Nano Energy 41 (2017) 10–17

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Nano Energy
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Highly efficient air-stable/hysteresis-free flexible inverted-type planar MARK

perovskite and organic solar cells employing a small molecular organic hole
transporting material
Saripally Sudhaker Reddya, Sungmin Shina, Um Kanta Aryala, Ryosuke Nishikubob,
⁎⁎ ⁎⁎ ⁎
Akinori Saekib, , Myungkwan Songc, , Sung-Ho Jina,
a
Department of Chemistry Education, Graduate Department of Chemical Materials, and Institute for Plastic Information and Energy Materials, Pusan National University,
Busan 46241, Republic of Korea
b
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
c
Advanced Functional Thin Films Department, Surface Technology Division, Korea Institute of Materials Science (KIMS), 797 Changwondaero, Sungsan-Gu, Changwon,
Gyeongnam 642-831, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Keywords: To acknowledge exceptionally productive flexible perovskite solar cells, low-temperature-processable efficient
Small molecular organic hole transporting organic hole transporting materials are very significant for the emerging photovoltaic research. A new organic
material small molecular hole transporting material (N-(4-(9H-carbazol-9-yl)phenyl)-7-(4-(bis(4-methoxyphenyl)amino)
Time-resolved microwave conductivity phenyl)-N-(7-(4-(bis(4-methoxyphenyl)amino)phenyl)-9,9-dioctyl-9H-fluoren-2-yl)-9,9-dioctyl-9H-fluoren-2-
Flexible/rigid inverted-type perovskite solar
amine (CzPAF-TPA)) has been rationally designed and synthesized for both highly efficient solution-processed
cells
flexible and rigid inverted-type planar heterojunction perovskite solar cells (i-PSCs) and flexible and rigid bulk
Bulk heterojunction organic solar cells
Hysteresis-free heterojunction inverted organic solar cells (BHJ IOSCs). The dopant-free CzPAF-TPA-based device displayed
Stability significantly improved device performance in solution-processed flexible i-PSCs and flexible BHJ IOSCs with
power conversion efficiencies (PCEs) of 12.46% and 7.52%, respectively, with negligible hysteresis, which is
superior to that of standard HTM. Furthermore, the high PCE was recorded on rigid ITO substrate in dopant-free
i-PSCs (PCE ~ 15.71%) and BHJ IOSCs (PCE ~ 8.74%). Notably, the promising technique of flash-photolysis
time-resolved microwave conductivity was also well correlated with the obtained results. In addition to their
high device performance in flexible as well as rigid i-PSCs and flexible BHJ IOSCs, they also showed long-term
stability over 500 h and 30 days with minimal loss of initial performance.

1. Introduction transparent electrodes (TCE) of polyethylene terephthalate (PET) or

Organic-inorganic hybrid perovskite solar cells (PSCs) have at-
tracted attention within the photovoltaic community as fascinating
solar light harvesting technologies, owing to their direct band-gap, high
extinction coefficient, broad absorption spectra, high charge carrier
mobility, and excellent semiconducting properties [1–6]. For potential
application of these advantageous perovskites, intensive research ef-
forts have been directed at modifying the fabrication techniques, ex-
ploring the interface engineering and device architectures such as me-
soporous and planar device structures (conventional- and inverted-type
PSCs (i-PSCs)) [7–20]. The substantial requirement of high processing
temperature (> 450 °C) for mesoporous TiO2 and its high cost limits its
practical compatibility with flexible substrates (for example,
polyethylene naphthalate (PEN) coated with indium-doped tin oxide
(ITO)) [14,15,21]. Despite PSC's superior power conversion efficiency
(PCE) of 22.1% (http://www.nrel.gov/ncpv), these difficulties have
suppressed the scope for its commercialization. In contrast, conven-
tional-type planar PSCs are comprised of a metal oxide electron trans-
porting layer (ETL) on a transparent electrode, followed by perovskite
layer that is covered by a hole transporting material (HTM) [22].
However, this also necessitates a very high temperature to process
metal oxide ETLs, which causes serious hysteresis [14].
Recently, i-PSCs have emerged as a promising approach to cir-
cumvent the aforementioned issues, wherein the perovskite is placed
between two organic layers: a hole transporting layer (HTL; bottom
layer) and an ETL (top layer). The facile fabrication approach at low-

⁎
Corresponding author.
⁎⁎
Co-corresponding authors.
E-mail addresses: saeki@chem.eng.osaka-u.ac.jp (A. Saeki), smk1017@kims.re.kr (M. Song), shjin@pusan.ac.kr (S.-H. Jin).

http://dx.doi.org/10.1016/j.nanoen.2017.09.009
Received 7 June 2017; Received in revised form 30 August 2017; Accepted 2 September 2017
Available online 06 September 2017
2211-2855/ © 2017 Elsevier Ltd. All rights reserved.
S.S. Reddy et al.
temperature of these i-PSCs and lower hysteresis means that they are
highly suitable for large area and flexible PSCs [14,23–29]. Ad-
ditionally, the commercial application of flexible i-PSCs will also re-
quire interfacial engineering for further improving PCE and long-term
stability [30–32]. Especially, HTL is the pre-requisite of PSCs for rea-
lizing high performance by facilitating high hole transport and reducing
the recombination. However, although PEDOT:PSS has been widely
utilized in i-PSCs as the HTM due to its efficient hole injection/trans-
port property and solution processability, the poor long-term device
performance and device stability have been identified as key limitations
due to its acidic nature and high hygroscopicity [33,34]. Thus, to
overcome these limitations associated with PEDOT:PSS, a few attempts
have been made to replace PEDOT:PSS by inorganic HTMs (NiOx,
CuSCN, Cu2O, and V2O5 etc.), most of which require high post-an-
nealing temperatures to enhance the film morphology and perfor-
mance, and thus hinder the fabrication of flexible i-PSCs [14]. Though
they have been fabricated at low-temperature by doping metal into an
inorganic conductor via combustion method to enhance efficiency [35],
the PCE of sputtered NiOx films on rigid substrates has not been sa-
tisfactory (< 10%) [36]. On the other hand, organic HTMs have been
recommended for high performance flexible as well as rigid i-PSCs
[13,32,37]. In particular, organic small molecular (SM) HTMs are
considered to be potential candidates for planar i-PSCs as well as or-
ganic solar cells (OSCs) on different substrates.
With their attractive features of defined molecular structure, tun-
able photophysical properties, promising yield, high purity, and less
variation from batch-to-batch [38,39], organic SM HTMs have attracted
enormous attention for enhancing the device performance of flexible
and rigid-based bulk heterojunction inverted OSCs (BHJ IOSCs), in
addition to their essential role in solution-processed flexible and rigid i-
PSCs. However, recent reports, including from our own research group,
have successfully demonstrated the potential of SM HTMs and their
multi-applications in PSCs and OSCs through rational design and
synthesis [40–42]. This research has demonstrated that organic SM
HTMs are the most promising candidate, and has emphasized the im-
portance of their design in maximizing the high device performance
and long-time durability for flexible and rigid i-PSCs with less hysteresis
and flexible and rigid BHJ IOSC applications. Formidable challenges
remain in developing a systematic design strategy for optimizing hys-
teresis-free and stable PCEs based on organic SM HTMs.
Herein, for the first time, we report the design and synthesis of a
new organic SM HTM, N-(4-(9H-carbazol-9-yl)phenyl)-7-(4-(bis(4-
methoxyphenyl)amino)phenyl)-N-(7-(4-(bis(4-methoxyphenyl)amino)
phenyl)-9,9-dioctyl-9H-fluoren-2-yl)-9,9-dioctyl-9H-fluoren-2-amine
(CzPAF-TPA) for both highly efficient solution-processed i-PSCs and
BHJ IOSCs on both flexible TCE system (PET/ITO) and rigid ITO sub-
strate. Importantly, the promising technique of flash-photolysis time-
resolved microwave conductivity (TRMC) [43] was used to quantify the
hole transfer yield from perovskite to the HTM, and obtained results are
in conjunction with the obtained high performance. The dopant-free
CzPAF-TPA-based device displayed significantly improved device per-
formance in solution-processed flexible i-PSCs and flexible BHJ IOSCs
with PCEs of 12.46% and 7.52%, respectively, with negligible hyster-
esis. Moreover, the PCE was dramatically increased on rigid ITO sub-
strate in both dopant-free i-PSCs (PCE ~ 15.71%) and BHJ IOSCs (PCE
~ 8.74%). This performance is superior to that of standard PEDOT:PSS
(10.52% and 6.82% in i-PSCs and BHJ IOSCs, respectively). In addition
to their high device performance in flexible i-PSCs and flexible BHJ
IOSCs, they also showed long-term stability over 500 h and 30 days
with minimal loss of initial performance.
2. Results and discussion
The organic SM structure of CzPAF-TPA was synthesized by ap-
plying coupling reactions, as depicted in Fig. 1a. Detailed synthetic
routes are presented in Scheme S1. The core (CzPAF-borate) was
11
Nano Energy 41 (2017) 10–17
synthesized according to our previous report [40]. Triarylamines have
attracted attention in optoelectronic applications due to their hole
transporting ability, and chemical and morphological stability [44].
Thus, we introduced N,N-bis(4-methoxyphenyl)aniline as terminal
groups to the core. Finally, CzPAF-TPA was successfully synthesized via
the Suzuki coupling reaction with a yield of 59%. The thermal property
of CzPAF-TPA was investigated by thermogravimetric analysis (TGA),
as shown in Fig. S1. CzPAF-TPA demonstrated excellent thermal sta-
bility, as shown by its high decomposition temperature (Td, corre-
sponding to 5% weight loss) of 438 °C. This high stability was mainly
attributed to its core structure and also the extended N,N-bis(4-meth-
oxyphenyl)aniline analogues.
To confirm the extent of hole transporting behavior of newly syn-
thesized HTM, we measured the photoluminescence spectra (PL) and
time-resolved PL decay measurements (Fig. S2). The samples were
prepared with the configuration of ITO/perovskite (MAPbI3), ITO/
PEDOT:PSS/MAPbI3 and ITO/CzPAF-TPA/MAPbI3. Fig. S2a, shows
high intensity PL spectrum of the MAPbI3 film without any HTM,
whereas the intensity of the MAPbI3 absorber was dramatically reduced
in CzPAF-TPA/MAPbI3 and PEDOT:PSS/MAPbI3. Particularly, CzPAF-
TPA showed efficient PL quenching than PEDOT:PSS, as evidenced by
its reduced intensity. In addition, the transient PL decays were mea-
sured for those samples, as shown in Fig. S2b. The attained average
transient decay values (τavg) were as follows: 8.68 ns for ITO/MAPbI3,
1.76 ns for ITO/PEDOT:PSS/MAPbI3, and 0.78 ns for ITO/CzPAF-TPA/
MAPbI3. The CzPAF-TPA-based film effectively reduced the decay time
as compared to that of PEDOT:PSS and MAPbI3. Further, the hole
transfer yield from MAPbI3 to CzPAF-TPA was quantified by using
TRMC. Encouragingly, CzPAF-TPA exhibited a high hole transfer yield
(ηsat) of 0.98 in the saturated region (ca. 3 μs) and a large hole transfer
rate (k) of 4.0 × 106/s (Fig. 1d,e), which are comparable to those of
standard HTMs [43]. Thus, this study suggests that CzPAF-TPA can
efficiently extract holes from the separated holes of photogenerated
excitons within the MAPbI3. These investigations confirmed that the
newly synthesized HTM CzPAF-TPA could efficiently extract and
transport holes to the electrode.
The UV–vis absorption, emission spectra, and photostability of
CzPAF-TPA are shown in Fig. 1b,c and Fig. S3. The optical band gap
(Egopt) was calculated to be 2.87 eV, using the onset UV–vis absorption
spectrum. The absorption maximum of CzPAF-TPA was observed at
385 nm in CHCl3 solution (molar extinction coefficient (ε) = 1.07 ×
105 L mol−1 cm−1); the same trend was observed in the film state. The
emission maximum of CzPAF-TPA in CHCl3 solution was at 436 nm
with a Stokes shift of 59 nm, whereas in the film state it was similar to
that of solution. Furthermore, to investigate the photostability of the
CzPAF-TPA films, we UV–vis exposed them under a solar simulator for
different time intervals (0–50 min) (Fig. 1c). The absorption peaks were
not significantly affected by the time interval, which demonstrated the
good photostability of CzPAF-TPA. Furthermore, we measured the
transmittance for PEDOT:PSS and CzPAF-TPA materials to investigate
the optical transparency in the UV–vis wavelength region. The thin
films of PEDOT:PSS and CzPAF-TPA were prepared by spin-coating on
ITO substrate. The ITO transmittance was measured for comparison, as
shown in Fig. S4. The transmittance of CzPAF-TPA was comparable to
that of PEDOT:PSS in the UV–vis region, which is advantageous to
enhance the photocurrent of the devices. Thus, CzPAF-TPA can be used
as a bottom layer in PSCs.
We conducted cyclic voltammetry (CV) experiment for CzPAF-TPA
in CH2Cl2 solution to estimate the highest occupied molecular orbital
(HOMO) and the lowest unoccupied molecular orbital (LUMO) energy
levels. As illustrated in Fig. 1f, CzPAF-TPA underwent irreversible
oxidation processes and exhibited multiple oxidation peaks. However,
the first onset oxidation peak was used to calculate the HOMO energy
levels. The HOMO and LUMO of CZPAF-TPA were calculated to be −
5.07 and − 2.20 eV, respectively. The HOMO energy level of CzPAF-
TPA was well matched with that valance band of MAPbI3, as expected
S.S. Reddy et al. Nano Energy 41 (2017) 10–17

Fig. 1. a) Molecular structure of the HTM, b) UV–vis absorption spectra of CzPAF-TPA in CHCl3 solution and film state, c) absorption spectra of CzPAF-TPA films after exposure to 1 sun
solar light with different time intervals (photostability), d) time-dependent hole transfer yields from MAPbI3-based perovskite to CzPAF-TPA evaluated by flash-photolysis TRMC (λex =
500 nm), e) normalized profiles of hole transfer yields. The gray lines are fitting curves of stretched exponential function, exp(-(kt)β), where k, β, η0, and ηsat were 4.0 × 106/s, 1.00, 0.84,
and 0.98, respectively (see experimental in SI), f) cyclic voltammogram of CzPAF-TPA in CH2Cl2 solution, calculated frontier molecular orbitals: g) DFT optimized molecular geometries
(3D structure), calculated spatial distributions of h) HOMO and i) LUMO of CzPAF-TPA.

from the good charge transfer at the interface.
To gain further insight into the geometrical and electronic dis-
tribution of CzPAF-TPA, the density functional theory (DFT) was in-
vestigated. The electron density of HOMO was localized on fluorene
moieties along with their adjacent end capped triphenylamine, whereas
the LUMO was distributed on π-conjugated fluorene and phenyl frag-
ments (Fig. 1g–i). Moreover, the HOMO/LUMO energy levels were
comparable to the experimentally calculated values.
Since the hole transporting behavior of HTMs is a major influence
on the performance of PSCs, we examined the hole transporting prop-
erty of CzPAF-TPA by space-charge-limited current (SCLC) method with
a configuration of ITO/MoO3/PEDOT:PSS or CzPAF-TPA/MoO3/Ag
(Fig. S5). The calculated hole mobility of CzPAF-TPA was 3.13 ×
10−4 cm2 V−1 s−1, which was superior than that of standard HTMs,
PEDOT: PSS (1.90 × 10−4 cm2 V−1 s−1) and spiroOMeTAD (0.4–2.0 ×
10−4 cm2 V−1 s−1) [45,46]. Hence, the high hole mobility of CzPAF-
TPA facilitates better hole transport from MAPbI3 to the respective
electrode.
The flexible and rigid i-PSCs were fabricated by employing a newly
synthesized HTM to explore its potentiality in dopant-free PSCs under
the AM 1.5G illumination at an intensity of 100 mW cm−2. Firstly,
these were processed at low temperature, which enabled us to use them
for flexible substrates that are highly significant for future commercial
applications. The flexible and rigid i-PSC are shown in Figs. 2a and 3a
and the configuration are PET/ITO/HTM/MAPbI3/PC61BM/ZnO/Ag
and ITO glass /HTM/MAPbI3/PC61BM/ZnO/Ag, respectively.
The optimized J-V characteristics of flexible as well as rigid i-PSCs
with CzPAF-TPA and PEDOT:PSS as dopant-free HTMs are displayed in
Figs. 2c and 3b. The corresponding photovoltaic properties are illu-
strated in Table 1 (flexible data) and Table 2 (rigid data). The optimized
PEDOT:PSS-based flexible i-PSCs showed a PCE of 10.52% with a short-
circuit current density (Jsc) of 16.42 mA cm−2, open-circuit voltage
(Voc) of 0.89 V, and fill factor (FF) of 71.74%. The PCE under the re-
verse scan condition was 10.35% with Jsc of 16.15 mA cm−2, Voc of
0.88 V, and FF of 72.42% under AM 1.5 G illumination at an intensity
of 100 mW cm−2. Whereas the PEDOT:PSS based rigid i-PSCs showed a
maximum PCE of 14.69% (under forward scan conditions, PCE =
14.45%, Jsc = 19.66 mA cm−2, Voc = 1.03 V, FF = 70.74%; and under
reverse scan conditions, PCE = 14.69; Jsc = 19.82 mA cm−2, Voc =
1.03 V, FF = 72.06%). The dopant-free CzPAF-TPA based device ex-
hibited the appreciable PCE of 12.37% with Jsc of 19.18 mA cm−2, Voc
of 0.89 V, and FF of 72.73% under the forward scan condition and
12.46% with Jsc of 18.97 mA cm−2, Voc of 0.90 V, and FF of 72.83%
under the reverse scan condition. Excitingly, the CzPAF-TPA based i-
PSCs on rigid substrate displayed a high PCE of 15.71% (under forward
scan conditions, PCE = 15.28%; Jsc = 20.34 mA cm−2, Voc = 1.02 V,
FF = 73.62%; and under reverse scan conditions, PCE = 15.71%; Jsc =
20.00 mA cm−2, Voc = 1.05 V, FF = 74.58%). The PCE of the CzPAF-
TPA-based device was superior to that of the PEDOT:PSS-based device
without any dopants on both flexible and rigid substrates, due to the
enhanced Jsc and slightly improved FF. To further confirm the photo-
current density, the incident photon-to-current conversion efficiency
(IPCE) spectrum was measured for flexible and rigid i-PSCs based on
PEDOT:PSS and CzPAF-TPA as HTMs, which are depicted in Figs. 2d
and 3c. The Jsc values obtained from the J-V profiles in flexible as well
as rigid i-PSCs with PEDOT:PSS and CzPAF-TPA-based devices were in

12
S.S. Reddy et al. Nano Energy 41 (2017) 10–17

Fig. 2. a) Flexible device structure, b) corresponding energy level diagram of MAPbI3-based i-PSCs, c) J-V characteristics, d) IPCE spectra of flexible i-PSCs with PEDOT:PSS and CzPAF-
TPA as the HTMs, e) histogram of flexible i-PSCs efficiencies, f) steady state PCE as a function of time and g) real PCEs of flexible i-PSCs as a function of time in hours.

good agreement with the calculated photocurrent densities from the
spectrum integration of the IPCE spectra (Tables 1 and 2).
Compared with PEDOT:PSS-based devices, the CzPAF-TPA-based
devices achieved higher PCE in both flexible and rigid i-PSCs, which
was ascribed to the improved Jsc (Figs. 2 and 3). Interestingly, flexible
and rigid i-PSCs based on CzPAF-TPA as an HTM did not exhibit any
significant J-V hysteresis, as per the scan direction and scan rate as
depicted in Figs. 2c and 3b, which is possibly attributed to the balanced
charge extraction from the MAPbI3. Furthermore, the integrated Jsc of
the IPCE was well matched to the obtained values from the J-V profiles.
The histogram of PCEs of flexible substrate based on both PEDOT:PSS
and CzPAF-TPA is shown in Fig. 2e.
Furthermore, the PCE of the flexible and rigid i-PSCs was dependent
on the measurement conditions, mainly due to the hysteresis effect,
which in general misleads the real efficiency [26,33]. Therefore, to
determine this point and obtain accurate values of the J-V scans, the
steady state PCE was measured by prebiasing the device at its maximum
power point as a function of time, as shown in Fig. 2f. However, the

Fig. 3. a) Rigid device structure of MAPbI3-based i-PSCs, b) J-V characteristics, c) IPCE spectra of rigid i-PSCs with PEDOT:PSS and CzPAF-TPA as dopant-free HTMs, d) histogram of rigid
i-PSCs efficiencies, e) steady state PCE as a function of time and f) real PCEs of rigid i-PSCs as a function of time in hours.

13
S.S. Reddy et al. Nano Energy 41 (2017) 10–17

Table 1
Photovoltaic performance of flexible i-PSCs with PEDOT:PSS and CzPAF-TPA as dopant-free HTMs.

HTM Scan direction Voc (V) Jsc (mA cm−2) FF (%) PCE (%) PCEavg (%) Integrated Jsc (mA cm−2) Rs (Ω cm2) Rsh (Ω cm2)

PEDOT:PSS Forward 0.89 16.42 71.74 10.52 10.44 16.77 2.96 5.0 × 106
PEDOT:PSS Reverse 0.88 16.15 72.42 10.35 16.36 2.53 8.6 × 106
CzPAF-TPA Forward 0.89 19.18 72.73 12.37 12.42 19.36 2.06 4.0 × 107
CzPAF-TPA Reverse 0.90 18.97 72.83 12.46 19.23 1.99 6.6 × 107

Table 2
Photovoltaic performance of rigid i-PSCs with PEDOT:PSS and CzPAF-TPA as dopant-free HTMs.

HTM Scan direction Voc (V) Jsc (mA cm−2) FF (%) PCE (%) PCEavg (%) Integrated Jsc (mA cm−2) Rs (Ω cm2) Rsh (Ω cm2)

PEDOT:PSS Forward 1.03 19.66 70.74 14.45 14.57 19.96 2.47 9.1 × 106
PEDOT:PSS Reverse 1.03 19.82 72.06 14.69 20.39 2.21 1.0 × 107
CzPAF-TPA Forward 1.02 20.34 73.62 15.28 15.50 20.62 1.93 6.9 × 107
CzPAF-TPA Reverse 1.05 20.00 74.58 15.71 20.29 1.21 9.8 × 107

stabilized PCE of flexible i-PSCs based on PEDOT:PSS and CzPAF-TPA
was linear with respect to time (s) and was found to be 10.44% and
12.42%, respectively, after 60 s. The same trend was followed on rigid
substrate for PEDOT:PSS and CzPAF-TPA and the PCE found to be
14.60% and 15.67%, respectively, after 60 s (Fig. 3e). Moreover, the
increased shunt resistance (Rsh) and decreased series resistance (Rs) of
flexible and rigid i-PSCs based on CzPAF-TPA suggest that the enhanced
conductivity provides an efficient extraction of holes from the MAPbI3
and transportation to the electrode [40]. Furthermore, mechanical
bending tests of the fabricated flexible i-PSCs were conducted to in-
vestigate the mechanical stability, and the flexible bending tests were
displayed in Figs. S6 and S7 (photographs). It reveals that the fabricated
flexible devices could bear even at 1 mm scale without decreasing the
PCE largely. The detail information of all parameters such as Voc, JSC
and FF versus bending radii was provided (Fig. S6). The resultant PCE
versus radii (mm) shows good mechanical stability even at 1.5 mm radii
bending scale.
Electrochemical impedance spectroscopy (EIS) measurements were
measured on the PEDOT:PSS and CzPAF-TPA-based flexible i-PSCs to
characterize their hole/charge transport behavior (Fig. S8). The pre-
viously reported equivalent circuit model was used to fit the obtained
EIS curves [40]. Rrec decreased in the order of CzPAF-TPA >
PEDOT:PSS at low and high voltages, which gave a longer charge car-
rier lifetime for better transport for CzPAF-TPA with PSCs, thereby
improving the performance of the PSCs. Additionally, the hole con-
ductivity (σHTM) increased with increasing voltage because of the
higher gradient of hole density in HTM due to the hole injection from
the MAPbI3 layer. Hence, the device performance of CzPAF-TPA was
better than that of PEDOT:PSS, as evidenced by the above investiga-
tions. The stability of flexible i-PSCs based on HTMs is discussed below.
Having the appropriate energy levels, mobility and solubility for
CzPAF-TPA prompted us to explore its hole transporting behavior in
BHJ IOSCs on both flexible and rigid substrates. Thus, firstly, we ex-
amined the photovoltaic properties of CzPAF-TPA and PEDOT: PSS as
HTMs in flexible BHJ IOSCs. These were fabricated with a flexible in-
verted structure of PET/ITO/ZnO/PTB7-Th:PC71BM/HTM/Ag, as dis-
played in Fig. 4a,b. Here, the HTM was spin-coated on the photoactive
layer (PTB7-Th:PC71BM), wherein PTB7-Th and PC71BM were used as
an electron donor and acceptor, respectively, to act as a bulk hetero-
junction blend in the active layer. The optimized J–V and IPCE curves of
flexible BHJ IOSCs with PEDOT:PSS and CzPAF-TPA are displayed in
Fig. 4c,d. The flexible BHJ IOSCs with PEDOT:PSS exhibited a max-
imum PCE of 6.82% with Jsc of = 17.08 mA cm−2, Voc of = 0.78 V, and
FF of = 51.50%, compared to a slightly superior PCE of 7.52% with Jsc
of = 17.32 mA cm−2, Voc of = 0.79 V, and FF of = 56.70% for the
flexible BHJ IOSCs based on CzPAF-TPA. The same trend was noticed
when fabricated on rigid substrate (Fig. 5). The rigid substrate based
BHJ IOSCs with PEDOT:PSS as HTM showed a maximum PCE of 8.28%
(Jsc = 16.68 mA cm−2, Voc = 0.80 V, and FF = 61.75%). The CzPAF-
TPA based BHJ IOSCs on rigid substrate exhibited a higher PCE of
8.74% with Jsc of = 16.72 mA cm−2, Voc = 0.80 V, and FF = 65.25%.
The slightly augmented PCE in the flexible as well as rigid BHJ IOSCs
based on CzPAF-TPA was due to their enhanced Jsc and FF values. Jsc
was enhanced because of a slightly higher mobility than that of PED-
OT:PSS (Fig. S5). Further, the improved Jsc values of CzPAF-TPA based
devices are correlated from their improved EQE spectra than PED-
OT:PSS. This increased FF of CzPAF-TPA devices could be due to the
increased Rsh and decreased Rs in flexible substrate and also in rigid
substrate based BHJ IOSCs (values are provided in Tables 3 and 4),
which in turn enhanced the PCE for CzPAF-TPA. The J–V characteristics
of flexible BHJ IOSCs were conducted under the dark at ambient con-
ditions to illustrate the hysteresis (Fig. 4e). The rectification ratios were
calculated for flexible BHJ IOSCs based on the dark J-V curves at ±
2.0 V. They had rectification ratios of 4.45 × 103 and 9.29 × 103 for
PEDOT:PSS and CzPAF-TPA HTMs, respectively. As shown in Fig. 4d,
the IPCE spectra of flexible BHJ IOSCs with CzPAF-TPA were in the
range of 300–800 nm, which was similar to that of the PEDOT:PSS-
based devices that designated a comparable device performance.
Moreover, the integrated Jsc of the IPCE are within the error limit (see
Table 3). The histogram of PCEs of flexible BHJ IOSCs based on two
HTMs was displayed in Fig. 4f. To further understand the charge
transport at the interface of flexible BHJ IOSCs, AC impedance mea-
surements were carried out on PEDOT:PSS and CzPAF-TPA-based de-
vices, as shown in Fig. S9. The AC impedance consists of a single de-
pressed semicircle for each flexible BHJ IOSC that could be utilized to
calculate the internal resistance of thin films. The equivalent resistance
of the flexible BHJ IOSCs made from CzPAF-TPA is around 0.62 kΩ,
which is smaller than the value of flexible BHJ IOSCs with PEDOT:PSS
(~ 1.32 kΩ). This indicates that the CzPAF-TPA layer enhanced the
contact between the photoactive layer and ZnO layer, charge transport
resistance from ZnO layer to the electrode, resulting in increased Jsc and
FF, which in turn enhanced the photovoltaic performance. Similarly,
the same trend was found in rigid BHJ IOSCs, and the histogram of
PCEs was showed in Fig. 5e.
Since the ambient stability is most vital parameter for realizing
practical solar cells, we performed stability tests for fabricating i-PSCs
and BHJ IOSCs on both flexible and rigid substrates without any en-
capsulation at room temperature for more than ~ 500 h and 30 days,
respectively. As seen in Figs. 2g, 3f, 4g, and 5f, the stability of CzPAF-
TPA-based devices was significantly better than that of PEDOT:PSS, the

14
S.S. Reddy et al. Nano Energy 41 (2017) 10–17

Fig. 4. a) Flexible device structure, b) corresponding energy level diagram of BHJ IOSCs, c) J-V characteristics, d) IPCE spectra of the flexible BHJ IOSCs with PEDOT:PSS and CzPAF-TPA
as HTMs, e) dark J-V curves, f) histogram of flexible BHJ IOSCs efficiencies and g) real PCEs of BHJ IOSCs as a function of time in days.

Fig. 5. a) Rigid device structure of BHJ IOSCs, b) J-V characteristics, c) IPCE spectra, d) dark J-V curves with PEDOT:PSS and CzPAF-TPA as HTMs, e) histogram of BHJ IOSCs efficiencies
and f) real PCEs of BHJ IOSCs as a function of time in days.

Table 3
Photovoltaic performances of flexible BHJ IOSCs with PEDOT:PSS and CzPAF-TPA as HTMs.

HTM Voc (V) Jsc (mA cm−2) FF (%) PCE (%) Integrated Jsc (mA cm−2) Rs (Ω cm2) Rsh (Ω cm2)

PEDOT:PSS 0.78 17.08 51.50 6.82 17.21 5.32 3.98 × 105

CzPAF-TPA 0.79 17.32 56.70 7.52 17.46 3.56 7.96 × 105

Table 4
Photovoltaic performances of rigid BHJ IOSCs with PEDOT:PSS and CzPAF-TPA as HTMs.

HTM Voc (V) Jsc (mA cm−2) FF (%) PCE (%) Integrated Jsc (mA cm−2) Rs (Ω cm2) Rsh (Ω cm2)

PEDOT:PSS 0.80 16.68 61.75 8.28 16.00 1.47 1.46 × 105

CzPAF-TPA 0.80 16.72 65.25 8.74 16.21 1.29 1.80 × 105

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S.S. Reddy et al. Nano Energy 41 (2017) 10–17

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16
S.S. Reddy et al.
Saripally Sudhaker Reddy is currently a Postdoctoral
Fellow at Pusan National University (PNU), Korea. He re-
ceived his M.Sc. from Vellore Institute of Technology in
2010, majoring in Organic Chemistry. He joined Albany
Molecular Research Incorp., (AMRI), in the department of
Research & Development, and worked as a Research
Scientist from 2010 to 2013. He received his Ph.D. in
Chemical Materials from PNU in 2017. His main research
interests include the design, synthesis and characterization
of new organic functional materials for the applications in
organic light-emitting diodes and organic & perovskite solar
cells.
Sungmin Shin received her B.S. (2015) from the
Department of Chemistry at Kyungsung University. He is
currently a master student at Pusan National University. His
research focuses on synthesis of new organic hole trans-
porting materials for perovskite solar cells and organic solar
cells.
Um Kanta Aryal received his M.Sc. from Tribhuvan
University, Nepal in 2013, majoring in solid state physics.
Currently, he is a Ph.D. student at Pusan National
University from 2015. His main research interests include
understanding the device physics and the fabrication of
organic solar cells.
Ryosuke Nishikubo received his bachelor degree in ap-
plied chemistry from Osaka University, Japan in 2016. He
is currently a master course student at Osaka University.
His research interest is in optoelectronic properties and
fundamental of physical chemistry involved in organic and
organic-inorganic hybrid materials.
17
Nano Energy 41 (2017) 10–17
Akinori Saeki is currently an associate professor at Osaka
University and a researcher of Precursory Research for
Embryonic Science and Technology (PRESTO) program of
Japan Science Technology Agency (JST). He received his
Ph.D. (engineering) in applied chemistry from Osaka
University in 2007. He had been an assistant professor in
2003–2014 at Osaka University, Japan. His research in-
terest is in nanometer-scale dynamics of chemical inter-
mediates in condensed matters such as organic semi-
conductors and organic liquids. He is the author or
coauthor of over 200 publications.
Myungkwan Song is currently a senior researcher in the
Korea Institute of Materials Science (KIMS). He received his
Ph.D. in chemistry material from Pusan National University
in 2011. His research interests include thin film (organic/
inorganic) photovoltaic, transparent conducting electrodes
(TCEs) with nanowire, metal mesh and their nanos-
tructured sensing devices.
Professor Sung-Ho Jin was born in Pusan, Korea, in 1964.
He received his B.S. in Chemistry from Pusan National
University in 1988 and his Ph.D. in Chemistry from the
Korea Advanced Institute of Science and Technology
(KAIST) in 1993. In the same year he joined the Samsung
Advanced Institute of Technology (SAIT) as a Senior
Researcher where he worked in the field of Display
Division. He joined the faculty of Pusan National University
in 1999. His main research interests are synthesis of new
functional materials for electronic devices. He is the author
or coauthor of over 450 publications and 65 patents.