Controlling disorder in host lattice by hetero-valence ion doping to manipulate luminescence in spinel solid solution phosphors

Qinqin Ma; Jie Wang; Wei Zheng; Qian Wang; Zhiheng Li; Hengjiang Cong; Huijun Liu; Xueyuan Chen; Quan Yuan

doi:10.1007/s11426-018-9311-0

SCIENCE CHINA Chemistry

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SCIENCE CHINA Chemistry, Volume 61, Issue 12: 1624-1629(2018) https://doi.org/10.1007/s11426-018-9311-0

Controlling disorder in host lattice by hetero-valence ion doping to manipulate luminescence in spinel solid solution phosphors

Qinqin Ma¹, Jie Wang¹, Wei Zheng², Qian Wang¹, Zhiheng Li¹, Hengjiang Cong¹, Huijun Liu³, Xueyuan Chen², Quan Yuan^1,*

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ReceivedMar 28, 2018
AcceptedJun 11, 2018
PublishedAug 16, 2018

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Abstract

Phosphor materials have been rapidly developed in the past decades. Developing phosphors with desired properties including strong luminescence intensity and long lifetime has attracted widespread attention. Herein, we show that hetero-valence ion doping can serve as a potent strategy to manipulate luminescence in persistent phosphors by controlling disorder in the host lattice. Specifically, spinel phosphor Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr is developed by doping ZnGa₂O₄:Cr with tetravalent Ge⁴⁺. Compared to the original ZnGa₂O₄:Cr, the doped Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr possesses significantly enhanced persistent luminescence intensity and prolonged decay time. Rietveld refinements show that Ge⁴⁺ enters into octahedral sites to substitute Ga³⁺, which leads to the co-substitution of Ga³⁺ by Zn²⁺ for charge compensation. The hetero-valence substitution of Ga³⁺ by Ge⁴⁺ and Zn²⁺ enriches the charged defects in Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr, making it possible to trap large amounts of charge carriers within the defects during excitation. Electron paramagnetic resonance measurement further confirms that the amount of Cr³⁺ neighboring charged defects increases with Ge⁴⁺ doping. Thus charge carriers released from defects can readily combine with the neighboring Cr³⁺ to produce bright persistent luminescence after excitation ceases. The hetero-valence ion doping strategy can further be employed to develop many other phosphors and contributes to lighting, photocatalysis and bioimaging.

Funded by

the National Key R&D Program of China(2017YFA0208000)

the National Natural Science Foundation of China(21675120,21325104)

and the CAS/SAFEA International Partnership Program for Creative Research Teams.

Acknowledgment

This work was supported by the National Key R&D Program of China (2017YFA0208000), the National Natural Science Foundation of China (21675120, 21325104), and the CAS/SAFEA International Partnership Program for Creative Research Teams. We sincerely thank Prof. Zhenxing Wang from Huazhong University of Science and Technology for his assistance in EPR simulation. The EPR simulation is conducted with the SPIN developed by Andrew Ozarowski in the National High Magnetic Field Laboratory, USA.

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

These authors contributed equally to this work.

Supplement

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Figure 1
(a) TEM images of ZnGa₂O₄:Cr, (b) Zn_1.1Ga_1.8Ge_0.1O₄:Cr and (c) Zn_1.2Ga_1.6Ge_0.2O₄:Cr nanoparticles. (d) Photoluminescence spectra of Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr nanoparticles. N2: N2 zero photon line. S-PSB: Stokes phonon sideband line. (e) Luminescence decay curves in Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr nanoparticles. (f) Luminescence decay images of ZnGa₂O₄:Cr and Zn_1.1Ga_1.8Ge_0.1O₄:Cr colloid dispersion (1?mg/mL) after excitation with a LED (color online).
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Figure 2
(a) Rietveld refinement of ZnGa₂O₄:Cr. (b) Schematic illustration of ZnGa₂O₄:Cr unit cell. (c) Rietveld refinement of Zn_1.1Ga_1.8Ge_0.1O₄:Cr. (d) Schematic illustration of Zn_1.1Ga_1.8Ge_0.1O₄:Cr unit cell. (e) Rietveld refinement of Zn_1.2Ga_1.6Ge_0.2O₄:Cr. (f) Schematic illustration of Zn_1.2Ga_1.6Ge_0.2O₄:Cr unit cell (color online).
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Figure 3
(a) EPR spectra of Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr. (b) Schematic illustration of charged defects increasing in Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr induced by hetero-valence ion doping (color online).

Table 1 Table 1 The luminescence intensity of decay images of ZnGa₂O₄:Cr and Zn_1.1Ga_1.8Ge_0.1O₄:Cr colloid dispersion shown in Figure 1(f)

	1st activation (10⁴)		2nd activation (10⁴)		3rd activation (10⁴)
	x=0	x=0.1	x=0	x=0.1	x=0	x=0.1
1?min	29.8	50.9	31.3	53.7	34.5	60.3
3?min	12.6	20.6	12.5	21.5	13.1	22.5
5?min	7.92	12.6	8.29	13.8	8.38	14.3
10?min	4.01	6.63	4.05	6.67	4.07	6.90

Table 2 Table 2 Charged defects in Zn(Ga_1?_xZn_x)(Ga_1?_xGe_x)O₄:Cr. Ge^o_Ga:Ge⁴⁺ ion in the octahedral site. Zn′_Ga:Zn²⁺ ion in the octahedral site. Ga^o_Zn:Ga³⁺ ion in the tetrahedral site. The negative and positive charges are represented by dash and dot respectively

Composition (x)
Ge^o_Ga
Zn′_Ga
Ga^o_Zn
0
0
0.03
0.03
0.1
0.1
0.18
0.08
0.2
0.2
0.38
0.18

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Controlling disorder in host lattice by hetero-valence ion doping to manipulate luminescence in spinel solid solution phosphors

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Composition (x)	Ge^o_Ga	Zn′_Ga	Ga^o_Zn
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