Mn2+掺杂NaBiF4∶Yb/Er体系的可调控上转换发光

doi:10.7503/cjcu20170620

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (12): 2135.doi: 10.7503/cjcu20170620

• 研究论文: 无机化学 • 上一篇下一篇

Mn²⁺掺杂NaBiF₄∶Yb/Er体系的可调控上转换发光

苏越^1,², 雷朋朋^1,², 冯婧¹(), 张洪杰¹()

1.中国科学院长春应用化学研究所稀土资源利用国家重点实验室, 长春 130022
2.中国科学院大学, 北京 100049

收稿日期:2017-09-15 出版日期:2017-12-10 发布日期:2017-11-22
作者简介:联系人简介: 冯婧, 女, 博士, 副研究员, 主要从事稀土发光材料研究. E-mail: fengj@ciac.ac.cn .张洪杰, 男, 博士, 研究员, 中国科学院院士, 主要从事稀土功能材料研究. E-mail: hongjie@ciac.ac.cn
基金资助:
国家自然科学基金(批准号: 21371165, 21590794, 21210001, 21521092)和中国科学院前沿科学重点研究项目(批准号: YZDY-SSW-JSC018)资助

Tunable Upconversion Luminescence of Mn²⁺ Doping NaBiF₄∶Yb/Er Particles^†

SU Yue^1,², LEI Pengpeng^1,², FENG Jing^1,^*(), ZHANG Hongjie^1,^*()

1. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry,Chinese Academy of Science, Changchun 130022, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2017-09-15 Online:2017-12-10 Published:2017-11-22
Contact: FENG Jing,ZHANG Hongjie E-mail:fengj@ciac.ac.cn;hongjie@ciac.ac.cn
Supported by:
Supported by the National Natural Science Foundation of China(Nos.21371165, 21590794, 21210001, 21521092) and the Frontier Science Research Project of Chinese Academy of Sciences, China(No.YZDY-SSW-JSC018)

摘要/Abstract

摘要：

采用溶剂热法制备了不同Mn²⁺掺杂量的NaBiF₄∶Yb/Er/Mn上转换发光体系, 研究了其形貌、晶相、上转换发光性能随Mn²⁺掺杂量的变化, 并探讨了该体系的能量传递机理. 实验结果表明, Mn²⁺的掺杂不会引起NaBiF₄从六方相转变为立方相, 但会增大其尺寸; 同时在NaBiF₄体系中, Mn²⁺可以与Er³⁺进行能量传递, 使红光发射得到增强, 并且随着Mn²⁺浓度的增加, 红/绿光发射强度比也会随之增大. 此外, 还考察了NaBiF₄∶Yb/Er/Mn体系的变温发射光谱, 发现当温度升高时, 红/绿光强度比以及520 nm绿光与540 nm绿光发射强度比都总体上呈增大趋势.

关键词: NaBiF₄, 上转换发光, 能量传递, 变温光谱, Mn²⁺掺杂

Abstract:

NaBiF₄∶Yb/Er/Mn samples with different concentrations of Mn²⁺ were fabricated via the solvothermal method. Also, the morphology and crystal phase, the changes of upconversion luminescence(UCL) upon different doping amounts of Mn²⁺ were investigated. Meanwhile, the mechanism of energy transfer in NaBiF₄∶Yb/Er/Mn was also discussed. The results indicate that, for NaBiF₄∶Yb/Er, Mn²⁺ doping does not induce transition from hexagonal to cubic phase, but increases the size of the particles. Meanwhile, the energy transfer processes between Er³⁺ and Mn²⁺ can take place in NaBiF₄ host, which eventually enhances the red emission to a certain degree. With the increasing of the concentration of Mn²⁺, the intensity ratio of red to green emission is also increased. In addition, the temperature-dependent UCL spectra of NaBiF₄∶Yb/Er/Mn was investigated, and the intensity ratios of red to green emission and 520 nm green emission to 540 nm green emission are generally increased with elevated temperature.

Key words: NaBiF₄, Upconversion luminescence, Energy transfer, Temperature-dependent spectrum, Mn²⁺ doping

TrendMD:

苏越, 雷朋朋, 冯婧, 张洪杰. Mn²⁺掺杂NaBiF₄∶Yb/Er体系的可调控上转换发光. 高等学校化学学报, 2017, 38(12): 2135.

SU Yue, LEI Pengpeng, FENG Jing, ZHANG Hongjie. Tunable Upconversion Luminescence of Mn²⁺ Doping NaBiF₄∶Yb/Er Particles^†. Chem. J. Chinese Universities, 2017, 38(12): 2135.

图/表 9

Fig.1 XRD patterns of NaBiF4∶Yb/Er/Mn x(Mn): a. 0; b. 6%; c. 12%; d. 18%. (B) shows the magnified peaks located at 29.2° in (A).

Fig.2 XPS spectra of NaBiF4∶Yb/Er/Mn[x(Mn)=18%] (A) Bi4f72 and Bi4f52; (B) Na1s; (C) F1s; (D) Yb4d; (E) Er4d; (F) Mn2p32 and Mn2p12.

Fig.3 SEM images of NaBiF4∶Yb/Er/Mn x(Mn): (A) 0; (B) 6%; (C) 12%; (D) 18%.

Fig.4 TEM images of NaBiF4∶Yb/Er/Mn x(Mn): (A) 0; (B) 6%; (C) 12%; (D) 18%. The inset in (D) is the HRTEM image of NaBiF4∶Yb/Er/Mn.

Fig.5 UCL spectra of NaBiF4∶Yb/Er/Mn [x(Mn)=0, 6%, 12%, 18%] under 980 nm excitation(A), Rr/g(a) and calculated overall UCL intensity(b) with increasing Mn2+ concentration(B) and the CIE chromaticity diagram of NaBiF4∶Yb/Er/Mn[x(Mn)=0, 6%, 12%, 18%)](C) (A) The power density is 14.15 W/cm2.

Fig.5 lg-lg plot of the UCL intensities of NaBiF4∶Yb/Er/Mn[x(Mn)=18%] as a function of 980 nm pump power a. 2H11/2, 4S3/2→4I15/2, slope=2.14; b. 4F9/2→4I15/2, slope=2.39.

Fig.7 Energy level diagram and upconversion mechanism of NaBiF4∶Yb/Er/Mn under 980 nm excitation The full arrows pointing upwards represent energy absorption, full arrows pointing downwards represent visible emission, dashed arrows represent the nonradiative relaxation process, and the curly dashed arrows represent energy transfer.

Fig.8 UCL spectra of NaBiF4∶Yb/Er/Mn[x(Mn)=18%]recorded from 25 K to 500 K λex=980 nm, the power density is 7.08 W/cm2.

Fig.9 Temperature-dependent intensity of green emission a(2H11/2-4I15/2, a), green emission b(4S3/2-4I15/2, b)(A), temperature-dependent intensity of red emission(4F9/2 - 4I15/2)(B) and intensity ratio of red to green emission(a) and green emission a to green emission b(b) recorded from 25 K to 500 K(C)

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Mn²⁺掺杂NaBiF₄∶Yb/Er体系的可调控上转换发光

Tunable Upconversion Luminescence of Mn²⁺ Doping NaBiF₄∶Yb/Er Particles^†

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