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

doi:10.7503/cjcu20180274

Abstract

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

CLC Number:

TrendMD:

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

Figures/Tables 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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