14:05-
特別講演
分子設計が拓く新しい発光分子ー高効率熱活性化遅延蛍光材料ーの登場
Materials design for highly efficient delayed fluorescence
安達 千波矢 先生
Dr. Chihaya Adachi
Director of Center for Organic Photonics and Electronics Research WPI
Professor, Department of Applied Chemistry and Biochemistry, Kyushu University
講演者プロフィール
安達 千波矢（あだち ちはや）
九州大学 最先端有機光エレクトロニクス研究センター/
九州大学 大学院工学研究院 応用化学部門 教授
1991年 九州大学大学院総合理工学研究科材料 開発工学専攻博士課程修了（工学博士）
1991年 （株）リコー化成品技術研究所研究員
1996年 信州大学繊維学部機能高分子学科助手
1999年 プリンストン大学Center for Photonics and Optoelectronic Materials研究員
2001年 千歳科学技術大学光科学部物質光科学科助教授
2004年 千歳科学技術大学光科学部物質光科学科教授
2002年 科学技術振興機構（JST） 戦略的創造研究振興事業（CREST）研究代表者
2005年 10月より九州大学未来化学創造センター教授
2003年 日本学術振興会第142C委員会（有機光エレクトロニクス）主査
2010年 4月より九州大学応用化学部門 教授（兼任：未来化学創造センター教授）5月より、主幹教授
Reaxys Prize Club Symposium in Japan 2014.3.28
Reaxys Prize Club Symposium in Japan 2014.3.28
Materials design for highly efficient delayed fluorescence
TADF: Thermally Activated Delayed Fluorescence
3/*!/&"07
!"!3!"
.$*!"
*)$"4
%"**"'&
!"&$%
$$*'$"*++
"0"1& $
$2"$=$" !+1" !+
" !"&3
100nm
4
)*!"
-.#")",.%*)
'$ ( $"'-()"
)!#")",.%*)
,!#")",.%*)
"*%'($
%(&%'($
1988
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2001
int 100%!
1965
int=?
"-
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2012
int 100%!
./,"
$" !+%".& %!&"*%
3rd generation organic light emitting diodes based on delayed fluorescence
TADF: Thermally Activated Delayed Fluorescence
: e/h injection, transport and recom. eff.
eff.
ext = iintt p = r PL p
~
~100% 25
5+% ~100% ~20%
25+%
h+
e–
25%
75%
O
Ir
O
N
S1
FLUO
r: exciton production efficiency
efficiency
PL: PL quantum efficiency
efficiency
p: light out-coupling efficiency
efficiency
2
T1
Intersystem
crossing
(ISC)
PHOS
1
Ir(ppy)3
ISC ~100%
phos~100%
Reaxys Prize Club Symposium in Japan 2014.3.28
1987~
2000~
$/')*&
2012~
2012~
!'*(!')*&
3()/')*&
TADF: Thermally Activated
Delayed Fluorescence
H SO
EST
First-order mixing
coefficient between singlet
and triplet states ()
Hso: Spin-orbit coupling
First observation of TADF: SnF2OEP:PVCz
2
Reaxys Prize Club Symposium in Japan 2014.3.28
")*+'*)0,'&6&@64
$/')*& !'*(!')*&
($+
:;G?>>
Emission intensity
400
&@
+)'& )
"&+&*"+33
!,& 300
200
:;GA>
100
:;G>
0
500
600
700
Wavelength (nm)
Thermally activated delayed fluorescence from Sn4+-porphyrin complexes and their application to organic light emitting diodes
- a novel mechanism for electroluminescence
Adv. Mater., 21, 4802-4906 (2009)
Ayataka Endo, Chihaya Adachi et al.
)&*"&+'@1+F9&@64
GB>>
T=300K
0
4
Time (ms)
6
8
550
500
550
600 650 700 750
Wavelength (nm)
RISC
S1
ISC
Time (ms)
2
600
650
700
Wavelength (nm)
750
GC
800
F91;=
T1
Flu. TADF
500
S0
3
550
600 650 700 750
Wavelength (nm)
800
Time (ms)
)'%(+
$/'7
$/')*& !'*(!')*&
Reaxys Prize Club Symposium in Japan 2014.3.28
%()+/)(&&'"&&@64
RISC
S1
$$
'%('&&+
F91;=
ISC
T1
2.5
Flu. TADF
2.0
S0
1.5
PL quantum efficiency (%)
3.0
1.0
$/')*&
0.5
0.0
!'*(!')*&
0
50
100
150
200
250
300
350
400
40
00
Temperature
(K)
6
898&@648 )'%(+
$/'7
)&*"&++GB>>
Oscilloscope
5
trigger
Pulse generator
10
550
Streak
scope
"&3
Resistor
(R=100 ohm)
/$*1"+!C>>&*
600 650 700 750
Wavelength
(nm)
<>7?F+&>7AF+GB>>
A. Endo and C. Adachi, Adv. Mater., 21, 4802-4906 (2009)
4
Time (ms)
0
Reaxys Prize Club Symposium in Japan 2014.3.28
(9'&0)*"'&'+)"($+2"+'&*"&+'*"& $+*++
'0$%'$/$)*" &')!" !/('&0)*"'&"&3
N
N
N
N
N
N
N
N
N
N
N
N
Appl. Phys. Lett.,
98, 083302 (2011)
Phys. Rev. Lett.
110, 247401 (2013)
Appl. Phys. Lett.,
101, 093306, (2012)
*" &)/$')*%$$EST
EH :HOMO Energy
EL : LUMO Energy
K :Exchange Energy
F324E
F3242
K = L (1)U (2)
(HOMO)
1
L (2)U (1)d 1d 2
r12
(LUMO)
(HOMO)
) EST
%$$EST
Donor
Molecular
Design
μ2
EST=2K
X
Acceptor
Donor-Acceptor backbone
X:Introduction of steric hindrance
Rather high radiative decay rate
μ=
(1)
L
U
(2)r 12L (2)U (1)d 1d 2
5
(LUMO)
Reaxys Prize Club Symposium in Japan 2014.3.28
Advanced Molecular Structure for TADF
S. Y. Lee, et al., Appl. Phys. Lett., 101, 093306, (2012)
Calculated by Gaussian 03 at the B3LYP/6-31G (d, p)
N
N
N
N
N
N
N
HOMO = 5.29 eV
CC2TA
LUMO = 2.03 eV
ES-T = 0.06 eV
L Large distortion between electrondonating and accepting units
L Small overlap between HOMO and LUMO
Strong electron-donating (bicarbazole)
Transient Photoluminescence
TADF confirmation
0
N
2
N
4
6
CC2TA
N
N
N
Time (μs)
0-200 ns
200 ns-10 μs
TADF
N
N
8
10
400
450
500
550
600
Wavelength (nm)
Temperature dependence of TADF
0
Intensity (a. u.)
10
5K
50 K
100 K
150 K
200 K
250 K
300 K
325 K
-1
10
-2
10
Fluorescence
Luminescence lifetime (by Streak camera)
-3
10
0
2
4
6
8
10
Time (μs)
6
Reaxys Prize Club Symposium in Japan 2014.3.28
OLED with TADF
Al 80 nm
LiF 0.8 nm
Al 80 nm
LiF 0.8 nm
Al 80 nm
LiF 0.8 nm
6 wt% CC2TA:DPEPO 20 nm
TPBi 30 nm
DPEPO 10 nm
6 wt% CC2TA:DPEPO 20 nm
TPBi 30 nm
DPEPO 10 nm
6 wt% CC2TA:DPEPO 20 nm
m-CP 10 nm
m-CP 10 nm
6 wt% CC2TA : m-CP 10 nm
-NPD 40 nm
-NPD 40 nm
-NPD 40 nm
ITO/Glass
ITO/Glass
O/G
ITO/Glass
DPEPO 40 nm
Device 1
Device 2
Device 3
L J-V characteristics
L EQE-J
External quantum efficiency (%)
Current density (mA/cm2)
30
Driving Voltage = 9.2 V
25
20
15
10
5
0
0
5
10
15
20
EQE > 12±1%
1
10
0
10
-1
10
-3
10
Voltage (V)
-2
10
-1
10
0
10
1
2
10
10
2
Current density (mA/cm )
)3!" !"&3
7
3
10
Reaxys Prize Club Symposium in Japan 2014.3.28
$""# 1
Al LiF
4CzIPN
4CzTPN-Ph
2CzPN
TPBi
-1
10
6wt% 4CzTPN/CBP
-NPD
0
10
2CzPN
4CzIPN
4CzPN
4CzTPN
4CzTPN-Me
4CzTPN-Ph
Normalized PL intensity
10
External EL quantum efficiency (%)
ITO/Glass
-2
10
-3
-2
10
10
-1
0
1
2
10
10
10
2
Current density (mA/cm )
400
10
500
600
Wavelength (nm)
700
HOMO
LUMO
5A>D
DFT (M06-2X/6-31G(d))
% 1)*")2")"!",%0.%0"-
Prompt
Delayed
-1
10
-2
10
-3
10
10
20
30
Time (μs)
40
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
400
0
500
600
Wavelength (nm)
50
100 150 200 250
Temperature (K)
14.2
EST = 83 meV
14.0
13.8
13.6
13.4
13.2
ln(kRISC)
0
Total
Prompt
Delayed
0.9
efficiency
PL quantum
Normalized PL intensity
1
1.0
T = 300 K
0
10
Normalized PL intensity
T = 300K
T = 200K
T = 100K
13.0
12.8
HOMO
LUMO
DFT (M06-2X/6-31G(d))
12.6
12.4
3.5
4.0
-3
4.5
-1
10 /T (K )
8
5.0
300
Reaxys Prize Club Symposium in Japan 2014.3.28
E0-0(3LE): 2CzPN>4CzTPN,4CzIPN>4CzPN
2CzPN
4CzPN
4CzIPN
4CzTPN
2.94 eV
1CT
3CT
2.63 eV
2.60 eV
3LE
2.53 eV
2.63 eV
2.43 eV
2.53 eV
2.45 eV
2.34 eV
Lifetime in toluene
166 μs
14 μs
5 μs
2 μs
The energy difference between 1CT and 3CT are almost the same in these four compounds.
CT molecules can emit efficient and short-lifetime (a few μs) TADF, satisfying the
requirements of a small energy gap between 1CT and 3CT states and higher energy of
the 3LE state than the 3CT one.
"Promising operational stability of high-efficiency organic light-emitting diodes based on thermally
activated delayed fluorescence” Scientific Reports, 3, 2127 (2013))
H. Nakanotani, K. Masui, J. Nishide, T. Shibata and C. Adachi
a
a
EOD
2.4
3.0
2.1
ITO 5.5
HAT
-CN
TrisPCz
5.6
2.4
mCBP
3.0
3.4
4CzIPN T2T
5.8
2.7
LiF/Al
ITO
BPyTP2
T2T
[30]
mCBP
[30]
3.4
T2T
4CzIPN [10]
5.8
6.0
6.5
5.7
6.0
3.0
2.7
LiF/Al
BPyTP2
[80]
5.7
6.5
6.5
-9.5
b
HOD
c
ITO 5.5
HAT
-CN
[10]
2.1
TrisPCz
[30]
5.6
2.4
mCBP
[30]
3.4
4CzIPN
5.8
2.1
TrisPCz
[50]
Au
5.6
6.0
-9.5
Projected half lifetime ~3000hr
9
Reaxys Prize Club Symposium in Japan 2014.3.28
/)$/%"**"'&)'%
J Am. Chem. Soc., 134, 14706 - 14709, 2012
EL
ITO/-NPD/TCTA/CzSi/10wt% emitter: DPEPO/TPBI/LiF/Al
Pure blue
CIE(0.14, 0.08)
tBuCz-PS
TADF only occurs in a bipolar system where donor and
acceptor centered 3* states are close to or higher than the
triplet intramolecular charge transfer (3CT) state, control of the
-conjugation length of both donor and acceptor is considered
to be as important as breaking the -conjugation between
them in blue TADF material design.
'#%"# "!
&
EQE20%
10
PLQY
0.70
0.80
10 μs
1 ms
Reaxys Prize Club Symposium in Japan 2014.3.28
'**""$"+3'))
Advanced Materials (in press)
EQE 17.5 ± 1.5%, EL~610nm
CIE (0.60, 0.40)
J. Li, T. Nakagawa, J. MacDonald, Q. Zhang, H. Nomura, H. Miyazaki, and
C. Adachi (Kyushu Univ. & CSIRO)
&$"%"+'$/$)+)/+/)*'
a))
CZ-PS
EST0.32eV
max419nm
EQE9.9%
J. Am. Chem. Soc.,
134, 14706 (2012)
4CzPN
EST0.12.eV
max531nm
EQE 18%
EST0.10eV
max485nm
EQE10%
Spiro-CN
EST0.025eV
max495nm
EQE16.5%
Spiro-CN
EST0.06eV
max540nm
EQE4.4%
Angew. Chem.
2012, 51, 11311
Chem. Comm.
(in preparation)
Chem. Com.,
48, 9580 (2012)
4CzIPN
EST0.01.eV
max513nm
EQE:19%
4CzTPN
EST0.06.eV
max544nm
EQE17%
Nature, 492, 234 (2012)
(2012)
PIC-TRZ
EST0.1eV
max466nm
EQE5.3%
Appl. Phys. Lett.,
98, 83302 (2011)
PIC-TRZ 2
EST0.01eV
max505nm
EQE14%
Phys. Rev. Lett.
(in press)
CC2TA
EST0.07eV
max493nm
EQE11%
PXZ-TRZ
EST0.0084.eV
max522nm
EQE15.5%
Appl. Phys. Lett.,
101, 93306 (2012)
Chem. Com.,
48, 11392 (2012)
EST0.24eV
max570nm
EQE0.01%
SnF2(OEP)
Adv. Mater.,
21, 4802 (2009)
11
Melem
HAP-3TPA
EST0.17.eV
max610nm
EQE17.5%
Adv. Mat., (online)
Reaxys Prize Club Symposium in Japan 2014.3.28
1'/+')"($+)0*,& ')" !9"&3
$/')*&**
A new route to harvest triplets for fluorescence OLED Intramolecular CT
./,"
Fluorescence based OLED
Long lifetimes of operational stabil
High color purity
Flexibility of material design
Theoretical limitation of r
25% - 62.5% (by using TTA proc
Intermolecular Exciplex
./,"$*.*
TADF as a host
&)*.)%".'/(%.."!
$/')*&1"+!!'*+
'& $",%*''(),'&$*+"$"+3
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!'),$$"%"+,'&')9?>>F
12
Reaxys Prize Club Symposium in Japan 2014.3.28
TADF molecules as a host for singlet exciton generation function Carrier
recombinatio
n
A new route
Conventional route
Förster
energy transfer
h+ e-
25%
h+ e-
75%
25%
75%
FRET
RISC
S1
2.30 eV ISC
S1
2.38 eV
S1
2.18 eV
T1
2.23 eV
T1
2.03 eV
Up-conversion
of triplet
excitons
T1
1.14 eV
N
O
N
O
N
N
Al
O
N
N
PXZ-TRZ
TBRb
N
O
Alq3
%+)"$')!'*+%'$/$*
High reverse intersystem crossing
efficiency (RISC) 41%
High photoluminescence quantum
efficiency in neat film. 45%
PXZ-TRZ
H. Tanaka et. al., Chem. Comm. 2012, 48,
11392. Delayed component
PXZ-TRZ neat film
)1
/#,3$#43D4 .&'%3D4 ."-3D4 .63D4
>=?
=>
;@
13
:;
=:
03*(4
:1<
Reaxys Prize Club Symposium in Japan 2014.3.28
Emission and absorption spectrum
N
O
Al
O
N
R0 6.5nm
N
O
R0 5.9nm
TBRb
Alq3
emission
TBRb Abs.
PXZTRZ
emission
Photoluminescence spectra of co-deposited films
N
N
PL = 80%
TBRb
14
O
Al
O
N
O
PL = 80%
Reaxys Prize Club Symposium in Japan 2014.3.28
Transient PL characteristics of co-deposited films
Delayed Fluorescence
Host
18ns Guest
~ 0.84 μs Clear delayed component was observed,
indicating efficient upconversion of triplet exciton
into singlet state and successive Forster energy
transfer from host to guest.
/))&+"&39/%"&&
N
O
N
15
O
Al
O
N
Reaxys Prize Club Symposium in Japan 2014.3.28
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' )
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")",.%*)
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$*-+$*,"- ") "
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Promising for RGB emission with 100%
electron into photon conversion with
conventional aromatic molecules
%,-.
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Reaxys Prize Club Symposium in Japan 2014.3.28
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