Double-excited states of charge transfer band and 4f-4f in single-phase K3Gd(VO4)2:Tb3+/Sm3+ phosphors with superior sensing sensitivity for potential luminescent thermometers

doi:10.1016/j.jmst.2021.02.041

Abstract

Abstract:

Temperature is one of the fundamental parameters for thermodynamics and its accurate detection is necessary. The novel strategy of luminescent materials based on the fluorescence intensity ratio technique has been promised for thermometers in more practical environments to overcome the drawbacks of conventional thermometers in recent. Herein, the novel single-phase K3Gd(VO4)2:Tb3+/Sm3+ phosphors were successfully prepared, and the 4G5/2 → 6H9/2 (Sm3+) and 5D4 → 7F5 (Tb3+) transitions could be promised for luminescent thermometers. Besides, under the double-excited states of charge transfer band (CTB, 317 nm) and 4f-4f (478 nm) excitations, the K3Gd(VO4)2:Tb3+/Sm3+ phosphors exhibited different concentration quenching mechanisms in energy transfer processes and also showed superior absolute sensing sensitivity (Sa) and relative sensing sensitivity (Sr). Especially, the maximum Sa and Sr values reached up to 0.568 K-1 and 11.24% K-1, respectively and the temperature resolution of the KGV:0.2Tb3+/0.01Sm3+ phosphor was higher than 0.004 K under the excitation wavelength of CTB (317 nm), indicating that the double-excited states in the single-phase KGV:Tb3+/Sm3+ phosphors with superior sensing sensitivity could be a novel candidate for potential optical thermometers.

Key words: Double-excited lines, FIR technique, Energy transfer, Sensing sensitivity

Yongbin Hua, Jae SuYu. Double-excited states of charge transfer band and 4f-4f in single-phase K₃Gd(VO₄)₂:Tb³⁺/Sm³⁺ phosphors with superior sensing sensitivity for potential luminescent thermometers[J]. J. Mater. Sci. Technol., 2021, 91: 148-159.

Figures/Tables 13

Fig. 1. (a) XRD patterns and (b) FT-IR spectra of the KGV, KGV:0.2Tb3+, and KGV:0.2Tb3+/0.05Sm3+ phosphors. (c) Crystal structure of the KGV host lattice.

Fig. 2. (a) XPS spectra and (b, c) high-resolution XPS spectra of the obtained samples. EDS spectra and elemental mapping images of the (d, e) KGV:0.2Tb3+ and (f, g) KGV:0.2Tb3+/0.05Sm3+ phosphors.

Fig. 3. TEM images, HR-TEM images, and SAED patterns of the (a-c) KGV:0.2Tb3+ and (d-f) KGV:0.2Tb3+/0.05Sm3+ phosphors.

Fig. 4. (a) PLE spectra, (b) zoomed PLE spectrum, and (c) PLE intensity of the KGV:Tb3+ phosphor under the 543 nm of emission wavelength. PL emission spectra, PL emission intensity, and log(x) vs. log(I/x) of KGV:xTb3+ phosphor at the excitation wavelengths of (d-f) CTB (317 nm) and (g-i) 4f-4f (478 nm).

Fig. 5. (a) PLE spectrum, (b) PL emission spectra, and (c) PL emission intensity of the KGV:0.1Sm3+ phosphor. (d) PLE spectra of the KGV:0.1Sm3+ and KGV:0.2Tb3+ phosphors.

Fig. 6. PL emission spectra, PL intensity, and ET efficiency of the KGV:0.2Tb3+/ySm3+ phosphors monitored at the excitation wavelengths of (a-c) CTB (317 nm) and (d-f) 4f-4f (478 nm).

Fig. 7. Normalized PL emission intensity of Tb3+ ion as a function of Sm3+ ion concentration in the KGV:0.2Tb3+/ySm3+ phosphor.

Fig. 8. Dependence of Is0/Is of Tb3+ on the Sm3+ ion concentration at the excitation wavelengths of (a-c) CTB (317 nm) and (d-f) 4f-4f (478 nm).

Fig. 9. Simplified ET diagram of the KGV:0.2Tb3+/xSm3+ phosphor under CTB (317 nm) and 4f-4f (478 nm) excitations.

Fig. 10. Dependence of (a, c) FIR value and (b, d) sensing sensitivity of the KGV:0.2Tb3+/0.05Sm3+ phosphor with the double-excited states of CTB (317 nm) and 4f-4f (478 nm) as a function of temperature.

Fig. 11. Reversible emission performance of the KGV:0.2Tb3+/0.05Sm3+ phosphor in cycles of heating and cooling.

Fig. 12. FIR and Sa values of the KGV:0.2Tb3+/0.01Sm3+ phosphor measured at the excitation wavelengths of (a) CTB (317 nm) and (b) 4f-4f (478 nm). (c) Relative sensor sensitivity values of the KGV:0.2Tb3+/0.01Sm3+ and KGV:0.2Tb3+/0.05Sm3+ phosphors pumped by the double-excited states. (d) Temperature resolution in the range of 303-423 K.

Table 1 Comparative sensing properties of some luminescent materials.

Phosphors	Temperature (K)	λ_ex (nm)	S_a (K^-1)	S_r (K^-1)	Ref.
NLM:Sm³⁺/Tb³⁺	303-443	380	0.02	0.68%	[18]
GdNbO₄:Bi³⁺/Eu³⁺	303-523	308	0.0367	3.81%	[19]
LaF₃:Er³⁺/Yb³⁺	15-105	988	0.0768	6.609%	[41]
Y₂Ti₂O₇:Pr³⁺	289-573	343	0.0983	5.25%	[42]
CaBaZn₂Ga₂O₇:Bi³⁺	298-473	330	0.154	1.453%	[43]
LaVO₄:Tb³⁺/Pr³⁺	303-443	322	0.193	5.30%	[44]
La₂Ti₃O₉:Tb³⁺/Pr³⁺	303-423	340	0.156	3.47%	[45]
Ca₂YZr₂Al₃O₁₂:Bi³⁺/Eu³⁺	297-573	278	0.00826	0.664%	[46]
Ca₁₄Al₁₀Zn₆O₃₅:Bi³⁺/Sm³⁺	303-523	340	0.0038	-	[47]
LiTaO₃:Er³⁺	100-500	980	0.00334	-	[48]
LaGdAlO₃:Eu²⁺/Eu³⁺	303-473	315	0.084	3.233%	[49]
SrGdLiTeO₆:Mn⁴⁺/Eu³⁺	300-550	302	0.0946	4.9%	[50]
KGV:Tb³⁺/Sm³⁺	303-383	CTB (317 nm)	0.568	11.24%	This work
	303-423	4f-4f (478 nm)	0.295	2.98%	This work

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Double-excited states of charge transfer band and 4f-4f in single-phase K₃Gd(VO₄)₂:Tb³⁺/Sm³⁺ phosphors with superior sensing sensitivity for potential luminescent thermometers

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