electrophosphorescence for solid - state lighting...χ fraction of usable excitons η r...
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Electrophosphorescence for Solid-State Lighting
Mark Thompson
Department of ChemistryUniversity of Southern California
Hole/electron recombination gives singlet and triplet excitons
Dopant
Emission
Dopant traps exciton and
emits
+
hole electron
or
singlet
tripletExperimentally determined singlet fraction for Alq3 based OLEDs = 22±3%
M.A. Baldo, et.al., Phys. Rev. B (1999)
• Expected singlet fraction = 25%
• Phosphorescence is a forbidden process, luminescent lifetimes typically min. - hours
• Luminescence lifetime must be comparable to OLED RC time constant, ca. 1 µsec
cathode
Organometallic Ir complexes in OLEDs
NIr
NIrF
S NIr
3
2
2
NIr
2
F
O
O
O
O
O
O
N
N
N
NB
pz
pzS
NIr
2
• Efficient phosphorescence with τ = 1-3 µs• Optimized OLEDs give external efficiency = 15-25% ⇒ Internal eff = 70-100%
Phosphorescenceefficiency of Ir emittersis ∼100%
0.0 0.2 0.4 0.6 0.8
0.0
0.2
0.4
0.6
0.8
y
x
Φph photoluminescent quantum efficiencies
χ Fraction of usable excitonsηr recombination efficiency (hole + electron ⇒ exciton)ηe emission coupling efficiency out of device
• Many Ir based emitters give Φph = 1
• Spin orbit coupling mixes singlet and triplet, χ = 1• Good devices can have ηr → 1
Phosphorescent OLED Efficiency
erPLEL ηχηΦ=Φ
Color Mixing to Achieve White Emission
• Color mixing with different colored OLEDs will give white light
400 500 600 7000.0
0.2
0.4
0.6
0.8
1.0
1.2 human eye RGB OLED
Inte
nsity
Wavelength (nm)
0.0 0.2 0.4 0.6 0.8
0.0
0.2
0.4
0.6
0.8
y
x
WOLED efficiencies from academic labs
From J. Ye, et. al., Adv. Mat., (2012), 24, 3410
Kido, Firpic/PQIr, all ph 2008
Kido, Ir-carbene, 3 ph 2010
Hybrid two color, blue fl dopant is the host for ph dopant (0.1%)
Konica Minolta WOLED (15 cm2)
Warm White Device Cool White Device
Device 1
Device 2CGL
K. Kato, T. Iwasaki and T. Tsujimura, J. Photopolym. Sci. Technol., 2015, 28, 335–340
• All phosphorescent• Tandem structure• Internal & external
extraction structures
OLEDWorks Bright-2
Cost: $62 for 145 cm2
J. Spindler et al. “24-2: Invited Paper: High Brightness OLED Lighting”, SID INT SYMP DIG TEC, 47 (2016)
https://www.oledworks.com/products/brite-2/
Light extraction to enhance outcoupling and stacking in increase lm/W.
Fluorescent/Phosphorescent (fl/ph) WOLED
• Singlet and triplet excitons are harvested independently:– Higher energy singlet excitons for blue emission– Remainder of lower-energy triplet excitons for green and red emission
Minimizes exchange energy losses Potential for 100% IQE
Stable color balance Enhanced stability
Comparatively simple architecture
S
S
T
HOSTExcitonformationzone
RED and GREEN
phosphorescent dopants
T
S
T
χs = 0.25
χt = 0.75
BLUEfluorescentdopant
Förster transfer
Diffusive transfer
T
Ener
gy
Total External Efficiencies
TOTAL light efficiencies at 500 cd/m2
• External Quantum Efficiency: (18.4 ±0.5)%
• Power Efficiency: (23.8 ±0.5) lm/W
• CIE = (0.40, 0.41), CRI = 85, CCT = 3750K
Y. Sun, et. al., Nature (2006)
BCzVBi:CBP
BCzVBi:CBP
ITO/Glass
NPD
BCP
LiF/Al
CBP
CBP
PQIr:CBP
Ir(ppy)3:CBP
BPhen 20nm/BPhen:Li
Singletfilter
Tripletemitter
400 500 600 700 800-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Wavelength (nm)
Norm
. EL
100mA/cm2
10mA/cm2
1mA/cm2
S
S
T
HOSTRED and GREEN
ph-dopants
T
S
T
χs = 0.25
χt = 0.75
BLUEfl-dopant
Förster transfer
Diffusive transfer
TE
nerg
y
BCzVBi
NN
Leo Device (1): Hybrid fl/ph WOLED• K. Leo, 2007, 2009: introduced neat 4P-NPD layer as
blue emitter, recombination at a single interface
N
N
4P-NPDΦPL(film) = 92% • Conductivity doped layers
• 45 lm/W at 1000 cd/m2
• CIE = (0.45, 0.43)
Hybrid fl/ph WOLED developments (cont.)
• B.-Q. Liu, et. al., Light: Sci. App. 2016 5, e16137• Simple structure
– Dual NPD/Be(Oppy)2 fl emitters– Ph dopant excited by carrier and triplet trapping
• 65 lm/W at 1000 cd/m2, CIE = (0.45, 0.49), CRI = 47– Problems: two color limits CRI, toxicity of Be, short lifetime of
NPD emitters, carrier trapping leads to color shift with intensity
erPLEL ηχηΦ=Φ
ΦEL limited by ηe
Phosphorescent OLED Efficiency
Emitter
Pulling out substrate and waveguiding modes:
D
A
Transition Dipole Moment (Vector) Dictates Direction of Light Emission
Maximum emission probability ⊥TDV
Maximum emission probability ⊥TDV
Zero emission probability ‖ TDV
Zero emission probability ‖ TDV
αSome emission probability
Emission probability ∝ sin2 𝛼𝛼
Emitter
Vertical Isotropic Horizontal
Light Outcoupling in OLEDs
B. Scholz et al., Opt. Exp. 2012, 20, A205
Only ~20% of light directly emitted for isotropically distributed dopant.
Orientation Measurement
J. Frischeisen, et. al., Org. Electron. 2011, 12, 1663
Θ = 0.6/2.6 = 0.24Θ = 1.0/3.0 = 0.33
Anisotropy factor:
Θ𝑣𝑣𝑣𝑣𝑣𝑣 =𝑝𝑝𝑧𝑧
𝑝𝑝𝑥𝑥 + 𝑝𝑝𝑦𝑦 + 𝑝𝑝𝑧𝑧=
𝑝𝑝⊥𝑝𝑝|| + 𝑝𝑝⊥
Orientation and EQE
S.-Y. Kim et al., Adv. Funct. Mater. 2013, 23 3896
Θ = 1 0.33 0Strong plasmon Weak plasmon coupling (loss) coupling
0.4 0.3 0.2 0.1 0.0
in CBP, Θ ≈ 0.05, ηEXT = 33%C. Adachi, et. al, APL, 2016
• Linear molecules– TDV along the long axis
of the molecule– Physical interactions
align dopant at the growing host surface
OLEDEQE (%)
Ir based emitters in amorphous host matrix
Emitter Host Orientation (θver)Ir(dhfpy)2(acac) NPD 0.25Ir(ppy)2(acac) CBP 0.23
TCTA/ B3PYMPM 0.24Ir(ppy)2(tmd) TCTA/ B3PYMPM 0.22Ir(MDQ)2(acac) NPD 0.24
NPD/ B3PYMPM 0.20Ir(bt)2(acac) BPhen 0.22Ir(chpy)3 NPD 0.23Ir(mphq)2(acac) NPD/ B3PYMPM 0.23Ir(phq)3 NPD/ B3PYMPM 0.30Ir(piq)3 NPD 0.22Ir(bppo)2(acac) CBP 0.22Ir(ppy)3 CBP 0.33
Graf, A. et al., J. Mater. Chem. C, 2014, 2, 10298-10304
NIr
3
Ir(ppy)3
acac tmd
O O O O
Dopant molecules present at 5-10% in an isotropic host matrix
All (C^N)2Ir(acac) give θver = 0.20-0.25
NIr
2
O
O
Ir(ppy)2(acac)
NIr
3
Ir(piq)3
NIr
3
Ir(chpy)3
Mechanisms for dopant alignment in isotropic host
• Irregular/”spherical” molecules, i.e. Ir based phosphors– Molecules are closer to spherical than linear– Vacuum/Organic boundary induces molecular orientation– Only isotropic host-dopant is observed for solution cast films– Chemical anisotropy within the molecule can drive alignment
M.J. Jurow, et al., Nat. Mater., 2015
HC N
HCIr
O
O
2
+ HOST
Vapor Deposition of
We are not measuring molecular orientation, but the orientation of the TDV. Fortunately we can get TDV from modeling.
N Ir N
OO
Ideal Orientations
• (ppy)2Ir(acac) and fac-Ir(ppy)3 emit from “Ir-ppy”– TDV should be in the Ir-ppy plane, but where?– Orientation of the transition dipole moment vectors (TDV)
measured in (ppy)Re(CO)4: Re-N-TDV = 18.5° *
* Vanhelmont, F. W. M., et. al, J. Phys. Chem. A, 1997, 101, 2946-2952
δ = 18°N
CRe(CO)4
N NN Ir
C3
fac-(C^N)3IrIf aligned θ whould
be near 0
(C^N)2Ir(L^X)θ is what we expect
C2
N Ir N
OO
High efficiency due to orientation?
NNIr
3
• Sky-blue emitter with high PLQY (Φ=0.61)
• Reported in OLEDs to have EQE’s above 30%
• Molecular frame is more planar and oblate than Ir(ppy)3 and thus might vapor deposit in a way conducive to alignment
• Candidate for molecular orientation
Kido, Adv. Mater. 2014, 26, 5062-5066
fac-Ir(mi)3
3D Representation of Ir(mi)3
• Deviation from spherical shape• Intoduction of a geometric
asymmetry from Ir(ppy)3
Ir(ppy)3Ir(mi)3
Top View – looking down the C3 axis
Side View
400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
mCP : Ir(pim)3 (10wt%)
0 10 20 30 40 50 60 70 80 900.0
0.5
1.0
1.5
2.0
Nor
mal
ized
Inte
nsity
Detector Angle [Degree]
Isotropic (θhor= 33.3%) Horizontal (θhor= 0%) Fit (θhor= 26.7 1.1%) mCP : Ir(pim)3 (10wt%)
Ir(mi)3 Angle Dependent PL
Layer Anisotropyfactor Orientation
TCTA : Ir(pim)3 26 ± 3 Horizontal
TCTA: 26DCzPPy :
Ir(pim)3
25 ± 3 Horizontal
mCP : Ir(pim)3 27 ± 1 Horizontal
• Orientation is matrix independent• High EL efficiency is tied to aligned
emitters• Can we get better discrimination by
substitution?
NNIr
3
NNIr
3
NNIr
3
FFF
Diversifying Ir(pim)3 to Study Alignment
Ir(pi)3
Ir(mip)3Ir(miF)3
• Increase geometric asymmetry to more oblate
• Introduce functional group to enhance chemical asymmetry
Structure of fac-Ir(miX)3Si
de V
iew
Top
View
Ir(miF)3 Ir(mi)3 Ir(mip)3
What the orientation of the transition dipole moment?
Transition Dipole Vector (TDV) Calculations
Angle of TDV determined using ZORA calculations• Developed by Van Lenthe, Baerends, and Snijders*• Zero Order Regular Approximation (ZORA)• Implemented in Schrödinger Inc., Materials Suite
NNIr
3
fac-Ir(pi)3
33° off of Ir-N bond 33° off of Ir-N bond
NNIr
3
fac-Ir(pip)3
NNIr
F FF 3
fac-Ir(piF)3
38° off of Ir-N bond
* E. Van Lenthe; E.J. Baerends and J.G. Snijders, J. Chem. Phys., 1993, 1994, 1996
These angles put the TDV for pi and pip cpds. at 85° to the C3 axis!!
Photophysical data mi family
400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
PL
Inte
nsity
(a.u
.)
Wavelength (nm)
Ir(pim)3 Ir(pimF)3 Ir(pimp)3
λem (nm) PLQY τ (μs) CIE θverIr(mi)3 470 .91 2.04 (0.20, 0.41) 0.26Ir(miF)3 484 .99 2.47 (0.19, 0.49) 0.22Ir(mip)3 472 .98 1.61 (0.16, 0.35) 0.15
Ir(pimp)3 shows substantial alignmentWith TDV 33° off of the Ir-N bond this is perfect alignment of C3 ⊥ to surface
0 10 20 30 40 50 60 70 80 900.0
0.5
1.0
1.5
2.0
Nor
mal
ized
Inte
nsity
Detector Angle [Degree]
TCTA:Irpimp3 (10 vol.%) Fit (θhor=0.150.04) θhor= 0.33 θhor= 0.00
Ir(mi)3 Ir(miF)3 Ir(mip)3
OLED Device Results
• Peak EQE
– Ir(mip)3 30.5%– Ir(mi)3 26.4%– Ir(mif)3 25.5%– Ir(ppy)3 22.3%
400 450 500 550 600 650 7000.0
0.2
0.4
0.6
0.8
1.0
1.2
Nor
mal
ized
Spe
ctru
m
Wavelength [nm]
Ir(mi)3
Ir(miF)3
Ir(mip)3
0 3 6 9 12 1510-7
10-6
10-5
10-4
10-3
10-2
10-1
100
101
102
103
mip mi miF Irppy
J OLE
D [m
A/c
m2 ]
VOLED [V]1E-3 0.01 0.1 1 10 1000
5
10
15
20
25
30
35
mip mi miF Irppy
EQE
[%]
JOLED [mA/cm2]
Strong correlation between orientation and EQE!!!!
Summary
• Multiple solutions for white OLEDs• Alignment can be used to enhance external efficiency for
all of them, fluorescent or phosphorescent
BCzVBi:CBP
BCzVBi:CBP
ITO/Glass
NPD
BCP
LiF/Al
CBP
CBP
PQIr:CBP
Ir(ppy)3:CBP
BPhen 20nm/BPhen:Li
Singletfilter
Tripletemitter
All phosphorHybrid flour. + phos.
Acknowledgements
• Mark Thompson, John Facendola, Daniel SylvinsonDepartment of Chemistry, University of Southern California
• Wolfgang Brütting, Tobias Schmidt, Thomas LampeInstitute of Physics, University of Augsburg
• Stephen Forrest, Jongchan KimDepartments of Physics and Electrical Engineering, Univ. Michigan
Bavaria California Technology Center
Universal DisplayCorporation
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