Advance in Red-emitting Mn4+-activated Oxyfluoride Phosphors

doi:10.15541/jim20190554

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 11

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]

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

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]

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

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]

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)

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]

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

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

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]

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]

References 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

Advance in Red-emitting Mn⁴⁺-activated Oxyfluoride Phosphors

RichHTML

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

Figures/Tables 11

References 34

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	CHEN Mingjun, MIAO Hongkang, XIAO Yingjun, DENG Jianbo, ZHANG Xiang, ZHAO Jiupeng, LI Yao. Photo- and Thermo-chromic Dual-responsive Materials: A Review on Design Strategies and Applications in Smart Windows [J]. Journal of Inorganic Materials, 2026, 41(6): 723-738.
[2]	SONG Kunjie, XIE Rongjun. Research Advances on Machine Learning-driven Development of Novel Luminescent Materials [J]. Journal of Inorganic Materials, 2026, 41(6): 689-703.
[3]	HU Yuqing, ZHU Yixin, LE Xianhao, WAN Qing. Lithium Tantalate Wafer: Advances in Thinning Technology and Application in Pyroelectric Infrared Detectors [J]. Journal of Inorganic Materials, 2026, 41(6): 764-774.
[4]	LIU Chunfan, CHEN Ke, GE Fangfang, HUANG Qing. Research Progress on Lead-bismuth Eutectic Corrosion Resistant Coatings [J]. Journal of Inorganic Materials, 2026, 41(6): 775-786.
[5]	HU Yang, XIE Min, ZHANG Xiaoyi, LI Xiang, GUO Xinwei, JIANG Nan, ZHOU Wenhan, ZHANG Shengli, ZENG Haibo. Research Progress on Computational and Data-driven Environmental-friendly Luminescent Materials [J]. Journal of Inorganic Materials, 2026, 41(6): 704-722.
[6]	WANG Junbu, HUANG Zeai, YANG Mingkai, MENG Ying, ZHOU Mingwei, ZHOU Ying. Research Progress on Anti-coking Catalytic Materials for Methane Conversion [J]. Journal of Inorganic Materials, 2026, 41(6): 739-750.
[7]	WANG Jinwen, YANG Zhen, ZHOU Huan, XIA Dan, YANG Lei. Biomedical Applications of Injectable Inorganic Biomaterials [J]. Journal of Inorganic Materials, 2026, 41(6): 751-763.
[8]	LI Hantao, SHEN Qiang, LUO Guoqiang, WANG Xuefei, GAO Ming, CHEN Chen. Research Progress on Structure and Performance Regulation of Silicon-based Anode Materials via Mechanical Ball Milling [J]. Journal of Inorganic Materials, 2026, 41(5): 561-572.
[9]	XIE Chenyi, MIAO Huaming, ZHANG Weiran, LIU Rongjun, WANG Yanfei, LI Duan. Research Progress on Theoretical Calculation in the Field of High-entropy Ceramics [J]. Journal of Inorganic Materials, 2026, 41(5): 545-560.
[10]	DONG Langping, LI Shixuan, YANG Shaoxing, HOU Jingshan, LIN Yandan, ZHOU Pengcheng, SUN Xuejiao, SUN Yiyang, CHEN Daqin, FANG Yongzheng. Anomalous Fluorescence Thermal Quenching in a Red-emitting RbZnF₃:Eu³⁺ Phosphor under Violet Excitation [J]. Journal of Inorganic Materials, 2026, 41(5): 673-680.
[11]	LI Xuan, YE Kuicai, FENG Jiayin, QIU Jiajun, QIAN Wenhao, XING Min. Surface Modification of Titanium-based Dental Implants for Soft Tissue Sealing: A Review [J]. Journal of Inorganic Materials, 2026, 41(4): 432-444.
[12]	PENG Dezhao, LI Rui, WANG Wenhong, WANG Zirui, ZHANG Zhizhen. Research Progress on Sodium Chloride Solid Electrolytes [J]. Journal of Inorganic Materials, 2026, 41(4): 409-420.
[13]	CHEN Kun, JIANG Yonggang, FENG Junzong, LI Liangjun, HU Yijie, FENG Jian. Research Progress on Lanthanum Zirconate Porous Materials for Thermal Insulation [J]. Journal of Inorganic Materials, 2026, 41(4): 421-431.
[14]	ZHOU Zichun, ZHANG Xiang, MING Chen, SUN Yiyang. Database of Eu²⁺ and Ce³⁺ Doped Phosphors for Development of Violet-light Excited White LEDs [J]. Journal of Inorganic Materials, 2026, 41(3): 393-400.
[15]	WEI Lianjin, QI Zhijie, WANG Xin, ZHU Junwu, FU Yongsheng. Modification of Nanodiamond and Its Application in Electrocatalytic Oxygen Reduction Reaction [J]. Journal of Inorganic Materials, 2026, 41(3): 273-288.