复合钙钛矿型NaLaMgWO6: Eu3+红色荧光材料的制备及发光性能研

doi:10.15541/jim20160623

摘要/Abstract

摘要：

采用固相法合成了新型白光LED用红色NaLa_1-xEu_xMgWO₆(0≤x≤1)系列荧光粉。分别采用X射线衍射、扫描电子显微镜、发光光谱等测试手段分析了粉体样品的物相、形貌与发光性质。XRD分析结果表明: NaLaMgWO₆具有单斜晶系的复合钙钛矿结构, 空间群为C2/m。光谱测试结果表明: NaLa_1-_xEu_xMgWO₆系列荧光粉均可被近紫外光(397 nm)和蓝光(465 nm)有效激发, 其最强发射峰位于617 nm处, 属于Eu³⁺的⁵D₀→⁷F₂电偶极跃迁。Eu³⁺的最佳掺杂浓度为x=0.5。对荧光粉的发光浓度猝灭曲线分析表明, 在NaLaMgWO₆基质中, Eu³⁺是通过电偶极-电偶极的多极矩相互作用的方式来实现能量传递的。采用Judd-Ofelt理论计算了基质的折射率、Eu³⁺离子的辐射跃迁强度参数(Ω_λ)和荧光分支(β)等辐射跃迁参数。

关键词: NaLaMgWO6: Eu3+红色荧光粉, 光致发光, 浓度猝灭, Judd-Ofelt理论

Abstract:

Series of NaLa_1-xEu_xMgWO₆(0≤x≤1) novel red phosphors were successfully synthesized by the conventional solid state method. The crystal structure, morphology, and luminescence properties of NaLa_1-xEu_xMgWO₆phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectra (PL), respectively. XRD results show that NaLaMgWO₆ phosphor has monoclinic double perovskite structure with space group C2/m. The excitation and emission spectra show that NaLaMgWO₆: Eu³⁺ phosphor can be effectively excited by near-UV (397 nm) and blue light (465 nm), and exhibits the strongest red emission peak located at 617 nm, which is ascribed to ⁵D₀→⁷F₂ transition of Eu³⁺ ion. The optimal doping concentration of Eu³⁺ is determined to be x=0.5. It can be confirmed that the dipole-dipole interaction plays an important role in the energy transfer in NaLaMgWO₆: Eu³⁺ phosphors through the concentration quenching curve. In addition, Judd-Ofelt theory is employed to evaluate various radiative parameters, such as the refractive index, the J-O parameters (Ω_λ) and the branching ration (β).

Key words: NaLaMgWO6: Eu3+ red phosphors, photoluminescence, concentration quenching, Judd-Ofelt theory

中图分类号:

TQ174

李桂芳, 杨倩, 卫云鸽. 复合钙钛矿型NaLaMgWO₆: Eu³⁺红色荧光材料的制备及发光性能研[J]. 无机材料学报, 2017, 32(9): 936-942.

LI Gui-Fang, YANG Qian, WEI Yun-Ge. Synthesis and Photoluminescence Properties of Double Perovskite NaLaMgWO₆: Eu³⁺Red Phosphor[J]. Journal of Inorganic Materials, 2017, 32(9): 936-942.

图/表 10

图1 (a) NaLa1-xEuxMgWO6荧光粉的XRD图谱和(b)位于2θ= 31o~33o之间的(112)和(020)晶面的衍射峰偏移图

Fig. 1 XRD patterns (a) and (112) and (020) diffraction peak position offset (b) of NaLa1-xEuxMgWO6 phosphors

图2 NaLaMgWO6基质的Rietveld精修图谱

Fig. 2 Rietveld refinement of XRD pattern for NaLaMgWO6 host

图3 NaLaMgWO6晶体结构图

Fig. 3 Crystal structure of NaLaMgWO6

图4 NaLa1-xEuxMgWO6荧光粉的SEM照片

Fig. 4 SEM images of NaLa1-xEuxMgWO6 phosphors (a) x=0; (b) x=0.2; (c) x=0.4; (d) x=0.6; (e) x=0.8; (f) x=1.0

图5 NaLa1-xEuxMgWO6荧光粉的激发光谱

Fig. 5 Excitation spectra of NaLa1-xEuxMgWO6 phosphors

图6 不同激发波长下NaLa0.5Eu0.5MgWO6荧光粉的发射光谱

Fig. 6 Emission spectra of NaLa0.5Eu0.5MgWO6 phosphors at different excitation wavelength Inset shows schematic energy-level diagram Eu3+ ions in NaLaMgWO6

图 7 NaLa1-xEuxMgWO6荧光粉的发射光谱图

Fig. 7 Emission spectra of NaLa1-xEuxMgWO6 phosphors Inset shows the relation between the lgC and lg (I/C) for 5D0→7F2 transition of Eu3+

图8 Eu3+离子5D0-7F2跃迁衰减曲线(λex=397 nm, λem=617 nm)

Fig. 8 Decay curves of 5D0-7F2 transition of Eu3+ (λex=397 nm, λem=617 nm)

表1 NaLaMgWO6中Eu3+离子的5D0→7FJ跃迁发射速率和荧光分支比

Table 1 Radiative transition rates and branch ratios for5D0→7FJ of NaLaMgWO6 phosphors

Transition	Wavelength/nm^-1	Transition rate/s^-1	β/%
⁵D₀→⁷F₀	17241.38	27.468	1.33
⁵D₀→⁷F₁	16891.89	220.392	10.70
⁵D₀→⁷F₂	16207.45	1795.735	87.18
⁵D₀→⁷F₃	15313.93	7.645	0.37
⁵D₀→⁷F₄	14388.49	8.523	0.42

表2 NaLaMgWO6: Eu3+荧光粉的J-O参数

Table 2 J-O parameters of NaLaMgWO6: Eu3+ phosphors

Host	Source	Ω₂/ (10^-20, cm²)	Ω₄/ (10^-20, cm²)	τ /ms
BaWO₄: Eu³⁺, Sm³⁺	[25]	8.650	3.67	0.55
NaY(WO₄)₂: Eu³⁺	[26]	8.610	1.12	1.03
Ba₅Gd₈Zn₄O₂₁	[27]	12.700	4.50	0.75
NaLaMgWO₆: Eu³⁺	Present work	8.735	0.82	0.45

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复合钙钛矿型NaLaMgWO₆: Eu³⁺红色荧光材料的制备及发光性能研

Synthesis and Photoluminescence Properties of Double Perovskite NaLaMgWO₆: Eu³⁺Red Phosphor

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