Supplementary Materials for · 10/24/2016 · Published 28 October 2016, Sci. Adv. 2, e1601428...
Transcript of Supplementary Materials for · 10/24/2016 · Published 28 October 2016, Sci. Adv. 2, e1601428...
advances.sciencemag.org/cgi/content/full/2/10/e1601428/DC1
Supplementary Materials for
Ultrahigh-efficiency solution-processed simplified small-molecule
organic light-emitting diodes using universal host materials
Tae-Hee Han, Mi-Ri Choi, Chan-Woo Jeon, Yun-Hi Kim, Soon-Ki Kwon, Tae-Woo Lee
Published 28 October 2016, Sci. Adv. 2, e1601428 (2016)
DOI: 10.1126/sciadv.1601428
This PDF file includes:
Supplementary Materials and Methods
table S1. Physical properties of 2PTPS, 3PTPS, and 4PTPS.
table S2. Work functions with a function of PFI concentration in GraHIL
compositions measured by UV photoelectron spectroscopy in air (AC2, Riken
Keiki Co. Ltd.).
table S3. Calculated HOMO, LUMO, ET, and dipole moment.
fig. S1. CV spectra of 2PTPS, 3PTPS, and 4PTPS.
fig. S2. UV-vis absorption and photoluminescence of 2PTPS.
fig. S3. UV-vis absorption and photoluminescence of 3PTPS.
fig. S4. UV-vis absorption and photoluminescence of 4PTPS.
fig. S5. Phosphorescence spectra of 2PTPS, 3PTPS, and 4PTPS at 77 K.
fig. S6. Chemical structure of PFI.
fig. S7. X-ray photoelectron spectroscopy molecular depth profiles of the GraHIL.
fig. S8. Angular EL distributions according to viewing angles of solution-
processed OLEDs.
fig. S9. Normalized EL spectra according to viewing angles of solution-processed
OLEDs.
fig. S10. CEs of solution-processed OLEDs.
fig. S11. Photoluminescence of mixed-host EMLs and UV-vis absorption of
phosphorescent dopants.
fig. S12. Photoluminescence of mixed-host EMLs according to concentration of
phosphorescent dopant.
fig. S13. Capacitance versus voltage characteristics of mixed-host EMLs.
fig. S14. Current density versus voltage of OLEDs using TCTA/2PTPS EML
according to phosphorescent dopants.
fig. S15. Schematic illustrations of device structure for solution-processed single-
carrier devices.
fig. S16. Current density versus voltage of single-carrier devices according to
phosphorescent dopants.
fig. S17. Negative differential susceptance versus frequency of EODs.
fig. S18. Calculated electron mobilities of 2PTPS, 3PTPS, 4PTPS, and TPBI.
fig. S19. Density functional theory calculations of 2PTPS, 3PTPS, and 4PTPS.
Supplementary Material
Supplementary Materials and Methods
Synthesis of 2-(tributylstannyl)pyridine: Preparation followed a procedure reported previously [J.
Organomet. Chem. 11, 499-502 (1968)]. Yield: 73% (51.2 g). 1H-NMR (300 MHz, CDCl3) [ppm] δ
8.75(d, 1H), 7.49(t, 1H), 7.42(d, 1H), 7.14(t, 1H), 1.55(m, 12H), 1.13(m, 6H), 0.92(m, 9H).
Synthesis of bis(3-bromophenyl)diphenylsilane: n-Butyllithium (1.6 M in hexane, 58.3 mL,
93.260 mmol) was added to a solution of 1,3-dibromobenzene (20 g, 84.782 mmol) in dehydrated
diethyl ether (200 mL) at -78 °C. The mixture was stirred at room temperature (RT) for 1 h. The
reaction mixture was cooled to -78 °C, then dichlorodiphenylsilane (9.66 g, 38.152 mmol) was added
to the reaction mixture and stirred for 12 h at RT. Finally, water was added to quench the reaction.
The product was extracted with diethyl ether, then dried with MgSO4. The solvent was evaporated,
then the crude product was purified by column chromatography (eluent: n-hexane / methylene
chloride = 10 / 1). Yield: 38.7% (16.20 g). 1H-NMR (300 MHz, CDCl3) [ppm] δ 7.62-7.63(m, 4H),
7.53(t, 2H), 7.36-7.46(m, 12H).
Synthesis of diphenylbis(3-(pyridine-2-yl)phenyl)silane (2PTPS): Bis(3-bromophenyl) diphenylsilane
(2 g, 4.046 mmol) and 2-(tributylstannyl)pyridine (3.43 g, 9.306 mmol) were mixed in 40 mL
dehydrated toluene. The mixture was degassed and tetrakis(triphenylphosphine)palladium (0.23 g,
5 mol%) was added in one portion under an atmosphere of N2. The solution was then heated under
reflux for 72 h under N2. The reaction mixture was cooled and added to a 2-N aqueous solution of
HCl. The resulting mixture was extracted with chloroform, then dried with MgSO4. After the solvent
was evaporated, the crude product was purified by column chromatography (eluent: n-hexane / ethyl
acetate (EA) = 5 / 1). Yield: 86% (1.71 g). 1H-NMR (300 MHz, CDCl3) [ppm] δ 8.68(d, 2H), 8.28 (s,
2H), 8.28(s, 2H), 7.69-7.73(m, 10H), 7.65-7.67(m, 2H), 7.44-7.56(m, 6H), 7.20(m, 2H); 13C-NMR
(300 MHz, CDCl3) δ: 157.5, 149.5, 138.7, 137.1, 136.8, 136.4, 134.7, 134.5, 133.9, 129.7, 128.6,
128.4, 127.9, 122.1, 120.8; HRMS (FAB+)m/z for C34H27N2Si (M+): 491.1899, .0, found 491.1941.
Synthesis of diphenylbis(3-(pyridine-3-yl)phenyl)silane (3PTPS): 3PTPS was obtained using the
Suzuki coupling reaction. Bis(3-bromophenyl)diphenylsilane (2 g, 4.046 mmol) and 3-pyridine
boronic acid (1.14 g, 9.306 mmol) were mixed in tetrahydrofuran (THF); 20 mL of aqueous 2 M
K2CO3 solution was added to the mixture. The mixture was then left under an N2 stream for 15 min.
Tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.5 g, 0.4 mmol) was added and the result
solution was refluxed for 24 h at 110 °C. After reaction was completed, the crude product was
worked up with 2-N HCl aqueous solution. The solvent was evaporated, then the crude product was
purified by column chromatography (eluent: n-hexane / ethyl acetate (EA) = 5 / 1). Yield: 61.4%
(2.44 g). 1H-NMR (300 MHz, CDCl3) [ppm] δ 8.82(s, 2H), 8.57(d, 2H), 7.85-7.80(m, 4H), 7.71-
7.66(m, 8H), 7.57-7.44(m, 8H), 7.33(m, 2H); 13C-NMR (300 MHz, CDCl3) δ: 148.4, 148.3, 137.3,
136.7, 136.4, 136.2, 135.2, 134.9, 134.5, 133.4, 130.0, 128.7, 128.6, 128.1, 123.6; C34H27N2Si (M+):
491.1899, found 491.1942
Synthesis of diphenylbis(3-(pyridine-4-yl)phenyl)silane (4PTPS): 4PTPS was obtained using the
same procedure used to produce 3PTPS. Yield: 36% (1.07 g). 1H-NMR (300 MHz, CDCl3) [ppm] δ
8.63(d, 4H), 7.88(s, 2H), 7.74-7.63(m, 8H), 7.58-7.43(m, 12H); 13C-NMR (300MHz, CDCl3) δ:
150.1, 148.4, 137.7, 137.1, 136.4, 135.2, 134.7, 133.2, 130.1, 128.8, 128.5, 128.2, 121.7; HRMS
(FAB+); C34H27N2Si (M+) : 491.1899, found 491.1942
Thermal properties
The thermal properties of 2PTPS, 3PTPS and 4PTPS were evaluated using thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC) in an N2 atmosphere. Although 2PTPS
and 3PTPS are small molecules, they can form stable amorphous film, which is a basic requirement
for materials to be used as hosts in OLEDs. 4PTPS has symmetric structure and therefore does not
show Tg.
table S1. Physical properties of 2PTPS, 3PTPS, and 4PTPS.
Compound λabs
(nm) λem
(nm) Tg
(ºC) Tm
(ºC) Td
(ºC) HOMO
(eV) ΔE
(eV) LUMO
(eV) ET
(eV)
2PTPS 252 324 175 - 314 -6.47 4.06 -2.41 2.82
3PTPS 250 316 190 - 340 -6.50 4.20 -2.30 2.82
4PTPS 257 355 - 193 348 -6.55 4.28 -2.27 2.90
Electrochemical Properties
To investigate the electrochemical properties and energy levels, cyclic voltammetry (CV)
measurements were performed in a conventional three-electrode configuration in acetonitrile
containing 0.1 M tetrabutylammonium perchlorate (Bu4NClO4) as the supporting electrolyte versus
an Ag/AgCl platinum disk as the working electrode and platinum wire as the counter electrode. All
three new phosphorescent host materials exhibited irreversible p-doping and n-doping processes (fig.
S1). The oxidation (p-doping) started at 2.06 V for 2PTPS, 2.09 V for 3PTPS, and 2.14 Vfor 4PTPS.
The reduction processes (n-doping) started at -2.0 V for 2PTPS, -2.11 V for 3PTPS, and -2.14 V for
4PTPS. The highest ocuppied molecular orbital (HOMO) and lowest unocuppied molecular orbital
(LUMO) levels depend on the electrochemical or redox properties of each individual component in
the system. The HOMO (ionization potential, IP) and LUMO (activation energy EA) values were
calculated using ferrocene (EFOC) as the internal standard (which has a value of -4.8 eV relative to the
vacuum level), and the EFOC was calibrated to be 0.39 V versus the Ag/AgCl electrode. According to
the equation IP = - ([Eonset]ox + 4.41) eV [Synth. Met. 87, 53-59 (1997)], the HOMO energy levels
were estimated, and the band gaps were calculated from the onset energy of optical absorption. The
HOMO levels were -6.47 eV for 2PTPS, -6.50 eV for 3PTPS, and -6.55 eV for 4PTPS. The LUMO
levels calculated from optical onset energy and HOMO level, were -2.41 eV for 2PTPS, -2.30 eV for
3PTPS, and -2.27 eV for 4PTPS.
fig. S1. CV spectra of 2PTPS, 3PTPS, and 4PTPS.
fig. S2. UV-vis absorption and photoluminescence of 2PTPS. UV-vis absorption (red) and
photoluminescence spectra (blue) of 2PTPS in 10-6 M CHCl3 solution at room temperature and the
absorption spectrum of FIrpic (black).
3 2 1 0 -1 -2 -3
Cu
rre
nt (a
.u.)
Potential (V) vs. Ag/AgCl
4-DPPS
3-DPPS
2-DPPS
250 300 350 400 450
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
PL
In
ten
sity (
a.u
.)
Wavelength (nm)
UV
Ab
so
rba
nce
(a
.u.)
fig. S3. UV-vis absorption and photoluminescence of 3PTPS. UV-vis absorption (red) and
photoluminescence spectra (blue) of 3PTPS in 10-6 M CHCl3 solution at room temperature and the
absorption spectrum of FIrpic (black).
fig. S4. UV-vis absorption and photoluminescence of 4PTPS. UV-vis absorption (red) and
photoluminescence spectra (blue) of 4PTPS in 10-6 M CHCl3 solution at room temperature and the
absorption spectrum of FIrpic (black).
Room temperature UV-vis absorption and photoluminescence (PL) spectra of 2PTPS (fig. S2),
3PTPS (fig. S3) and 4PTPS (fig. S4) were measured in CHCl3 solution and displayed with the
absorption spectrum of bis[2-(4,6-difluorophenyl)pyridinato-N,C2] (picolinato)iridium. The
absorption spectra peaks at 251 nm for 2PTPS, 250 nm for 3PTPS and 257 nm for 4PTPS can be
attributed to their π-π* transitions. Upon UV excitation, the fluorescent spectra peaked at 324 mn for
2PTPS, 316 nm for 3PTPS and 355 nm for 4PTPS. The slightly red-shifted absorption and
fluorescence of 4PTPS may be attributed to its higher polarity and thus stronger molecular
interaction, compared to 2PTPS and 3PTPS [Adv. Funct. Mater. 19, 1260-1267 (2009)]. From
absorption edges, the energy band gaps can be estimated to be 4.06 eV for 2PTPS, 4.20 eV for
3PTPS and 4.28 eV for 4PTPS.
250 300 350 400 450
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Wavelength (nm)
PL
In
ten
sity (
a.u
.)
UV
Ab
so
rba
nce
(a
.u.)
250 300 350 400 450
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Wavelength (nm)
PL
In
ten
sity (
a.u
.)
UV
Ab
so
rba
nce
(a
.u.)
Photophysical Properties
Phosphorescence of 2PTPS, 3PTPS and 4PTPS was measured in a CHCl3 matrix at 77 K (fig. S5).
The highest-energy 0-0 phosphorescent emissions located at 2.82 eV for 2PTPS, 2.82 eV for 3PTPS
and 2.90 eV for 4PTPS were used to calculate their triplet energy (ET) gaps.
fig. S5. Phosphorescence spectra of 2PTPS, 3PTPS, and 4PTPS at 77 K.
Hole injection layer
Our HILs are composed of PEDOT:PSS and a perfluorinated ionomers (PFI), tetrafluoroethylene-
perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid copolymer (fig. S6), which develops a gradient
work function (WF) by self-organization (We call “GraHIL”).
C
C
C
C
F
F
F
F
F
F
F
O
C
m n
CF
FF
O
C
C
S
F
F
F
F
O
O
OH
CF3
fig. S6. Chemical structure of PFI.
Because PFI has lower surface energy (~20 mN/m) than PEDOT:PSS, PFI preferentially tends to be
located toward the surface of the HIL film. Because PFI has higher ionization potential energy than
PEDOT:PSS, the concentration gradient of PFI from the bottom to the top through the film generates
a gradient work function in the HIL film [Adv. Funct. Mater. 17, 390 (2007)].
400 420 440 460 480
0.0
0.2
0.4
0.6
0.8
1.0P
L I
nte
nsity (
a.
u.)
Wavelength (nm)
2PTPS
3PTPS
4PTPS
fig. S7. X-ray photoelectron spectroscopy molecular depth profiles of the GraHIL (4).
To determine the surface composition and molecular distribution according to sputter time (i.e., film
depth), X-ray photoelectron spectroscopy (XPS) was used. Deconvoluted S2p peaks for PEDOT
(164.5 eV), sulfonic acid (168.4, 168.9 eV), sulfide (162 eV), and sulfone (166.6 eV) concentrations
and C1s peak at 291.6 eV for the PFI concentration were used [Adv. Funct. Mater. 17, 390 (2007)].
We used the C1s peak at 292 eV to calculate the PFI concentration in the GraHIL. This peak can be
assigned to CF2, which is evidently a component of PFI. In the GraHIL, the measured molecular
concentration of PFI was rich at the surface, but gradually decreased with a depth; this trend is
evidence of a gradient chain morphology in the film. Because the PFI increases the ionization
potential in the composition, the gradient PFI concention implies formation of a gradient work
function in the GraHIL film.
table S2. Work functions with a function of PFI concentration in GraHIL compositions
measured by UV photoelectron spectroscopy in air (AC2, Riken Keiki Co. Ltd.) (31).
Sample code PEDOT/PSS/PFI Work function
(eV) (AC2)
AI4083 1 / 6 / 0 5.20
GraHIL 1 / 6 / 25.4 5.95
0 20 40 60 80
0
10
20
30
40
50
60
70 PEDOT
Sulfonic acid
Sulfone
Sulfide
CF3
Mo
lec
ula
r c
on
ce
ntr
ati
on
(%
)
Sputter time (sec)
External quantum efficiencies
By measuring the spectral radiances according to the viewing angle, we calculated external quantum
efficiencies (EQEs) of solution-processed OLEDs (figs. S8–10).
fig. S8. Angular EL distributions according to viewing angles of solution-processed OLEDs.
Angular EL distributions of (A) orange-red (Bt2Ir(acac)), green (Ir(ppy)3), blue (FIrpic), and white
(FIrpic/Bt2Ir(acac)) OLEDs that use TCTA/2PTPS-host EML, (B) orange-red (Bt2Ir(acac)), and (C)
green (Ir(ppy)3) OLEDs that use TCTA/ 2PTPS-host, TCTA/3PTPS-host, TCTA/4PTPS-host and
TCTA/TPBI-host EMLs.
fig. S9. Normalized EL spectra according to viewing angles of solution-processed OLEDs.
Normalized EL spectra (A) orange-red (Bt2Ir(acac)), (B) green (Ir(ppy)3), (C) blue (FIrpic), and (D)
white (FIrpic/Bt2Ir(acac)) OLEDs that use TCTA/2PTPS-host EML.
0
30
60
90
Lambertian
2PTPS
3PTPS
4PTPS
TPBI
1.0
0.8
0.6
0.4
0.2
0
Inte
nsity (
a.u
.)
0
30
60
90
Lambertian
2PTPS
3PTPS
TPBI
1.0
0.8
0.6
0.4
0.2
0
Inte
nsity (
a.u
.)
0
30
60
90
Lambertian
Bt2Ir(acac)
Ir(ppy)3
FIrpic
FIrpic:Bt2Ir(acac)
1.0
0.8
0.6
0.4
0.2
0
Inte
nsity (
a.u
.)
CBA
400 500 600 7000.0
0.2
0.4
0.6
0.8
1.0
Spectr
al ra
dia
nce (
W/s
r nm
m2)
Wavelength (nm)
0
10
20
30
40
50
60
70
500 600 700 8000.0
0.2
0.4
0.6
0.8
1.0
Spectr
al ra
dia
nce (
W/s
r nm
m2)
Wavelength (nm)
0
10
20
30
40
50
60
70
400 500 600 7000.0
0.2
0.4
0.6
0.8
1.0
Spectr
al ra
dia
nce (
W/s
r nm
m2)
Wavelength (nm)
0
10
20
30
40
50
60
70
400 500 600 7000.0
0.2
0.4
0.6
0.8
1.0
Spectr
al ra
dia
nce (
W/s
r nm
m2)
Wavelength (nm)
0
10
20
30
40
50
60
70
BA
DC
Relatively large variation of EL spectrum in WOLEDs according to viewing angles could originate
from the variation in the cavity effect according to the wavelength of emitted light. Extraction
efficiency of OLEDs increases with wavelength, so more blue light than orange-red light could be
trapped by a glass substrate. Therefore, in WOLEDs in which geometry causes a cavity effect
(GraHIL with low refractive index (n) ~1.4 and ITO with high n ~1.9), the slight difference of
extraction efficiency between blue and orange-red light can cause EL spectral change according to
viewing angles because trapping of short-wavelength light causes edge-emitted light to be relatively
bluish [Appl. Phys. Lett. 92, 033303, (2008)].
fig. S10. CEs of solution-processed OLEDs. Current efficiencies of (A) orange-red (Bt2Ir(acac)),
(B) green (Ir(ppy)3), (C) blue (FIrpic), and (D) white (FIrpic/Bt2Ir(acac)) OLEDs that use TCTA:
2PTPS, TCTA/3PTPS, TCTA/4PTPS, and TCTA/TPBI EML (insets: optical images of solution-
processed OLEDs).
10-3
10-2
10-1
100
101
10-1
100
101
102
2PTPS
3PTPS
4PTPS
TPBICurr
ent effic
iency (
cd/A
)
Current density / mA cm-2
10-3
10-2
10-1
100
101
10-1
100
101
102
2PTPS
3PTPS
4PTPS
TPBICurr
ent effic
iency (
cd/A
)
Current density (mA/cm2)
D
10-3
10-2
10-1
100
101
10-1
100
101
102
2PTPS
3PTPS
TPBICurr
ent effic
iency (
cd/A
)
Current density (mA/cm2)
10-3
10-2
10-1
100
101
10-1
100
101
102
2PTPS
3PTPS
TPBICurr
ent effic
iency (
cd/A
)
Current density (mA/cm2)
BA
C
Exciton generation mechanism
fig. S11. Photoluminescence of mixed-host EMLs and UV-vis absorption of phosphorescent
dopants. Normalized photoluminescence spectra of solution-processed film of (A) TCTA, TPBI,
TCTA:TPBI, (B) TCTA, 2PTPS, TCTA/2PTPS, and (C) Absorption spectra of phosphorescent
dopants, and normalized photoluminescence spectra of solution-processed mixed-host films.
fig. S12. Photoluminescence of mixed-host EMLs according to concentration of phosphorescent
dopant. Normalized photoluminescence spectra of solution-processed film of (A)
TCTA/2PTPS/Bt2Ir(acac), and (B) TCTA/TPBIBt2Ir(acac) according to concentration of
phosphorescent dopant.
fig. S13. Capacitance versus voltage characteristics of mixed-host EMLs. Capacitance versus
voltage characteristics of solution-processed OLEDs that use (A) TCTA/TPBI/Bt2Ir(acac) and (B)
TCTA/2PTPS/Bt2Ir(acac) according to concentration of phosphorescent dopant.
300 350 400 450 500
PL
inte
nsity
(a.u
.)
Ab
so
rptio
n (
a.u
.)
Wavelength (nm)
Bt2Ir(acac)
Ir(ppy)3
FIrpic
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
TCTA:2PTPS
TCTA:TPBI
350 400 450 5000.0
0.2
0.4
0.6
0.8
1.0
1.2
PL
in
ten
sity (
a.u
.)
Wavelength (nm)
PL_TCTA
PL_TPBI
PL_TCTA:TPBI
350 400 450 5000.0
0.2
0.4
0.6
0.8
1.0
1.2
PL
in
ten
sity (
a.u
.)
Wavelength (nm)
PL_TCTA
PL_2PTPS
PL_TCTA:2PTPS
A B C
350 400 450 500 550 600 650 700
0.0
0.2
0.4
0.6
0.8
1.0
Wavelength (nm)
PL
in
ten
sity (
a.u
.)
0%0.1%
0.3%0.5%
1%5%
15%
350 400 450 500 550 600 650 700
0.0
0.2
0.4
0.6
0.8
1.0
Wavelength (nm)
PL inte
nsity (
a.u
.)
0%0.1%
0.3%0.5%
1%5%
15%
A B
0 2 4 6 8 10
0.6
0.8
1.0
1.2
1.4
1.6
No
rma
lize
d c
ap
acita
nce
(C
p/C
0)
Voltage (V)
TCTA:TPBI
0.3%
5%
15%
A B
0 2 4 6 8
0.6
0.8
1.0
1.2
1.4
1.6
No
rma
lize
d c
ap
acita
nce
(C
p/C
0)
Voltage (V)
TCTA:2PTPS
0.3%
1%
5%
15%
0 5 10 155
6
7
8
Vm
ax
Dopant concentration (%)
The TCTA/TPBI mixed host forms exciplexes that recombine in the EML (fig. S11). Light emitted
from exciplexes is absorbed by phosphorescent dopants via energy transfer processes (fig. S12).
Although charge carriers are partially trapped or directly injected into phosphorescent dopants in the
exciplex-forming TCTA/TPBI mixed-host EML, comparison of the capacitance versus voltage
characteristics with those of TCTA/2PTPS (fig. S13A, B) suggests that the dominant exciton
generation and recombination mechanism can be regarded as energy transfer from exciplexes.
In contrast, in the TCTA:2PTPS mixed host that does not form exciplexes, most of the holes are
readily trapped or directly injected into phosphorescent dopants, because TCTA has deeper HOMO
energy level (5.7-5.9 eV) than do phosphorescent dopants such as Ir(ppy)3 and Bt2Ir(acac) (~5.2-5.6
eV) (fig. S11) [J. Appl. Phys. 92, 1598 (2002),.Appl. Phys. Lett. 85, 17, (2004), Appl. Phys. Lett. 106,
123306 (2015)]. The cationic excited state of the dopant formed by hole trapping provides an
electron trap in the EML [Adv. Funct. Mater. 13, 439 (2003)]. Because 2PTPS has much shallower
LUMO energy level (~2.41 eV) than does phosphorescent dopant (e.g., Bt2Ir(acac): ~3.4 eV),
dopants provide deep traps for electrons in the TCTA/2PTPS mixed host, and charge transport is
influenced by slow release of electrons from dopant [IEEE J. Sel. Topics Quantum Electron. 4, 119,
(1998)]. Therefore, in devices that use a TCTA/2PTPS EML, low concentration of phosphorescent
dopants reduces charge-carrier transport and increase accumulated charges (fig. S13B). However,
high concentration of phosphorescent dopants can provide favorable charge carrier hopping sites
between dopants for conduction, thereby leading more efficient charge transfer and direct
recombination in phosphorescent dopants [J. Appl. Phys. 92, 1598 (2002)]. Furthermore, direct
injection from a hole injection layer can improve the charge balance in the EML that has high dopant
concentration. Therefore, the dominant exciton generation mechanism of exciplex-free type
TCTA/2PTPS can be considered to be direct recombination in phosphorescent dopants by charge
trapping on dopants; the direct charge injection and trapping on phosphorescent dopant in
TCTA/2PTPS facilitate balanced charge transport and efficient direct recombination.
When we compare the current densities of the solution-processed orange-red (Bt2Ir(acac)), green
(Ir(ppy)2(acac)), blue (FIrpic), white (Bt2Ir(acac)/FIrpic) OLEDs using TCTA/2PTPS mixed host
used in our manuscript, orange-red and green emitting devices had much higher current densities
than did the blue-emitting device (fig. S14). The white OLED showed slightly higher current density
than the blue OLED; i.e., addition of a small amount of Bt2Ir(acac) (4.5 wt% to FIrpic) increased the
current density of white OLED.
fig. S14. Current density versus voltage of OLEDs using TCTA/2PTPS EML according to
phosphorescent dopants. Current densities of orange-red (Bt2Ir(acac)), green (Ir(ppy)2(acac)), blue
(FIrpic), and White (Bt2Ir(acac)/FIrpic) solution-processed OLEDs that use TCTA/2PTPS host.
0 4 8 12 16
2
4
6
8
10
Curr
ent den
sity (
mA
/cm
2)
Voltage (V)
Bt2Ir(acac)
Ir(ppy)3
FIrpic
Bt2Ir(acac):FIrpic
To investigate influences of dopant materials on charge injection and transport characteristics, we
additionally fabricated hole-only devices (HODs) and electron-only devices (EODs) using solution-
processed EML (~100 nm) that consists of TCTA/2PTPS mixed host with various dopant materials
(fig. S15). To fabricate HODs, the GraHIL was used to facilitate hole injection from indium-tin-
oxide (ITO) anode to the EML, and a 5-nm-thick MoO3 / Al cathode was used to block electron
injection from the cathode (fig. S15A), and a 10-nm-thick branched polyethylenimine (PEI)
interfacial layer was used on top of the ITO anode to block hole injection from the anode, and 1-nm-
thick LiF/ Al cathode and TPBI electron transport layer were used to allow favorable electron
injection and transport into the solution-processed EML from the cathode (fig. S15B). To quantify
the effect of dopant materials on charge injection and transport in OLEDs, each host material was
doped with 15 wt% phosphorescent dopant.
fig. S15. Schematic illustrations of device structure for solution-processed single-carrier
devices. (A) hole-only-devices, and (B) electron-only-devices that use TCTA/2PTPS mixed-host
with various dopant materials.
Both addition of Ir(ppy)3 and Bt2Ir(acac) greatly improved hole current density of HODs compared
with undoped TCTA/2PTPS mixed-host film (fig. S16A). Although FIrpic also showed increased
hole current density compared with that of undoped film, the value was much lower than those with
Ir(ppy)3 or Bt2Ir(acac). Ir(ppy)3 has HOMO energy level of ~5.2 eV and Bt2Ir(acac) has HOMO
energy level of ~5.6 eV [Appl. Phys. Lett. 94, 193305 (2009), Nature Mater.12, 652 (2013)], which
are shallower than those of TCTA (~5.7 eV) [Appl. Phys. Lett. 91, 263503 (2017)] and 2PTPS (~6.47
eV). Therefore, hole injection can be increased by direct charge injection into dopant materials from
HIL; this injection reduces the energy barrier to hole injection into host materials. However, FIrpic
has deeper HOMO energy level of ~5.9 eV [J. Mater. Chem. 17, 1692 (2007)] than do Ir(ppy)3 and
Bt2Ir(acac). Because addition of 15 wt% FIrpic can reduce the hole injection energy barrier between
2PTPS (HOMO: ~6.47 eV) and HIL, hole current density increased as FIrpic concentration increased.
However, the deeper HOMO energy level of FIrpic than that of TCTA hole transporting host did not
yield dramatic increase of hole injection in HODs compared to those with the other dopants.
All the phosphorescent dopant materials also increased electron current density of each EOD because
LUMO energy levels of TCTA (~2.3 eV) and 2PTPS (~2.41 eV) in the EML are both much
shallower than that of the TPBI electron transporting layer (~ 2.7 eV) [Appl. Phys. Lett. 91, 263503
(2007)]. Addition of dopant materials that have deeper LUMO energy level than that of TPBI
reduces the energy barrier for electron injection by directly injecting electrons from the overlying
ETL into the dopants. Relatively lower electron current density of EOD that uses Bt2Ir(acac) doped
EML may be attributed to relatively deep trapping of electrons during electron transport in the EML
A B
compared with the others. In contrast, FIrpic is an electron-transporting emitter [Adv. Mater. 20,
4189 (2008)], and its device showed the highest electron current density.
fig. S16. Current density versus voltage of single-carrier devices according to phosphorescent
dopants. (A) hole-only-devices, and (B) electron-only-devices that use TCTA/2PTPS mixed-host
with various dopant materials.
Doping of phosphorescent emitter molecules in the solution-processed TCTA/2PTPS mixed-host
structured EML increased both hole and electron injection of single-carrier-devices. However, the
difference in electron current densities of devices with different kinds of phosphorescent dopants was
smaller in EODs than in HODs. Therefore, overall current density in blue OLEDs was lowest
because doping of FIrpic showed the poorest hole injection among devices, and white OLED had
slightly increased current density compared with that of the blue OLED due to increased hole
injection by Bt2Ir(acac) addition in the white OLED. Because the capacitance-voltage characteristics
of solution-processed orange-red OLEDs in the manuscript proved that Bt2Ir(acac) doped
TCTA/2PTPS has the best-balanced charge injection and transport, relatively unfavorable hole
injection into the FIrpic-doped TCTA/2PTPS compared with the other devices can disrupt the
balance of charge injection in the EML. In this regard, unbalanced charge injection and transport in
the FIrpic doped EML can decrease the luminous efficiency of the solution-processed blue OLEDs.
Electron mobilities
We performed impedance spectroscopy measurement to determine charge carrier mobility in our
electron-transporting materials. We fabricated electron-only-devices to measure electron mobility
(e) of 2PTPS, 3PTPS, 4PTPS and TPBI: [Al (100 nm)/ electron transporting layer (200 nm)/ TPBI
(10 nm)/ LiF (1 nm)/ Al (100 nm)]. The capacitance of the device changed drastically at ω𝑡𝑡 ~1
where is angular frequency and 𝑡𝑡 is transit time because the current induced by carriers lags
behind AC voltage when ω𝑡𝑡 > 1 [Jpn. J. Appl. Phys. 2014, 53, 02BE02, Phys. Rev. B, 2001, 63,
125328, Eur. Phys. J. Appl. Phys. 2014, 68, 30202]. Therefore, we can determine the charge carrier
mobility of materials by obtaining the frequency at which transit time effect occurs. We measured
frequency dependences of capacitance in EODs under various applied DC bias. Transit time is
observed in the plot of negative differential susceptance (−∆B = C − 𝐶𝑔𝑒𝑜), where Cgeo is
geometrical capacitance according to frequency. The maximum frequency of EODs gradually
increased as applied DC voltage was increased (fig. S17A). Comparison of the negative differential
susceptances of EODs with various electron host materials revealed that the maximum frequency
induced by transit time effect increased in the order TPBI < 4PTPS < 3PTPS < 2PTPS.
BA
0 10 20 300
5
10
15
20
Cu
rren
t d
en
sity (
mA
/cm
2)
Voltage (V)
undoped
Bt2Ir(acac)
Ir(ppy)3
FIrpic
0 5 10 15 20 250.0
0.2
0.4
0.6
0.8
1.0
Curr
ent den
sity (
mA
/cm
2)
Voltage (V)
undoped
Bt2Ir(acac)
Ir(ppy)3
FIrpic
fig. S17. Negative differential susceptance versus frequency of EODs. Negative differential
susceptance versus frequency characteristics of electron-only-devices with (A) TPBI varying DC
applied bias, and (B) 2PTPS, 3PTPS, 4PTPS, and TPBI at 8 V.
By using frequency (fmax) at the maximum magnitude of −∆B, 𝑡𝑡 can be determined as 𝑡𝑡 ≈0.72/𝑓𝑚𝑎𝑥
[Jpn. J. Appl. Phys. 2014, 53, 02BE02, Phys. Rev. B, 2001, 63, 125328, Eur. Phys. J.
Appl. Phys. 2014, 68, 30202]. Therefore, charge carrier mobility in a diode can be calculated as
μ =4
3
𝑑2
𝑡𝑡(𝑉𝑑𝑐−𝑉𝑏𝑖) (S1)
We also calculated e of electron transporting host materials by using eq. S1 and transit time which
were determined in the plot of negative susceptance versus frequency (fig. S17B). Calculated e of
TPBI was ~10-5 cm2/(V∙s), which concurs with that measured by using time-of-flight in a previous
report (fig. S18) [Appl. Phys. Lett. 2006, 88, 064102]. e of 2PTPS according to electric field was ~
10-4 cm2/(V∙s), which is one order of magnitude higher than that of TPBI. e obviously increases in
the order TPBI < 4PTPS < 3PTPS < 2PTPS (fig. S18); this order is identical with those of current
density in solution-processed EODs and OLEDs described in the manuscript.
fig. S18. Calculated electron mobilities of 2PTPS, 3PTPS, 4PTPS, and TPBI.
105
106
10-7
10-6
10-5
10-4
10-3
2PTPS
3PTPS
4PTPS
TPBI
- d
elta
B (
s)
Frequency (Hz)
104
105
106
10-8
10-7
10-6
10-5
- d
elta
B (
s)
Frequency (Hz)
4 V
5 V
6 V
7 V
8 V
9 V
10 V
A B
400 450 500 550 600 650 70010
-6
10-5
10-4
10-3
(
cm
2/(
Vs
))
E1/2
(V/cm)1/2
2PTPS
3PTPS
4PTPS
TPBI
DFT calculation
fig. S19. Density functional theory calculations of 2PTPS, 3PTPS, and 4PTPS.
Density function theory (DFT) calculations were performed using B3LYP 6-311+G(d,p)//B3LYP 6-
31G as a base set, and electron-density distributions of the orbitals of the 2PTPS, 3PTPS, and 4PTPS
as shown in fig. S19. 2PTPS, 3PTPS, and 4PTPS have highly-twisted tetrahedral structure. The
electron density distributions of HOMO and LUMO are both located on pyridine-substituted phenyl
groups. The calculated HOMO levels, band gap, triplet energy and dipole moment increased as the
substituted position of pyridine was changed from the 2 position to the 4 position. Especially, 4PTPS
has drastically increased dipole moment (table S3).
table S3. Calculated HOMO, LUMO, ET, and dipole moment.
HOMO
(eV)
LUMO
(eV)
Et
(eV)
Dipole Moment
(Debye)
2PTPS -8.63 -5.02 3.06 3.30
3PTPS -8.64 -4.84 3.26 3.47
4PTPS -8.96 -4.98 3.35 4.84
HOMO: -8.63 LUMO: -5.02
µ = 3.47 DebyeLUMO: -4.84HOMO: -8.64
µ = 3.30 Debye
HOMO: -8.96 LUMO: -4.98 µ = 4.84 Debye
Si
N
N
Si
N
N
Si
N
N
2PTPS
3PTPS
4PTPS