Mn4+激活氧氟化物红光荧光粉的研究进展

doi:10.15541/jim20190554

摘要/Abstract

摘要：

稳定可靠的高光子能量发光(620~650 nm)红光荧光粉, 对于构建低色温、高显指荧光粉转换型白光发光二极管(WLED)至关重要。Mn ⁴⁺激活红光荧光粉是当前WLED用荧光粉研究热点之一。本文介绍了Mn ⁴⁺离子的能级跃迁与光致发光特性, 详细叙述了目前所报道的七种Mn ⁴⁺激活含d ⁰/d ¹⁰/s ⁰离子氧氟化物系列红色荧光粉(如Na₂WO₂F₄:Mn ⁴⁺等)的制备方法、晶体结构及其发光特性。目前Mn ⁴⁺在氧氟化物结构中得到强R线发光的情况少, 微观配位体仍是[MnF₆]或[MnO₆], 其化学稳定性和量子效率研究也很缺乏。最后对Mn ⁴⁺激活氧氟化物红光荧光粉的研究进行了展望。

关键词: 白光LED, 荧光粉, Mn⁴⁺, 氧氟化物, 综述

Abstract:

The stable and reliable red phosphor with high-photon energy emission (620-650 nm) is critical for the fabrication of the phosphor-converted white light-emitting diode (WLED) with low correlated color temperature and high color rendering index. Mn ⁴⁺-activated phosphor is an emerging kind of red-emitting phosphor for WLED. Herein, the energy levels transition and photoluminescence characteristics of the Mn ⁴⁺ ion were introduced; then, the preparation, crystal structure and luminescent properties of as-far reported seven kinds of Mn ⁴⁺-doped oxyfluoride red phosphors (such as Na₂WO₂F₄:Mn ⁴⁺) containing d ⁰, d ¹⁰ or s ⁰ cations were reviewed. Currently, only in quite rare case of oxyfluoride, Mn ⁴⁺ was found to exhibit strong R-line emission, with local coordination remaining as either [MnF₆] or [MnO₆]. The studies on the chemical stability and quantum efficiency of Mn ⁴⁺-doped oxyfluoride phosphors are still insufficient. Finally, we prospected the future development of Mn ⁴⁺-doped oxyfluoride phosphor.

Key words: white LED, phosphor, Mn⁴⁺, oxyfluoride, review

中图分类号:

TQ174

姬海鹏, 张宗涛, XU Jian, TANABE Setsuhisa, 陈德良, 解荣军. Mn⁴⁺激活氧氟化物红光荧光粉的研究进展[J]. 无机材料学报, 2020, 35(8): 847-856.

JI Haipeng, ZHANG Zongtao, XU Jian, TANABE Setsuhisa, CHEN Deliang, XIE Rongjun. Advance in Red-emitting Mn⁴⁺-activated Oxyfluoride Phosphors[J]. Journal of Inorganic Materials, 2020, 35(8): 847-856.

图/表 11

图1 d3离子的自由离子能级(C = 4.5B) (a), 描述d3离子在八面体晶体场中能级劈裂的Tanabe-Sugano图(C = 4.5B) (b), 八面体晶体场中五种d轨道相对于配体的取向(黑点表示配体离子)(c)和d轨道在八面体晶体场中的晶体场劈裂(d)[16]

Fig. 1 Energy levels arising from a d3 configuration for a free transition metal ion (C=4.5B) (a), Tanabe-Sugano diagram for the d3 electron configuration in an octahedral crystal field (C=4.5B) (b), orientation of the five d-orbitals with respect to the ligands of an octahedral complex (black dots showing the ligands around the transition metal ion) (c), and crystal field splitting for the d-orbitals in an octahedral crystal field (d)[16]

图2 规则八面体配位和畸变八面体配位

Fig. 2 Regular octahedron coordination and distorted octahedra coordination (a) Point symmetry of Oh; (b) Central cation shifting to a vertex, C4v; (c) Central cation shifting to an edge, C2v; (d) Central cation shifting to a face, C3v

表1 目前所报道的Mn4+激活氧氟化物荧光粉

Table 1 The reported Mn4+ activated oxyfluoride phosphors

Cation	Phosphor host	Peaking wavelength/nm	(R-line/ν₆ intensity ratio)/%	T_50%/K	Ref.
d⁰	Na₂WO₂F₄	619	125	340	[21-22]
	Cs₂WO₂F₄	632	5	350	[23]
	Cs₂NbOF₅	632	10	-	[24-25]
	BaNbOF₅	629	10	-	[26]
	Sr₂ScO₃F	690	-	320	[27]
	BaTiOF₄	632	5	-	[28]
d¹⁰	Mg₂₈Ge_7.55O₃₂F_15.04	657	-	700	[29]
s⁰	LiAl₄O₆F	662	5-10	-	[30]

图3 Na2WO2F4的晶胞(a), 具有较大畸变的[WO2F4]八面体(b)和Na2WO2F4:Mn4+的发光光谱(c)(插图为其在460 nm激发下照片)[21]

Fig. 3 Unit cell of Na2WO2F4 (a), highly-distorted [WO2F4] octahedra (b), and emission spectrum of Na2WO2F4:Mn4+ (c) [21] with inset showing phosphor image under 460 nm light Na: yellow; W: blue; O: red; F: gray

图4 (a) Cs2WO2F4的晶体结构, 其含有具有较小畸变的W(O,F)6配位八面体, 右下所示为Mn4+在K2MnF6中的微观配位八面体; (b) Cs2WO2F4:Mn4+的激发与发射光谱(插图为其在365 nm激发下照片)[23]

Fig. 4 (a) Unit cell of Cs2WO2F4 which contains slightly- distorted [W(O,F)6] octahedra, with the bottom-right showing the local coordination of Mn4+ in K2MnF6; (b) Excitation and emission spectra of Cs2WO2F4:Mn4+ with inset showing the phosphor image under 365 nm light[23]

图5 Cs2NbOF5:Mn4+的激发光谱(PLE)与漫反射光谱(DRS) (a)和Cs2NbOF5:Mn4+的变温发光光谱(b)[24]

Fig. 5 PLE and DRS spectra of the Cs2NbOF5:Mn4+ phosphor (a) and temperature-dependent emission spectra of Cs2NbOF5:Mn4+ (b)[24] with the inset showing the intensity evolution of the integrated emission (Ie), the stokes emission (Is) and the anti-stokes emmission (Ia)

图6 T=78和298 K时BaNbOF5:Mn4+的激发光谱(a)与发光光谱(b) (插图为该荧光粉在自然光和紫外光照射下照片)[26]

Fig. 6 The PLE (a) and PL (b) spectra of the BaNbOF5:Mn4+ phosphor at temperature of 78 and 298 K with insets showing the phosphor images under natural or UV light[26]

图7 Sr2ScO3F的晶胞(a)和Sr2ScO3F:Mn4+的变温发光光谱(b)[27]

Fig. 7 Unit cell of Sr2ScO3F (a) and temperature-dependent emission spectra of Sr2ScO3F:Mn4+ (b)[27]Sr: yellow; Sc: blue; O: red; F: gray

图8 BaTiOF4:Mn4+的室温激发与发射光谱(a), BaTiOF4:Mn4+的室温和低温发光光谱(b), BaTiOF4的晶胞(c)和[Ti2OF4]畸变八面体(d)[28]

Fig. 8 Excitation and emission spectra of BaTiOF4:Mn4+ at room temperature (a), emission spectra of BaTiOF4:Mn4+ at 77 K and 293 K (b), unit cell of BaTiOF4 (c), and distorted octahedron coordination of [Ti2OF4] (d)[28]Ba: yellow; Ti: blue; O: red; F: gray

图9 Mn4+占据Mg28Ge7.55O32F15.04结构中八面体配位Ge/Mg格位时计算所得4T2g和4T1g能级位置与实测光谱的比较[29]

Fig. 9 Comparison of the calculated Mn4+ energy levels in Mg28Ge7.55O32F15.04 for all possible Mn4+ positions in Ge/Mg sites with the measured spectrum[29]

图10 LiAl4O6F的晶胞及Al3+/Li+的配位多面体(a)和LiAl4O6F:Mn4+的变温发光光谱(b)[30]

Fig. 10 Unit cell of LiAl4O6F and coordination of Al3+/Li+ (a) and emission spectra of LiAl4O6F:Mn4+ at temperature of 298-523 K (b) [30]

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Mn⁴⁺激活氧氟化物红光荧光粉的研究进展

Advance in Red-emitting Mn⁴⁺-activated Oxyfluoride Phosphors

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