2020 J. Alloys Compd. 822 153449 Google Scholar
[29]	Rakov N, Maciel G S 2014 Dalton Trans. 43 16025 Google Scholar
[30]	Cortés-Adasme E, Vega M, Martin I R, Llanos J 2017 RSC Adv. 7 46796 Google Scholar
[31]	Girisha H R, Lavanya D R, Daruka P B, Sharma S C, Nagabhushana H 2022 Opt. Mater. 134 113053 Google Scholar
[32]	Raju G S R, Pavitra E, Rao G M, Jeon T J, Jeon S W, Huh Y S, Han Y K 2018 J. Alloys Compd. 756 82 Google Scholar
[33]	Sahu M K, Jayasimhadri M, Haranath D 2022 Solid State Sci. 131 106956 Google Scholar
[34]	Fu J, Zhou L Y, Chen Y L, Lin J H, Ye R G, Lei L, Shen Y, Deng D G, Xu S 2023 J. Am. Ceram. Soc. 106 1333 Google Scholar
[35]	Zhu Y, Li X F, Guo Z Z, Sun H Q, Zhang Q W, Hao X H 2020 J. Am. Ceram. Soc. 103 3205 Google Scholar
[36]	Banwal A, Bokolia R 2022 Ceram. Int. 48 2230 Google Scholar
[37]	Fan Y, Xiao Q, Yin X M, Lv L, Wu X Y, Dong X Y, Xing M M, Tian Y, Luo X X 2022 Solid State Sci. 132 106966 Google Scholar
[38]	Liu Q, Pan E, Deng H, Liu F C 2023 Ceram. Int. 49 14981 Google Scholar
[39]	Chen Y L, Lin J H, Fu J, Ye R G, Lei L, Shen Y, Deng D G, Xu S Q 2022 J. Lumin. 252 119404 Google Scholar
[40]	Yin X M, Xiao Q, Lü L, Wu X Y, Dong X Y, Fan Y, Zhou N, Luo X X 2023 Spectrochim. Acta, Part A 291 122324 Google Scholar
[41]	Zhou W, Yang J, Jin X L, Peng Y, Luo J 2022 J. Lumin. 252 119275 Google Scholar
[42]	Liu Y W, Meng L S, Wang H, Jiao J X, Xing M M, Peng Y, Luo X X, Tian Y 2021 Dalton Trans. 50 960 Google Scholar

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Vol. 72, Issue 24 - 2023-12-20

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Dual-mode up/down-conversion optical thermometry of Pr³⁺-regulated Li_0.9K_0.1NbO₃:Er³⁺ phosphors

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Corresponding author: Gao Dang-Li, gaodangli@163.com

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