An Efficient Narrow-band Blue-emitting Phosphor Ba3Y2B6O15:Bi3+ and Its Application

doi:10.6023/A23010003

Abstract

At present, the development of efficient (high quantum efficiency and high thermal stability) narrow-band emitting phosphors is a crucial problem in the application of white light emitting diodes (WLED) for high-performance liquid crystal display (LCD) backlights. In this work, an efficient narrow-band blue emitting phosphor Ba₃Y₂B₆O₁₅:Bi³⁺ was prepared by high temperature solid state method, and its structure and properties were characterized and calculated. By using the density functional theory (DFT), Ba₃Y₂B₆O₁₅ is calculated to be a direct band gap material with a high band gap value of 4.67 eV, which is a necessary condition for achieving high quantum efficiency phosphors. The experiment results show that Ba₃Y₂B₆O₁₅:0.5%Bi³⁺ has a narrow-band blue-emitting spectrum with a full width at half maximum (FWHM) of 2168 cm⁻¹ (36.2 nm) at 409 nm, which is owing to the ³P₁→¹S₀ transition of Bi³⁺ ions. The emission spectra of Ba₃Y₂B₆O₁₅:0.5%Bi³⁺ can be split into two peaks at 406 and 422 nm, respectively, because there are two kinds of Y ions (Y1 and Y2) in the crystal cell of Ba₃Y₂B₆O₁₅. Under the 365 nm UV radiation, the Ba₃Y₂B₆O₁₅:0.5%Bi³⁺ exhibits high internal quantum efficiency (IQE=93.8%), and ultra-high color purity (98.9%). The high quantum efficiency and narrow-band emission spectrum are mainly due to the compact and highly symmetric crystal structure of Ba₃Y₂B₆O₁₅ matrix. The photoluminescence (PL) intensity of Ba₃Y₂B₆O₁₅:0.5%Bi³⁺ remains 73.9% of the initial intensity at 150 ℃, and there is almost no color drift. The thermal quenching activation energy (E_a) of Ba₃Y₂B₆O₁₅:0.5%Bi³⁺ was calculated to be 0.290 eV by the Arrhenius Equation, which indicates that Ba₃Y₂B₆O₁₅:0.5%Bi³⁺ has high thermal stability. When Y³⁺ is partially substituted by Sc³⁺, the emission spectrum of Ba₃Sc_xY_2-_xB₆O₁₅:Bi³⁺(0≤x≤1.6) is redshifted with the increase of x. Finally, the blue phosphor Ba₃Y₂B₆O₁₅:0.5%Bi³⁺ was mixed with commecial green and red phosphors and then coated them on a 365 nm chip to fabricate a WLED device. Under a driven current of 20 mA, the correlated color temperature of the obtained WLED is 5679 K and the color gamut can reach 95.3% NTSC. Above results indicate that Ba₃Y₂B₆O₁₅:Bi³⁺ is a promising phosphor for high-performance LCD backlights.

Key words: highly-efficient phosphor, narrow-band emitting, blue phosphor, Ba₃Y₂B₆O₁₅:Bi³⁺

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Pan Liang, Hongshu Zhang, Hongsheng Huang, Saying Li, Xiaotian Zhang, Ying Wang, Lianqing Li, Zhihong Liu. An Efficient Narrow-band Blue-emitting Phosphor Ba₃Y₂B₆O₁₅:Bi³⁺ and Its Application[J]. Acta Chimica Sinica, 2023, 81(4): 371-380.

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Fig. & Tab. 12

Figure 1. (a) XRD patterns of Ba3Y2B6O15:yBi3+(0.1%≤y≤3.0%); (b) XRD patterns of Ba3ScxY2-xB6O15: 0.5%Bi3+(0.2≤x≤1.6); (c) Rietveld refinement XRD pattern of Ba3ScYB6O15; (d) typical crystal structure of Ba3Y2B6O15 and the coordination environment of Ba2+, Y3+, B3+

Parameter	Value
Formula	Ba₃Y₂B₆O₁₅	Ba₃ScYB₆O₁₅^a	Ba₃YScB₆O₁₅^b
Crystal system	Cubic	Cubic	Cubic
Space group	Ia$ \overline{3} $	Ia$ \overline{3} $	Ia$ \overline{3} $
a	1.42530 nm	1.40940 nm	1.40941 nm
Volume	2.895469 nm³	2.799634 nm³	2.799712 nm³
R_p	—	9.06	9.22
R_wp	—	11.7	11.8
Chi²	—	2.22	2.29

Table 1. Structure refinement parameters obtained through refinement of XRD of Ba3ScYB6O15 and Ba3YScB6O15

Atom	x	y	z	B	Occ	Mult
Ba	0.36801	0.00000	0.25000	1.073	0.500	24
Sc	0.00000	0.00000	0.50000	1.864	0.167	8
Y	0.25000	0.25000	0.25000	0.000	0.167	8
B	0.12284	0.06192	0.30846	2.555	1.00	48
O1	0.03270	0.04157	0.33679	1.103	1.00	48
O2	0.15503	0.00000	0.25000	4.058	0.50	24
O3	0.15752	0.14748	0.31299	0.000	1.00	48

Table 2. Refined atom positions, occupancies, thermal parameters and multiplicity of Ba3ScYB6O15 from X-ray powder diffraction data

Figure 2. (a) XPS survey spectum of Ba3Y2B6O15:Bi3+; (b~e) high-resolution XPS spectra of Ba, O, B, Bi, Y

Figure 3. (a) The energy band structure of Ba3Y2B6O15; (b) total density of states and partial density of states of Ba3Y2B6O15 All the results are calculated based on the PBE function

Figure 4. (a, b) The PLE and PL spectra of Ba3Y2B6O15:yBi3+; (c) the room temperature PL spectra and Gaussian fitting curve of the representative Ba3Y2B6O15:0.5%Bi3+; (d) the decay curves of Ba3Y2B6O15:0.5%Bi3+ monitored at 406 nm and 422 nm; (e) CIE coordinates of Ba3Y2B6O15:0.5%Bi3+; (f) QE spectra of Ba3Y2B6O15:0.5%Bi3+

Phosphor	IQE/%	FWHM/nm	CP/%	Reference
BaMgAl₁₀O₁₇:Eu²⁺^a	92.4	51.7	88.0	[50]
Sr₅(PO₄)₃Cl:Eu²⁺^b	80.5	≈40	99.0	[50]
Ba₃Lu₂B₆O₁₅:0.5%Bi³⁺	90.6	35.5	97.8	[35]
Ba₃Y₂B₆O₁₅:0.5%Bi³⁺	93.8	36.2	98.9	This work

Table 3. The IQE, FWHM and CP of Ba3Y2B6O15:0.5%Bi3+ versus some other blue emitting phosphor

Figure 5. (a) Temperature-dependent PL of Ba3Y2B6O15:0.5%Bi3+; (b) Thermal quenching properties of Ba3Y2B6O15:0.5%Bi3+ in the temperatures range of 298~473 K; (c) Fitted thermal quenching activation energy (Ea) for Ba3Y2B6O15:0.5%Bi3+

Figure 6. The normalized PL spectra of Ba3ScxY2-xB6O15:0.5%Bi3+ (0.2≤x≤1.6)

x值	IQE/%	Abs	EQE/%
0	93.8	0.337	31.6
0.2	78.5	0.352	27.6
0.4	84.2	0.344	29.0
0.6	90.4	0.283	25.6
0.8	81.6	0.316	25.8
1.0	86.2	0.227	19.6
1.2	74.7	0.220	16.4
1.4	65.7	0.223	14.7
1.6	54.2	0.259	14.0

Table 4. IQE, EQE and absorption coefficient of Ba3ScxY2-xB6O15: 0.5%Bi3+ (0.2≤x≤1.6)

Figure 7. (a) Electroluminescence spectra of manufactured WLED driven by 20 mA current. The insets graph shows as-fabricated WLED device taken in natural light and when it is in operation; (b) color gamut of the NTSC standard (red triangle) and the as-manufactured WLED device (black triangle); (c) electroluminescence spectra of manufactured WLED driven by different currents; (d) electroluminescence spectra of manufactured WLED measured at diffeent working time. The insert graph shows the correlated color temperature of manufactured WLED measured at different working time

电流/mA	20	40	60	80	100	120
色坐标x	0.328	0.325	0.324	0.321	0.320	0.320
色坐标y	0.349	0.336	0.330	0.327	0.325	0.323
相关色温/K	5679	5841	5906	6084	6138	6202

Table 5. Color coordinates and correlated color temperature of the obtained WLED driven by different currents

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一种高效窄带蓝色荧光粉Ba₃Y₂B₆O₁₅:Bi³⁺及其应用研究

An Efficient Narrow-band Blue-emitting Phosphor Ba₃Y₂B₆O₁₅:Bi³⁺ and Its Application

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一种高效窄带蓝色荧光粉Ba3Y2B6O15:Bi3+及其应用研究