晶体基质对稀土上转换纳米材料中能量转换机理的影响

doi:10.7503/cjcu20180274

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (10): 2136.doi: 10.7503/cjcu20180274

晶体基质对稀土上转换纳米材料中能量转换机理的影响

唐可云, 李萝园, 付立民(), 艾希成(), 张建平

中国人民大学化学系, 北京 100872

收稿日期:2018-04-10 出版日期:2018-09-29 发布日期:2018-09-29
作者简介:
联系人简介: 付立民, 男, 博士, 副教授, 主要从事稀土发光材料能量传递机理研究. E-mail: lmfu@ruc.edu.cn ;艾希成, 男, 博士, 教授, 主要从事光电功能材料电荷转移和能量传递机理研究. E-mail: xcai@ruc.edu.cn
基金资助:
国家自然科学基金(批准号: 21373268, 21227803)、中国人民大学基金(批准号: 15XNLQ04, 10XNI007)和吉林大学集成光电国家重点实验室开放基金(批准号: IOSKL2015KF33)资助.

Effect of Crystal Matrix on Energy Transfer Mechanism in Rare-earth Upconversion Nanomaterials^†

TANG Keyun, LI Luoyuan, FU Limin^*(), AI Xicheng^*(), ZHANG Jianping

Department of Chemistry, Renmin University of China, Beijing 100872, China

Received:2018-04-10 Online:2018-09-29 Published:2018-09-29
Contact: FU Limin,AI Xicheng E-mail:lmfu@ruc.edu.cn;xcai@ruc.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21373268, 21227803), the Open Funding of Renmin University of China(Nos.15XNLQ04, 10XNI007) and the Open Funding of the State Key Laboratory on Integrated Optoelectronics of Jilin University, China(No.IOSKL2016KF33).

摘要/Abstract

摘要：

采用溶剂热法制备了尺寸均一、形貌规整的 Yb³⁺, Er³⁺共掺NaREF₄ (RE³⁺=Lu³⁺, Y³⁺, Yb³⁺)纳米材料, 借助稳态发光光谱和时间分辨光谱技术表征了3种基质纳米材料上转换发光行为的特性, 并评估了能量传递机制. 结果表明, NaLuF₄:20%Yb³⁺, 2%Er³⁺纳米材料具有较强的稳态发光强度、较高的绿红比(540 nm/654 nm)和较长的发光寿命, NaYbF₄:2%Er³⁺纳米材料具有较弱的上转换发光强度、较低的绿红比(540 nm/654 nm)和较短的发光寿命. 结合实验数据及能量传递机制, 探讨了不同基质(NaLuF₄, NaYF₄, NaYbF₄)在稀土掺杂纳米材料中对上转换能量传递机制的影响, 解释了 NaLuF₄ 基质纳米材料是较好基质材料的原因.

关键词: 稀土掺杂纳米材料, 上转换发光, 基质材料, 能量传递机制, 时间分辨荧光光谱

Abstract:

Yb³⁺, Er³⁺ doped NaREF₄(RE³⁺=Lu³⁺, Y³⁺, Yb³⁺) nanoparticles with uniform size and hexagonal-phase were prepared by the solvothermal method. The steady-state luminescence spectra and the time-resolved luminescence spectra were characterized to explore the luminescence properties for the evaluation of energy transfer mechanisms in three matrix(NaLuF₄, NaYF₄, NaYbF₄) nanomaterials. The experimental data showed that NaLuF₄:20%Yb³⁺, 2%Er³⁺ nanomaterial performed stronger upconversion luminescence(UCL) intensity, relatively higher green/red ratio(I_{540 nm}/I_{654 nm}) and longer luminescence lifetimes, while NaYbF₄:2%Er³⁺ nanomaterial presented relatively weaker properties in these aspects. The difference of energy transfer mechanisms in three matrix(NaLuF₄, NaYF₄, NaYbF₄) nanoparticles was also displayed and analyzed. Comparative results showed why the NaLuF₄ matrix nanoparticles were the best matrix materials from the perspective of the UCL energy transfer mechanisms. This work provides new insights that the energy transfer process can be influenced via changing the matrix nanoparticles, and can give helpful guidance for the future optical UCL applications of rare-earth doped nanomaterials.

Key words: Rare earth doped nanomaterial, Upconversion luminescence, Matrix material, Energy transfer mechanism, Time-resolved luminescence spectroscopy

中图分类号:

TrendMD:

唐可云, 李萝园, 付立民, 艾希成, 张建平. 晶体基质对稀土上转换纳米材料中能量转换机理的影响. 高等学校化学学报, 2018, 39(10): 2136.

TANG Keyun,LI Luoyuan,FU Limin,AI Xicheng,ZHANG Jianping. Effect of Crystal Matrix on Energy Transfer Mechanism in Rare-earth Upconversion Nanomaterials^†. Chem. J. Chinese Universities, 2018, 39(10): 2136.

图/表 8

Fig.1 TEM images(A1—A3) HRTEM images(B1—B3) and dynamic light scatter(C1—C3) of NaREF4:20%Yb3+, 2%Er3+(RE3+=Lu3+, Y3+, Yb3+) nanocrystals(A1)—(C1) RE=Lu; (A2)—(C2) RE=Y; (A3)—(C3) RE=Yb3+.

Fig.2 XRD patterns of NaLuF4:20%Yb3+, 2%Er3+(a), NaYF4:20%Yb3+, 2%Er3+(b) and NaYbF4:2%Er3+(c)

Fig.3 Upconversion luminescence spectra of NaREF4:20%Yb3+, 2%Er3+(RE3+=Lu3+, Y3+, Yb3+) nanoparticles under 980 nm laser excitation

Scheme 1 Crystal field effect diagram of hexagonal phase NaLuF4:20%Yb3+, 2%Er3+(A), NaYF4:20%Yb3+, 2%Er3+(B) and NaYbF4: 2%Er3+(C)

Fig.4 Time-resolved luminescence spectra of NaREF4: 20%Yb3+, 2%Er3+[RE3+=Lu3+(A), Y3+(B), Yb3+(C)] nanocrystals upon 974 nm excitation410 nm: for the blue band; 520 and 540 nm: for the green bands; 654 nm: for the red band.

Table 1 Calculated luminescence lifetimes of NaREF4:20%Yb3+, 2%Er3+(RE3+=Lu3+, Y3+, Yb3+) samples

Sample	Transition	λ/nm	A₁	τ_r	A₂	τ_d
NaLuF₄:20%Yb³⁺, 2%Er³⁺	²H_9/2→⁴I_15/2	410	-1.5	31.4±0.3	2.1	97.4±0.4
	²H_11/2→⁴I_15/2	520	-1.8	40.5±0.4	2.3	121.2±0.5
	⁴S_3/2→⁴I_15/2	540	-1.6	39.9±0.3	2.1	130.7±0.4
	⁴F_9/2→⁴I_15/2	654	-1.8	49.7±0.4	1.6	321.5±1.1
NaYF₄:20%Yb³⁺, 2%Er³⁺	²H_9/2→ ⁴I_15/2	410	-1.2	25.1±0.2	2.3	88.0±0.3
	²H_11/2→⁴I_15/2	520	-2.2	35.7±0.5	2.6	88.4±0.7
	⁴S_3/2→⁴I_15/2	540	-1.8	36.9±0.3	2.2	113.8±0.5
	⁴F_9/2→⁴I_15/2	654	-2.1	51.0±0.7	2.0	180.7±1.3
NaYbF₄:2%Er³⁺	²H_9/2→⁴I_15/2	410	-1.4	3.3±0.1	1.5	23.8±0.2
	²H_11/2→⁴I_15/2	520	-0.6	2.3±0.1	1.2	35.7±0.1
	⁴S_3/2→⁴I_15/2	540	-1.9	1.2±0.1	1.1	52.3±0.3
	⁴F_9/2→⁴I_15/2	654	-0.5	5.3±0.2	1.1	152.8±0.4

Scheme 2 Different energy transfer mechanism diagram in different crystal matrix of UCNPsDirect transitions are indicated with solid lines. Dotted lines indicate energy transfer paths. (A) RE3+=Lu3+, Y3+; (B) RE3+=Yb3+.

Scheme 3 Yb3+ trimmers-Er3+ cooperative mode

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晶体基质对稀土上转换纳米材料中能量转换机理的影响

Effect of Crystal Matrix on Energy Transfer Mechanism in Rare-earth Upconversion Nanomaterials^†

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晶体基质对稀土上转换纳米材料中能量转换机理的影响

Effect of Crystal Matrix on Energy Transfer Mechanism in Rare-earth Upconversion Nanomaterials†

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Effect of Crystal Matrix on Energy Transfer Mechanism in Rare-earth Upconversion Nanomaterials^†