Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Luminescence Mechanisms
Content
8.1 Luminescence Definition, Materials and Processes
8.2 Absorption
8.3 Excitation Mechanisms
8.4 Energy Transfer
8.5 Cross-Relaxation
8.6 Loss Processes
8.7 Configuration Coordinate Diagram
8.8 Thermal Quenching
8.9 Lifetime of the Excited State
8.10 Luminescence of Transition Metal Ions
8.11 Luminescence of Ions with s2-Configuration
8.12 Luminescence of Rare Earth Ions
8.13 Down-Conversion
8.14 Up-Conversion
8.15 Afterglow
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
EC
ED
ED
ED
(a)
(b)
(c)
(d)
Eg
Eg
Eg
Eg
EA
EA
EV
0,8
Intensity
YPO4-Tb
YPO4-Dy
YPO4-Tm
0,6
0,4
0,2
0,0
300
350
400
450
500
550
600
650
Wavelength [nm]
700
Dopants
Cr3+, Mn4+, Sb3+, Pb2+, Eu2+/3+, Ce3+, ...
Selection and concentration depend on host lattice and application area:
Solubility, mobility, oxidation state stability, CT state location
Defects
VK, VA, F, interstitials, ...
cause:
Afterglow and charge storage
Concentration and thermal quenching
Reduction of stability and colour point shift
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Nanoscale particles
-sized particles
1 nm
10 nm
100 nm
1 m
10 m
100 m
1 mm
10 mm
Emission
Heat
Heat
A
ET
ET
A
ET
ET
A
Heat
Emission
Heat
Heat
Band gap Eg
Acceptor levels (A)
Valence band
(VB)
YBO3 (Vaterite)
Band gap Eg = 6.5 eV
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Absorption via
Host lattice
Charge-Transfer or VB to CB
Defects (colour centers)
Donor and acceptor levels
Chapter Luminescence Mechanisms
Slide 7
100
1,0
Reflectance [%]
80
60
40
20
0
200
300
400
500
600
700
0,8
0,6
0,4
0,2
0,0
200
300
400
500
600
Wavelength [nm]
Wavelength [nm]
700
CB
(VO43-)*
(Eu3+)*
Eg
Acceptor levels (A)
VO43-
VB
Eu3+
VB
Absorption via
Host lattice
Defects (colour centers)
Dopants (impurities)
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Charge-Transfer or VB to CB
Donor and acceptor levels
Activators and sensitizers
Chapter Luminescence Mechanisms
Slide 9
S2
S1
S0
Fluorescence
Relaxation
~10-9s
Eg
Excitation process
Energy [eV]
ISC
A2
T1
ET
A1
A0
- Sensitizer energy levels - Activator energy levels Valence band (anion orbitals filled by electrons)
S0, S1, S2, T1, A0, A1 = Energy levels of the activators and sensitizers
ISC = Intersystem Crossing spin-forbidden singulett-triplett transition
ET = Energy transfer
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Electron configuration
1s2 2s1
1s2
[Ne]3s1
[Ar]3d1
[Ar]3d3
[Ar]3d5
[Ar]3d10
[Xe]4f1
[Xe]4f6
[Xe]4f7
[Xe]4f8
[Xe]4f14
1.
S = 0
2.
l = 1
3.
J = 0, 1 (but not J = 0 J = 0)
L = 0, 1 (but not L = 0 L = 0)
4.
g u or u g
not g g or u u
Examples:
Ce3+
Eu3+
allowed
forbidden
~ ns
~ ms
Excitation by
Example
Scintillation
high-energy physics
PET detectors
X-ray amplifier, CT
CRTs, oscilloscopes
X-ray luminescence
Cathode luminescence
Photo luminescence
Electro luminescence
Chemo luminescence
Bio luminescence
Thermo luminescence
Sono luminescence
Mechano luminescence
Fluorescent lamps
LEDs, EL displays
Emergency signals
Jelly fish, glow worms
Afterglow phosphors
Peeling scotch tape
8.2 Absorption
Penetration depth of photons and electrons
Photons (Lambert-Beer law)
Absorption
by activators
or sensitizers
Absorption
by host lattice
R
[nm]
617.8
347.6
534.4
424.8
379.8
446.4
560.4
Energy
e-
e-
CB
[Xe]5d1
Traps
Ce3+
h+
h+
h+ e-
Conversion Transfer
Primary
holes
[Xe]4f1
VB
Luminescence
h+ Core band
Chapter Luminescence Mechanisms
Slide 15
CB
A1
transfer
Eg
A+
VB
act esc
A0
Host lattice
MgF2
Al2O3
Y2O3
ZnS
ZnSe
ZnTe
CdS
CdTe
CB
A2
A1
Sensitizer excitation
CB
S1
transfer
act esc
kr knr
A0
VB
A1
act esc
A0
VB
S0
Host lattice
Host lattice
1,0
4f - 4f 5d
4f 5d - 4f
80,0
Relative Intensity
Reflection [%]
0,8
60,0
40,0
2+
Eu
7
6
1
4f - 4f 5d
20,0
0,0
100
0,4
0,2
200
300
400
500
W avelength [nm]
0,6
600
700
800
0,0
100
200
300
400
500
600
700
Wavelength [nm]
Host material VB CB
180 nm (7.0 eV)
Eu2+
[Xe]4f7 [Xe]4f65d1
250 nm (5.0 eV) and 310 nm (4.0 eV)
Allowed transition Intense absorption bands and fast decay (~1 s)
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
800
100,0
Host lattice
1,0
1,0
2+
Mn
5
5
3d - 3d
80,0
2+
Mn
5
5
3d - 3d
Relative intensity
Reflection [%]
0,8
60,0
2+
Mn
5
5
3d - 3d
40,0
20,0
0,0
100
200
300
400
500
W avelength [nm]
600
700
800
0,8
0,6
0,6
0,4
0,4
0,2
0,2
0,0
100
200
300
400
500
600
700
W avelength [nm]
Host material VB CB
180 nm (7.0 eV)
Mn2+
[Ar]3d5 [Ar]3d5
200 nm (6.2 eV) and 450 nm (2.8 eV)
Forbidden transition Weak absorption bands and slow decay (~10 ms)
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
0,0
800
100,0
1,0
3+
Ce
1
1
5d - 4f
80,0
60,0
Relative Intensity
Reflection [%]
0,8
Host
Lattice
40,0
20,0
0,6
0,4
0,2
3+
Ce
1
1
4f -5d
0,0
0,0
200
300
400
500
W avelength [nm]
600
700
800
200
300
400
500
600
700
W avelength [nm]
Host material VB CB
150 nm (8.2 eV)
Ce3+
[Xe]4f1 [Xe]5d1
200 nm (6.2 eV) and 450 nm (2.8 eV)
Allowed transition Intense absorption bands and fast decay (~ 30 ns)
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
800
100
1,0
Band
gap
F0 - DJ
D0 - FJ
0,8
Relative intensity
Reflection [%]
80
Band Chargegap
Transfer
60
40
20
0,6
0,4
0,2
ChargeTransfer
F0 - D3
0
200
300
F0 - D2
400
500
600
700
800
0,0
150
200
250
300
350
400
500
550
F0 - D1
450
600
650
700
Wavelength [nm]
Host material VB CB
210 nm (5.9 eV)
Charge-Transfer
230 nm (5.4 eV)
Eu3+
[Xe]4f6 [Xe]4f6
395 nm (3.1 eV) and 465 nm (2.2 eV)
Forbidden transitions Weak absorption bands and slow decay (~3 ms)
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
750
CT level
Relaxation
5D
7F
J
Simplified energy
level scheme of Eu3+
Chapter Luminescence Mechanisms
Slide 22
Ce3+ - Eu2+
Ce3+ - Tb3+
unknown
Mn2+ - Mn2+
Spectral overlap
= gS(E).gA(E).dE
gS(E) and gA(E): Normalised optical line shape
functions for sensitizer and activator ions
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
1,0
LaPO4:Ce
Ce3+ (Ce3+)*
(Ce3+)* Ce3+
Excitation 4f - 5d
Emission 5d - 4f
Intensity (a.u.)
0,8
0,6
0,4
0,2
0,0
200
300
400
500
600
700
800
W avelength [nm]
1,0
Excitation 4f - 5d
Relaxation
Emission 4f - 4f
3+
Tb
4f5d absorption
3+
4f4f emission
0,8
Intensity (a.u.)
LaPO4:Tb
Tb3+ (Tb3+)**
(Tb3+)** (Tb3+)*
(Tb3+)* Tb3+
Tb
254 nm
0,6
0,4
0,2
0,0
200
400
500
600
1,0
Excitation 4f - 5d
ET from Ce3+ to Tb3+
Emission 4f - 4f
Tb
3+
absorption
Ce
3+
Tb
3+
800
4f4f emission
absorption
0,8
0,6
0,4
0,2
0,0
200
300
400
500
600
W avelength [nm]
700
Sample V1377
W avelength [nm]
Intensity (a.u.)
LaPO4:Ce,Tb
Ce3+ (Ce3+)*
(Ce3+)* + Tb3+ Ce3+ + (Tb3+)*
(Tb3+)* Tb3+
300
700
800
UV
1
Energy Transfer
Divalent RE ions
Divalent TM ions
Trivalent TM ions
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Eu2+, Yb2+
Mn2+, Co2+
Cr3+, Ti3+
(Eu2+)* Eu3+
Eu2+
(Eu2+)*
[Xe]4f 5d - [Xe]4f
0,8
Intensity [a.u.]
BaMgAl10O17:Eu
Host
lattice
7
6
1
[Xe]4f - [Xe]4f 5d
Absorption 4f - 5d
Emission 5d - 4f
0,6
0,4
0,2
0,0
100
300
400
500
600
700
800
Wavelength [nm]
1,0
Absorption 3d - 3d
Emission 3d 3d
2+
Mn 3d-3d emission
254 nm
0,8
Intensity [a.u.]
BaMgAl10O17:Mn
Mn2+ (Mn2+)*
(Mn2+)* Mn2+
200
0,6
0,4
0,2
0,0
100
Absorption 3d - 3d
ET from Eu to Mn
Emission 3d 3d
200
300
400
500
600
1,0
800
2+
Mn 3d-3d Emission
0,8
0,6
0,4
0,2
0,0
100
200
300
400
500
600
Wellenlnge [nm]
700
Wavelength [nm]
Intensitt [a.u.]
BaMgAl10O17:Eu,Mn
Eu2+ (Eu2+)*
(Eu2+)* + Mn2+ Eu2+ + (Mn2+)*
(Mn2+)* Mn2+
700
800
Conduction Band
VUV Excitation
Eg = 7.0 eV
(~ 180 nm)
[Xe]4f65d1
254 nm
[Ar]3d5*
515 nm
453 nm
370 nm
Mn2+
Eu2+
[Ar]3d5
Emission
Energy
172 nm
[Xe]4f7
Valence Band
8.5 Cross-Relaxation
Cross-relaxation
processes
are
responsible for the quenching of
luminescence of higher 4f levels of Tb3+
at a high Tb3+ concentration
(transfer)
2.
(act)
3.
(esc)
CB
abs
Eg
A*
transfer
A+
act
A
VB
Light Yield
LY
= EQE * abs = EQE*(1-R )
(No correlation to decay time!)
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
CB
(An+)*
Eg
An+
Causes afterglow in
scintillators
persistent phosphors
VB
Stokes shift
Energy gap between absorption and
emission band
S = Sehe + Sghg
emission band
FWHM ~ S
Eabs Eem
Sghg
rg
re
r
Chapter Luminescence Mechanisms
Slide 34
Weak to no electron-phonon-coupling
High IQE, EQE determined by ET processes
Thermal quenching mainly due to photoionization
4f 4f transitions (shielded 4f-shell: small crystal field
splitting [CFS])
Lines
Eu3+, Tb3+, .
2.
Moderate electron-phonon-coupling
High to moderate IQE
Thermal quenching due to tunnelling or photoioniz.
4f 5d transitions (large CFS)
Narrow bands
Eu2+, Ce3+, .
3.
Strong electron-phonon-coupling
High to low IQE at RT, strong thermal quenching
Thermal quenching mainly due to tunnelling
ns2 ns1np1 or CT transitions
Broad bands
Pb2+, Bi3+, .
Chapter Luminescence Mechanisms
Slide 35
: Integration
M
r0
Emission intensity
T25
T75
T150
T200
T250
T300
T330
10000
5000
Peak intensity
A1
1,0110
A2
0,01594
x0
179,41
dx
26,696
1,0
15000
0,8
0,6
Integral
A1
0,99900
A2
0,002116
x0
169,99
dx
30,894
0,4
0,2
y = A2 + (A1-A2)/(1 + exp((x-x0)/dx))
0
450
0,0
500
550
Wavelength [nm]
600
650
50
100
150
200
250
300
Temperature [C]
T1/2 = Temperature at which the phosphor loses 50% of its initial emission
intensity (here ~ 170 C)
T1/2 depends on the extent of the activator-host lattice interaction
In many industrially important phosphors the quantum yield starts
increasing distinctly between 100 150 C
350
Light yield
as a function of the temperature
60000
BAM25C
BAM75C
BAM150C
BAM200C
BAM250C
BAM300C
BAM330C
50000
1,0
0,8
0,6
0,4
(Sr,Ca)2SiO4:Eu
(Ba,Sr)2SiO4:Eu
BaMgAl10017:Eu
0,2
50
100
150
200
Temperature [C]
Stokes shift
Thermal quenching
30000
20000
10000
0,0
0
40000
250
300
350
0
400
450
500
Wavelength [nm]
Blue shift due to thermal expansion of the host lattice and thus reduction in crystal field
splitting
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
550
dNe/dt = - Ne*Peg
e
Peg
Ng
Transition
allowed
weak
forbidden
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Time scale
~ 10-9 s
~ 10-6 s
~ 10-3 s
Oscillator strength
f ~ 0.1
f ~ 0.001
f ~ 10-5
Activators
Eu2+, Ce3+
Pr3+, Nd3+
Eu3+, Mn2+
1000
Intensity at 595 nm
Intensity at 453 nm
100
0,1
0,01
1E-3
10
Excitation at 160 nm
Excitation at 254 nm
1E-4
t [s]
10
10
20
30
t [ms]
40
2T
2
Ion
Ti3+
Cr3+
Mn4+
Mn2+
Fe3+
Configuration
[Ar]d1
[Ar]d3
[Ar]d3
[Ar]d5
[Ar]d5
2D3/2
2T2 + 2E
Example
Al2O3:Ti (Sapphire)
Al2O3:Cr (Ruby)
Mg4GeO5.5F:Mn
Zn2SiO4:Mn (Willemite)
LiAlO2:Fe
Configuration
d1
Colour
violet, brown
Pigment
Structure type
V3+
V4+
Cr3+
d2
d1
d3
green
green, blue
green, yellow
(Zr,V)SiO4
Cr2O3
Zircon
Corundum
Mn2+
Mn3+
Mn4+
d5
d4
d3
light pink
violet
red, brown
MnO
Mn2O3
MnO2
NaCl
Corundum
Rutile
Fe3+
Fe2+
d5
d6
yellow, brown
blue, green
Fe2O3
Fe(C2O4).2H2O
Corundum
Co2+
Ni2+
Cu2+
d7
d8
d9
blue, violet
green
blue, green
CoAl2O4
NiO
CuO
Spinel
NaCl
Absorption [cm-1]
40000
35000
CN
4
6
Polyhedron
Tetrahedron
Octahedron
Position of the CT state decreases with increasing CN and effective charge of the
metal center
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
1,0
3P
2
3P
1
3P
0
0,8
Relative intensity
1P
1
0,6
0,4
0,2
0,0
200
1S
300
400
Wavelength [nm]
500
600
Sample UV-A28/98
Excitation
Emission
0,8
0,6
0,4
0,2
SrLaBO4:Pb
Excitation
Em ission
250
300
350
400
450
500
Wavelength [nm]
550
600
0,6
Emission
0,6
0,4
0,4
0,2
0,2
0,0
250
300
350
400
450
500
W avelength [nm]
Phosphor
Structure type Stokes shift [cm-1]
BaSi2O5:Pb
Sanbornite
10600
Sr2MgSi2O7:Pb Akermanite
12000
SrLaBO4:Pb
17700
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Excitation
0,8
0,8
0,0
0,0
1,0
1,0
BaSi2O5:Pb
550
600
250
300
350
400
450
500
550
600
W avelength [nm]
QA [%]
90
75
65
Orbital
Parity
ml
-1, 0, 1
-2, ..., 2
-3, ..., 3
La Ce Pr
2
2
2
1
0
0
0
2
3
Nd Pm Sm
2
2
2
0
0
0
4
5
6
Eu Gd Tb
2
2
2
0
1
0
7
7
9
Dy Ho
2
2
0
0
10 11
Er
2
0
12
Tm Yb
2
2
0
0
13 14
Lu
2
1
14
La3+ Ce3+ Pr3+ Nd3+ Pm3+ Sm3+ Eu3+ Gd3+ Tb3+ Dy3+ Ho3+ Er3+ Tm3+ Yb3+ Lu3+
Ce4+ Pr4+ Nd4+
Sm2+ Eu2+
Tm2+ Yb2+
0
1
2
3
4
5
6
7
8
9
10
11 12 13 14
Example
Gd3+/Eu2+
ml
-3 -2 -1 0 1
2 3
4f
S = s = 7/2
L = |l| = 0
2S+1 = 8
S
-2 -1 0 1
-1 0
6s
6p
5d
Spectroscopic
Terms
2S+1LJ
ml = -3 -2 -1 0 1 2 3
7F
6
4f
ml = -3 -2 -1 0 1 2 3
5D
4f
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
4.0x104
254 nm
4f72p-1
5d1
6I
7/2
4f65d1
3.5x104
6P
7/2
Energy [cm-1]
3.0x104
5D
3
5D
3
2.5x104
450 nm
5D
4
5D
2
2.0x104
5D
1
5D
0
1.5x104
1.0x104
0.5x104
2F
0.0
6
5
4
3 2
1 0
7/2
2F
Ce3+
[Xe] 4f1
0 1
2
3
4
5
7F
5/2
Eu3+
4f6
8S
7/2
Eu2+
4f7
8S
7/2
Gd3+
4f7
7F
Tb3+
4f8
Electrostatic interactions
Spin-orbit coupling
For Tb3+
Ground state:
Excited state:
7F
6,5,4,3,2,1,0
5D
4,3,2,1,0
Intensity [a.u.]
Lu3Al5O12:Nd3+
4F
4
3/2 I11/2
E = 203 cm-1
six levels without
external magnetic
field
1,25
1,00
0,75
0,50
0,25
0,00
1000 1010 1020 1030 1040 1050 1060 1070 1080 1090 1100
Wavelength [nm]
Dodecahedral coordination
Ce (Yb)
Pr (Tm)
Nd (Er)
Gd
SL
17
47
73
119
119
SLJ
13
41
107
198
295
327
SLJM
91
364
1001
2002
3003
3432
P.S. Peijzel, A. Meijerink, R.T. Wegh et al, J. Solid State Chem. 178 (2005) 448
~
~
~
~
~
~
Yb3+
Tm3+
Er3+
Ho3+
Dy3+
Tb3+
1,0
ChargeTransfer
0,8
0,6
0,4
7
7
0,2
0,0
100
150
200
250
F0 - D3
F0 - L6
7
F0 - D4
300
350
400
F0 - D2
450
F0 - D1
500
550
600
W avelength [nm]
5
1,0
D0 - F2
0,8
0,6
5
5
0,4
0,2
0,0
500
D0 - F1
5
D0 - F0
550
600
D0 - F4
D0 - F3
650
700
750
800
W avelength [nm]
1,0
LuBO3:Eu
Calcite
F1
0,8
1,0
0,6
0,4
0,2
0,0
500
550
F2
600
650
F4
700
750
(Y,Gd)BO3:Eu
Vaterite
F1
0,8
7
0,4
0,2
F4
550
600
1,0
Y2O3:Eu
F2
Bixbyite
0,8
0,6
0,4
0,2
0,0
500
550
F1
600
650
F4
700
Wavelength [nm]
700
750
800
750
Y(V,P)O4:Eu
Xenotime
F2
650
Wavelength [nm]
Wavelength [nm]
1,0
F2
0,6
0,0
500
800
800
0,8
0,6
0,4
7
7
0,2
0,0
500
550
F4
F1
600
650
700
750
800
Wavelength [nm]
D 0 - F1
D 0 - F2
D 0 - F3
Intensity
Phosphor
D0 - F 4
(Y,Gd)BO3:Eu
(Y,Gd)BO3:Eu
0.640
0.360
Y2O3:Eu
Y2O3:Eu
0.641
0.344
YVO4:Eu
0.645
0.343
Y2O2S:Eu
0.650
0.342
YVO4:Eu
Y2O2S:Eu
600
650
700
750
Wavelength [nm]
4f72p-1
Energy [cm-1]
3.5x104
3.0x104
5D
3
2.5x104
5D
2
5D
1
5D
0
2.0x104
1.5x104
1.0x104
0.5x104
7F
6
5
4
32
10
0.0
Eu3+
[Xe]4f6
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
b) No inversion symmetry
Electric dipole transitions 5D0 -7F2,4
J 6 (Ji = 0 Jf = 2, 4, 6)
Y2O3:Eu (Bixbyite), Y(V,P)O4:Eu (Xenotime)
~ 2 - 5 ms
Chapter Luminescence Mechanisms
Slide 65
D0 - FJ
1,0
ChargeTransfer
1,0
BaMgAl10O17:Eu2+
0,8
0,6
0,4
0,2
5
F0 - D2
F0 - D3
0,0
150
200
250
300
350
400
500
550
4f 5d - 4f
7
4f - 4f 5d
0,8
0,6
0,4
0,2
F0 - D1
450
600
650
Wavelength [nm]
Eu3+ (Eu3+)**
CT
(Eu3+)** (Eu3+)*
Relaxation
4f-4f
(Eu3+)* Eu3+
Strong CT absorption band (broad)
Weak 4f-4f absorption lines (narrow)
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
B and
g ap
700
750
0,0
150
20 0
250
3 00
350
4 00
450
500
550
600
650
700
W avelength [nm ]
Eu2+ (Eu2+)**
4f-5d
(Eu2+)** (Eu2+)*
Relaxation
(Eu2+)* Eu2+
5d-4f
Strong 4f-5d absorption bands (broad)
Chapter Luminescence Mechanisms
Slide 66
7 50
[Xe]4f1
[Xe]5d1
Eu2+
60
2D
J
50
40
30
40
30
6D
9/2
6I
7/2
8H
J
6P
7/2
20
20
10
10
[Xe]4f65d1
60
50
[Xe]4f7
2F
7/2
2F
5/2
8S
7/2
Centroid shift
Crystal field
splitting
Stokes shift
[Xe]4fn-15d1
c
cfs
Ce3+
Pr3+
Nd3+
Gd3+
Eu2+
49340 cm-1
61580 cm-1
72100 cm-1
95200 cm-1
34000 cm-1
[Xe]4fn
c:
cfs:
phosphates
PO43-
sulfates
SO42-
phyllo-silicate
[Si4O10]4montmorillonite
talc
kaolinite
Chapter Luminescence Mechanisms
Slide 69
Cation
Y3+
3O
O-P-O
O
tetrahedral PO43-
Y3Al5O12
Y3+
5O
O-Al-O
O
9-
O
O-Al-O
O O
tetrahedral AlO45- + octahedral AlO69P5+ attracts more charge density of the O2- anions than Al3+
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
4 x O(1)
7.248
4 x O(2)
7.193
Low charge density on oxygen
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Y3Al5O12
4 x O(1)
7.528
4 x O(2)
7.504
High charge density on oxygen
Chapter Luminescence Mechanisms
Slide 72
1,0
Distorted dodecahedral
Y-O distances
E
cfs
4x 2.24
4x 2.24
0,8
4f5d
Free ion
4f5d
4f5d
cfs
0,6
0,4
0,2
0,0
100
c
200
300
400
500
600
700
800
Wavelength [nm]
Free ion
4f5d
cfs
Distorted dodecahedral
Y-O distances
E
cfs
4x 2.30
4x 2.44
0,6
Band gap
Emission intensity
0,8
4f5d
4f5d
0,4
0,2
0,0
100
c
200
300
400
500
600
700
800
Wavelength [nm]
1,0
1,0
0,8
0,8
0,8
0,6
0,6
0,6
0,4
0,4
0,4
0,2
0,2
0,2
0,0
100
200
300
400
500
Wavelength [nm]
600
700
0,0
100
Y2O3:Pr
0,0
200
300
400
500
600
700
100
200
300
400
500
600
700
Wavelength [nm]
Wavelength [nm]
800
[Xe]4f2
3H
J
60
4f
4f
5d
1S
40
30
20
10
0
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
3P
2 3
P1, 1I6
3P
0
1D
2
E = 61580 cm-1
50
5d
Energy [103 cm-1]
[Xe]4f15d1
1G
4
3F 3F4
3
3H 3F2
6
3H
3H
5
4
[Xe]4f15d1 Kh
site
Oh site distorted
Oh site
60
50
1S
40
30
20
10
3P
2 3 ,1
P1 I6
3P
0
1D
2
1G
4
3F 3F4
3
3H 3F2
6
3H
5
3H
4
UV line emission
1S
0
213, 236
252, 271
407 nm
1S
0
Blue emission
1D
2
Red emission
line emission
Y2O3:Pr
CaTIO3:Pr,Na
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
615 nm
615 nm
Chapter Luminescence Mechanisms
Slide 78
4f 5d
1,0
S0 I6
Intensity [a.u.]
0,8
0,6
S0 G4
0,4
3
1
PJ H6
S0 FJ
0,2
PJ H4
3
Distorted square-antiprismatic
Energy
Y-F distances
4x 2.28
2x 2.30
2x 2.31
cfs
CF splitting
~ 8000 cm-1
Centroid shift
~ 5600 cm-1
S0 HJ
PJ FJ
S0 D2
0,0
200
300
400
500
600
700
800
Wavelangth [nm]
4f 5d
1,0
H4
3
H5
0,8
0,6
Host
lattice
H6
3
FJ
0,4
0,2
Distorted dodecahedral
Energy
Y-O distances
4x 2.24
4x 2.24
cfs
CF splitting
~ 12000 cm-1
Centroid shift
~ 9600 cm-1
0,0
100
200
300
400
W avelength [nm]
500
1,0
Host lattice
3
1
4f 5d
0,8
P0 - H4
4f 5d - HJ
0,6
0,4
0,2
Distorted dodecahedral
Energy
Y-O distances
4x 2.30
4x 2.44
cfs
CF splitting
~ 22500 cm-1
Centroid shift
~ 14700 cm-1
0,0
100
200
300
400
500
600
Wavelength [nm]
700
8.13 Down-Conversion
First examples (1974)
Sommerdijk et al., J. Lumin. 8 (1974) 288 (Philips)
Sommerdijk et al., J. Lumin. 8 (1974) 341 (Philips)
Piper et al., J. Lumin. 8 (1974) 344 (GE)
YF3:Pr(0.1%) and NaYF4:Pr(0.1%)
1S - 3P , 1I transition @ 407 nm
0
1
6
3P - 3H , 3F transitions in the red
0
J
2
Internal QY = 166% (total) @ 214 nm exc.
Derived from line ratio UV to blue to green/red
Oxidic luminescent materials to show photon cascade emission (PCE)
A.M. Srivastava, D.A. Doughty, W.W. Beers (GE)
Pr3+ on host lattice sites with high CN (> 8)
SrAl12O19:Pr,Mg
LaMgB5O10:Pr
LaB3O6:Pr
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
8.13 Down-Conversion
Example: LiGdF4:Eu
Energy level diagram
202 nm
Gd
Gd**
ET
Gd + Eu*
Eu + h
QYA = 195%
Chapter Luminescence Mechanisms
Slide 83
8.13 Down-Conversion
Example: LiGdF4:Er,Tb
Energy level diagram
Er
545 nm
> 210 nm
Er**
Er** + Gd
Er*
CR
Er* + Gd*
Er + h
Gd* + Tb
Tb*
ET
Gd + Tb*
Tb + h
QYA = 130%
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
8.14 Up-Conversion
Yb3+ - Er3+
Principle
Examples
YF3:Yb,Tm
YF3:Yb,Er
NaYF4:Yb,Er
BaY2F8:Yb,Er
YOCl:Yb,Er
20-35% Yb3+
1-5% Er3+ or Tm3+
8.15 Afterglow
Cause:
Deep traps:
CB
F+/F(F-)
8.2eV
VB
Example: BaFBr:Eu
F+/F(Br-)
(Eu2+/Eu3+)*
Eu2+/Eu3+
8.15 Afterglow
Example: Cs2NaYF6:Ce and Cs2NaYF6:Pr (elpasolite)
According to: Th. Pawlik and J.-M. Spaeth, J. Appl. Phys. 82 (9), 4236 (1997)
8.15 Afterglow
Shallow traps: Thermal emptying of the traps at room temperature
CB
Eu2+*
transfer
6.5 eV
VB
Example
SrAl2O4:Eu,Dy
Incoherent Light Sources
Prof. Dr. T. Jstel, FH Mnster
Dy3+ + h+ ~ 0.65 eV
Eu3+
Eu2+
8.15 Afterglow
Afterglow phosphors
Sr4Al14O25:Eu2+,Ln3+
max [nm]
440 nm
469 nm
490 nm
499 nm
520 nm
530 nm
570 nm
620 nm
648 nm
655 nm
660 nm
685 nm
DD001 Eu
2+
3+
DD004 Eu ,Dy
2+
3+
DD005 Eu ,Tm
2+
3+
3+
DD006 Eu ,Dy ,Tm
100000
Intensity
colour
blue
blue
cyan
cyan
green
green
yellow
red
red
red
red
red
80000
60000
40000
20000
0
400
450
500
550
600
650
700
Wavelength [nm]
14000
2+
DD001 Eu
2+
3+
DD004 Eu ,Dy
2+
3+
DD005 Eu ,Tm
2+
3+
3+
DD006 Eu ,Dy ,Tm
Ex= 350 nm
Em= 488 nm
12000
10000
2500
Intensity
Composition
CaAl2O4:Eu,Nd
Sr2MgSi2O7:Eu,Dy
Sr4Al14O25:Eu,Dy
Mg2SnO4:Mn2+
SrAl2O4:Eu,Dy
ZnS:Cu,Co
Sr2SiO4:Eu,Dy
Y2O2S:Eu,Ti,Mg
CaZnGe2O6:Mn
CaS:Eu,Tm
MgSiO3:Eu,Dy,Mn
SrSc2O4:Eu
2+
Emission
Ex= 350nm
120000
2000
8000
1500
6000
1000
500
4000
0
3
2000
0
0
Time [min]