6. (sla) (sms) x value 0 5 10 15 20 25 30 wavelength (nm)rsliu/poster/2018/fmh-poster... · 2020....
TRANSCRIPT
Control of High Color Rendition Phosphors and
Their Application in White Light-emitting DiodesMu-Huai Fang and Ru-Shi Liu*
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan Abstract
The first part focuses on narrow red emission band fluoride phosphors Rb2SiF6:Mn4+ and KNaSiF6:Mn4+ for warm white light-emitting diodes. The photoluminescence properties are
found to be highly related to the pressure especially for the zero-phonon line (ZPL), which is strongly correlated to the local coordination environment. The distortion of the MnF62-
octahedron will then enhance the intensity of the ZPL.
Photoluminescence properties
Structure
In the second part, a series of SrLiAl3N4:Eu2+ red phosphors are synthesized at a different pressure from 1 atm to 1,000 atm. the photoluminescence intensity, particle size, and
quantum efficiency increase with increasing applied pressure. a series of Sr(Li1-xSix)(Al1-xMgx)3N4:Eu2+ phosphors solid-solution are successfully synthesized. It also leads to the
unexpected red-shift in PL spectra from 650-679 nm, which is out of range of SLA (650 nm) and SMS (610 nm).
In the third part, Sr4.7−xBaxEu0.3(PO4)3Cl (0 ≤ x ≤ 2.5) materials were synthesized. Real full-spectrum lighting can be achieved by Sr3.4Ba1.3Eu0.3(PO4)3Cl. The LED package device not
only possesses high Ra and R9 values ( > 95) but also compensates for the 480 – 520 nm cyan gap, which widens the research on full-spectrum lighting.
Photoluminescence properties
Structure
14 15 16 17 18
amb. (after)
29.9 GPa
27.8 GPa
26.0 GPa
24.0 GPa
21.5 GPa
18.9 GPa
16.5 GPa
14.5 GPa
12.2 GPa
10.4 GPa
8.0 GPa
6.3 GPa
4.1 GPa
1.9 GPa
amb.
Inte
nsit
y (a
.u.)
Wavenumber (103 cm
-1)
ZPL2E
g to
4A
2g
20 25 30 35
30.4 GPa
27.2 GPa
24.5 GPa
20 GPa
15.8 GPa
12 GPa
8.4 GPa
4.5 GPa
ambient
Inte
nsity
(a.u
.)
Wavenumber (103 cm
-1)
4A
2→
4A
2→
amb. after
0 5 10 15 20 25 300.86
0.88
0.90
0.92
0.94
0.96
0.98
1.00
1.02
IZPL
/ I6
Inte
nsi
ty (
a.u
.)
Pressure (GPa)0 5 10 15 20 25 3015.0
15.2
15.4
15.6
15.8
16.0
16.2
22
24
26
28
30
32
emission
4A
2g
4T
2g
2E
g
4A
2g
4A
2g
4T
1g
Wa
ven
um
ber
(10
3 c
m-1
)
Pressure (GPa)
ZPL
excitation
LED package
Structure
Photoluminescence properties
350 400 450 500 550 600
Inte
nsi
ty (
a.u
.)
Wavelength (nm)
100 MPa
50 MPa
0.9 MPa
0.7 MPa
0.5 MPa
0.3 MPa
0.1 MPa
600 650 700 750
100 MPa
50 MPa
0.9 MPa
0.7 MPa
0.5 MPa
0.3 MPa
0.1 MPa
Inte
nsi
ty (
a.u
.)
Wavelength (nm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
100500.9 0.7 0.5 0.3 0.1
IQE
Absorption
EQE
Pressure (MPa)
Quantum Efficiency
Sample Ex. (nm) Em. (nm) FWHMRelative Int.
(%)
RQ O .
(%, relative)
100 Mpa 460 654 62 100 100
50 Mpa 460 654 65 91 96
0.9 Mpa 460 650 58 59 56
0.7 Mpa 460 651 57 55 52
0.5 Mpa 460 651 56 52 49
0.3 Mpa 460 652 58 53 50
0.1 Mpa 460 653 57 47 45
Morphology
ICP-AES / XANES
ion
Pressure
(MPa)
Sr (mol%) Li (mol%) Al (mol%) Sr:Li:Al
0.1 19.5(4) 14.7(5) 65.8(4) 1:0.75(3):3.36(3)
0.3 19.6(0) 18.2(9) 61.9(4) 1:0.92(5):3.12(2)
0.5 19.4(4) 17.3(5) 63.3(2) 1:0.89(3):3.27(1)
0.7 19.5(8) 17.0(5) 63.5(1) 1:0.87(3):3.26(1)
0.9 19.1(4) 17.0(0) 63.8(1) 1:0.89(0):3.33(1)
50 19.1(5) 19.6(6) 61.2(1) 1:1.02(3):3.19(1)
100 19.1(5) 19.6(0) 61.3(2) 1:1.03(0):3.22(1)
Theoretical
value20 20 60 1:1:3 6970 6975 6980
Energy (eV)
No
rma
lize
d i
nte
nsi
ty
0.1 MPa
0.3 MPa
0.5 MPa
0.7 MPa
0.9 MPa
50 MPa
100 MPa
Eu2+
Eu3+
Device
Structure Photoluminescence
550 600 650 700 750 800
SLA
0.1 Mg/Si
0.2 Mg/Si
0.3 Mg/Si
0.4 Mg/Si
0.5 Mg/Si
0.6 Mg/Si
0.7 Mg/Si
0.8 Mg/Si
0.9 Mg/Si
SMS
Inte
nsi
ty (
a.u
.)
Wavelength (nm)
350 400 450 500 550 600
SLA
0.1 Mg/Si
0.2 Mg/Si
0.3 Mg/Si
0.4 Mg/Si
0.5 Mg/Si
0.6 Mg/Si
0.7 Mg/Si
0.8 Mg/Si
0.9 Mg/Si
SMS
Inte
nsi
ty (
a.u
.)
Wavelength (nm)
Morphology Morphology
XANES
6960 6965 6970 6975 6980 6985 6990 6995 70000.0
0.2
0.4
0.6
0.8
1.0 SLA
0.1 Mg/Si
0.2 Mg/Si
0.3 Mg/Si
0.4 Mg/Si
0.5 Mg/Si
0.6 Mg/Si
0.7 Mg/Si
0.8 Mg/Si
0.9 Mg/Si
SMS
Eu2+
Eu3+
No
rma
lize
d i
nte
nsi
ty
Energy (eV)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.00.0
0.2
0.4
0.6
0.8
1.0
(SLA) (SMS)
Rel
ati
ve
Eu
2+ c
on
cen
trati
on
x value
Structurex = 0
x = 0.5
x = 1
x = 1.3
x = 1.5
x = 2
2 (degree)
In
ten
sit
y (
a.u
.)
x = 2.25
x = 2.5
PDF#83-0974, Sr5(PO4)3Cl
20 30 40 50 60 70
PDF#70-2318, Ba5(PO4)3Cl
0.5 1.0 1.5 2.0 2.5
0.0
0.2
0.4
0.6
0.8
1.0
Occ
up
ati
on
x
Ba at Sr(I)
Ba at Sr(II)
Photoluminescence
450 500 550 600
Inte
nsi
ty (
a.u
.)
Wavelength (nm)
x = 0
x = 0.5
x = 1
x = 1.3
x = 1.5
x = 2
x = 2.5
33000 30000 27000 24000 21000 18000
x = 1.5
x = 1
x = 0.5
Inte
nsi
ty (
a.u
.)
Wavenumber (cm-1
)
Sr4.7-x
BaxEu
0.3(PO
4)
3Cl
x = 0
350 400 450 500 550 600
Wavelength (nm)
0.0 0.5 1.0 1.50.1
0.2
0.3
0.4
0.5
0.6
0.7
Sr4.7-x
BaxEu
0.3(PO
4)3Cl
obs
= 480 - 520 nm
Lif
eti
me (
s)
Ba concentration (x)
obs
= 440 - 460 nm
33000 30000 27000 24000 21000 18000
temp. 10 K
Sr3.2
Ba1.5
Eu0.3
(PO4)3Cl
440
437
435
432
430
Inte
nsi
ty (
a.u
.)
Wavenumber (cm-1
)
obs = 500 nm
temp. 77 K
420
exc
(nm)
obs = 450 nm
300 350 400 450 500 550 600
Wavelength (nm)
0.0 0.5 1.0 1.5 2.0 2.510
0
101
102
103
104
obs
= 440 - 460 nm
x = 1.5
x = 1.5
x = 0
x = 0.5
Sr4.7-x
BaxEu
0.3(PO
4)
3Cl
Inte
nsi
ty (
a.u
.)
Time (s)
x = 1
x = 0.5
x = 1
obs
= 480 - 520 nm
Eu Oxidation
Device
400 600
BAM
Sr4.7
Eu0.3
(PO4)3Cl
400 450 500 550 600 650 700
Wavelength (nm)
Sr3.4
Ba1.3
Eu0.3(PO
4)
3Cl
Mechanism
Publication:
Paper(1) Fang, M. H.; Wu, W. L.; Jin, Y.; Lesniewski, T.; Mahlik, S.; Grinberg, M.; Brik, M. G.; Srivastava, A. M.; Chiang, C. Y.;
Zhou, W.; Jeong, D.; Kim, S. H.; Leniec, G.; Kaczmarek, S. M.; Sheu, H. S.; Liu, R. S. Control of Luminescence via Tuning of
Crystal Symmetry and Local Structure in Mn4+-Activated Narrow Band Fluoride Phosphors. Angew. Chem. Int. Ed. 2018, 57,
1797 –1801.
(2) Leaño, J. L.; Fang, M. H.; Liu, R. S. Critical Review-Narrow-Band Emission of Nitride Phosphors for Light-Emitting
Diodes: Perspectives and Opportunities. ECS J. Solid State Sci. Technol. 2018, 7, R3111-R3133.
(3) Zhang, X.; Fang, M. H.; Tsai, Y.-T.; Lazarowska, A.; Mahlik, S.; Lesniewski, T.; Grinberg, M.; Pang, W. K.; Pan, F.; Liang,
C.; Liu, R. S. Controlling of Structural Ordering and Rigidity of β-SiAlON:Eu through Chemical Cosubstitution to Approach
Narrow-Band-Emission for Light-Emitting Diodes Application. Chem. Mater. 2017, 29, 6781-6792.
(4) Zhang, N.; Tsai, Y. T.; Fang, M. H.; Ma, C. G.; Lazarowska, A.; Mahlik, S.; Grinberg, M.; Chiang, C. Y.; Zhou, W.; Lin, J.
G.; Liu, R. S. Aluminate Red Phosphor in Light-Emitting Diodes: Theoretical Calculations, Charge Varieties, and High-
Pressure Luminescence Analysis. ACS Appl. Mater. Interfaces 2017, 9, 23995-24004.
(5) Wu, W. L.; Fang, M. H.; Zhou, W.; Lesniewski, T.; Mahlik, S.; Grinberg, M.; Brik, M. G.; Sheu, H. S.; Cheng, B. M.; Wang,
J.; Liu, R. S. High Color Rendering Index of Rb2GeF6:Mn4+ for Light-Emitting Diodes. Chem. Mater. 2017, 29, 935-939.
(6) Lin, C. C.; Tsai, Y. T.; Johnston, H. E.; Fang, M. H.; Yu, F.; Zhou, W.; Whitfield, P.; Li, Y.; Wang, J.; Liu, R. S. Enhanced
Photoluminescence Emission and Thermal Stability from Introduced Cation Disorder in Phosphors. J. Am. Chem. Soc. 2017,
139, 11766-11770.
(7) Huang, Y. K.; Jena, A.; Chen, Y. T.; Fang, M. H.; Yang, N. H.; Chang, H.; Liu, R. S. Nanosized-Fe3PtN Supported on
Nitrogen-Doped Carbon as Electro-Catalyst for Oxygen Reduction Reaction. Int. J. Hydrogen Energy 2017, 42, 15761-15769.
(8) Jin, Y.; Fang, M. H.; Grinberg, M.; Mahlik, S.; Lesniewski, T.; Brik, M.; Luo, G.-Y.; Lin, J. G.; Liu, R. S. Narrow Red
Emission Band Fluoride Phosphor KNaSiF6:Mn4+ for Warm White Light-Emitting Diodes. ACS Appl. Mater. Interfaces 2016, 8,
11194-11203.
(9) Fang, M. H.; Ni, C.; Zhang, X.; Tsai, Y. T.; Mahlik, S.; Lazarowska, A.; Grinberg, M.; Sheu, H. S.; Lee, J. F.; Cheng, B. M.;
Liu, R. S. Enhance Color Rendering Index via Full Spectrum Employing the Important Key of Cyan Phosphor. ACS Appl.
Mater. Interfaces 2016, 8, 30677-30682.
(10) Wei, L. L.; Lin, C. C.; Wang, Y.-Y.; Fang, M. H.; Jiao, H.; Liu, R. S. Photoluminescent Evolution Induced By Structural
Transformation through Thermal Treating in the Red Narrow-Band Phosphor K2GeF6:Mn4+. ACS Appl. Mater. Interfaces 2015,
7, 10656-10659.
(11) Wei, L. L.; Lin, C. C.; Fang, M. H.; Brik, M. G.; Hu, S. F.; Jiao, H.; Liu, R. S. A Low-Temperature Co-Precipitation
Approach to Synthesize Fluoride Phosphors K2MF6:Mn4+ (M= Ge, Si) for White LED Applications. J. Mater. Chem. C 2015, 3,
1655-1660.
(12) Fang, M. H.; Nguyen, H. D.; Lin, C. C.; Liu, R. S. Preparation of a Novel Red Rb2SiF6:Mn4+ Phosphor with High
Thermal Stability through a Simple One-Step Approach. J. Mater. Chem. C 2015, 3, 7277-7280.
(13) Nguyen, H. D.; Lin, C. C.; Fang, M. H.; Liu, R. S. Synthesis of Na2SiF6:Mn4+ Red Phosphors for White LED Applications
by Co-precipitation. J. Mater. Chem. C 2014, 2, 10268-10272.
Patent1. “螢光粉的製備方法” 段南岩、方牧懷、林群哲、劉如熹、蔡松祐 (台灣專利-已通過)
2. “一種具高演色性與高熱特性之紅色氮化物螢光粉” 林英志、王立群、吳信謀、洪浩恩、謝繼興、劉如熹、蔡宜
廷、林群哲、方牧懷(台灣專利-已通過)
3. “發光二極體裝置” 段南岩、方牧懷、林群哲、劉如熹、蔡松祐 (台灣專利-已通過)
4. “螢光粉的製備方法” 段南岩、方牧懷、林群哲、劉如熹、蔡松祐 (台灣專利-審查中)
5. “一種具高演色性與高熱特性之紅色氮化物螢光粉” 林英志、王立群、吳信謀、洪浩恩、謝繼興、劉如熹、蔡宜
廷、林群哲、方牧懷 (台灣專利-審查中)
6. “發光二極體之波長轉換結構” 方牧懷、王筱姍、劉如熹 (台灣專利-審查中)
Topic 1 – Mn4+-doped narrowband fluoride phosphor
Topic 2 – Eu2+-doped narrowband nitride phosphor
Topic 3 – Eu2+-dopedbroadband cyan phosphor