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IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS
Organic Photovoltaic Devices Using an Amorphous
Molecular Material With High Hole Drift Mobility,
Tris[4-(2-Thienyl)Phenyl]Amine
Hiroshi Kageyama, Hitoshi Ohishi, Masatake Tanaka, Yutaka Ohmori, Fellow, IEEE, and Yasuhiko Shirota
Abstract—A planar p-n heterojunction organic photovoltaic
(OPV) device using an amorphous molecular material with a high
hole drift mobility of 1.1 × 10−2 cm2 /V·s at an electric field of
1.0 × 105 V/cm at 293 K, tris[4-(2-thienyl)phenyl]amine (TTPA),
as an electron donor, and C6 0 , as an electron acceptor, indium-tin-
oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(4-
styrene sulfonate) (PEDOT:PSS) (ca.30 nm)/TTPA (30 nm)/C6 0
(40 nm)/LiF (0.1 nm)/Al (150 nm), exhibited high performance with
a fill factor of 0.62 and a power conversion efficiency (PCE) of 1.5%
under air-mass 1.5G illumination at an intensity of 100 mW/cm2 .
A p-i-n-type OPV device having a mixed interlayer of TTPA and
C6 0 , ITO/PEDOT (ca.30 nm)/TTPA (27 nm)/TTPA:C6 0 (1:4 mo-
lar ratio, 20 nm)/C6 0 (23 nm)/LiF (0.1 nm)/Al (100 nm), exhibited
higher performance with a PCE of 1.8% under the same irradi-
ation conditions. A bulk p-n heterojunction OPV devices fabri-
cated by spin coating from solution of TTPA and [6,6]-phenyl-
C6 1 -butyric acid methyl ester ([6,6]-PCBM), ITO/PEDOT:PSS
(ca. 30 nm)/TTPA:[6,6]-PCBM (1:4 molar ratio, ca. 73 nm)/LiF
(0.1 nm)/Al (100 nm), exhibited a PCE of 1.3%. The high perfor-
mance of the present devices is attributed to the high charge-carrier
mobilities of the materials and the relatively high ionization poten-
tial of TTPA.
Index Terms—Amorphous molecular material, bulk p-n het-
erojunction device, charge transport, organic photovoltaic (OPV)
device, p-i-n-type device, planar p-n heterojunction device,
tris(oligoarylenyl)amine.
I. INTRODUCTION
RGANIC photovoltaic (OPV) devices have been receiv-
O ing a great deal of attention as candidates for next-
generation solar cells and photodetectors due to their poten-
tially low cost, light weight, and the capability of large-area,
thin-film devices [1]–[4]. Since it was reported that an OPV de-
vice using copper phthalocyanine (CuPc) as an electron donor
and a perylene pigment as an electron acceptor exhibited a
power conversion efficiency (PCE) of ∼1% under simulated
sunlight irradiation [1], conversion efficiencies of OPV devices
have recently been significantly improved up to several per-
Manuscript received November 11, 2009; revised December 21, 2009.
H. Kageyama, H. Ohishi, and M. Tanaka are with the Department of Applied
Chemistry, Faculty of Engineering, Osaka University, Suita 565-0871, Japan
(e-mail: kageyama@chem.eng.osaka-u.ac.jp; ohishi@chem.eng.osaka-u.ac.jp;
masatake@chem.eng.osaka-u.ac.jp).
Y. Ohmori is with the Center for Advanced Science and Innovation, Osaka
University, Suita 565-0871, Japan (e-mail: ohmori@casi.osaka-u.ac.jp).
Y. Shirota is with the Department of Environmental and Biological Chemistry,
Fukui University of Technology, Fukui 910-8505, Japan (e-mail: shirota@fukui-
ut.ac.jp).
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/JSTQE.2009.2039699
1077-260X/$26.00 © 2010 IEEE
1
cent by the use of copper phthalocyanine [5], [6] or poly(3-
hexylthiophene) [7], [8] as an electron donor, and fullerene
(C60 ) [5], [6] or its derivative, [6,6]-phenyl-C61 -butyric acid
methyl ester ([6,6]-PCBM) [7]–[9], as an electron acceptor, in
devices with elaborate structures.
Polycrystalline materials have mostly been used for OPV de-
vices; however, amorphous molecular materials, i.e., small or-
ganic molecules that readily form stable amorphous glasses with
well-defined glass-transition temperatures (Tg s) [10], [11], have
also been receiving growing attention as good candidates for
OPV device materials. Grain-boundary-free amorphous molec-
ular materials that permit the formation of smooth, uniform
amorphous thin films by both thermal deposition and solution
methods are attractive from the standpoint of practical applica-
tions. As discussed later, PCEs of ∼1.85% have been reported
for the OPV devices using amorphous molecular materials.
Photocurrent generation in donor-/acceptor-based OPV de-
vices has been understood as consisting of the following se-
quential steps [3], [4], [12], [13]:
1) light absorption to form excitons;
2) exciton diffusion to the donor/acceptor interface;
3) exciton dissociation that involves charge transfer between
the donor and the acceptor to generate geminate hole–electron
pairs, and then, charge separation into free holes and electrons
in competition with the recombination of hole–electron pairs;
4) charge transport;
5) charge collection by electrodes.
The charge separation probability has been understood in
terms of the Onsager theory [12], [13]. Recent studies have
shown that the step of the charge separation of hole–electron
pairs remaining bound at the donor/acceptor interface greatly
affects the conversion efficiency of OPV devices [12]–[17] and
also the separation probability is largely influenced by the mo-
bilities of charge carriers [17], i.e., a Monte Carlo model of
charge-carrier separation and recombination predicts that the
increase in the carrier mobility reduces the recombination pro-
cess of hole–electron pairs, resulting in the facilitation of the
charge separation process, and hence, leading to an increase in
the short-circuit current (JSC ) and the fill factor (FF) [17]. An-
other simulation model has also shown that for attaining a large
mean carrier distance, which leads to high JSC , carrier mobility
should be large [18].
In the light of the OPV device material requirement of
high charge-carrier mobility [4], [16], [17], we have aimed at
developing high-performance OPV devices using amorphous
molecular materials with high charge-carrier mobilities. A few
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2 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS
molecular design concepts for high charge-carrier mobility have
been obtained from the studies of the correlation between molec-
ular structures and charge-carrier drift mobilities, which in-
clude the reduction of both molecular size and conformational
change caused by the bond rotation and the avoidance of the
incorporation of polar groups [3], [10], [11], [19]–[21]. We
have found that several amorphous molecular materials of the
tris(oligoarylenyl)amine family show high charge-carrier drift
mobilities and reported hole drift mobilities of several mate-
rials of this family, including tris[4-(2-thienyl)phenyl]amine
(TTPA), in a previous communication [22]. We have also
demonstrated that the amorphous molecular materials of the
tris(oligoarylenyl)amine family function as good candidates for
electron donors in bilayer p-n heterojunction OPV devices [23].
This paper presents a full account of charge transport in the
TTPA amorphous glass, and the fabrication and performance of
a planar p-n heterojunction OPV device, including the exper-
imental details. In addition, this paper reports on a p-i-n-type
OPV device fabricated by thermal deposition of TTPA and C60 ,
and bulk p-n heterojunction OPV devices fabricated by spin
coating from the solution of TTPA as an electron donor and
[6,6]-PCBM as an electron acceptor, and discusses the perfor-
mance of these devices.
II. EXPERIMENTAL
A. Materials
TTPA was synthesized by the Grignard coupling re-
action of thiophen-2-ylmagnesium bromide with tris(4-
iodophenyl)amine in tetrahydrofuran (THF). It forms an amor-
phous glass with a glass-transition temperature of 70 ◦ C when
the melted sample was cooled [24].
C60 and [6,6]-PCBM were purchased from Tokyo Chemical
Industry and Luminescence Technology Corporation, respec-
tively, and used without further purification.
B. Measurements
Cyclic voltammetry was carried out using Ag/AgNO3
(0.01 mol/dm3 ) as a reference electrode in CH2 Cl2 . The half-
wave oxidation potential (E1/2 ) versus ferrocene/ferrocenium
(Fc/Fc+ ) was calibrated using E1/2 = 0.20 V versus Ag/AgNO3
(0.01 mol/dm3 ) for ferrocene in CH2 Cl2 .
Charge-carrier drift mobility was measured by a time-of-flight
(TOF) method for the TTPA single-layer device. An appropriate
amount of TTPA was heated to melt on an indium-tin-oxide
(ITO) coated glass, which was pressed by another ITO glass,
and then cooled on standing in air. The thickness of the sample
was 15–32 µm. The cell was mounted in a cryostat and irradiated
with pulsed N2 laser light (wavelength: 337 nm; pulse duration:
3 ns).
Current density–voltage characteristics in the dark and
under air-mass (AM) 1.5G illumination (Yamashita Denso,
USS-40) at room temperature were recorded using a Keithley
2400 source meter. Light intensity was measured using a power
meter (NEOARK, PM-341). The intensity of the monochro-
matic light was measured using a calibrated Si photodiode
(Hamamatsu Photonics, S1336-18BQ). The spectral mismatch
factors for the devices were 1.06, as determined by the method
described in the literature [25].
C. OPV Device Fabrication
Planar p-n heterojunction OPV devices were fabricated as
follows: an ITO-coated glass substrate was cleaned by suc-
cessive washing with neutral detergent, deionized water, THF,
and trichloroethene in an ultrasonic bath, followed by exposure
to trichloroethene vapor. Finally, the substrate was irradiated
with ultraviolet light. Poly(3,4-ethylenedioxythiophene) doped
with poly(4-styrene sulfonate) (PEDOT:PSS) (BAYTRON P
AI4038) was spin-coated onto the ITO-coated glass substrate.
TTPA amorphous film was prepared by thermal deposition onto
the PEDOT:PSS layer at ∼2 × 10−4 Pa at a deposition rate
of ∼0.1 nm/s at room temperature. Then C60 was vacuum-
deposited onto the TTPA film at ∼2 × 10−4 Pa at a deposition
rate of 0.1–0.2 nm/s at room temperature. The mixed inter-
layer was prepared by codeposition of TTPA and C60 . Finally,
lithium fluoride (0.1 nm) and aluminum (100–150 nm) were
thermally deposited onto C60 at deposition rates of ca. 0.01 and
ca. 0.2–0.5 nm/s, respectively. Bulk p-n heterojunction OPV
devices were fabricated using the film of a mixture of TTPA
and [6,6]-PCBM prepared by spin coating at 2000 r/min from
its chlorobenzene solution with a concentration of 3.5 wt% onto
the PEDOT:PSS-coated ITO glass substrate. All the fabricated
devices were sealed using glass plates with epoxy resin in an
argon-filled glove box. Atomic force microscopy images were
taken using a scanning probe microscope (JEOL, JSPM-5200).
III. RESULTS AND DISCUSSION
A. Properties of TTPA
TTPA undergoes reversible anodic oxidation, showing one
anodic and the corresponding cathodic waves in its cyclic
voltammogram (see Fig. 1). The ratio of the cathodic peak cur-
rent (ip c ) to the anodic peak current (ipa ), ip c /ipa , was 0.966,
as calculated according to the method described in the litera-
ture [26]. E1/2 of TTPA, which was determined as the midpoint
of Epa and Ep c , namely, (Epa + Ep c )/2, where Epa and Ep c
are the potentials at which the anodic and cathodic currents,
respectively, reach the maximum values, was 0.36 V versus fer-
rocene/ferrocenium (Fc/Fc+ ) reference electrode [0.20 V ver-
sus Ag/AgNO3 (0.01 mol/dm3 )] in dichloromethane (CH2 Cl2 ).
The half-wave oxidation potential of TTPA is 0.17 V less
than the half-peak oxidation potential (Ep/2 , the potential at
which the anodic current is half of the anodic peak current) of
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KAGEYAMA et al.: ORGANIC PHOTOVOLTAIC DEVICES USING AN AMORPHOUS MOLECULAR MATERIAL
Fig. 1. Cyclic voltammogram of TTPA. Solvent: CH2 Cl2 ; sweep rate :
100 mV/s; supporting electrolyte: n-Bu4 NClO4 (0.1 mol/dm3 ).
TABLE I
ELECTRONIC ABSORPTION BAND MAXIMA (λm a x ), MOLAR EXTINCTION
COEFFICIENTS (ε), HALF-WAVE OXIDATION POTENTIAL (E1 / 2 ), AND HOMO
AND LUMO ENERGY LEVELS OF TTPA
triphenylamine (TPA) (0.53 V versus Fc/Fc+ in CH2 Cl2 ). Thus,
TTPA has a stronger electron-donating property than TPA. The
highest occupied molecular orbital (HOMO) energy level of
TTPA was estimated to be −5.60 eV on the basis of the oxida-
tion potential and the solid-state ionization potential (Ip ) of
4,4 ,4 -tris[3-methylphenyl(phenyl)amino]triphenylamine (m-
MTDATA) (E1/2 = −0.14 V versus Fc/Fc+ in CH2 Cl2 and
Ip = 5.1 eV, as determined by ultraviolet photoemission spec-
troscopy in air [27]). The lowest unoccupied molecular orbital
(LUMO) energy level of TTPA was estimated to be −2.50 eV
from its HOMO energy level and the optical bandgap deter-
mined from its long-wavelength absorption edge. The optical
bandgap of TTPA was determined to be 3.10 eV, which is ca.
0.40 eV smaller than that of TPA (3.50 eV). Thus, the LUMO
level of TTPA is ca. 0.23 eV lower than that of TPA.
Table I summarizes the electronic absorption band maxima
(λm ax ), molar extinction coefficients (ε) at the band maxima,
the half-wave oxidation potential (E1/2 ), and the HOMO and
LUMO energy levels of TTPA.
B. Charge Transport in TTPA
The TOF method was used for the measurement of hole drift
mobilities. As Fig. 2 shows, the molecular glass of TTPA ex-
hibited nondispersive transient photocurrents. The transit time
(tτ ) was determined from the cusp of the double logarithm plots
of the transient photocurrent. The hole drift mobility was cal-
culated from the formula µ = L2 /tτ V, where L is the thickness
of the sample and V is the applied voltage. The hole drift mo-
3
Fig. 2. Typical transient photocurrent observed for the molecular glass of
TTPA. Thickness of the sample: 22 µm; applied voltage: 220 V; temperature:
293 K.
bility of TTPA was determined to be 1.1 × 10−2 cm2 /V·s at
an electric field of 1.0 × 105 V/cm and at 293 K. This value
is of the highest level among those reported for organic disor-
dered systems, which is comparable to the field-effect mobility
of polycrystalline CuPc [28].
The temperature and electric-field dependencies of the hole
drift mobilities were analyzed in terms of the disorder formal-
ism, which assumes that charge transport in disordered sys-
tems takes place by hopping through a manifold of states with
Gaussian-type density of states (DOS), subject to fluctuations
in both hopping site energies and intermolecular wave function
overlap, i.e., energetic disorder and positional disorder, respec-
tively. According to the disorder formalism, the electric-field
and temperature dependencies of charge-carrier drift mobilities
are given by (1) [29], [30], where σ and Σ are the parameters that
characterize the energetic and positional disorder, respectively,
µ0 represents a hypothetical mobility in the energetic disorder-
free system, E is the electric field, k is the Boltzmann constant,
T is the temperature, and C is an empirical constant

 2   
2σ σ 2
µ = µ0 exp − exp C −Σ E 2 1/2
.
3kT kT
(1)
In the experimental setup reported previously, a xenon stro-
boscopic lamp with pulsewidths of 1–4 µs was used [24]. Since
hole drift mobilities greater than 10−3 cm2 /V·s could not be
measured, temperature dependence of hole drift mobilities was
examined at low temperature below 193 K. In the present TOF
experimental setup, a pulsed N2 laser with a pulsewidth of 3 ns
was employed as the light source; this enabled the measure-
ment of drift mobilities greater than 10−3 cm2 /V·s in the higher
temperature region.
Fig. 3 shows the electric-field dependence of hole drift mo-
bilities in the glassy state of TTPA at a temperature region wider
(up to 293 K) than that of the previous temperature setup (up to
193 K). The logarithm of the hole drift mobilities was propor-
tional to the square root of the electric field. Fig. 4 shows the
temperature dependence of the hole drift mobilities at the zero
electric field, µ(E = 0), which were obtained by the extrapolation
 This article has been accepted for inclusion in a future issue of this journal. Content is final as presented, with the exception of pagination.
4 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS
Fig. 3. Electric-field dependence of the hole drift mobilities of TTPA molec-
ular glass.
Fig. 4. Temperature dependence of the hole drift mobilities of TTPA molecular
glass at zero electric field.
of the electric-field dependence of the hole drift mobilities to
the zero electric field at each temperature. A linear dependence
of the logarithm of µ(E = 0) versus 1/T2 was observed in the
temperature region of ca. 293–195 K, a deviation from the lin-
ear dependence being observed in the temperature region below
ca. 195 K. This kind of discontinuity has been reported as aris-
ing from the nondispersive-to-dispersive charge-transport tran-
sition [31], i.e., in the temperature region above this transition
temperature (Tc ), a packet of charge carriers, which was initially
energetically random, relaxes to the thermodynamically equi-
librium state within the Gaussian DOS. The activation energy
for charge transport above Tc , which is assumed to be the energy
difference between the equilibration energy of charge carriers
and the center of the DOS, is σ 2 /kT, whereas in the tempera-
ture region below Tc , the apparent activation energy for charge
transport becomes less than σ 2 /kT because the packet of charge
carriers has not yet reached the thermodynamically equilibrium
state, and hence, the equilibration energy of charge carriers is
Fig. 5. Plots of S versus (σ/kT)2 . Here, S = ∂ ln(µ/µ 0 )/∂E 1 / 2 .
higher than that for the packet of charge carriers that reached
the thermodynamically equilibrium state.
The values of µ0 and σ in the thermodynamically equilibrium
state were obtained from the intersect and the slope, respectively,
of the linear dependence of the logarithm of µ(E = 0) versus 1/T2
in the temperature region above Tc in Fig. 4. Fig. 5 shows the
plot of the slope of the electric-field dependence of the hole drift
mobility (S = ∂ ln(µ/µ0 )/∂E1/2 ) versus (σ/kT)2 . The positional
disorder Σ was determined from the intersect (S = 0) under the
condition (σ/kT)2 = Σ 2 . The hole-transport parameters in terms
of the disorder formalism for the amorphous glass of TTPA
were determined as follows: µ0 = 1.1 × 10−1 cm2 /V·s, σ =
0.064 eV, Σ = 1.1, and C = 3.3 × 10−4 (cm/V)1/2 .
The results show that while the values of Σ and C for the
molecular glass of TTPA are more or less similar to those for
other amorphous molecular materials, the preexponential factor
µ0 for the TTPA glass is approximately one order of magnitude
greater than for a number of other amorphous molecular materi-
als [3]. In addition, the value of σ for the TTPA molecular glass
is less than that for other amorphous molecular materials [3]. It
is, therefore, indicated that both the large preexponential factor
µ0 and the relatively small energetic disorder σ are responsible
for the high hole drift mobility of the TTPA molecular glass.
The preexponential factor µ0 , namely, the hypothetical mo-
bility in the absence of energetic disorder, is determined by the
attempt frequency and the degree of intermolecular wavefunc-
tion overlap [32]. The X-ray crystal structure analysis data of
the dihedral angles of 6.5◦ , 20.2◦ , and 26.4◦ between the phenyl
rings and the thiophene ring for TTPA [24] suggest that the
three thiophene-containing oligoarylenyl groups in TTPA have
relatively high degree of planarity, which leads to a high degree
of intermolecular wavefunction overlap.
The energetic disorder σ, namely, the fluctuation of the hop-
ping site energy, is understood as the fluctuation of polarization
energy resulting from van der Waals and charge-dipole interac-
tions [33], and is affected by the variation of molecular geometry
caused by bond rotation. It is thought that small conformational
changes caused by the rotations of C–N and/or C–C bonds
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KAGEYAMA et al.: ORGANIC PHOTOVOLTAIC DEVICES USING AN AMORPHOUS MOLECULAR MATERIAL
Fig. 6. Configurations of planar p-n heterojunction and p-i-n-type OPV
devices.
Fig. 7. EQE action spectrum of ITO/PEDOT:PSS (ca. 30 nm)/TTPA
(30 nm)/C6 0 (40 nm)/LiF (0.1 nm)/Al (150 nm) (device A, circle) and
ITO/PEDOT:PSS (ca. 30 nm)/TTPA (27 nm)/TTPA:C6 0 (1:4, 20 nm)/C6 0
(23 nm)/LiF (0.1 nm)/Al (100 nm) (device B, square) for transmitted light
through ITO electrode and electronic absorption spectra of vapor-deposited
films of TTPA (30 nm) and C6 0 (40 nm).
together with the absence of polar moieties in TTPA lead to the
smaller value of σ.
C. Fabrication and Performance of Planar p-n Heterojunction
and p-i-n-Type OPV Devices Using TTPA as an Electron Donor
A planar p-n heterojunction OPV device using TTPA
as an electron donor and C60 as an electron acceptor,
ITO/PEDOT:PSS (ca. 30 nm)/TTPA (30 nm)/C60 (40 nm)/LiF
(0.1 nm)/Al (150 nm) (device A), was fabricated, and the per-
formance was examined. Fig. 6 shows the device configuration.
Fig. 7 shows the external quantum efficiency (EQE) action
spectrum for the photogeneration of charge carriers for de-
vice A under illumination with transmitted monochromatic light
through the ITO electrode, together with the electronic absorp-
tion spectra of TTPA and C60 as their vapor-deposited film.
EQE for the photogeneration of charge carriers for transmitted
monochromatic light through the ITO electrode was calculated
from the equation EQE = (JSC /e)/(Iλ/hc), where JSC is the
short-circuit current, e is the elementary electronic charge, I and
λ are the intensity and the wavelength of transmitted monochro-
matic light, respectively, h is the Planck constant, and c is the
velocity of light in vacuum. The action spectra for the device
resembled the superposition of the absorption spectra of TTPA
and C60 , exhibiting a peak EQE of ∼38%.
5
TABLE II
PERFORMANCE OF DEVICES A AND B
Fig. 8. J–V characteristics of ITO/PEDOT:PSS (ca. 30 nm)/TTPA
(30 nm)/C6 0 (40 nm)/LiF (0.1 nm)/Al (150 nm) (device A, circle) and
ITO/PEDOT:PSS (ca. 30 nm)/TTPA (27 nm)/TTPA:C6 0 (1:4, 20 nm)/C6 0
(23 nm)/LiF (0.1 nm)/Al (100 nm) (device B, square) in dark (dashed line)
and under AM1.5G illumination at an intensity of 100 mW/cm2 (solid line).
Fig. 8 shows the current density (J)–voltage (V) characteris-
tics of device A in the dark and under AM1.5G illumination at an
incident light intensity of 100 mW/cm2 . The performance of de-
vice A is listed in Table II. Device A exhibited an open-circuit
voltage (VOC ) of 0.95 ± 0.01 V, a short-circuit photocurrent
(JSC ) of 2.5 ± 0.1 mA/cm2 , an FF of 0.62 ± 0.01, and a PCE
of 1.5% for the incident AM1.5G light at 100 mW/cm2 .
It has recently been reported that a p-n heterojunction
OPV device using N,N -diphenyl-N,N -di(α-naphthyl)benzidine
(α-NPD) as an electron donor and C60 as an electron
acceptor, ITO/PEDOT:PSS (30 nm)/α-NPD (10 nm)/C60
(48 nm)/MgAg (170 nm), gave 1% PCE under AM1.5G il-
lumination at intensities of 97 mW/cm2 [34]. Later, it was
also reported that a p-n heterojunction OPV device us-
ing N,N -diphenyl-N,N -bis(3-methylphenyl)benzidine (TPD)
as an electron donor and C60 as an electron acceptor gave
PCEs of 0.34%–1.0%, depending on the heat treatment
[35]. Other amorphous molecular materials that have hith-
erto been studied as OPV materials include 4,4 ,4 -tris[5-
(dimesitylboryl)thiophen-2-yl]triphenylamine [36], 4,4 ,4 -
tris[4-nitrophenyl(4-methylphenyl)amino]triphenylamine [36],
m-MTDATA [37], [38], siloles containing carbazolyl groups
[39], π-conjugated systems consisting of triphenylamine and
oligothiophene [40], triarylamine-substituted carbazole-based
dendrimers with an oligothiophene core [41] perylene di-
imide derivatives [42], diphenylaminofluorenyl-capped thia-
diazoloquinoxaline [43], π-conjugated systems consisting of
triphenylamine and benzothiadiazole [44], and dithiafulvenyl-
derivatized triphenylamines [45]. The devices using these amor-
phous molecular materials as electron donors have been reported
 This article has been accepted for inclusion in a future issue of this journal. Content is final as presented, with the exception of pagination.

6 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS

to exhibit JSC of 1–4 mA/cm2 , VOC of 0.3–0.9 V, FFs of 0.3–

0.5, and PCEs of 0.1%–1.3% under white-light irradiation. A
p-n heterojunction device using dicyanovinyl-substituted TTPA
as an electron donor and C60 as an electron acceptor has been re-
ported to give a PCE of 1.85% under AM1.5G illumination [46].
As compared with the reported performance of OPV de-
vices using the aforementioned amorphous molecular materi-
als [34]–[36], [40]–[45], the performance, in particular, the FF
value of 0.62 for device A is very high, which is comparable
to those reported for p-n heterojunction OPVs using polycrys-
talline CuPc [1].
It has been reported that the performance of OPV devices
Fig. 9. (a) Absorption spectra of mixed films of TTPA and [6,6]-PCBM pre-
is improved by the incorporation of a mixed interlayer be- pared from chlorobenene solution (film thickness: ca. 73 nm). (b) EQE action
tween electron donor and acceptor materials due to the in- spectra of ITO/PEDOT:PSS (ca. 30 nm)/TTPA:[6,6]-PCBM (ca. 73 nm)/LiF
crease in the fraction of photogenerated excitons that diffuse (0.1 nm)/Al (100 nm) for transmitted light through ITO electrode. TTPA:[6,6]-
PCBM ratios are 1:0.8 (solid line), 1:2 (dotted line), and 1:4 (dashed line).
to the donor/acceptor interface [6], [47]. In the present study,
a p-i-n-type OPV device, ITO/PEDOT:PSS (ca. 30 nm)/TTPA
(20 nm)/TTPA:C60 (1:4 molar ratio, 20 nm)/C60 (23 nm)/LiF
(0.1 nm)/Al (100 nm) (device B), was fabricated by the thermal
deposition method, and its performance was examined.
As shown in Fig. 7, device B, in which a mixed interlayer
with a thickness of 20 nm and a molar ratio of TTPA:C60 = 1:4
is incorporated into the TTPA and C60 layers, showed higher
EQEs than device A with a simple bilayer structure. The J–V
characteristics and the performance of device B are shown in
Fig. 8 and Table II, respectively. Device B exhibited a higher
JSC of 3.8 mA/cm2 and a higher PCE of 1.8% under AM1.5
illumination at an intensity of 100 mW/cm2 than device A.

D. Fabrication and Performance of Bulk p-n Heterojunction
OPV Devices
It is expected that in the future, organic thin-film OPV devices
will be fabricated by preparing organic thin films by solution
methods. Amorphous molecular materials are attractive in that
they permit the formation of smooth, uniform thin films by solu-
Fig. 10. J–V characteristics of ITO/PEDOT:PSS (ca. 30 nm)/TTPA:[6,6]-
PCBM (ca. 73 nm)/LiF (0.1 nm)/Al (100 nm) in dark (dashed line) and under
AM1.5G illumination at an intensity of 100 mW/cm2 (solid line). TTPA:[6,6]-
PCBM ratios are 1:0.8 (circle), 1:2 (square), and 1:4 (triangle).
TABLE III
PERFORMANCE OF BULK p-n HETEROJUNCTION OPV DEVICES USING TTPA
AND [6,6]-PCBM AS ELECTRON DONOR AND ACCEPTOR MATERIALSa

tion methods. We have fabricated bulk p-n heterojunction OPV

devices, where the mixed-layer thin films of TTPA and C60
were prepared by spin coating from chlorobenzene solution,
ITO/PEDOT:PSS (ca. 30 nm)/TTPA:[6,6]-PCBM (ca. 73 nm
with molar ratios of 1:0.8, 1:2, and 1:4)/LiF (0.1 nm)/Al
(100 nm), and examined the performance.
Fig. 9 shows the EQE action spectrum for the devices together
with the electronic absorption spectra of the spin-coated mixed
films of TTPA and [6,6]-PCBM. It was found that both the EQE of [6,6]-PCBM to TTPA. The device using the active layer with
and the cell performance greatly depend on the molar ratios of a molar ratio of TTPA:[6,6]-PCBM = 1:4 exhibited a JSC of
TTPA and [6,6]-PCBM, and increase with the increasing molar 3.3 mA/cm2 , an FF of 0.40, and a PCE of 1.3% under the same
fraction of [6,6]-PCBM. The observed peak EQE was ca. 47% irradiation conditions.
at around 345 nm for the OPV device with a TTPA:[6,6]-PCBM
ratio of 1:4. Fig. 10 shows the J–V characteristics of the devices
in the dark and under AM1.5G illumination at an incident light E. Discussion
intensity of 100 mW/cm2 . The device performance is listed in Fig. 11 shows the schematic energy level diagram for the
Table III. The device using an active layer with a molar ratio device. It has been understood that VOC corresponds to the
of TTPA:[6,6]-PCBM = 1:0.8 exhibited poor performance with difference between the HOMO level of the donor and the LUMO
a VOC of 0.95 V, a JSC of 1.1 mA/cm2 , an FF of 0.27, and a level of the acceptor [4]. The VOC value of 0.95 V obtained for
PCE of 0.3% for the incident AM1.5G light at 100 mW/cm2 ; the present device corresponds to the difference between the
however, JSC and FF increased with the increasing molar ratio HOMO energy level of TTPA and the LUMO energy level of
 This article has been accepted for inclusion in a future issue of this journal. Content is final as presented, with the exception of pagination.
KAGEYAMA et al.: ORGANIC PHOTOVOLTAIC DEVICES USING AN AMORPHOUS MOLECULAR MATERIAL
Fig. 11. Schematic energy level diagram for the present device (values are
given in electronvolts with respect to vacuum level). The energy levels of
PEDOT:PSS, C6 0 , and Al were taken from [2] and [50].
Fig. 12. Topographic AFM images of (a) PEDOT:PSS film (ca. 30 nm) on
ITO glass substrate and (b) TTPA amorphous film (20 nm) on the PEDOT:PSS
film. The size of the images is 1 µm × 1 µm.
C60 . The relatively high solid-state Ip of TTPA leads to the high
VOC for the present device.
The photocurrent results mainly from the photoabsorption by
C60 or [6,6]-PCBM, as evidenced from the absorption spectra
of TTPA, C60 , and [6,6]-PCBM in Figs. 7 and 9. Therefore, the
high EQEs for the photogeneration of charge carriers, relatively
high JSC , and the high FF for the present devices are suggested to
be due to the large exciton diffusion length of C60 (ca. 40 nm) [2]
and the high charge-carrier mobilities of TTPA, C60 [48], and
[6,6]-PCBM [49].
The observed current density (Jobs ) under illumination is ex-
pressed as the subtraction of the dark current density from the
photocurrent density. The dark current density is the sum of
the diode current density and the leakage current density. For
attaining high FF, Jobs under given forward voltage should be
large. Since Jobs decreases when the series resistance is large,
the series resistance should be small. It has also been reported
that series resistance of OPV devices plays an important role
in ensuring high FF [34]. The high charge-carrier mobilities of
TTPA and C60 may contribute to reduce the series resistance of
the present devices.
Leakage current density, which flows through the shunt, in-
creases linearly with the increasing forward voltage, and the
existence of the leakage current density at a given forward volt-
age decreases Jobs , and hence, FF. Therefore, for attaining high
FF, the shunt resistance should be as large as possible. The ho-
mogeneous, grain-boundary-free films of TTPA are suggested to
prevent any “shorts” between electrodes, leading to high shunt
resistance. Fig. 12 shows the topographic AFM images of the
PEDOT:PSS film (ca. 30 nm) on the ITO glass substrate and
7
the amorphous TTPA film (20 nm) on the PEDOT:PSS film.
The surface of the PEDOT:PSS film on the ITO glass substrate
exhibited a granular shape with a diameter of ∼50 nm and an
rms roughness of ca. 0.8 nm. The rms roughness of the surface
of the TTPA film was smaller than that of the PEDOT:PSS film,
which is ca. 0.1 nm. This result suggests that the amorphous
TTPA film smoothly covers the rough surface of PEDOT:PSS,
serving to prevent direct contact between the two electrodes.
Higher performance of the p-i-n-type OPV device (device B)
with the thin mixed interlayer relative to the planar p-n het-
erojunction device (device A) is thought to be due to more
efficient charge transfer between TTPA and C60 to generate
hole–electron pairs.
It is of interest to note that bulk p-n heterojunction devices
consisting of a single layer of a mixture of TTPA and [6,6]-
PCBM, which is prepared by spin coating from solution, ex-
hibited high performance, greatly depending on the molar ratio
of TTPA and [6,6]-PCBM. It is suggested that charge transfer
between the donor and the acceptor to generate hole–electron
pairs becomes more efficient and that the recombination of hole–
electron pairs is not significant. The improvement in perfor-
mance with the increasing molar fraction of [6,6]-PCBM from
1:0.8 to 1:4 (TTPA:[6,6]-PCBM) may be attributed partly to
the improvement of the light absorption efficiency and partly to
more facile electron transport, which leads to better balanced
hole and electron mobilities.
The present results have shown that amorphous molecular
materials, which permit the formation of uniform thin films by
both thermal deposition and solution methods, are promising
candidates for materials in OPV devices. The poor overlap be-
tween the absorption spectrum of TTPA and the solar spectrum
limits the performance of the present OPV devices. Amorphous
molecular materials with both high charge-carrier mobilities
and the absorption spectrum that overlapped well with the solar
spectrum are expected to give much higher PCE, and the de-
velopment of such materials is required for further research and
development of OPV devices. In addition, higher Tg s are desir-
able from the standpoint of long-term stability of OPV devices
for practical applications. The incorporation of aryl groups into
TTPA or the replacement of the phenyl group in TTPA by an-
other rigid moiety can be molecular design concepts for high Tg
materials, according to the proposed molecular design concepts
for attaining high Tg [10], [11].
IV. CONCLUSION
Charge transport in the TTPA amorphous glass and the per-
formance of OPV devices using TTPA as an electron donor and
C60 or [6,6]-PCBM as an electron acceptor are discussed in
this paper. The TTPA amorphous glass exhibited a hole drift
mobility of 1.1 × 10−2 cm2 /V·s at an electric field of 1.0 ×
105 V/cm and at 293 K, as determined by the TOF method.
This value is the highest level among amorphous molecular ma-
terials. A planar p-n heterojunction OPV device using TTPA
as an electron donor and C60 as an electron acceptor showed
high performance, exhibiting an FF of 0.62 and a PCE of 1.5%
under AM1.5G illumination at 100 mW/cm2 . A p-i-n-type OPV
 This article has been accepted for inclusion in a future issue of this journal. Content is final as presented, with the exception of pagination.

8 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS

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Hiroshi Kageyama was born in 1969. He received
the B.Eng., M.Eng., and Ph.D. degrees from the De-
partment of Applied Chemistry, Faculty of Engineer-
ing, Osaka University, Suita, Japan, in 1992, 1994,
and 1997, respectively.
In 1997, he was appointed as a Research Associate
at Osaka University, where he has been an Assistant
Professor since 2006. His current research interests
include charge transport in organic disordered sys-
tems.
Dr. Kageyama is a member of the Chemical Soci-
ety of Japan, the Society of Polymer Science, Japan, the Japanese Photochem-
istry Association, and the Japan Society of Applied Physics.
Hitoshi Ohishi received the B.Eng. and M.Eng. degrees from the Department
of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Japan,
in 1999 and 2001, respectively.
He is currently with the Department of Applied Chemistry, Faculty of Engi-
neering, Osaka University.
9
Masatake Tanaka received the B.Eng. and M.Eng. degrees from the Depart-
ment of Applied Chemistry, Faculty of Engineering, Osaka University, Suita,
Japan, in 2002 and 2004, respectively.
He is currently with the Department of Applied Chemistry, Faculty of Engi-
neering, Osaka University.
Yutaka Ohmori (M’79–SM’97–F’05) received the
B.Eng. degree in 1972 and the Dr. Eng. degree in
1979 from the Department of Electrical Engineer-
ing, Faculty of Engineering, Osaka University, Suita,
Japan.
In 1977, he joined Nippon Telegraph Telephone
Public Corporation (now NTT Corporation), where
he was mainly involved in optical semiconductor de-
vices. In 1989, he became an Associate Professor in
the Department of Electronic Engineering, Faculty of
Engineering, Osaka University, where he has been a
Professor in the Collaborative Research Center for Advanced Science and Tech-
nology (Center for Advanced Science and Innovation since 2004), Electronic
Materials and Systems Engineering, since 2000, and was engaged in optical and
electrical devices utilizing organic materials, including conducting polymers.
Prof. Ohmori is a Fellow of the Institute of Electronics, Information and
Communication Engineers in Japan, and a member of the Japan Society of
Applied Physics, the American Physical Society, and the Materials Research
Society.
Yasuhiko Shirota was born in 1940. He received the
B.Eng. degree in 1963 and the Dr. Eng. degree in 1968
from the Department of Applied Chemistry, Faculty
of Engineering, Osaka University, Suita, Japan.
In 1968, he was appointed as a Research Associate
at Osaka University, where he was promoted to an
Associate Professor in 1972, a full Professor in 1986,
and has been a Professor Emeritus since 2003. Since
2003, he has also been a Professor at Fukui University
of Technology, Fukui, Japan. His current research
interests include a wide field of organic materials
science, including the synthesis, structures, reactions, properties, functions of
both molecular materials and polymers, and their applications in devices.
Prof. Shirota is a member and a Fellow of the Chemical Society of Japan, and a
member of the Society of Polymer Science, Japan, the Japanese Photochemistry
Association, the Society of Synthetic Organic Chemistry, and the Japan Society
of Applied Physics.