Effect of monovalent charge compensators on the photoluminescence properties of Ca3(PO4)2:Tb3+, A+ (A = Li, Na, K) phosphors

doi:10.1016/j.jmst.2020.11.065

Abstract

Abstract:

Ca_3-_x(PO₄)₂:xTb³⁺ (0.2 ≤ x ≤ 0.4), Ca_2.3(PO₄)₂:0.35Tb³⁺, 0.35A⁺ (A = Li, Na, K), and Ca_2.3(PO₄)₂:0.35Tb³⁺, yLi⁺ (0.35 ≤ y ≤ 0.455) phosphors were prepared by solid-state reaction. All the prepared phosphors formed a rhombohedral unit cell with the R3c space group. To improve the photoluminescence (PL) properties of the Ca_2.65(PO₄)₂:0.35Tb³⁺ phosphor, monovalent charge compensators such as Li⁺, NA⁺, and K⁺ were added to the Ca_2.65(PO₄)₂:0.35Tb³⁺ phosphor. The charge compensators acted as fluxes, so they improved the crystallinity. The excitation and emission properties were significantly improved through the incorporation of charge compensators. In particular, among the charge compensators, Li⁺ ion substantially enhanced the emission intensity and color purity. Furthermore, considering the evaporation of Li₂CO₃ during the annealing process, we optimized the concentration of Li⁺ charge compensator to enhance its PL performance. Impressively, the green emission intensity of the Ca_2.3(PO₄)₂:0.35Tb³⁺, 0.385Li⁺ phosphor was 260 % higher than that of the Ca_2.65(PO₄)₂:0.35Tb³⁺ phosphor. We believe that the effect of charge compensators on the PL properties and the optimum concentration of Li⁺ charge compensator are useful for the design of phosphors in light-emitting diodes.

Key words: Optical properties, Ca₃(PO₄)₂, Emission, Excitation, Charge compensator

G.W. Jung, K. Park. Effect of monovalent charge compensators on the photoluminescence properties of Ca₃(PO₄)₂:Tb³⁺, A⁺ (A = Li, Na, K) phosphors[J]. J. Mater. Sci. Technol., 2021, 82: 187-196.

Figures/Tables 10

Fig. 1. XRD patterns of Ca3-x(PO4)2:xTb3+ (0.2 ≤ x ≤ 0.4) phosphors.

Fig. 2. (a) Excitation spectra of Ca3-x(PO4)2:xTb3+ (0.2 ≤ x ≤ 0.4) phosphors monitored at 545?nm. Emission spectra of Ca3-x(PO4)2:xTb3+ (0.2 ≤ x ≤ 0.4) phosphors under (b) 234?nm and (c) 371?nm excitations. (d) Emission intensity from the 5D3 → 7F5 and 5D4 → 7F5 transitions for Ca3-x(PO4)2:xTb3+ (0.2 ≤ x ≤ 0.4) phosphors under 234?nm excitation.

Fig. 3. CIE chromaticity diagrams ofCa3-x(PO4)2:xTb3+ (x?=?0.2(), 0.25(), 0.3(), 0.35(), and 0.4()) under (a) 234?nm and (b) 371?nm excitations.

Fig. 4. XRD patterns of (a) Ca2.3(PO4)2:0.35Tb3+, 0.35A+ (A = Li, Na, K) and (b) Ca2.3(PO4)2:0.35Tb3+, yLi+ (0.35 ≤ y ≤ 0.455) phosphors.

Table 1 FWHM of the (0 2 10) XRD peak for Ca2.65(PO4)2:0.35Tb3+ and Ca2.3(PO4)2:0.35Tb3+, 0.35A+ (A =?Li, Na, K) phosphors.

Sample		FWHM (°)
Ca_2.65(PO₄)₂:0.35Tb³⁺ phosphors		0.144
Ca_2.3(PO₄)₂:0.35Tb³⁺, 0.35A⁺ phosphors	A = Li	0.134
	A = Na	0.135
	A = K	0.137

Fig. 5. (a) Observed and calculated XRD patterns of Ca2.3(PO4)2:0.35Tb3+, 0.385Li+ phosphor. (b) Crystal structure of Ca2.3(PO4)2:0.35Tb3+, 0.385Li+ phosphor drawn using the obtained Rietveld refinement data.

Table 2 Crystallographic data and reliability factors of Ca2.3(PO4)2:0.35Tb3+, 0.385Li+ phosphor.

Crystal structure	Rhombohedral
Space group	R3c
Lattice parameters
a (Å)	10.3852
b (Å)	10.3852
c (Å)	37.1059
α = β (°)	90
γ (°)	120
Volume (Å³)	3465.7987
Reliability factors
R_wp (%)	8.52
R_exp (%)	4.05
χ²	4.43

Table 3 Atomic coordinate, isotropic thermal parameter (Biso), and occupancy of Ca2.3(PO4)2:0.35Tb3+, 0.385Li+ phosphor obtained from the XRD Rietveld refinement.

Atom	Atomic coordinates				Isotropic thermal parameter B_iso (Å²)	Occupancy
Atom	Site	x	y	z	Isotropic thermal parameter B_iso (Å²)	Occupancy
Ca(1)	18b	0.7247	0.8536	0.1675	0.4512	0.8192
Tb(1)	18b	0.7247	0.8536	0.1675	0.4512	0.1808
Ca(2)	18b	0.6214	0.8160	-0.0343	1.1535	0.8367
Tb(2)	18b	0.6214	0.8160	-0.0343	1.1535	0.1633
Ca(3)	18b	0.7246	0.8472	0.0614	0.5066	0.9797
Tb(3)	18b	0.7246	0.8472	0.0614	0.5066	0.0203
Ca(4)	6a	0.0000	0.0000	-0.0567	0.6176	0.0286
Li(1)	6a	0.0000	0.0000	-0.0567	0.6176	0.1936
Ca(5)	6a	0.0000	0.0000	0.7356	0.4466	0.1165
Li(2)	6a	0.0000	0.0000	0.7356	0.4466	0.2169
P(1)	6a	0.0000	0.0000	0.0000	0.1444	0.3333
P(2)	18b	0.6852	0.8583	0.8689	0.9214	1.0000
P(3)	18b	0.6475	0.8539	0.7668	0.7165	1.0000
O(1)	18b	0.7324	-0.1041	-0.0929	2.5060	1.0000
O(2)	18b	0.7587	0.7641	0.8585	0.2693	1.0000
O(3)	18b	0.7337	0.0077	0.8499	0.1881	1.0000
O(4)	18b	0.5127	0.7600	0.8640	2.4770	1.0000
O(5)	18b	0.6019	-0.0453	0.7822	0.2364	1.0000
O(6)	18b	0.5844	0.6945	0.7808	0.2097	1.0000
O(7)	18b	0.0984	0.9119	0.7771	1.2677	1.0000
O(8)	18b	0.6226	0.8266	0.7273	2.5776	1.0000
O(9)	18b	0.0088	0.8604	-0.0112	2.3972	1.0000
O(10)	6a	0.0000	0.0000	0.0404	1.7667	0.3333

Fig. 6. Excitation spectra of (a) Ca2.3(PO4)2:0.35Tb3+, 0.35A+ (A = Li, Na, K) and (b) Ca2.3(PO4)2:0.35Tb3+, yLi+ (0.35 ≤ y ≤ 0.455) phosphors monitored at 545?nm. Emission spectra of (c) Ca2.3(PO4)2:0.35Tb3+, 0.35A+ (A = Li, Na, K) and (d) Ca2.3(PO4)2:0.35Tb3+, yLi+ (0.35 ≤ y ≤ 0.455) phosphors under 234?nm excitation. Emission intensities from the 5D4 → 7F5 (545?nm, green) and 5D3 → 7F5 (415?nm, blue) transitions for (e) Ca2.3(PO4)2:0.35Tb3+, 0.35A+ (A = Li, Na, K) and (f) Ca2.3(PO4)2:0.35Tb3+, yLi+ (0.35 ≤ y ≤ 0.455) phosphors. Note that “none” in (a)-(e) corresponds to Ca2.65(PO4)2:0.35Tb3+ phosphor.

Fig. 7. CIE chromaticity diagrams of (a) Ca2.65(PO4)2:0.35Tb3+( ) and Ca2.3(PO4)2:0.35Tb3+, 0.35A+ (A?=?Li( ), Na( ), and K( )) phosphors and of (b) Ca2.65(PO4)2:0.35Tb3+( ) and Ca2.3(PO4)2:0.35Tb3+, yLi+ (y?=?0.35( ), 0.385( ), 0.42( ), and 0.455( )) phosphors under 234?nm excitation.

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Effect of monovalent charge compensators on the photoluminescence properties of Ca₃(PO₄)₂:Tb³⁺, A⁺ (A = Li, Na, K) phosphors

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