Lanta Nidos

8.
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
Chapter Luminescence Mechanisms

Slide 1
8.1 Luminescence - Definition

Luminescence is a process that corresponds to emission of electromagnetic radiation
beyond thermal equilibrium.
Inorganic materials: Radiative recombination involving impurity levels:
(a) Conduction-bandacceptor-state transition
(b) Donor-statevalence-band transition
(c) Donor-acceptor recombination
(d) Bound-exciton recombination
EC
ED
ED
ED
(a)
(b)
(c)
(d)
Eg
Eg
Eg
Eg
EA
EA
EV
Thus: Luminescence requires localisation of absorbed energy by discrete states!


Slide 2
8.1 Luminescence - Definition

Thermal and non-thermal radiators
Thermal radiators emit a radiation spectrum
that equals black body radiation at a corresponding
temperature
Planck radiation
Examples: Cosmic background radiation,
cosmic objects, halogen- and incandescent lamps
1,0
Examples: Luminescent materials, LEDs, Lasers
0,8
Intensity
Non-thermal radiators emit a radiation spectrum

originating from electronic transitions between
discrete electronic energy levels
Luminescence
YPO4-Tb
YPO4-Dy
YPO4-Tm
0,6
0,4
0,2
0,0
300
350
400
450
500
550
600
650
Wavelength [nm]


Slide 3
700
8.1 Luminescence Materials

Inorganic luminescent materials = Host lattice + defects + dopants
Host lattice
Y2O3, Y3Al5O12, ZnS, CaAlSiN3, Sr2Si5N8,
Selection in accordance to requirements defined by the application area:
Excitation energy, absorption strength, chemical environment, temperature
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

Slide 4

Inorganic luminescent materials - Morphology
Nanoscale particles
-sized particles
Large single crystals

Ceramics
Glasses
1 nm
10 nm

Molecular imaging, precursors

Lamps, LEDs, CRTs, PDPs, EL Displays, x-ray
converter films
Scintillators, Lasers
LEDs, scintillators, LEDs
Detectors, Lasers
100 nm
1 m
10 m
100 m
1 mm
10 mm

Slide 5

Inorganic luminescent materials Requirements for high efficiency
Strong absorption
Highly crystalline particles, low defect density
High purity (99,99% or higher)
Homogeneous distribution of activator and sensitizer ions
Low phonon frequencies
Excitation
Source
Emission
Absorption process related to

Optical centres (impurities)
activators
(A)
sensitizers
(S)
defects
(D)
host lattice
(band edge)
Heat
Heat
A
ET
ET
A
ET
ET
A
Heat
Energy transfer often occurs prior to

emission process!
Emission
Heat
Heat

Slide 6

Inorganic luminescent materials The role of the host lattice
Conduction band
(CB)
Donor levels (D)
Band gap Eg
Acceptor levels (A)
Valence band
(VB)
YBO3 (Vaterite)
Band gap Eg = 6.5 eV
Absorption via
Host lattice
Charge-Transfer or VB to CB
Defects (colour centers)
Donor and acceptor levels
Slide 7

Inorganic luminescent materials The role of the host lattice
Reflection spectrum of YBO3
Emission spectrum of YBO3 upon 160 nm excitation
100
1,0
Emission intensity [a.u.]
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]
Band gap absorption at 170 nm
Exciton luminescence at 260 nm


Slide 8
700

Inorganic luminescent materials The role of the dopants
YVO4 (tetragonal), Eg = 4.2 eV
YPO4:V,Eu (tetragonal), Eg = 8.2 eV

CB
CB
(VO43-)*
Donor levels (D)

Eg
(Eu3+)*
Eg
Acceptor levels (A)
VO43-
VB
Eu3+
VB
Absorption via
Host lattice
Defects (colour centers)
Dopants (impurities)
Charge-Transfer or VB to CB
Donor and acceptor levels
Activators and sensitizers
Slide 9
8.1 Luminescence - Processes

The overall picture
S2
S1
S0
Fluorescence
Relaxation
~10-9s
Eg
Excitation process
Energy [eV]
Conduction band (empty metal orbitals)

Defect
Storage
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

Slide 10

Electronic Ground States of Atoms and Ions (Dopants)
The electronic energy levels are defined by the spin and orbital momentum of the
electrons and by the coupling of these to the total spin and total (orbital) momentum
Atom/Ion
Li0
Li+
Na0
Ti3+
Cr3+/Mn4+
Mn2+/Fe3+
Zn2+/Cu+
Ce3+
Eu3+
Eu2+ /Gd3+/Tb4+
Tb3+
Lu3+
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

Spectroscopic term 2S+1LJ

2S
1/2
1S
0
2S
1/2
2D
3/2
4F
3/2
6S
5/2
1S
0
2F
5/2
7F
0
8S
7/2
7F
6
1S
0
Slide 11

Selection rules for electric dipole radiation (transitions)
Overall requirement: Conservation of momentum of the system atom/ion + photon
1.
Spin selection rule
S = 0
2.
Angular momentum (single electron)
l = 1
3.
Angular momentum (multi electron)
J = 0, 1 (but not J = 0 J = 0)
L = 0, 1 (but not L = 0 L = 0)
4.
Laporte selection rule
g u or u g
not g g or u u
Examples:
Ce3+
Eu3+

[Xe]4f1 (2F5/2) [Xe]5d1 (2D3/2)

[Xe]4f6 (7F0) [Xe]4f6 (5D0)
allowed
forbidden
~ ns
~ ms

Slide 12

Type
Excitation by
Example
Scintillation
High energy particles

-rays
X-rays
Electrons
(high voltage)
UV/Vis photons
Electrical field
(low voltage)
Chemical reaction
Biochemical reaction
Heat
Ultra sound
Mechanical energy
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
Nature 455 (2008) 1089, blue + UV + x-ray!


Slide 13
8.2 Absorption
Penetration depth of photons and electrons
Photons (Lambert-Beer law)
Absorption
by activators
or sensitizers
Absorption
by host lattice
Electrons (Feldman equation: R in [])
For 5.7 keV

Density
R
electrons
[g/cm]
[]
SiO2
2.20
6171
3.97
3476
Al2O3
Mg3(PO4)2
2.56
5345
ZnS
4.04
4248
MgO
3.59
3799
MgF2
3.15
4464
MgS
2.68
5603
Simplified R ~ 0.046*U5/3/ [m]
R
[nm]
617.8
347.6
534.4
424.8
379.8
446.4
560.4
For a material with r = 5.0 g/cm3 (Y2O3)

10 kV electrons R ~ 400 nm
2 kV electrons
R ~ 30 nm

Slide 14

High energy particles, - ray, x-ray and high voltage electron excitation
Primary
electrons
eBand gap
Energy
1. Excitation of highly energetic

core states
2. Thermalization of electron-hole
pairs with band gap energy
3. Energy transfer to activator
ions or centers
4. (Center) Luminescence
e-
e-
CB
[Xe]5d1
Traps
Ce3+
Efficiency surprisingly well

understood, but with two
different models:
1. Robbins
2. Bartram-Lempicki
h+
h+
h+ e-
Conversion Transfer
Primary
holes
[Xe]4f1
VB
Luminescence
h+ Core band
Slide 15

Photons with an energy > band gap of the host lattice: PDPs and Xe excimer lamps
CB
A1
transfer
Eg
A+
VB
act esc
A0
Host lattice
MgF2
Al2O3
Y2O3
ZnS
ZnSe
ZnTe
CdS
CdTe
Band gap Eg [eV]

12.2
8.0
5.6
3.9
2.8
2.4
2.6
1.6
Internal quantum efficiency: IQE = r/(r + nr) = act

External quantum efficiency: EQE = act* transfer* esc

Slide 16

Photons with an energy < band gap of the host lattice: Fluorescent lamps and LEDs
Activator excitation
CB
A2
A1
Sensitizer excitation
CB
S1
transfer
act esc
kr knr
A0
VB
IQE = act = kr/(kr + knr) = /0

with kr + knr = 1/ and kr = 1/0
A1
act esc
A0
VB
S0
EQE = act * transfer *esc

Slide 17

Example: BaMgAl10O17 doped by 10% Eu2+
Reflection spectra
100,0
Emission and excitation spectra
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)

Slide 18
800

Example: BaMgAl10O17 doped by 5% Mn2+
Reflection spectra
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)

Slide 19
0,0
800

Example: LaPO4 doped by 20% Ce3+
Reflection spectra
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)

Slide 20
800

Example: Y2O3 doped by 5% Eu3+
Reflection spectra
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)

Slide 21
750

Sensitisation to enhance absorption strength
3dn - 3dn and 4fn - 4fn transitions are very weak
Ways to enhance absorption:
Taking advantage of allowed transitions

Charge-Transfer (CT) states Eu3+, Yb3+
Low-lying energy levels of the
[Xe]4fn-15d1 configuration Tb3+, Eu2+, Ce3+, Pr3+
Sensitisation (via energy transfer)
Tb3+
Ce3+
Pr3+
Tb3+
Nd3+
Gd3+
Pr3+
Gd3+
Bi3+
Eu3+
Sb3+
Mn2+
Ce3+
Mn2+
Eu2+
Mn2+
CT level
Relaxation
5D
7F
J
Simplified energy
level scheme of Eu3+
Slide 22
8.4 Energy Transfer

Requirements for ET (S* + A S + A*)
Sensitizer S and activator A interact with each other by

Coulomb interaction (multipolare interaction)
Dipole-Dipole:
PSA= (1/S)(r0/rSA)6
Dipole-Quadrupole:
PSA= (1/S)(r0/rSA)8
Quadrupole-Quadrupole:
PSA= (1/S)(r0/rSA)10
Exchange interaction
PSA~ J.exp(-2 rSA )
for rSA < 5 with J = coupling constant
Ce3+ - Eu2+
Ce3+ - Tb3+
unknown
Mn2+ - Mn2+
Spectral overlap ( Energy conservation law!)


Slide 23
8.4 Energy Transfer

Probability PET
The probability PET for an energy transfer
is given by the following term:
PET = (2/).() < i | H | f >
i:
f:
H:
:
Wave function of the initial state

Wave function of the final state
Operator coupling the states
Spectral overlap (energy conservation)
Spectral overlap
= gS(E).gA(E).dE
gS(E) and gA(E): Normalised optical line shape
functions for sensitizer and activator ions

Slide 24
8.4 Energy Transfer

Consequences for luminescence processes
ET causes
Energy migration
Concentration quenching
Thermal quenching
Cross-relaxation
Possibility of sensitization
Some rules
ET from a broad band emitter to a line emitter only possible for nearest neighbors in
the host lattice (Ce3+ - Tb3+)
ET from a line emitter to a band absorber proceeds over long distances (Gd3+ - Ce3+)
ET strongly depends on average distance and thus concentration of luminescent
centers (Eu3+ - Eu3+)


Slide 25
8.4 Energy Transfer

Example: ET in LaPO4:Ce,Tb
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
Fluorescent lamps Excitation at 254 nm
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

Slide 26
700
800
8.4 Energy Transfer

Example: ET in BaMgAl10O17:Eu co-doped by transition metal ions
UV
1
Energy Transfer
Divalent RE ions
Divalent TM ions
Trivalent TM ions
Ba2+ sites in the conduction layer

tetrahedral gaps in the spinel blocks
octahedral gaps in the spinel blocks
Eu2+, Yb2+
Mn2+, Co2+
Cr3+, Ti3+

Slide 27
8.4 Energy Transfer

Example: ET in BaMgAl10O17:Eu co-doped by transition metal ions
1,0
(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
BaMgAl10O17:Eu(Mn) can be excited at 172 nm, 254 and 370 nm

Application in PDPs, FLs (and near UV emitting LEDs)
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+

Slide 28
700
800
8.4 Energy Transfer

Energy pathways in BaMgAl10O17:Eu,Mn
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


Slide 29
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
Cross-relaxation also occurs in Eu3+,

Sm3+ , Pr3+, and Dy3+ doped materials
Concentration quenching for Sm3+ or

Dy3+ activated materials by crossrelaxation and not by energy migration
Relaxation to the first excited state can

also be triggered by high-energy
photons

Slide 30
8.6 Loss Processes

Overview of the most relevant processes leading to luminescence quenching
1.
The absorbed energy does not reach the activator ion

a) Competitive absorption
b) ET to defects or non-luminescent impurity ions
c) Excited state absorption (ESA)
d) Auger processes
(transfer)
2.
The absorbed energy reaches the activator ion, but non-radiative

channels dominate the radiative return to the ground state
a) Crossing of excited and ground state parabola
b) Multi-phonon relaxation
c) Cross-relaxation
d) Photoionization
e) Energy transfer to quenching sites = f(T)
(act)
3.
Emitted radiation is re-absorbed by the luminescent material

a) Self-absorption due to spectral overlap between excitation
and emission band
b) Additional absorption bands due to degradation of the material,
e.g. by colour centre formation
(esc)


Slide 31
8.6 Loss Processes

Related to the host lattice and host lattice activator interaction
CB
abs
Eg
A*
transfer
A+
act
A
Internal Quantum Efficiency

IQE
= act
= r/(r + nr)
= /0
(Anti proportional to decay time)
esc External Quantum Efficiency
EQE
= Nh(emitted)/Nh(absorbed)
= transfer* act* esc
(No correlation to decay time!)
VB
Light Yield
LY
= EQE * abs = EQE*(1-R )
(No correlation to decay time!)

Slide 32
8.6 Loss Processes

Photoionization
CB
(An+)*
Eg
An+
Excited An+ ion gets ionised
Released electron is re-trapped,

e.g. by anion vacancies
Causes afterglow in
scintillators
persistent phosphors
VB


Slide 33
Stokes shift
Energy gap between absorption and
emission band
S = Sehe + Sghg
Sehe Full width at half maximum of the
emission band
FWHM ~ S
Eabs Eem
Sghg
rg
re

Thermal quenching decreases with

increasing R = re - rg
r
Slide 34

1.

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+, .
Slide 35

Width of the transitions can be explained by the model harmonic oscillator
F = -k*(r - r0)
E = -1/2*k*(r - r0)2
: Integration
M
r0
Quantum mechanics provides: Ev = (v + 1/2)*h

Franck-Condon principle:
Electrons motion is much faster than nuclear

motion vertical transitions
Transitions: Eg(vg = 0) Ee(ve = x)

r0g = r0e
r0g < r0e
for ve = 0 zero-phonon line
narrow bands or lines (4f 4f absorption lines)

broad bands (4fn 4fn+1L-1, 4fn 4fn-15d, 6s2 6s6p)


Slide 36

Example: SrGa2S4:Eu2+
Emission spectrum
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
Relative emission intensity
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


Slide 37
350

Example: Other Eu2+ activated phosphors
Spectral width of the emission band of
BaMgAl10O17:Eu as a function of the temperature
Light yield
as a function of the temperature
60000
BAM25C
BAM75C
BAM150C
BAM200C
BAM250C
BAM300C
BAM330C
50000
Relative emission intensity
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]
BaMgAl10O17:Eu < (Ba,Sr)2SiO4:Eu < (Sr,Ca)2SiO4:Eu

BaMgAl10O17:Eu < (Ba,Sr)2SiO4:Eu < (Sr,Ca)2SiO4:Eu
Blue shift due to thermal expansion of the host lattice and thus reduction in crystal field
splitting

Slide 38
550

Some Rules
Decreases with increasing energy separation of the ground and excited state
Increases with increasing phonon frequencies (thus most organic compounds
exhibit luminescence only at low temperatures)
Increases with r = re rg
Thermal quenching due to photoionization concerns luminescent materials, where
the excited state is located close to the conduction band


Slide 39

Description equal to 1st order kinetics (no energy transfer!)
Ne
dNe/dt = - Ne*Peg
e
Peg
dNe/Ne = -Peg*dt : Integration

ln(dNe(t)/Ne(0)) = -Peg*t
Ng
Ne(t) = Ne(0)*exp(-Peg/) with = 1/Peg
Transition
allowed
weak
forbidden
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+

Slide 40

Typical decay curves
BaMgAl10O17:Eu2+ ( = 1 s)
(Y,Gd)BO3:Eu3+ ( = 3.5 ms)
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]
Mono-exponential decay No energy transfer e.g. to impurities such as Fe3+ or Cr3+

Deviation from mono-exponential decay quenching, energy transfer, afterglow, .

Slide 41
40

Absorption processes of dn-ions Tanabe-Sugano diagrams
Energy level diagram of a d1-ion (Ti3+, V4+, Cr5+, Mn6+): RS-terms
CF-terms
2E
2T
2
Crystal field strength (CFS)

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
d-d transitions are parity-forbidden

low absorption coefficient
high concentration needed
Slide 42

Absorption in glasses, laser crystals and phosphors
Ion
Ti3+
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


Slide 43

Absorption processes of transition metal ions with d0-configuration
Examples: VO43-, NbO43-, TaO43-, CrO42-, MoO42-, WO42- , MnO4Absorption due to ligand to metal charge-transfer (LMCT)
O2- Men+ or p(non-bonding) d(eg: anti-bonding)
Bond is weakened R >> 0 broad absorption band
Phosphor
CaWO4
Ca3WO6
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

Slide 44

Examples: Ga+, In+, Tl+, Ge2+, Sn2+, Pb2+, As3+, Sb3+, Bi3+
Electron configuration of s2-ions
Energy level diagram of s2-ions
Ga+, Ge2+ and As3+:

[Ar]3d104s2
In+, Sn2+ and Sb3+:
[Kr]4d105s2
Tl+, Pb2+ and Bi3+:
[Xe]4f145d106s2
Excitation and emission spectra of BaYB9O16:Sb3+
Emission spectrum
Excitation spectrum
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

Slide 45

Example: Pb2+ Luminescence process: [Xe]4f145d106s2 [Xe] 4f145d106s16p1
Sr2MgSi2O7:Pb
1,0
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
Excitation
0,8
0,8
0,0
0,0
1,0
Normalized emission intensity
1,0
BaSi2O5:Pb
550
600
250
300
350
400
450
500
550
600
W avelength [nm]
Half width [cm-1]

2700
4300
5300
QA [%]
90
75
65

Slide 46

Lanthanides originates from the Greek word , which means to lie
hidden
Instead of to lie hidden ,
a better name would be to be outstanding
epifanides (A. Meijerink, PGS 2011)


Slide 47

Properties of electronic orbitals
Shape and orientation

Orbital
Parity
ml
-1, 0, 1
-2, ..., 2
-3, ..., 3

Slide 48

Electron configuration of rare earth metals and ions
Metals
[Xe]
6s
5d
4f
Ions
[Xe]
4f
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
strongly paramagnetic ions

LS-Term symbol 8S
2S+1LJ

Slide 49

History of distangling the energy level structure
1908 Becquerel
Sharp lines in optical spectra of lanthanide ions
1937 Van Vleck
The Puzzle of Rare-Earth Spectra in Solids
1960s Judd, Wybourne, Dieke, Carnall
Theory for energy level structure and transition
probabilities of 4f-4f transitions


Slide 50

Energy level structure of [Xe]4fn ions
Partly filled 4f-shell results in multiple electron configurations
Example: Tb3+ [Xe]4f8 8 electrons in 7 f-orbitals: 3003 different arrangements!
Free ion energy levels due to:
1. Electrostatic interactions (comparable to 3dn ions)
2. Spin-orbit coupling (larger than for 3dn ions )
3. Crystal field splitting (smaller than for 3dn ions)
Ground state
ml = -3 -2 -1 0 1 2 3

7F
6
4f
1st excited state
ml = -3 -2 -1 0 1 2 3

5D
4f

Slide 51

Typical emission spectrum of Tb3+ (Example: Lu3Al5O12:Tb)
Characteristic luminescence of lanthanides

- Sharp emission lines
- Almost independent of chemical environment,
e. g. green-yellow emission of Tb3+ phosphors
- High quantum yield (> 90%), due to small Stokes shift

Slide 52

Simplified energy level diagram of selected Ln3+ ions
4f75d1
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
Line emitting ions

Pr3+
Nd3+
Sm2+/3+
Eu3+ (Eu2+)
Gd3+
Tb3+
Dy3+
Ho3+
Er3+
Tm3+
Yb3+
Band emitting ions
Ce3+
Pr3+
Nd3+
Eu2+
Yb2+

Slide 53

1.
Electrostatic interactions
Shielding due to inner electrons described by the so-called Slater parameters

(comparable to Racah parameters)
Electrostatic interaction increases with effective charge on

the activator ion (ion charge density)
Therefore splitting between different terms depends on
Oxidation state
Nucleus charge
Charge flow back from ligands (polarizibility of surrounding anions)

Slide 54

2.
Spin-orbit coupling
Spin-orbit coupling constant increases throughout the lanthanide series,

i.e. from (Ce) = 650 cm-1 to (Yb) = 2930 cm-1
Further splitting of LS terms into J-levels by
energy, assuming weak spin-orbit coupling:
Complete term symbol:
2S+1L
J
with |L-S| < J < L+S
For Tb3+
Ground state:
Excited state:

7F
6,5,4,3,2,1,0
5D
4,3,2,1,0

Slide 55

3.
Crystal field splitting
Further splitting of J multiplets into a maximum of 2J+1 levels

Crystal field splitting ~ 100 cm-1 + sensitive function of site symmetry
2,00
1,75
1,50
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
Extra fitting parameters Bkq to graphically fit experimentally observed levels:


Slide 56

In summary: RE ions exhibit a great number of energy levels 2S+1LJ
Ce (Yb)
Pr (Tm)
Nd (Er)
Pm (Ho) Sm (Dy) Eu (Tb)
Gd
SL
17
47
73
119
119
SLJ
13
41
107
198
295
327
SLJM
91
364
1001
2002
3003
3432
Early experimental and theoretical work on LaCl3:Ln3+ and LaF3:Ln3+ by Dieke

and Carnall (experiment) and Judd, Crosswhite and Wybourne (theory):
Dieke diagram and the Blue book

Slide 57

Dieke diagram (1968): Energy levels of trivalent RE ions


Slide 58

Extended Dieke diagram (2005): Energy levels of trivalent RE ions up to the VUV
P.S. Peijzel, A. Meijerink, R.T. Wegh et al, J. Solid State Chem. 178 (2005) 448


Slide 59

Complete energy level diagram
Ce3+
Pr3+
Nd3+
Pm3+
Sm3+
Eu3+
Gd3+
~
~
~
~
~
~
Yb3+
Tm3+
Er3+
Ho3+
Dy3+
Tb3+
Energy level splitting increases

from Ce3+ to Yb3+ due to increasing
nucleus charge


Slide 60

Characteristic optical properties
1) Sharp lines (atomic like), Stokes shift ~ 0 cm-1
2) Little influence of environment on energy level scheme
3) Parity forbidden transitions (~ms life time, f ~10-5)
Origin: Shielding of 4fn electrons
by outer filled 5s and 5p shells
no shift of excited state parabola
and strong zero-phonon lines (ZPL)


Slide 61

Example: Eu3+ - Typical excitation and emission spectra (Y2SiO5:Eu)
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]


Slide 62

Emission spectra and colour points of Eu3+ activated phosphors
7
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]

Slide 63

D 0 - F1
D 0 - F2
D 0 - F3
Intensity
Phosphor
D0 - F 4
CIE(1931) colour point

x
y
(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]
Colour saturation: Y2O2S:Eu > YVO4:Eu > Y2O3:Eu > (Y,Gd)BO3:Eu


Slide 64

4.0x104
4f72p-1
Energy [cm-1]
3.5x104
3.0x104
5D
3
2.5x104
5D
2
5D
1
5D
0
2.0x104
1.5x104
Observed emission spectrum due to

5D 7F transitions (lines)
0
J
a) Inversion symmetry (S6, D3d)
Magnetic dipole transitions, e.g. 5D0 - 7F1
J = 0, 1 (J = 0 J = 0 forbidden)
MeBO3:Eu (Calcite, Vaterite)
~ 8 - 16 ms
1.0x104
0.5x104
7F
6
5
4
32
10
0.0
Eu3+
[Xe]4f6
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
Slide 65

Excitation and emission spectra of Eu3+ and Eu2+ activated phosphors
Y2O3:Eu3+
Band
gap
D0 - FJ
1,0
ChargeTransfer
Emisison Intensity (a.u.)
Emission intensity (a.u.)
1,0
BaMgAl10O17:Eu2+
0,8
Spin- and parity

forbidden transitions
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
Spin- and parity

allowed transitions
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)
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)
Slide 66
7 50

Ce3+
[Xe]4f1
[Xe]5d1
Eu2+
60
2D
J
50
Energy [103 cm-1]
40
30
40
30
6D
9/2
6I
7/2
8H
J
6P
7/2
20
20
10
10
[Xe]4f65d1
60
50
Energy [103 cm-1]
[Xe]4f7
2F
7/2
2F
5/2

8S
7/2

Slide 67

Energy gap between the [Xe]4fn and [Xe]4fn-15d1 states
Electrostatic
interaction
Centroid shift
Crystal field
splitting
Stokes shift
Energy [103 cm-1]
[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:
Centroid energy proportional to the spectroscopic polarizability sp

(3000 20000 cm-1)
Crystal field splitting (< 23000 cm-1)


Slide 68

Centroid shift ~ electron density between activator and ligands
Polarizability of the anions
selenides > sulfides > nitrides > oxides > fluorides
Charge density of the surrounding anions
Type of network former:
oxides
aluminates silicates
borates
O2AlO45SiO44BO33 Degree of networking
neso-silicate soro-silicate
cyclo-silicate
[SiO4]4[Si2O7]6[Si3O9]6garnet
akermanite
benitoite
zircon
thortveitite
olivine
phosphates
PO43-
sulfates
SO42-
phyllo-silicate
[Si4O10]4montmorillonite
talc
kaolinite
Slide 69

Crystal field splitting
Crystal field theory ionic interaction between metal center and point charges
Energy splitting of the d-orbitals depends on:
Anionic charge / anionic radius (spectrochemical series)
I- < Br- < Cl- < S2- < F- < O2- < N3- < C4
Symmetry (coordination number and symmetry)

octahedral > cubic, dodecahedral, square-antiprismatic > tetrahedral
Metal-ligand distance (strong distance dependence)

D = 35Ze/4R5
R = Cation-anion distance
Z = Valence of the anion
e = Electron charge

Slide 70

Covalent character of ionic bonds
Host lattice
YPO4
Cation
Y3+
Type of network former
3O
O-P-O
O
Low charge density

3/4- per oxygen
tetrahedral PO43-
Y3Al5O12
Y3+
5O
O-Al-O
O
9-
O
O-Al-O
O O
High charge density

5/4- or 9/4- per oxygen
tetrahedral AlO45- + octahedral AlO69P5+ attracts more charge density of the O2- anions than Al3+

Slide 71

Electron density on the anions
YPO4
4 x O(1)
7.248
4 x O(2)
7.193
Low charge density on oxygen
Y3Al5O12
4 x O(1)
7.528
4 x O(2)
7.504
High charge density on oxygen
Slide 72

Luminescence of YPO4:Ce
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]
Crystal field splitting ~ 18000 cm-1

Centroid shift ~ 9600 cm-1
(P. Dorenbos, Phys. Rev. B, 64, 2001, 1251)
Large 4f-5d energy gap
Emission bands at 335 and 355 nm
Slide 73

Luminescence of Y3Al5O12:Ce
1,0
Free ion
4f5d
cfs
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]
Crystal field splitting ~ 27000 cm-1

Centroid shift ~ 14700 cm-1
(P. Dorenbos, Phys. Rev. B, 65, 2002, 2351)
Small 4f-5d energy gap
Emission bands at 560 nm
Slide 74

Excitation and emission spectra of Pr3+ activated phosphors
YPO4:Pr
YF3:Pr
1,0
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]
4f15d1-4f2 band emission

4f2-4f2 line emission
4f2-4f2 line emission
The nature of the luminescence spectrum of Pr3+

is strongly determined by the host lattice!

Slide 75
800

Fundamentals of Pr3+ luminescence
[Xe]4f2
Pr3+ ground state configuration

[Xe]4f2 13 SLJ-States
3H
J
60
4f
4f
5d
[Xe]4f2 [Xe]4f2 transitions
[Xe]4f2 [Xe]4f15d1 transitions
1S
40
30
20
10
0
3P
2 3
P1, 1I6
3P
0
1D
2
E = 61580 cm-1
Pr3+ excited state configuration

[Xe]4f15d1
2 SLJ-States
50
5d
Energy [103 cm-1]
[Xe]4f15d1
1G
4
3F 3F4
3
3H 3F2
6
3H
3H
5
4

Slide 76

Fundamentals of Pr3+ luminescence
[Xe]4f2
[Xe]4f15d1 Kh
site
Oh site distorted
Oh site
60
50
Energy [103 cm-1]
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


Slide 77

UV band emission
UV line emission
1S
0
2S+1LJ line emission

YF3:Pr
NaYF4:Pr
SrAl12O19:Pr
LaMgB5O10:Pr
LaB3O6:Pr
213, 236
252, 271
407 nm
1S
0
2S+1LJ lines and 4f15d1 4f2 band emission

240, 250, 271 nm
KY3F10:Pr
Blue emission
1D
2
Red emission
4f15d1 4f2 band emission

218 nm
LiYF4:Pr
232 nm
YPO4:Pr
235 nm
KYF4:Pr
245 nm
YAlO3:Pr
263 nm
YBO3:Pr
273 nm
Lu2Si2O7:Pr
310 nm
Lu3Al5O12:Pr
320 nm + line emission
Y3Al5O12:Pr
1D - 3H
2
J
line emission
Y2O3:Pr
CaTIO3:Pr,Na
615 nm
615 nm
Slide 78
Energy of the lowest crystal field component of [Xe]4f15d1 config.
Emission spectra of Pr3+ phosphors

Luminescence of YF3:Pr
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]
CFS + centroid shift reduces energy

of lowest crystal field component of the
[Xe]4f15d1 configuration by ~ 10000 cm-1
E(4f15d1) > E(1S0)
1S0 2S+1LJ line emission
Slide 79

Luminescence of YPO4:Pr
4f 5d
1,0
H4
3
H5
0,8
0,6
Host
lattice
H6
3
FJ
0,4
0,2
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]

E(4f15d1) < E(1S0)
[Xe]4f15d1 - [Xe]4f2 band emission
Slide 80
500

Luminescence of Y3Al5O12:Pr
1,0
Host lattice
3
1
4f 5d
0,8
P0 - H4
4f 5d - HJ
0,6
0,4
0,2
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]

E(4f15d1) << E(1S0)
UV band emission (320 nm) and visible
line emission (> 450 nm)
Slide 81
700
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

Slide 82
Example: LiGdF4:Eu
Energy level diagram
202 nm
Gd
Gd**
Gd** + Eu CR Eu* + Gd*

Eu*
Eu + h
Gd* + Eu
Eu*
612 nm

ET
Gd + Eu*
Eu + h
QYA = 195%
Slide 83
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%

Slide 84
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+
Implementation of IR radiation into visible

(in frequency multipliers, laser diodes, night vision goggles)

Slide 85
8.15 Afterglow
Cause:
Storage of electrons / holes in certain sites in the lattice

(vacancies, impurities)
Deep traps:
Emptying of the traps is done by activation (LASER)
CB
F+/F(F-)
8.2eV
VB
Example: BaFBr:Eu

F+/F(Br-)
(Eu2+/Eu3+)*
Eu2+/Eu3+
Storage phosphor for imaging plates (detection of x-rays)

(Y. Iwabuchi et al., J. Appl. Phys. 33 (1994) 178)
Slide 86
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)


Slide 87
8.15 Afterglow
Shallow traps: Thermal emptying of the traps at room temperature
CB
Eu2+*
transfer
6.5 eV
VB
Example
SrAl2O4:Eu,Dy
Dy3+ + h+ ~ 0.65 eV
Eu3+
Eu2+
(Nemoto Ltd., JECS 143 (1996) 2670)

Slide 88
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]


Slide 89

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8.

Chapter Luminescence Mechanisms

8.1 Luminescence - Definition

Thus: Luminescence requires localisation of absorbed energy by discrete states!

Chapter Luminescence Mechanisms

8.1 Luminescence - Definition

Examples: Luminescent materials, LEDs, Lasers

Non-thermal radiators emit a radiation spectrum

Incoherent Light Sources

Chapter Luminescence Mechanisms

8.1 Luminescence Materials

Chapter Luminescence Mechanisms

8.1 Luminescence Materials

Large single crystals

Incoherent Light Sources

Molecular imaging, precursors

Chapter Luminescence Mechanisms

8.1 Luminescence Materials

Absorption process related to

Energy transfer often occurs prior to

Chapter Luminescence Mechanisms

8.1 Luminescence Materials

Donor levels (D)

8.1 Luminescence Materials

Emission spectrum of YBO3 upon 160 nm excitation

Emission intensity [a.u.]

Band gap absorption at 170 nm

Exciton luminescence at 260 nm

Incoherent Light Sources

Chapter Luminescence Mechanisms

8.1 Luminescence Materials

YPO4:V,Eu (tetragonal), Eg = 8.2 eV

Donor levels (D)

8.1 Luminescence - Processes

Conduction band (empty metal orbitals)

Chapter Luminescence Mechanisms

8.1 Luminescence - Processes

Incoherent Light Sources

Spectroscopic term 2S+1LJ

8.1 Luminescence - Processes

Spin selection rule

Angular momentum (single electron)

Angular momentum (multi electron)

Laporte selection rule

Incoherent Light Sources

[Xe]4f1 (2F5/2) [Xe]5d1 (2D3/2)

Chapter Luminescence Mechanisms

8.1 Luminescence - Processes

High energy particles

Nature 455 (2008) 1089, blue + UV + x-ray!

Chapter Luminescence Mechanisms

Electrons (Feldman equation: R in [])

For 5.7 keV

For a material with r = 5.0 g/cm3 (Y2O3)

Chapter Luminescence Mechanisms

8.3 Excitation Mechanisms

1. Excitation of highly energetic

Efficiency surprisingly well

8.3 Excitation Mechanisms

Band gap Eg [eV]

Internal quantum efficiency: IQE = r/(r + nr) = act

Chapter Luminescence Mechanisms

8.3 Excitation Mechanisms

IQE = act = kr/(kr + knr) = /0