Tm3+, Yb3+共掺Bi2WO6上转换发光材料的制备及其温度传感性质

阿热帕提·夏克尔; 王林香; 李晴; 柏云凤; 穆妮热·买买提

doi:10.7498/aps.72.20222143

摘要

用高温固相法制备了不同浓度的Tm³⁺和Yb³⁺共掺杂Bi₂WO₆上转换发光材料. 对合成粉末的微结构、上转换发射光谱, 以及材料的光学温度传感性质进行了表征和分析. X射线衍射谱结果显示, Tm³⁺和Yb³⁺离子的掺杂基本不影响Bi₂WO₆基质材料的正交晶系结构. 在980 nm激发下, Tm³⁺和Yb³⁺掺杂摩尔分数分别是1%和6%时获得样品中Tm³⁺发射强度最大. 随激发泵浦功率从199 mW增加到400 mW, 1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆样品中Tm³⁺的4个发射峰强度均增强. 199—400 mW激发功率下, 样品光强I和激发功率Pⁿ呈现线性关系. 计算该范围激发泵浦功率和Tm³⁺发射强度的关系, 得到Tm³⁺的4个发射峰478, 650, 685和705 nm分别对应n值为1.01, 1.34, 1.77和1.75, 这表明以上发射峰均源于双光子吸收. 980 nm激发(功率379 mW)下, 当温度从298 K升高到573 K时, 1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆样品中Tm³⁺的热耦合能级对(³F₃, ³F₂)产生705 nm和685 nm处发射强度分别增加了28.4倍和31.6倍. 拟合样品中Tm³⁺的热耦合能级对(³F₃, ³F₂)的荧光强度比与温度的关系, 计算得到在298 K时, 样品最大绝对测温灵敏度为0.00254 K^–1, 最大相对测温灵敏度为0.00144 K^–1. 同样条件下, 拟合非热耦合能级对(³F₃, ¹G₄)产生的705 nm和650 nm荧光强度比与温度关系, 计算得到在573 K时, 最大绝对测温灵敏度为0.167 K^–1. 298 K时最大相对测温灵敏度为0.0378 K^–1, 比热耦合能级(³F₃, ³F₂)表征温度的相对最大测温灵敏度S_r提高了26倍.

关键词:

Abstract

Tm³⁺ and Yb³⁺, with different concentrations, co-doped Bi₂WO₆ up-conversion luminescence materials are prepared by high temperature solid state method. The microstructure, upconversion emission spectra, and optical temperature sensing properties of the synthesized powders are characterized and analyzed. The X-ray diffraction results show that the doping of Tm³⁺ and Yb³⁺ ions has little effect on the orthorhombic structure of Bi₂WO₆ matrix material. Under the 980 nm excitation, the maximum emission intensity of Tm³⁺ ions is obtained when the doping concentration of Tm³⁺ and Yb³⁺ are 1% and 6%, respectively. The intensities of four emission peaks of Tm³⁺ in 1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆ sample increase with the excitation pump power increasing from 199 to 400 mW. With the excitation power of 199–400 mW, the sample light intensity I and the excitation power Pⁿ show a linear relationship. The relationship between the excitation pump power and the emission intensity of Tm³⁺ in this range is investigated. The four emission peaks of Tm³⁺ at 478, 650, 685 and 705 nm correspond to the n values of 1.01, 1.34, 1.77 and 1.75, respectively, indicating that the above emission peaks are derived from two-photon absorption. Under 980 nm excitation (power 379 mW), when the temperature increases from 298 to 573 K, the thermal coupling energy levels of Tm³⁺ in 1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆ samples produce 705 and 685 nm emission whose intensities are increased by 28.4 times and 31.6 times, respectively. The relationship between the fluorescence intensity ratio of the thermal coupling energy levels (³F₃, ³F₂) of Tm³⁺ in the sample and the temperature is fitted. The maximum absolute temperature sensitivity of the sample is 0.00254 K^–1 at 298 K, and the maximum relative temperature sensitivity is 0.00144 K^–1. Under the same conditions, the relationship between the fluorescence intensity ratio of 705 and 650 nm produced by the non-thermal coupling energy level pair (³F₃, ¹G₄) and the temperature is fitted, and the maximum absolute temperature sensitivity is calculated to be 0.167 K^–1 at 573 K. The maximum relative temperature sensitivity is 0.0378 K^–1 at 298 K, which is 26 times higher than the relative maximum temperature sensitivity S_r of the thermal coupling level (³F₃, ³F₂).

Keywords:

作者及机构信息

1.
新疆师范大学物理与电子工程学院, 乌鲁木齐　830054

2.
新疆师范大学, 新疆发光矿物与光功能材料研究重点实验室, 乌鲁木齐　830054

通信作者: 王林香, wanglinxiang23@126.com

基金项目: 国家自然科学基金(批准号: 12164048)和新疆师范大学重点实验室项目(批准号: KWFG202204)资助的课题.

Authors and contacts

1.
School of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054, China

2.
Xinjiang Key Laboratory for Luminescence Minerals and Optical Functional Materials, Xinjiang Normal University, Urumqi 830054, China

Corresponding author: Wang Lin-Xiang, wanglinxiang23@126.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 12164048) and the Project of Key Laboratory Of Xinjiang Normal University, China (Grant No. KWFG202204).

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参考文献

[1]	Ruiz D, Rosal B, Acebrón M, et al. 2017 Adv. Funct. Mater. 27 1604629 Google Scholar
[2]	周慧丽, 吴锋, 张志宏, 张雁, 叶林华 2022 发光学报 43 192 Google Scholar Zhou H L, Wu F, Zhang Z H, Zhang Y, Ye L H 2022 Chin. J. Lumin. 43 192 Google Scholar
[3]	谢宇 2016 硕士学位论文 (沈阳: 辽宁大学) Xie Y 2016 M. S. Thesis (Shenyang: Liaoning University) (in Chinese)
[4]	吴中立, 吴红梅, 唐立丹, 李煜, 郭宇, 姚震 2017 光子学报 46 0916003 Google Scholar Wu Z L, Wu H M, Tang L D, Li Y, Guo Y, Yao Z 2017 Acta Photonica Sin. 46 0916003 Google Scholar
[5]	Xing J H, Shang F, Chen G H 2021 J. Non-Cryst. Solids 569 120989 Google Scholar
[6]	Saidi K, Dammak M, Soler-Carracedo K, Martín I 2022 Dalton Trans. 51 5108 Google Scholar
[7]	Meng M Z, Zhang R, Fa X M, et al. 2022 CrystEngComm 24 1752 Google Scholar
[8]	Zhuang Y F, Wang D W, Yang Z P 2022 Opt. Mater. 126 112167 Google Scholar
[9]	Zheng T, Runowski M, Stopikowska N, Skwierczyńska M, Lis S, Du P, Luo L H 2021 J. Alloys Compd. 890 161830 Google Scholar
[10]	蒙铭周, 张瑞, 法信蒙, 杨江华, 欧俊 2021 发光学报 42 1763 Google Scholar Meng M Z, Zhang R, Fa X M, Yang J H, Ou J 2021 Chin. J. Lumin. 42 1763 Google Scholar
[11]	郑龙江, 李雅新, 刘海龙, 徐伟, 张志国 2013 物理学报 62 240701 Google Scholar Zheng L J, Li Y X, Liu H L, Xu W, Zhang Z G 2013 Acta Phys. Sin. 62 240701 Google Scholar
[12]	Wu Z L, Zhang Y P, Bao D M, Li H Q, Hou X Q, Wang J L 2022 J. Lumin. 245 118766 Google Scholar
[13]	Lü H C, Du P, Li W P, Luo L H 2022 ACS Sustainable Chem. Eng. 10 2450 Google Scholar
[14]	Gao Z L, Wang J R, Yu D C, Pun E Y B, Lin H 2022 Adv. Mater. Interfaces 9 2101869 Google Scholar
[15]	张志宏, 周慧丽, 吴锋, 张雁, 叶林华 2021 发光学报 42 1872 Google Scholar Zhang Z H, Zhou H L, Wu F, Zhang Y, Ye L H 2021 Chin. J. Lumin. 42 1872 Google Scholar
[16]	Wang T W, Zhao S L, Lei R S, Huang L H, Xu S Q 2022 J. Non-Cryst. Solids 579 121379 Google Scholar
[17]	Tong X, Zhou X, Tang X Z, Min Y G, Li X L, Wang W G, Qian Y N 2022 CrystEngComm 24 1407 Google Scholar
[18]	Wang X F, Liu Q, Bu Y Y, Liu C S, Liu T, Yan X H 2015 RSC Adv. 5 86219 Google Scholar
[19]	Liu Z H, Long S W, Zhu Y Z, Wang W J, Wang B 2020 J. Alloys Compd. 867 158986 Google Scholar
[20]	Sun Z, Liu G F, Fu Z L, et al. 2018 Dyes Pigm. 151 287 Google Scholar

施引文献

图 1 (a) xTm³⁺, 6%Yb³⁺:Bi₂WO₆的XRD图谱(x = 0.5%, 1%, 1.5%, 2%); (b) 1%Tm³⁺, yYb³⁺:Bi₂WO₆ (y = 4%, 6%, 8%, 10%)的XRD图谱

Fig. 1. (a) XRD patterns of xTm³⁺, 6%Yb³⁺:Bi₂WO₆ (x = 0.5%, 1%, 1.5%, 2%); (b) XRD patterns of 1%Tm³⁺, yYb³⁺:Bi₂WO₆ (y = 4%, 6%, 8%, 10%).

下载: 全尺寸图片幻灯片

图 2 980 nm激光(379 mW)激发下Tm³⁺, Yb³⁺共掺Bi₂WO₆的上转换发射光谱　(a) xTm³⁺, 6%Yb³⁺:Bi₂WO₆; (b) 1%Tm³⁺, yYb³⁺:Bi₂WO₆

Fig. 2. Upconversion emission spectra of Tm³⁺, Yb³⁺ co-doped Bi₂WO₆ excited by 980 nm laser (379 mW): (a) xTm³⁺, 6%Yb³⁺:Bi₂WO₆; (b) 1%Tm³⁺, yYb³⁺:Bi₂WO₆.

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图 3 Yb³⁺敏化Tm³⁺的上转换发光过程

Fig. 3. Upconversion luminescence process of Yb³⁺ sensitized Tm³⁺.

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图 4 980 nm激光激发下, 不同泵浦功率时1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆的上转换光谱

Fig. 4. Upconversion spectra of 1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆ excited by 980 nm laser at different pump powers.

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图 5 1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆的上转换发射强度与泵浦功率的关系

Fig. 5. Relationship between upconversion luminescence intensity and pump power of 1%Tm³⁺, 6% Yb³⁺:Bi₂WO₆.

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图 6 (a) 不同温度下1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆的上转换发射谱; (b) 红色荧光强度的变化(685, 705 nm)

Fig. 6. (a) Upconversion emission spectra of 1%Tm³⁺, 6%Yb³⁺:Bi₂WO₆ at different temperatures; (b) change of red fluorescence intensity (685, 705 nm).

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图 7 Tm³⁺热耦合能级对³F₃/³F₂产生的705和685 nm处荧光强度比与温度的关系

Fig. 7. Relationship between the fluorescence intensity ratio at 705 and 685 nm and the absolute temperature for ³F₃/³F₂ produced by Tm³⁺ thermal coupling energy level.

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图 8 样品的热耦合能级对³F₃/³F₂表征温度时对应的(a)绝对灵敏度和(b)相对测温灵敏度

Fig. 8. (a) Absolute temperature sensitivity and (b) relative temperature sensitivity of samples characterized by thermal coupling energy level ³F₃/³F₂.

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图 9 非热耦合能级对³F₃/¹G₄产生的705和650 nm处荧光强度比与温度的关系

Fig. 9. Temperature dependence of fluorescence intensity ratio at 705 and 650 nm produced by ³F₃/¹G₄ at non-thermal coupling level.

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图 10 非热耦合能级对³F₃/¹G₄表征温度时的绝对测温灵敏度(a)和相对测温灵敏度(b)

Fig. 10. Absolute temperature sensitivity (a) and relative temperature sensitivity (b) of ³F₃/¹G₄ at characterization temperature by non-thermal coupling level.

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图 11 298和573 K下R_FIR1 (a)以及R_FIR2 (b)稳定性测试

Fig. 11. Stability test of R_FIR1 (a) and R_FIR2 (b) at 298 and 573 K .

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表 1 800 ℃下煅烧3 h合成不同浓度Tm³⁺, Yb³⁺共掺Bi₂WO₆材料

Table 1. Synthesis of Tm³⁺, Yb³⁺ co-doped Bi₂WO₆ materials with different doping concentration at the sintering temperature and time of 800 ℃ and 3 h.

Sample No.	Mole fraction of Tm³⁺/%	Mole fraction of Yb³⁺/%	Mole fraction of Bi₂WO₆/%
1	0.5	6	93.5
2	1	6	93
3	1.5	6	92.5
4	2	6	92
5	1	4	95
6	1	8	91
7	1	10	89

下载: 导出CSV

表 2 不同基质材料中Tm³⁺温度传感性能

Table 2. Temperature sensing performance of Tm³⁺ in various host materials.

Host material	Energy level	Temperature range/K	Relative temperature measurement sensitivity/K^–1	Ref.
SiO₂@Tm³⁺:NaYbF₄	³F_{2, 3}, ³H₄→³H₆	100—700	Max = 0.00054@298 K	[18]
Tm³⁺, Yb³⁺:LuYO₃	³F₂, ³F₃→³H₆	223—723	Max = 0.00461@516.3 K	[15]
Tm³⁺, Yb³⁺:LiNbO₃	¹G₄→³F₄, ³H₄→³H₆	80—260	Max = 0.0125@80 K	[19]
Tm³⁺, Yb³⁺:Bi_3.84W_0.16O_6.24	³H₄₍₁₎, ³H₄₍₂₎→³H₆	323—573	Max = 0.00068@323 K	[20]
Li⁺, Tm³⁺, Yb³⁺:Bi_3.84W_0.16O_6.24	³H₄₍₁₎, ³H₄₍₂₎→³H₆	323—573	Max = 0.00103@323 K
Mg²⁺, Tm³⁺, Yb³⁺:Bi_3.84W_0.16O_6.24	³H₄₍₁₎, ³H₄₍₂₎→³H₆	323—573	Max = 0.00070@323 K
Tm³⁺, Yb³⁺:Bi₂WO₆	³F₂, ₃→³H₆	298—573	Max = 0.00144@298 K	This work
	³F₂, ₃→³H₆	313	0.0013 K^–1
	³F₂, ₃→³H₆	323	0.0012 K^–1
	³F₃→³H₆, ¹G₄→³F₄	298—573	Max = 0.0378@298 K
	³F₃→³H₆, G₄→³F₄	313	0.0343 K^–1
	³F₃→³H₆, ¹G₄→³F₄	323	0.0322 K^–1

下载: 导出CSV

[1]	Ruiz D, Rosal B, Acebrón M, et al. 2017 Adv. Funct. Mater. 27 1604629 Google Scholar
[2]	周慧丽, 吴锋, 张志宏, 张雁, 叶林华 2022 发光学报 43 192 Google Scholar Zhou H L, Wu F, Zhang Z H, Zhang Y, Ye L H 2022 Chin. J. Lumin. 43 192 Google Scholar
[3]	谢宇 2016 硕士学位论文 (沈阳: 辽宁大学) Xie Y 2016 M. S. Thesis (Shenyang: Liaoning University) (in Chinese)
[4]	吴中立, 吴红梅, 唐立丹, 李煜, 郭宇, 姚震 2017 光子学报 46 0916003 Google Scholar Wu Z L, Wu H M, Tang L D, Li Y, Guo Y, Yao Z 2017 Acta Photonica Sin. 46 0916003 Google Scholar
[5]	Xing J H, Shang F, Chen G H 2021 J. Non-Cryst. Solids 569 120989 Google Scholar
[6]	Saidi K, Dammak M, Soler-Carracedo K, Martín I 2022 Dalton Trans. 51 5108 Google Scholar
[7]	Meng M Z, Zhang R, Fa X M, et al. 2022 CrystEngComm 24 1752 Google Scholar
[8]	Zhuang Y F, Wang D W, Yang Z P 2022 Opt. Mater. 126 112167 Google Scholar
[9]	Zheng T, Runowski M, Stopikowska N, Skwierczyńska M, Lis S, Du P, Luo L H 2021 J. Alloys Compd. 890 161830 Google Scholar
[10]	蒙铭周, 张瑞, 法信蒙, 杨江华, 欧俊 2021 发光学报 42 1763 Google Scholar Meng M Z, Zhang R, Fa X M, Yang J H, Ou J 2021 Chin. J. Lumin. 42 1763 Google Scholar
[11]	郑龙江, 李雅新, 刘海龙, 徐伟, 张志国 2013 物理学报 62 240701 Google Scholar Zheng L J, Li Y X, Liu H L, Xu W, Zhang Z G 2013 Acta Phys. Sin. 62 240701 Google Scholar
[12]	Wu Z L, Zhang Y P, Bao D M, Li H Q, Hou X Q, Wang J L 2022 J. Lumin. 245 118766 Google Scholar
[13]	Lü H C, Du P, Li W P, Luo L H 2022 ACS Sustainable Chem. Eng. 10 2450 Google Scholar
[14]	Gao Z L, Wang J R, Yu D C, Pun E Y B, Lin H 2022 Adv. Mater. Interfaces 9 2101869 Google Scholar
[15]	张志宏, 周慧丽, 吴锋, 张雁, 叶林华 2021 发光学报 42 1872 Google Scholar Zhang Z H, Zhou H L, Wu F, Zhang Y, Ye L H 2021 Chin. J. Lumin. 42 1872 Google Scholar
[16]	Wang T W, Zhao S L, Lei R S, Huang L H, Xu S Q 2022 J. Non-Cryst. Solids 579 121379 Google Scholar
[17]	Tong X, Zhou X, Tang X Z, Min Y G, Li X L, Wang W G, Qian Y N 2022 CrystEngComm 24 1407 Google Scholar
[18]	Wang X F, Liu Q, Bu Y Y, Liu C S, Liu T, Yan X H 2015 RSC Adv. 5 86219 Google Scholar
[19]	Liu Z H, Long S W, Zhu Y Z, Wang W J, Wang B 2020 J. Alloys Compd. 867 158986 Google Scholar
[20]	Sun Z, Liu G F, Fu Z L, et al. 2018 Dyes Pigm. 151 287 Google Scholar

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Tm³⁺, Yb³⁺共掺Bi₂WO₆上转换发光材料的制备及其温度传感性质

Preparation and temperature sensing properties of Tm³⁺, Yb³⁺ co-doped Bi₂WO₆ upconversion luminescent materials

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作者及机构信息

1.
新疆师范大学物理与电子工程学院, 乌鲁木齐　830054

2.
新疆师范大学, 新疆发光矿物与光功能材料研究重点实验室, 乌鲁木齐　830054

通信作者: 王林香, wanglinxiang23@126.com

Authors and contacts

1.
School of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054, China

2.
Xinjiang Key Laboratory for Luminescence Minerals and Optical Functional Materials, Xinjiang Normal University, Urumqi 830054, China

Corresponding author: Wang Lin-Xiang, wanglinxiang23@126.com

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