Ultraviolet and Near-infrared Luminescence of Ce 3+/Yb 3+ Co-doping LiLuF4 Single Crystal

doi:10.15541/jim20190215

Abstract

Abstract:

LiLuF₄ single crystals doped with Ce ³⁺ ion of 0.1mol% and Yb ³⁺ ion of concentration varying from 0 to 2.0mol% were successfully synthesized by an improved Bridgman method. Intense near-infrared emission at around 1020 nm, attributed to the ²F_5/2→ ²F_7/2 transition of Yb ³⁺, and ultraviolet emission of Ce ³⁺ at 300-350 nm (5d→4f) was observed using excitation at 291 nm. Influence of Yb ³⁺ ions concentration on the spectroscopic properties of Ce ³⁺/Yb ³⁺ co-doped LiLuF₄ single crystal and the mechanism of energy transfer from Ce ³⁺ to Yb ³⁺ ions were explored through optical absorption and emission spectra. The temperature dependent emission indicated that the emission intensity constantly decreases with the increase of temperature from 298 to 443 K due to the enhancement of non-radiative quenching at high temperature. Ce ³⁺/Yb ³⁺ co-doped LiLuF₄ single crystals mainly emit in the ultraviolet and near-infrared ranges. This unique property may be suitable for applications in anti-counterfeiting techniques and public security affairs.

Key words: Ce ³⁺ and Yb ³⁺, ultraviolet and infrared emissions, LiLuF₄ single crystal, energy transfer

CLC Number:

TQ174

ZHOU Xiong, FANG Lizhi, HUANG Shuangwu, XIA Haiping, HU Jianxu, ZHANG Jianli, CHEN Baojiu. Ultraviolet and Near-infrared Luminescence of Ce ³⁺/Yb ³⁺ Co-doping LiLuF₄ Single Crystal[J]. Journal of Inorganic Materials, 2020, 35(5): 556-560.

Figures/Tables 8

Table 1 Molar fractions of Ce3+ and Yb3+ in raw materials and the number of Ce3+ ions (N) and Yb3+ ions in single crystals

Sample	C0	CY1	CY2	CY3	CY4
Ce³⁺ in raw material/mol%	0.1	0.1	0.1	0.1	0.1
Ce³⁺molar concentration in crystal/mol%	0.023	0.022	0.024	0.022	0.024
Ce³⁺measured in crystal/(×10²⁰, ions·cm^-1)	0.023	0.022	0.024	0.022	0.024
Yb³⁺ in raw material/mol%	0	0.5	1.0	1.5	2.0
Yb³⁺molar concentration in crystal/mol%	0	0.499	0.987	1.486	1.982
Yb³⁺measured in crystal/(×10²⁰, ions·cm^-1)	0	0.502	0.993	1.495	1.994

Fig. 1 (a) Photo of the grown single crystal; (b) XRD patterns of C0, CY3 and standard card of LiLuF4 (1) XRD pattern of 0.1mol% Ce3+ doped LiLuF4 single crystal; (2) XRD pattern of 0.1mol% Ce3+/1.5mol% Yb3+ co-doped LiLuF4 single crystal; (3) Standard card of (JCPD No.27-1251) of LiLuF4

Fig. 2 (a) Crystal structure of LiLuF4, and (b) coordination for lithium and (c) lutetium sites

Fig. 3 Absorption spectra of the LiLuF4 single crystals (a) 0.1mol%Ce3+/1.5mol%Yb3+ co-doped; (b) 0.1mol%Ce3+ singly doped LiLuF4

Fig. 4 (a) Emission spectra of Ce3+/Yb3+ co-doped LiLuF4 single crystals excited at 291 nm, and (b) emission intensity of Ce3+ and Yb3+ ions as a function of Yb3+ concentration

Fig. 5 Partial energy level diagram in Ce3+/Yb3+ co-doped LiLuF4 single crystal

Fig. 6 (a) Fluorescence decay curves of active Ce3+ ions near 326 nm in Ce3+ singly doped LiLuF4 single crystal; (b) Fitting curves with Inokuti-Hirayama model

Fig. 7 (a) Temperature dependent emission spectra of 0.1mol% Ce3+/1.5mol% Yb3+ sample under 291 nm excitation, and (b) emission intensity of Ce3+ and Yb3+ as a function of temperature

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Ultraviolet and Near-infrared Luminescence of Ce ³⁺/Yb ³⁺ Co-doping LiLuF₄ Single Crystal

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