浏览全部资源
扫码关注微信
1.佛山科学技术学院 物理与光电工程学院, 粤港澳智能微纳光电技术联合实验室, 广东 佛山 528225
2.华南理工大学 发光材料与器件国家重点实验室, 广东省光纤激光材料与应用技术重点实验室, 广东 广州 510640
[ "陈孔岚(1999-),男,广东清远人,硕士研究生,2021年于佛山科学技术学院获得学士学位,主要从事Mn4+激活红色荧光粉的研究。Email:15916191341@163.com" ]
[ "邓婷婷(1989-),女,广东茂名人,博士,副教授,2018年于华南理工大学获得博士学位,主要从事过渡金属/稀土离子掺杂无机发光材料的研究。 E-mail: tingtingdeng0803@163.com" ]
纸质出版日期:2023-02-05,
收稿日期:2022-08-27,
修回日期:2022-09-15,
移动端阅览
陈孔岚,张学亮,宋恩海等.CaTiF6·2H2O∶Mn4+窄带红色荧光粉的发光性能及其高显指暖白光LED应用[J].发光学报,2023,44(02):259-270.
CHEN Konglan,ZHANG Xueliang,SONG Enhai,et al.Luminescence Properties of Narrow‐band Red Phosphor CaTiF6·2H2O∶Mn4+ for Warm White Light-emitting Diodes with High Color Rendering Index[J].Chinese Journal of Luminescence,2023,44(02):259-270.
陈孔岚,张学亮,宋恩海等.CaTiF6·2H2O∶Mn4+窄带红色荧光粉的发光性能及其高显指暖白光LED应用[J].发光学报,2023,44(02):259-270. DOI: 10.37188/CJL.20220310.
CHEN Konglan,ZHANG Xueliang,SONG Enhai,et al.Luminescence Properties of Narrow‐band Red Phosphor CaTiF6·2H2O∶Mn4+ for Warm White Light-emitting Diodes with High Color Rendering Index[J].Chinese Journal of Luminescence,2023,44(02):259-270. DOI: 10.37188/CJL.20220310.
报道了一种新型的Mn
4+
掺杂水合六氟钛酸钙CaTiF
6
·2H
2
O∶Mn
4+
红色荧光粉,详细研究了基质的结构转变和荧光粉的发光性能及高显色指数(显指)暖白光LED应用。CaTiF
6
·2H
2
O∶Mn
4+
在130~200 ℃间脱水转化为CaTiF
6
∶Mn
4+
,荧光光谱发生改变,重新吸附水分子可恢复到CaTiF
6
·2H
2
O∶Mn
4+
,发光性能不可逆。重要的是,该荧光粉在较长波626 nm和635 nm处分别发射锐线极强的零声子线(ZPL)和ν
6
振动峰,色坐标为(0.701, 0.299),更接近人眼敏感的红光边界650 nm(色坐标
x
~0.72,
y
~0.28),有助于提高暖白光LED的显色指数、拓宽背光源的色域。晶体结构和晶体场强度计算指出,Mn
4+
在CaTiF
6
·2H
2
O∶Mn
4+
中占据低对称性的格位,所受到的晶体场强度较弱,Mn—F键的共价性较强。另外,通过表面疏水化显著提升了荧光粉耐湿性能,共掺小离子半径的Si
4+
增强了荧光粉发光热稳定性。以CaTiF
6
·2H
2
O∶Mn
4+
作为红光成分,获得了高显色指数(
R
a
=90,
R
9
=68)的暖白光LED,在高品质的暖白光照明中具有潜在的应用。
Herein, a new Mn
4+
-doped hydrate calcium hexafluorotitanic CaTiF
6
·2H
2
O∶Mn
4+
red phosphor is reported. Physical properties of host, luminescence properties and warm white LED application of this phosphor are studied carefully. CaTiF
6
·2H
2
O∶Mn
4+
removes H
2
O to be CaTiF
6
∶Mn
4+
with changed emission spectrum. CaTiF
6
∶Mn
4+
could adsorb H
2
O and recover to CaTiF
6
·2H
2
O∶Mn
4+
except emission intensity. Importantly, it emits extremely strong zero phonon line(ZPL) and ν
6
vibration peaking at longer wavelength of 626 nm and 635 nm in sequence. This unique emission gives color coordinates of (0.701, 0.299), more closing to the red-light boundary of human eyes sensibility(650 nm, chromaticity coordinate
x
~0.72,
y
~0.28), which could enhance the color rendering index(
R
a
) of WLED and widen the color gamut of backlight display. The combination of crystal structure and crystal field strength calculation demonstrates that Mn
4+
ion locates at a highly unsymmetric lattice and experiences weak crystal field strength with strongly covalent Mn—F bond in CaTiF
6
·2H
2
O∶Mn
4+
. Moreover, coating with hydrophobic layer enhances the moisture resistant of CaTiF
6
·2H
2
O∶Mn
4+
. Codoping small ionic radius Si
4+
improves its thermal stability. Using CaTiF
6
·2H
2
O∶Mn
4+
as red-light component, a warm white LED with high
R
a
~90 and
R
9
~ 68 was achieved, showing potential in high color quality warm white lighting applications.
Mn4+掺杂氟化物CaTiF6·2H2O∶Mn4+极强零声子线高显色指数暖白光LED
Mn4+-doped fluoridesCaTiF6·2H2O∶Mn4+strong zero-phonon linehigh color rendering indexwarm WLED
FANG M H, BAO Z, HUANG W T, et al. Evolutionary generation of phosphor materials and their progress in future applications for light-emitting diodes [J]. Chem. Rev., 2022, 122(13): 11474-11513. doi: 10.1021/acs.chemrev.1c00952http://dx.doi.org/10.1021/acs.chemrev.1c00952
WANG B, LIN H, HUANG F, et al. Non-rare-earth BaMgAl10-2xO17∶xMn4+, xMg2+: a narrow-band red phosphor for use as a high-power warm w-LED [J]. Chem. Mater., 2016, 28(10): 3515-3524. doi: 10.1021/acs.chemmater.6b01303http://dx.doi.org/10.1021/acs.chemmater.6b01303
ERDEM T, NIZAMOGLU S, SUN X W, et al. A photometric investigation of ultra-efficient LEDs with high color rendering index and high luminous efficacy employing nanocrystal quantum dot luminophores [J]. Opt. Express, 2010, 18(1): 340-347. doi: 10.1364/oe.18.000340http://dx.doi.org/10.1364/oe.18.000340
UHEDA K, HIROSAKI N, YAMAMOTO Y, et al. Luminescence properties of a red phosphor, CaAlSiN3∶Eu2+, for white light-emitting diodes [J]. Electrochem. Solid⁃State Lett., 2006, 9(4): H22-H25. doi: 10.1149/1.2173192http://dx.doi.org/10.1149/1.2173192
CHEN Y B, WU K L, HE J, et al. A bright and moisture-resistant red-emitting Lu3Al5O12∶Mn4+,Mg2+ garnet phosphor for high-quality phosphor-converted white LEDs [J]. J. Mater. Chem. C, 2017, 5(34): 8828-8835. doi: 10.1039/c7tc02514ahttp://dx.doi.org/10.1039/c7tc02514a
OHNO Y. Color rendering and luminous efficacy of white LED spectra [C]. Proceedings of the Fourth International Conference on Solid State Lighting, Denver, 2004: 88-98. doi: 10.1117/12.565757http://dx.doi.org/10.1117/12.565757
NGUYEN H D, LIU R S. Narrow-band red-emitting Mn4+-doped hexafluoride phosphors: synthesis, optoelectronic properties, and applications in white light-emitting diodes [J]. J. Mater. Chem. C, 2016, 4(46): 10759-10775. doi: 10.1039/c6tc03292chttp://dx.doi.org/10.1039/c6tc03292c
ZHU Y W, HUANG L, BRIK M G, et al. Anomalous photoluminescence from a K2LiInF6∶Mn4+ phosphor [J]. J. Mater. Chem. C, 2020, 8(24): 8085-8090. doi: 10.1039/d0tc01799jhttp://dx.doi.org/10.1039/d0tc01799j
周亚运, 王玲燕, 邓婷婷, 等. Mn4+掺杂氟化物窄带发射红色荧光粉的研究进展 [J]. 中国科学: 技术科学, 2017, 47(11): 1111-1125.
ZHOU Y Y, WANG L Y, DENG T T, et al. Recent advances in Mn4+-doped fluoride narrow-band red-emitting phosphors [J]. Sci. Sinica (Technol.), 2017, 47(11): 1111-1125. (in Chinese).
HOU Z Y, TANG X Y, LUO X F, et al. A green synthetic route to the highly efficient K2SiF6∶Mn4+ narrow-band red phosphor for warm white light-emitting diodes [J]. J. Mater. Chem. C, 2018, 6(11): 2741-2746. doi: 10.1039/c8tc00133bhttp://dx.doi.org/10.1039/c8tc00133b
ZHOU Q, LIANG Z B, SHI D X, et al. Double sites occupancy of Mn4+ in Cs2NaAlF6 with enhanced photoluminescence for white light-emitting diodes [J]. J. Alloys Compd., 2020, 832: 154884-1-9. doi: 10.1016/j.jallcom.2020.154884http://dx.doi.org/10.1016/j.jallcom.2020.154884
HU T, LIN H, CHENG Y, et al. A highly-distorted octahedron with a C2v group symmetry inducing an ultra-intense zero phonon line in Mn4+-activated oxyfluoride Na2WO2F4 [J]. J. Mater. Chem. C, 2017, 5(40): 10524-10532. doi: 10.1039/c7tc03655hhttp://dx.doi.org/10.1039/c7tc03655h
WANG Z W, JI H P, ZHANG Z T, et al. Solution growth of millimeter-scale Na2SiF6 single crystals for Mn4+-doping as red phosphor [J]. J. Am. Ceram. Soc., 2021, 104(10): 5077-5085. doi: 10.1111/jace.17739http://dx.doi.org/10.1111/jace.17739
WU W L, FANG M H, ZHOU W L, et al. High color rendering index of Rb2GeF6∶Mn4+ for light-emitting diodes [J]. Chem. Mater., 2017, 29(3): 935-939.
ZHOU Q, WAN J, ZHOU Y Y, et al. Ultraintense zero-phonon line from a Mn4+ red-emitting phosphor for high-quality backlight display applications [J]. Inorg. Chem., 2021, 60(24): 19197-19205. doi: 10.1021/acs.inorgchem.1c02938http://dx.doi.org/10.1021/acs.inorgchem.1c02938
MING H, ZHANG J F, LIU S F, et al. A green synthetic route to K2NbF7∶Mn4+ red phosphor for the application in warm white LED devices [J]. Opt. Mater., 2018, 86: 352-359. doi: 10.1016/j.optmat.2018.10.031http://dx.doi.org/10.1016/j.optmat.2018.10.031
ZHOU Y Y, MING H, ZHANG S, et al. Unveiling Mn4+ substitution in oxyfluoride phosphor Rb2MoO2F4∶Mn4+ applied to wide-gamut fast-response backlight displays [J]. Chem. Eng. J., 2021, 415: 128974-1-7. doi: 10.1016/j.cej.2021.128974http://dx.doi.org/10.1016/j.cej.2021.128974
TAN H Y, RONG M Z, ZHOU Y Y, et al. Luminescence behaviour of Mn4+ ions in seven coordination environments of K3ZrF7 [J]. Dalton Trans., 2016, 45(23): 9654-9660. doi: 10.1039/c6dt01693fhttp://dx.doi.org/10.1039/c6dt01693f
WANG Z L, WANG N, YANG Z Y, et al. Luminescent properties of novel red-emitting phosphor Na3TaF8 with non-equivalent doping of Mn4+ for LED backlighting [J]. J. Lumin., 2017, 192: 690-694. doi: 10.1016/j.jlumin.2017.07.064http://dx.doi.org/10.1016/j.jlumin.2017.07.064
ADACHI S. Full understanding of KNaSiF6∶Mn4+ properties under hydrostatic pressure based on the Tanabe-Sugano energy-level diagram [J]. J. Lumin., 2021, 239: 118358-1-8. doi: 10.1016/j.jlumin.2021.118358http://dx.doi.org/10.1016/j.jlumin.2021.118358
ADACHI S. Photoluminescence spectra and modeling analyses of Mn4+-activated fluoride phosphors: a review [J]. J. Lumin., 2018, 197: 119-130. doi: 10.1016/j.jlumin.2018.01.016http://dx.doi.org/10.1016/j.jlumin.2018.01.016
ARAI Y, ADACHI S. Photoluminescent properties of K2SnF6·H2O∶Mn4+ hydrate phosphor [J]. J. Electrochem. Soc., 2011, 158(3): J81-J85. doi: 10.1149/1.3532784http://dx.doi.org/10.1149/1.3532784
BODE H, JENSSEN H, BANDTE F. Über eine neue Darstellung des Kalium-hexafluoromanganats(Ⅳ) [J]. Angew. Chem., 1953, 65(11): 304-304. doi: 10.1002/ange.19530651108http://dx.doi.org/10.1002/ange.19530651108
CAI P Q, WANG S, XU T M, et al. Mn4+ doped zero-dimensional organic-inorganic hybrid material with narrow-red emission [J]. J. Lumin., 2020, 228: 117661-1-7. doi: 10.1016/j.jlumin.2020.117661http://dx.doi.org/10.1016/j.jlumin.2020.117661
ZHOU J B, CHEN Y Y, JIANG C Y, et al. High moisture resistance of an efficient Mn4+-activated red phosphor Cs2NbOF5∶Mn4+ for WLEDs [J]. Chem. Eng. J., 2021, 405: 126678. doi: 10.1016/j.cej.2020.126678http://dx.doi.org/10.1016/j.cej.2020.126678
DENG T T, SONG E H, SU J, et al. Stable narrowband red emission in fluorotellurate KTeF5∶Mn4+ via Mn4+ noncentral-site occupation [J]. J. Mater. Chem. C, 2018, 6(16): 4418-4426. doi: 10.1039/c8tc00689jhttp://dx.doi.org/10.1039/c8tc00689j
章伟, 何梦婷, 乔旭升, 等. Mn4+激活的典型LED红色荧光粉研究进展 [J]. 发光学报, 2021, 42(9): 1345-1364. doi: 10.37188/CJL.20210148http://dx.doi.org/10.37188/CJL.20210148
ZHANG W, HE M T, QIAO X S, et al. Research progress of Mn4+ activated typical LED red phosphors [J]. Chin. J. Lumin., 2021, 42(9): 1345-1364. (in Chinese). doi: 10.37188/CJL.20210148http://dx.doi.org/10.37188/CJL.20210148
SENDEN T, VAN DIJK-MOES R J A, MEIJERINK A. Quenching of the red Mn4+ luminescence in Mn4+-doped fluoride LED phosphors [J]. Light. Sci. Appl., 2018, 7: 8-1-13. doi: 10.1038/s41377-018-0013-1http://dx.doi.org/10.1038/s41377-018-0013-1
BRIK M G, CAMARDELLO S J, SRIVASTAVA A M, et al. Spin-forbidden transitions in the spectra of transition metal ions and nephelauxetic effect [J]. ECS J. Solid State Sci. Technol., 2015, 5(1): R3067-R3077. doi: 10.1149/2.0091601jsshttp://dx.doi.org/10.1149/2.0091601jss
ADACHI S. Review—Mn4+-activated red and deep red-emitting phosphors [J]. ECS J. Solid State Sci. Technol., 2020, 9(1): 016001-1-. doi: 10.1149/2.0022001jsshttp://dx.doi.org/10.1149/2.0022001jss
DU M M, TANG F, LONG J Q, et al. Optical and thermal behaviors of high efficient K2TiF6∶Mn4+ red phosphor prepared by modified two-step co-precipitation method [J]. Mater. Res. Bull., 2016, 83: 316-323. doi: 10.1016/j.materresbull.2016.05.011http://dx.doi.org/10.1016/j.materresbull.2016.05.011
DENG T T, SONG E H, ZHOU Y Y, et al. Implementation of high color quality, high luminous warm WLED using efficient and thermally stable Rb3AlF6∶Mn4+ as red color converter [J]. J. Alloys Compd., 2019, 795: 453-461. doi: 10.1016/j.jallcom.2019.04.305http://dx.doi.org/10.1016/j.jallcom.2019.04.305
SONG E H, WANG J Q, SHI J H, et al. Highly efficient and thermally stable K3AlF6∶Mn4+ as a red phosphor for ultra-high-performance warm white light-emitting diodes [J]. ACS Appl. Mater. Interfaces, 2017, 9(10): 8805-8812. doi: 10.1021/acsami.7b00749http://dx.doi.org/10.1021/acsami.7b00749
ZHU Y W, HUANG L, ZOU R, et al. Hydrothermal synthesis, morphology and photoluminescent properties of an Mn4+-doped novel red fluoride phosphor elpasolite K2LiAlF6 [J]. J. Mater. Chem. C, 2016, 4(24): 5690-5695. doi: 10.1039/c6tc01366jhttp://dx.doi.org/10.1039/c6tc01366j
WANG L Y, SONG E H, DENG T T, et al. Luminescence properties and warm white LED application of a ternary-alkaline fluoride red phosphor K2NaAlF6∶Mn4+ [J]. Dalton Trans., 2017, 46(30): 9925-9933. doi: 10.1039/c7dt02036hhttp://dx.doi.org/10.1039/c7dt02036h
ZHOU Q, ZHOU Y Y, LIU Y, et al. A new and efficient red phosphor for solid-state lighting: Cs2TiF6∶Mn4+ [J]. J. Mater. Chem. C, 2015, 3(37): 9615-9619. doi: 10.1039/c5tc02290hhttp://dx.doi.org/10.1039/c5tc02290h
LIU Y, GAO G J, HUANG L, et al. Co-precipitation synthesis and photoluminescence properties of BaTiF6∶Mn4+: an efficient red phosphor for warm white LEDs [J]. J. Mater. Chem. C, 2018, 6(1): 127-133. doi: 10.1039/c7tc04196ahttp://dx.doi.org/10.1039/c7tc04196a
YANG Z Y, YANG Z F, WEI Q W, et al. Luminescence of red-emitting phosphor Rb5Nb3OF18∶Mn4+ for warm white light-emitting diodes [J]. J. Lumin., 2019, 210: 408-412. doi: 10.1016/j.jlumin.2019.03.003http://dx.doi.org/10.1016/j.jlumin.2019.03.003
0
浏览量
316
下载量
4
CSCD
关联资源
相关文章
相关作者
相关机构