Mn4+激活氧氟化物红光荧光粉的研究进展

doi:10.15541/jim20190554

无机材料学报 ›› 2020, Vol. 35 ›› Issue (8): 847-856.DOI: 10.15541/jim20190554

所属专题：功能材料论文精选(二)：发光材料

• 综述 • 下一篇

Mn⁴⁺激活氧氟化物红光荧光粉的研究进展

姬海鹏¹(),张宗涛¹,XU Jian²,TANABE Setsuhisa²,陈德良¹(),解荣军³()

1.郑州大学材料科学与工程学院, 郑州 450001
2.Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501, Japan
3.厦门大学材料学院, 厦门 361000

收稿日期:2019-10-31 修回日期:2019-11-20 出版日期:2020-08-20 网络出版日期:2020-03-06
作者简介:姬海鹏(1989-), 男, 讲师. E-mail: <email>jihp@zzu.edu.cn</email><br/>JI Haipeng (1989–), male, lecturer. E-mail: <email>jihp@zzu.edu.cn</email>
基金资助:
国家自然科学基金(51902291);河南省博士后科研项目(19030025);中国博士后科学基金(2019M662524)

Advance in Red-emitting Mn⁴⁺-activated Oxyfluoride Phosphors

JI Haipeng¹(),ZHANG Zongtao¹,XU Jian²,TANABE Setsuhisa²,CHEN Deliang¹(),XIE Rongjun³()

1. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China
2. Graduate School of Human and Environmental Studies, Kyoto University, Kyoto 606-8501, Japan
3. School of Materials, Xiamen University, Xiamen 361000, China

Received:2019-10-31 Revised:2019-11-20 Published:2020-08-20 Online:2020-03-06
Supported by:
National Natural Science Foundation of China(51902291);Postdoctoral Research Sponsorship in Henan Province(19030025);China Postdoctoral Science Foundation(2019M662524)

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]

参考文献 34

[1]	WANG L, XIE R J, SUEHIRO T, et al. Down-conversion nitride materials for solid state lighting: recent advances and perspectives. Chemical Reviews, 2018,1184:1951-2009. DOI URL PMID
[2]	XIA Z, LIU Q. Progress in discovery and structural design of color conversion phosphors for LEDs. Progress in Materials Science, 2016,84:59-117. DOI URL
[3]	LIN C C, MEIJERINK A, LIU R S. Critical red components for next-generation white LEDs. Journal of Physical Chemistry Letters, 2016,73:495-503. DOI URL PMID
[4]	HU Y, ZHUANG W, YE H, et al. Preparation and luminescent properties of (Ca_1-xSr_x)S:Eu ²⁺ red-emitting phosphor for white LED . Journal of Luminescence, 2005,1113:139-145. DOI URL
[5]	XIE R J, HINTZEN H T. Optical properties of (oxy)nitride materials: a review. Journal of the American Ceramic Society, 2013,963:665-687. DOI URL
[6]	PUST P, WEILER V, HECHT C, et al. Narrow-band red-emitting Sr[LiAl₃N₄]:Eu ²⁺ as a next-generation LED-phosphor material . Nature Materials, 2014,139:891-896. DOI URL
[7]	SCHMIECHEN S, SCHNEIDER H, WAGATHA P, et al. Toward new phosphors for application in illumination-grade white pc-LEDs: the nitridomagnesosilicates Ca[Mg₃SiN₄]:Ce ³⁺, Sr[Mg₃SiN₄]:Eu ²⁺, and Eu[Mg₃SiN₄] . Chemistry of Materials, 2014,268:2712-2719. DOI URL
[8]	ADACHI S. Photoluminescence spectra and modeling analyses of Mn ⁴⁺-activated fluoride phosphors: a review . Journal of Luminescence, 2018,197:119-130. DOI URL
[9]	ADACHI S. Mn⁴⁺-activated red and deep red-emitting phosphors. ECS Journal of Solid State Science and Technology, 2020, 9(1): 016001-1-34.
[10]	SIJBOM H F, VERSTRAETE R, JOOS J J, et al. K₂SiF₆:Mn ⁴⁺ as a red phosphor for displays and warm-white LEDs: a review of properties and perspectives . Optical Materials Express, 2017,79:3332-3365. DOI URL
[11]	PAULUSZ A G. Efficient Mn(IV) emission in fluorine coordination. Journal of the Electrochemical Society, 1973,1207:942-947. DOI URL
[12]	LIU Y H, GAO W, CHEN G T, et al. Research progress and development trend of fluoride phosphor for white LED. China Light & Lighting, 2018(2):20-24.
[13]	VERSTRAETE R, SIJBOM H F, KORTHOUT K, et al. K₂MnF₆ as a precursor for saturated red fluoride phosphors: the struggle for structural stability. Journal of Materials Chemistry C, 2017,541:10761-10769. DOI URL
[14]	ZHOU Z, ZHOU N, XIA M, et al. Research progress and application prospects of transition metal Mn ⁴⁺-activated luminescent materials . Journal of Materials Chemitry C, 2016,439:9143-9161.
[15]	ZHOU Y Y, WANG L Y, DENG T T, et al. Recent advances in Mn ⁴⁺-doped fluoride narrow-band red-emitting phosphors . Scientia Sinica Technologica, 2017,4711:1111-1125.
[16]	TIM S. New Narrow Band Red Phosphors for White Light Emitting Diodes. Utrecht: Doctoral Dissertation of Utrecht University, 2018.
[17]	TANABE Y, SUGANO S. On the absorption spectra of complex ions II. Journal of the Physical Society of Japan, 1954,9:766-779. DOI URL
[18]	BRIK M G, CAMARDELLO S J, SRIVASTAVA A M. Spin-forbidden transitions in the spectra of transition metal ions and nephelauxetic effect. ECS Journal of Solid State Science and Technology, 2016,51:R3067-R3077. DOI URL
[19]	BRIK M G, BEERS W W, COHEN W, et al. On the Mn ⁴⁺ R-line emission intensity and its tunability in solids . Optical Materials, 2019,91:338-343. DOI URL
[20]	JI H, UEDA J, BRIK M G, et al. Intense deep-red zero phonon line emission of Mn ⁴⁺ in double perovskite La₄Ti₃O₁₂ . Physical Chemistry Chemical Physics, 2019,2145:25108-25117. DOI URL PMID
[21]	HU T, LIN H, CHENG Y, et al. A highly-distorted octahedron with a C_2v group symmetry inducing an ultra-intense zero phonon line in Mn ⁴⁺-activated oxyfluoride Na₂WO₂F₄ . Journal of Materials Chemistry C, 2017,540:10524-10532. DOI URL
[22]	CAI P, WANG X, SEO H J. Excitation power dependent optical temperature behaviors in Mn ⁴⁺ doped oxyfluoride Na₂WO₂F₄ . Physical Chemistry Chemical Physics, 2018,203:2028-2035. DOI URL PMID
[23]	CAI P, QIN L, CHEN C, et al. Luminescence, energy transfer and optical thermometry of a novel narrow red emitting phosphor: Cs₂WO₂F₄:Mn ⁴⁺ . Dalton Transcations, 2017,4641:14331-14340.
[24]	WANG Q, YANG Z, WANG H, et al. Novel Mn ⁴⁺-activated oxyfluoride Cs₂NbOF₅:Mn ⁴⁺ red phosphor for warm white light- emitting diodes . Optical Materials, 2018,85:96-99. DOI URL
[25]	MING H, ZHANG J, LIU L, et al. A novel Cs₂NbOF₅:Mn ⁴⁺ oxyfluoride red phosphor for light-emitting diode devices . Dalton Transcations, 2018,4745:16048-16056.
[26]	DONG X, PAN Y, LI D, et al. A novel red phosphor of Mn ⁴⁺ ion-doped oxyfluoroniobate BaNbOF₅ for warm WLED applications . CrystEngComm, 2018,2037:5641-5646. DOI URL
[27]	KATO H, TAKATA Y, KOBAYASHI M, et al. Photoluminescence properties of layered perovskite-type strontium scandium oxyfluoride activated with Mn ⁴⁺ . Frontiers in Chemistry, 2018,6:467. DOI URL PMID
[28]	LIANG Z, YANG Z, TANG H, et al. Synthesis, luminescence properties of a novel oxyfluoride red phosphor BaTiOF₄:Mn ⁴⁺ for LED backlighting . Optical Materials, 2019,90:89-94. DOI URL
[29]	BRIK M G, SRIVASTAVA A M. A computation study of site occupancy in the commercial Mg₂₈Ge_7.55O₃₂F_15.04:Mn ⁴⁺ phosphor . Optical Materials, 2016,54:245-251. DOI URL
[30]	WANG Q, LIAO J, KONG L, et al. Luminescence properties of a non-rare-earth doped oxyfluoride LiAl₄O₆F:Mn ⁴⁺ red phosphor for solid-state lighting . Journal of Alloys and Compounds, 2019,772:499-506. DOI URL
[31]	SRIVASTAVA A M, ACKERMAN J F. Synthesis and luminescence properties of Cs₂NbOF₅ and Cs₂NbOCl₅ with isolated [NbOX₅] ^-2 (X=F -, Cl -) octahedra . Materials Research Bulletin, 1991,266:443-448. DOI URL
[32]	SRIVASTAVA A M, ACKERMAN J F. Synthesis and luminescence properties of barium niobium oxide fluoride (BaNbOF₅) with isolated [NbOF₅] ²- octahedra . Chemitry of Materials, 1992,45:1011-1013.
[33]	BLESS P W, VON DREELE R B, KOSTINER E, et al. Anion and cation defect structure in magnesium fluorogermanate. Journal of Solid State Chemistry, 1972,42:262-268. DOI URL
[34]	BEERS W W, SMITH D, COHEN W E, et al. Temperature dependence (13-600 K) of Mn ⁴⁺ lifetime in commercial Mg₂₈Ge_7.55O₃₂F_15.04 and K₂SiF₆ phosphors . Optical Materials, 2018,84:614-617. DOI URL

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 34

相关文章 15

编辑推荐

Metrics

本文评价

[1]	郭隐犇, 陈子曦, 王宏志, 张青红. 基于无机填料复合薄膜的摩擦纳米发电机研究进展[J]. 无机材料学报, 2021, 36(9): 919-928.
[2]	刘云鹏, 盛伟繁, 吴忠华. 同步辐射及其在无机材料中的应用进展[J]. 无机材料学报, 2021, 36(9): 901-918.
[3]	郝策, 刘自若, 刘炜, 史彦涛. 用于氧还原反应的碳基负载金属单原子催化剂研究进展[J]. 无机材料学报, 2021, 36(8): 820-834.
[4]	彭星淋, 李淑星, 刘泽华, 姚秀敏, 解荣军, 黄政仁, 刘学建. 大功率固态照明用荧光陶瓷研究进展[J]. 无机材料学报, 2021, 36(8): 807-819.
[5]	李江, 丁继扬, 黄新友. 稀土离子掺杂Gd₂O₂S闪烁陶瓷的研究进展[J]. 无机材料学报, 2021, 36(8): 789-806.
[6]	李华鑫, 陈俊勇, 肖洲, 乐弦, 余显波, 向军辉. 纳米材料形貌和性能调控的仿生自组装研究进展[J]. 无机材料学报, 2021, 36(7): 695-710.
[7]	彭飞, 姜勇刚, 冯坚, 蔡华飞, 冯军宗, 李良军. 耐高温氧化铝气凝胶隔热复合材料研究进展[J]. 无机材料学报, 2021, 36(7): 673-684.
[8]	肖鹏, 祝玉林, 王松, 余艺平, 李浩. 超高熔点Ta_xHf_1-_xC固溶陶瓷的制备工艺与性能研究进展[J]. 无机材料学报, 2021, 36(7): 685-694.
[9]	武晓玮, 李佳艳. 多晶硅表面金属催化化学腐蚀法制绒研究现状[J]. 无机材料学报, 2021, 36(6): 570-578.
[10]	苏莉, 杨建平, 兰悦, 王连军, 江莞. 纳米铁颗粒及其复合材料的界面设计及环境修复应用[J]. 无机材料学报, 2021, 36(6): 561-569.
[11]	李婷婷, 张志明, 韩正波. 基于静电纺丝技术的聚合物基MOFs纳米纤维膜的研究进展[J]. 无机材料学报, 2021, 36(6): 592-600.
[12]	李子宜, 章佳佳, 邹小勤, 左家玉, 李俊, 刘应书, 裴有康. 菱沸石分子筛膜的合成调控与气体分离研究进展[J]. 无机材料学报, 2021, 36(6): 579-591.
[13]	王金敏, 后丽君, 马董云. 氧化钼电致变色材料与器件[J]. 无机材料学报, 2021, 36(5): 461-470.
[14]	张翔, 李文杰, 王乐滨, 陈曦, 赵九蓬, 李垚. 无机电致变色材料反射特性研究进展[J]. 无机材料学报, 2021, 36(5): 451-460.
[15]	王兆武, 姬海鹏, 王飞翔, 侯星慧, 易莎莎, 周颖, 陈德良. 调控Al₂O₃晶型控制MgAl₂O₄:Mn⁴⁺荧光粉中Mn价态研究[J]. 无机材料学报, 2021, 36(5): 513-520.