Nano Energy 121 (2024) 109219

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Nano Energy
journal homepage: www.elsevier.com/locate/nanoen

High-performance semi-transparent organic solar cells driven by the

dipole-controlled optoelectrical response of bilateral self-assembled
monolayer strategy
Muh Fadhil Albab a, b, Muhammad Jahandar a, Yong Hyun Kim b, Yong-Ki Kim c,
Myunghun Shin c, *, Adi Prasetio a, Soyeon Kim a, *, Dong Chan Lim a, *
a
Department of Energy & Electronic Materials, Surface Materials Division, Korea Institute of Materials Science (KIMS), Changwon 51508, Republic of Korea
b
Department of Smart Green Technology Engineering, Pukyong National University, Busan 48513, Republic of Korea
c
School of Electronics and Information Engineering, Korea Aerospace University, Goyang-city, Gyeonggi-do 412-791, Republic of Korea

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

Keywords: A bilateral self-assembled monolayer (SAM) strategy is proposed to improve the performance of both opaque/
Electron transport layer translucent and rigid/flexible organic solar cells (OSCs), which have great potential for various high-value ap­
Interfacial modification plications such as portable, building-integrated and vehicle-integrated photovoltaics. By applying the dipole-
Organic solar cells
controlled SAMs to both ITO/ZnO and ZnO/active layer interfaces, the work function of the ZnO electron
Self-assembled monolayer
transport layer was reduced, which improved charge transport and reduced carrier recombination at the inter­
Semi-transparent organic solar cells
face. The opaque OSCs with the bilateral SAM demonstrated significant performance improvement with power
conversion efficiencies (PCEs) reaching 17.20% and 16.96% for rigid and flexible OSCs. When used in semi-
transparent OSCs together with MoO3/Ag/MoO3 electrode, in semi-transparent (ST) OSCs, PCE and average
visible transmittance (AVT) can be improved simultaneously, and 10.37% PCE and 36.27% AVT demonstrate a
remarkable light utilization efficiency (LUE) of 3.85%. Finally, the large area (10 × 10 cm2) ST-OSC module was
fabricated and demonstrated a PCE of 8.17% and LUE of 2.5%, among the best-reported values for inverted
module devices. The developed bilateral SAM strategy can be useful in developing high-performance OSCs of
both opaque/translucent and rigid/flexible types for various practical applications.

1. Introduction (AVT) [4,5].

Numerous approaches have been implemented to improve both PCE
Organic solar cells (OSCs) have many advantages for high-value and AVT of ST-OSCs, including the utilization of multi-component active
applications such as portable photovoltaics (PV), vehicle-integrated layers, optimizing the donor/acceptor ratio and structure of the active
photovoltaics (VIPV), and building-integrated photovoltaics (BIPV); layer, and developing near-infrared (NIR) absorption materials such as
OSCs have easily tunable optoelectronic properties, can be manufac­ non-fullerene acceptors [6–8]. However, achieving high PCE while
tured inexpensively using solution processes, and can be lightweight and maintaining high transmission in the visible spectrum remains a sig­
translucent even with excellent mechanical flexibility [1–3]. nificant challenge. Recent studies have introduced the concept of light
Semi-transparent organic solar cells (ST-OSCs) have gained particular utilization efficiency (LUE, calculated as the multiplication product of
interest in BIPV, smart greenhouses, and VIPV and possess useful and PCE and AVT) to evaluate the trade-off between AVT and PCE and to
essential properties (selective light transmission, color reproduction, provide a fair comparison of overall system efficiency [9–11]. This
and flexibility) for these applications. For practical use, the ST-OSCs approach allows for a more comprehensive assessment of ST-OSCs for
need to solve several technical challenges: the intrinsic narrow absorp­ practical applications. Additionally, the development of translucent
tion spectra in the near-infrared spectrum, mismatched molecular en­ organic solar cells on flexible substrates is still technologically less
ergy levels of donor and acceptor, as well as the trade-off between the mature compared to rigid substrates so flexible solar cells have much
power conversion efficiency (PCE) and average visible transmittance lower PCE than rigid solar cells which is one of the major obstacles to

* Corresponding authors.
E-mail addresses: [email protected] (M. Shin), [email protected] (S. Kim), [email protected] (D.C. Lim).

https://doi.org/10.1016/j.nanoen.2023.109219
Received 31 October 2023; Received in revised form 14 December 2023; Accepted 17 December 2023
Available online 20 December 2023
2211-2855/© 2024 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M.F. Albab et al. Nano Energy 121 (2024) 109219

realizing high-performance, large-area flexible PV in roll-to-roll PCE between flexible and rigid solar cells. We present the surface
methods. properties and chemical structures of the bilateral SAMs and apply
Especially for inverted OSCs, engineering the interface between the bilateral SAMs to opaque/translucent and rigid/flexible OSCs to inves­
bottom electrode (cathode) and the photoactive layer is considered a tigate the performance enhancement of various OSCs. The bilateral
feasible method to further improve the PCE of the conventional OSCs, SAMs can control the work function of ZnO ETL to aid carrier transport
and thus modifying the electron transport layer (ETL) is an essential part and reduce carrier recombination. The improved charge transport was
of interfacial engineering. As one of the most widely used ETLs, zinc verified through current density and voltage measurements and analysis
oxide (ZnO) offers high electron mobility, a suitable solution processing of external quantum efficiency (EQE) and time-resolved photo­
method, low cost, and simple modification [12–14]. Despite the ad­ luminescence (TRPL). The carrier recombination suppression is also
vantages of solution processing, it is still difficult to control the internal proven by measuring the bimolecular recombination coefficient, ideal­
gap state of ZnO ETL caused by surface defects [15]. These intragap ity factor, dark current density, and parasitic resistance. The fabricated
states serve as recombination sites for photogenerated charge carriers, ST-OSCs contain an oxide-metal-oxide (OMO of MoO3/Ag/MoO3
resulting in significant photocurrent loss and reduction of the charge structure) electrode structure, so not only PCE but also transparency and
selectivity. If a strategy is available to promote carrier transport and color can be adjusted by changing the Ag thickness. Transparency and
prevent carrier recombination in the ZnO ETL layer, this could signifi­ color coordinates (CIE 1931 chromaticity diagram) are measured and
cantly improve organic solar cell performance. The self-assembled analyzed with optical simulations. Finally, large-area (10 × 10 cm2) ST-
monolayers (SAMs) containing polar functional groups are frequently OSC of rigid and flexible modules are demonstrated with improved
employed to fine-tune the interfacial and optoelectronic properties of transparency and PCE. The strategy using bilateral SAMs can be used for
organic solar cells [2,16,17]. In addition, utilizing the interfacial dipole high-performance organic PV devices in various practical applications.
that results from molecule orientation allows for deliberate control of
surface work function and the light absorption ability of active mate­ 2. Results and discussion
rials. Prior studies on SAM interfacial modification were predominantly
focused on a single interface, either the interlayer between the transport 2.1. Surface characteristics and chemical structures of self-assembled
layer and an active layer or between the transport layer and cath­ monolayers
ode/anode material.
In this study, we propose a novel strategy of bilateral self-assembled The device architecture of organic solar cells (OSCs) using bilayer
monolayer (structure with SAM applied to both ITO/ZnO and ZnO/ SAM and the chemical structures of the SAMs are illustrated in Fig. 1. In
active layer interfaces) of ZnO ETL for ST-OSCs, suitable for large area this study, the SAMs of 1,2 ethanedithiol (EDT) and 2-aminothiophenol
BIPV and VIPV applications. This approach can influence optoelectronic (2-ATP) in combination with a ternary active layer material are used to
modulation, leading to enhancements in charge carrier transport and the improve the performance of OSCs. At first, surface characteristics are
suppression of carrier recombination near the interface with the pho­ investigated using the contact angle measurements (Fig. S1). Without
toactive layer, which can increase the LUE performance index consid­ the SAM formation, the static contact angle of water on the bare indium
ering both the PCE and AVT of the ST-OSCs, and reduce the difference in tin oxide (ITO) and pristine ZnO surfaces was 10.6◦ and 38.0◦ ,

Fig. 1. Schematic diagram of proposed bilateral self-assembled monolayers (SAMs) strategy: a) device architecture of organic solar cell (OSC) and b) chemical
structure of SAMs and the interaction mechanism.

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M.F. Albab et al. Nano Energy 121 (2024) 109219

respectively. EDT and 2-ATP treatments subsequently modified the ITO commonly used as an electron transport layer (ETL) in inverted OSCs,
and ZnO surfaces; the contact angle of EDT-modified ITO increased to where the ZnO selectively facilitates electron transport and blocks hole
20.2◦ , and that of bilayer SAM-modified ZnO increased to 47.8◦ . It in­ transport [23]. However, the presence of Fermi-level pinning still cre­
dicates that the surface hydrophobicity improved and the SAM layers ates the discontinuity (band offset) on the conduction band at the
were successfully formed. The improved hydrophobicity is due to the interface with the active layer, which relaxes the bending of the active
presence of a hydrophobic functional group (aromatic ring) at the layer conduction band, weakening the internal electric field near the
opposite end of the binding site; thus, it can be expected that the active layer, and unfavorable electron transport. An interface monolayer
adhesion with the active layer will be improved [15]. with net dipoles pointing away from ZnO can reduce the potential
The surface morphology did not change significantly after SAM barrier between the ZnO and the active layers and help to form the
treatment. The height profile and surface roughness of the samples were ohmic contact between the two layers. On the other hand, a monolayer
observed using atomic force microscopy (AFM) before and after SAM with net dipoles oriented toward the ZnO layer can act as a severe charge
treatment (Fig. S2). The bare ITO substrate exhibits larger domains, injection barrier and degrade the device’s performance [15]. Therefore,
whereas the EDT film exhibits smaller domains but a slightly smoother to find the influence of the interfacial dipoles on the WF of the ZnO,
surface. The roughness of the unmodified ZnO layer has a root-mean- ultraviolet photoelectron spectroscopy (UPS) was performed to measure
square (RMS) value of ~3.27 nm, and after 2-ATP modification, it the WFs of the ZnO and ITO layers and ultraviolet-visible (UV-Vis)
slightly increases to ~4.25 nm, contributing to the increase in hydro­ spectroscopy was conducted to examine the optical transmittance of
phobicity of the surface [18]. Despite the increased hydrophobicity by ZnO and SAMs-modified ZnO films deposited on ITO glass substrates
the SAM treatments, the roughness of both active layers on the pristine (Fig. S7). Fig. 2a depicts the energy band diagram of a bilateral
ZnO and the SAMs-modified ZnO were similar in the AFM images SAMs-modified inverted OSC (shown in Fig. 1a) based on the UPS and
(Fig. S3). Moreover, a topological investigation of surface potential was UV-Vis spectroscopy. The WF of the pristine ZnO is approximately
also performed using Kelvin probe force microscopy (KPFM) of SAMs 4.18 eV. Upon modification with 2-ATP, the WF of the treated ZnO is
coating on top of ITO and ZnO, respectively as shown in Fig. S4, con­ tailored to 3.95 eV. Additionally, the WF of the ZnO films grown on the
firming self-assembled monolayers’ horizontal uniformity distribution. EDT-modified substrate is lowered to 4.00 eV. Compared to the bandgap
The XPS spectra of S 2p, N 1s, Zn 2p, and O 1s (Fig. S5) can provide structure of the pristine ITO/ZnO interface (Fig. 2b), the lowered WF of
insights into the surface chemistry of the un-modified and 2-ATP-modi­ the electron transport layer ZnO, induced by the interfacial dipole, re­
fied ZnO nanoparticles. The deconvolution of the S 2p line of the 2-ATP duces the band offset between the ZnO and the active layer and pulls
on ZnO reveals two primary components with peak maxima at 162 and down both the lowest unoccupied molecular orbital (LUMO) and highest
163.4 eV, respectively. The peak at lower binding energy corresponds to occupied molecular orbital (HOMO) levels of active layer at the inter­
the thiol bonding in the bulk ZnO matrix, and the thiol molecules face as shown in Fig. 2c,d; it is expected that strong internal electric field
covalently bind onto the ZnO nanoparticles to form zinc thiolates [19]. formed, and the internal field can allow electrons to easily pass through
The formation of the Zn-S (thiolate) bond can be attributed to the ZnO and repel holes, reducing recombination losses. Furthermore, the
presence of the zinc interstitial (Zni) and oxygen vacancies (VO) in the WF of the EDT-modified indium tin oxide (ITO) was measured to be
ZnO structure. In contrast, the peak at higher binding energy is ascribed 4.32 eV, whereas that of non-modified ITO was 4.62 eV.
to the unreacted thiol from the SAM-forming molecules. The Zn 2p peaks To provide further insight into the effect of dipole moment (DM) on
exhibit a slight shift to higher binding energy, which indicates that the the modification of the WF, we conducted observations on various SAM
Zn atoms become more electron-rich with the SAM due to the interaction materials. Fig. S6 also presents the DM values: TP (DM = 1.53 D), 2-ATP
between Zn and S 2p [20]. The deconvoluted N 1s XPS spectrum exhibits (DM = 1.28 D), and 4-ATP (DM = 1.69 D). The WF values of ZnO for the
two peaks at 398.8 and 400.2 eV, which correspond to the nitrogen atom SAM treatment were determined from the secondary electron cut-off in
present in 2-ATP. This observation suggests that the nitrogen atoms have the UPS measurements (Fig. S8), which is summarized in Table S1. Our
been adsorbed onto the ZnO surface, and some amine bonding has taken findings indicate that SAMs with higher dipole moments tend to sub­
place. This bonding may be attributed to the N-O and Zn-N bonding stantially reduce the WF of ZnO. Specifically, the order of WF with DM is
within the bulk ZnO matrix. Furthermore, the O 1s XPS spectra reveal as follows: untreated ZnO (4.18 eV without DM) > ZnO/2-ATP (3.95 eV
two distinctive peaks at 531.1 and 532.8 eV. The higher binding energy with 1.28 D) > ZnO/TP (3.92 eV with 1.53 D) > ZnO/4-ATP (3.86 eV
peak is often linked to weak oxygen surface bonds, like OH groups, while with 1.69 D). Nonetheless, the work function calculations indicate that
the lower binding energy peak is connected to the Zn-O bulk network the ZnO/2-ATP (3.95 eV) configuration exhibited superior alignment
[21,22]. In addition, the deconvolution of the S 2p line for EDT-modified with the LUMO of the photoactive layer compared to other SAM
ITO depicted in Fig. S5 reveals that some of the thiols are bonded to the materials.
bulk ITO structure at low binding energy (161.2 eV) and that some of the To further investigate the impact of the SAM modification on the
S atoms unbounded in the surface as indicated at higher binding energy defect density of ZnO, the photoluminescence (PL) spectra were
(162.2 eV). Therefore, XPS provides evidence for the molecular grafting measured (Fig. S9). The observed peak intensities of ZnO PL are strong
of 2-ATP and EDT on the ZnO and ITO substrates, respectively, along in the following order: UV emission at ~370 nm (near band edge
with the corresponding chemical interactions at the surfaces. emission), blue emission at ~ 401 nm (recombination of free excitons in
conduction and valence bands), and broad visible-emission at ~470 nm
2.2. Proposed interaction mechanism of self-assembled monolayers (radiative transitions via defects) [24]. These PL emissions are sub­
stantially suppressed after the bilateral SAM treatment. Moreover, the
The underlying interaction mechanism that the proposed SAM en­ slight red shift (from 401 to 404 nm) of the blue emission peak observed
hances OSC performance can be elucidated as such: The SAM with the after 2-ATP-modified ZnO implies an exciton transition, which is mainly
aligned dipole moment effectively decreases the work functions (WF) of found in oxygen-deficient materials. This peak shift in PL emission
the interfacial layer and the photoactive material, subsequently suggests that the 2-ATP and EDT were grafted onto the ZnO matrix,
reducing the energy barrier (or band offset) at the interface. This resulting in a decrease in oxygen content [25,26]. The broad
reduction engenders an internal electric field in the active layer near the visible-emission (Table S2) refers to radiative transitions via defects, and
interface. Such a field facilitates the efficient separation of electrons and its reduction shows that defect densities decreased after the bilateral
holes within the active layer and aids in the electron transport process. SAMs treatment.
Furthermore, this electric field expels holes, thereby reducing the carrier
recombination loss. A more detailed elucidation is presented henceforth.
Because of the deep energy level of the valence band, ZnO is

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M.F. Albab et al. Nano Energy 121 (2024) 109219

Fig. 2. Energy band structure: a) schematic illustration of energy band of OSC, and energy band structure near ZnO interface b) without dipole moment modification
from SAMs, c) with EDT-modified ITO, and d) 2-ATP-modified ZnO.

2.3. Device performance of organic photovoltaic devices conducted on the device with a different dipole moment of
self-assembled molecules to examine the findings further, as represented
To verify the effects of the SAM treatment, the performance of OSCs in Fig. S10. The experimental results demonstrate that the incorporation
is evaluated and compared for the various ETLs modified by the self- of 2-ATP small molecules, followed by TP and 4-ATP, led to a notable
assembled small molecules. The results are shown in Fig. 3a and the enhancement in not only photocurrent density and EQE but also the
corresponding device parameters are listed in Table 1. The OSCs with device performance and electron mobility, as shown in Table S3 and
pristine ZnO ETL demonstrated a maximum PCE of 15.33% with a JSC of Table S4, respectively.
26.69 mA/cm2, a VOC of 0.80 V, and an FF of 71%. Comparatively, the This enhancement occurred sequentially, as indicated by the pre­
OSCs with self-assembled small molecule modified ZnO ETL showed ceding discussion on WF calculations. It was seen that 2-ATP, although
improved PV performance. The OSCs with EDT-modified ITO exhibited the dipole moment is slightly lower than that of 4-ATP, exhibits the most
a PCE of 16.02%, and the OSCs with bilateral SAM (ITO/EDT/ZnO/2- pronounced enhancements in terms of electrical characteristics when
ATP) showed an even better PCE of 17.20%. compared to other small molecules coating. This happens due to its well-
The observed enhancement can be attributed to the interaction of the matched energy level alignment with the Y6 acceptor layer.
active layer with the SAM induced by the dipole moment, which in­ Carrier transport characteristics are also related to carrier mobility.
creases the carrier transport and light absorption ability, and it is The carrier with low mobility values can limit the JSC and FF of the
consistent with the literature about the beneficial effects of modifying device. In this research, the electron mobility of both pristine ZnO films
the ZnO transport layer with SAMs containing EDGs or ultrathin poly­ and SAMs-modified layers was investigated using space charge limited
mer films with similar polarity [27]. This can be seen in Table 1 in this current (SCLC) measurements. As shown in Fig. 3c, the J-V curves of the
study as the increase in JSC contributed the most to performance two devices correspond well with an R2 value maintained at over 99% by
improvement, followed by the increase in VOC and FF. The EQE was the SCLC mode, suggesting an ohmic contact region and an SCLC region
measured for devices with and without SAM modification (Fig. 3b). The without a trapped space charge region. Table 2 records the electron
integral current density values estimated from EQE spectra and JSC mobility values obtained from the measurements, where electron mo­
values at the J-V curves are in good agreement. Given that both un­ bilities improve from 1.16x10-4 cm2/Vs for pristine ZnO to 8.86x10-4
modified and modified ZnO exhibit similar optical absorbance, it is ex­ cm2/Vs for bilateral SAMs modification. The higher mobility implies the
pected that the greater EQE value of the SAMs-modified ZnO is related to presence of a strong internal field, which shows that the bilateral SAMs
more effective charge extraction [28]. The EQE spectra of strategy is beneficial for efficient charge extraction.
SAMs-modified OSCs showed a clear enhancement in the range of 300 – The charge transport and generation properties of photovoltaics with
800 nm. As aforementioned, the increase of EQE in the 300 – 400 nm pristine ZnO, ITO/EDT, ZnO/2-ATP, and EDT/ZnO/2-ATP were
region can be partially attributed to the light absorption slightly analyzed by examining the dependence of photocurrent density (Jph) on
enhanced by the dipoles of the molecules. Electrical investigations were effective voltage (Veff), depicted in Fig. 3d. The graph shows that the

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M.F. Albab et al. Nano Energy 121 (2024) 109219

Fig. 3. Performance and carrier transport analysis of OSCs: a) current density-voltage (J-V) curves under 1-sun condition (100 mW/cm2), b) external quantum
efficiency (EQE) curve, c) space charge limited current (SCLC) density (JSCLC) of the devices with various SAMs modifications, d) photocurrent density (Jph) versus
effective voltage (Veff) characteristics, e) time-resolved photoluminescence curve, and f) J-V curves of flexible devices without and with bilateral SAM interfacial
modification.

photocurrent density reaches saturation (Jsat) in the high effective the bilateral SAMs modification (EDT/ZnO/2-ATP), the decay time
voltage regime (> 0.2 V). This regime indicates that excitons can (1.15 ns) was substantially shorter than the others, implying that elec­
dissociate and generate free charge carriers with the aid of an applied tron extraction from the active layer is more efficient than those of
field, which is then collected by the corresponding electrodes [29]. pristine ZnO and ZnO/2-ATP layers [31].
Therefore, exciton dissociation efficiency (ηdiss) can be determined by The stability of the devices was further examined to assess their
JSC/Jsat. The graph shows that the JSC/Jsat value for 2-ATP-modified ZnO performance under continuous light exposure (100 mW/cm2). Fig. S11
is 94% for both ZnO/2-ATP and EDT/ZnO/2-ATP, whereas the values demonstrates the stability between SAMs-modified ZnO and pristine
for pristine ZnO and ITO/EDT are 90% and 93%, respectively. These ZnO. Compared to its counterpart, the proposed strategy of bilateral
results suggest that efficient electron transport from the active layer to SAMs effectively ensures stability after 100 h of continuous illumina­
the electron transport layer in 2-ATP-modified ZnO can reduce recom­ tion. The enhanced stability of the bilateral SAM devices is attributed to
bination and is advantageous for enhancing the fill factor [30]. the elimination of excess hydroxyl (-OH) groups on the surface of zinc
Further investigation was carried out into the phenomena of charge oxide (ZnO), where Zn-S(thiolate) bonds from SAMs replace these -OH
extraction from the Y6 acceptor layer deposited on various SAM modi­ groups. This interaction effectively prevents the ZnO film from under­
fications using TRPL decay characterization. Fig. 3e depicts the TRPL going photocatalytic degradation [32]. Furthermore, the enhanced sta­
curves for an emission wavelength of 850 nm with an excitation wave­ bility of the current density was significantly achieved due to suppressed
length of 405 nm. The decay time of the TRPL spectrum of Y6 on ZnO/2- recombination and the presence of photogenerated charge centres at the
ATP is 1.23 ns, which is shorter than the ZnO decay time of 1.29 ns. For interface, as previously revealed in the photoluminescence analysis.

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Table 1 To demonstrate that the proposed bilateral SAMs approach is also

The comprehensive device performance of rigid OSCs comprised PM6:Y6:PCBM useful for flexible devices, flexible OSCs with an inverted structure and a
as the photoactive layer with different SAMs-modified ETL measured under AM PM6:Y6:PCBM active layer were fabricated on flexible PET/ITO sub­
1.5 G illumination. strates. Fig. 3f and Table S5 provide measurements and summaries of the
ETL PCE (%) VOC (V] JSC (mA/ FF Calculated JSC J-V curves for the devices with pristine ZnO and SAM-modified ZnO. The
material (PCEAVE)a cm2) (mA/cm2) flexible OSC with pristine ZnO exhibited a low performance (PCE of only
ZnO 15.33 0.80 26.69 0.71 25.60 13.21%, VOC of 0.82 V, JSC of 23.48 mA/cm2, and FF of 0.70). In
(15.15 (0.79 (26.59 (0.70 contrast, the flexible OSC with the EDT/ZnO/2-ATP cathode interlayer
± 0.36) ± 0.01) ± 0.39) ± 0.01) achieved higher performance (PCE of 16.96%, VOC of 0.83 V, JSC of
ZnO/2- 16.39 0.82 27.97 0.72 26.94
ATP (16.30 (0.81 (27.63 (0.71
28.12 mA/cm2, and an FF of 0.72). Noticeably, the PCE ratio between
± 0.13) ± 0.01) ± 0.32) ± 0.01) rigid- and flexible-type devices ETL was found to be 98.6%, which was
EDT/ ZnO 16.02 0.82 27.52 0.71 25.87 one of the highest ratios compared to those of ZnO, which had a flexible
(15.83 (0.81 (27.31 (0.70 to rigid (F2R) PCE ratio of 77.9%. This high F2R PCE ratio demonstrates
± 0.18) ± 0.01) ± 0.13) ± 0.01)
that the proposed bilateral SAMs are a very important strategy to
EDT/ 17.20 0.83 28.38 0.73 27.03
ZnO/2- (16.74 (0.82 (28.16 (0.72 improve the performance of flexible devices and are essential for the
ATP ± 0.37) ± 0.01) ± 0.16) ± 0.01) further development of high-performance flexible OSCs.
a
)The numbers in parentheses represent a mean performance across 8 different
devices 2.4. Charge carrier recombination analysis

The power law expression governs the relationship between the JSC
Table 2
and light intensity as JSC ∝Iα , where I is light intensity, and the exponent
Mobility (μ) of charge carriers as measured by space
charge limited current (SCLC) method.
α describes the bimolecular recombination coefficient. The closer the
value of α is to one, the smaller the recombination loss. In Fig. 4a, the α
ETL material µe
values for the OPV devices with ZnO, ZnO/2-ATP, EDT/ZnO, and EDT/
(cm2 /Vs)
ZnO/2-ATP were found to be 0.92, 0.93, 0.94, and 0.95, respectively. In
ZnO 1.16 × 10-4
addition, the VOC can be represented as VOC (I) = nkqB T ln(I) + C, where n,
ZnO/2-ATP 4.15 × 10-4
EDT/ZnO 2.85 × 10-4 kB , T, q, and C denote the ideality factor, Boltzmann constant, temper­
EDT/ZnO/2-ATP 8.86 × 10-4 ature, elementary charge, and a constant, respectively. In general, the
ideality factor n is extracted from the slope of the graph of Fig. 4b, the

Fig. 4. Carrier recombination analysis of OSCs: a) light intensity as a function of short circuit current density (JSC), b) light intensity as a function of open circuit
voltage (Voc), c) measured J-V curve under dark conditions and d) Nyquist plot with various SAM modifications measured under AM 1.5 G 1-sun illumination.

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M.F. Albab et al. Nano Energy 121 (2024) 109219

smaller the n value, the smaller the recombination current component; wavelength range (> 700 nm) are advantageous for ST OSCs, which can
the values of 1.43, 1.28, 1.42, and 1.27 were obtained for the ZnO, ZnO/ simultaneously improve AVT and PCE [40,41]. Thus, the highly trans­
2-ATP, EDT/ZnO, and EDT/ZnO/2-ATP devices, respectively. The re­ parent OSC has been produced as shown in Fig. 5c. Adjusting the Ag
sults obtained by observing α and n values suggest that OSCs containing thickness can change not only the AVT but also the transmission color of
EDT/ZnO/2-ATP have the lowest trap-associated recombination loss the OSCs. In Fig. 5d, with the increasing Ag thickness, the transmission
due to intragap state passivation of ZnO and repelling holes by the color shifts toward blue on the CIE 1931 color coordinates. The device
enhanced internal electric field following SAMs modification [33,34]. It featuring a 10 nm Ag interlayer thickness demonstrated color co­
increases VOC and FF [35]. ordinates of (0.27, 0.29), which is nearer to a neutral color sensation
To obtain a more comprehensive understanding of the improved VOC when viewed through the film under AM 1.5 G illumination, in contrast
and FF observed in the OSC devices, dark J–V characteristics were to other Ag layer thicknesses that evoke a light-blue sensation to the
measured (Fig. 4c), and shunt resistance (RSH) and ideality factor (n) are human eye. Fig. 5e exhibits the dependency of J-V curves for the Ag
listed for the ETL materials in Table 3. The RSH is a crucial path leaking interlayer thickness, as the detailed device performance and AVT are
the generated current and reducing both VOC and FF [36]. In the range of provided in Table S7. The high PCE of devices with 50-nm (16.66%) and
− 0.5 to 0 V, the reverse-biased EDT/ZnO/2-ATP devices exhibited 40-nm (15.66%) Ag exhibit a transmittance of less than 10% in the
significantly suppressed leakage currents (RSH of 4.80 × 106 Ω cm2) visible region. Notably, the general transmittance standard for BIPV
when compared to the pristine ZnO, ZnO/2-ATP, and EDT/ZnO devices, applications is considered to be above 25% [42]. Therefore, 10 nm and
of which RSH values are 5.52 × 105, 6.53 × 105, and 8.56 × 105 Ω cm2, 20 nm of Ag thickness are preferred for this application considering the
respectively. transmittance of 36.27% (PCE of 10.37%) and 25.74% (PCE of 12.14%),
The interfacial charge transport properties of the organic photovol­ respectively. These results demonstrate one of the best-reported PCEs in
taic (OPV) devices were also analyzed through electrochemical imped­ inverted semi-transparent organic solar cells, which shows a light uti­
ance spectroscopy (EIS). Fig. 4d shows the semi-circle curves from EIS lization efficiency (LUE) exceeding 3.5% as indicated in Fig. 5f and
measurements, which were fitted using an equivalent circuit (inset of Table S8.
Fig. 4d). The extracted parameters from this analysis are summarized in The material structure of the photoactive layer also contributes to the
Table S6 in Supporting Information. The left x-intercept represents the performance enhancement of the ST-OSCs. PM6, Y6, and PCBM of the
series resistance (RS) including the electrodes, the bulk resistance within active layer serve as donor, acceptor, and acceptor additives (weight
the active layer, and interface impedance. Therefore, the smaller RS ratio of 1:1:0.2, respectively). The absorption profile of the active layer
value for the EDT/ZnO/2-ATP device indicates less impedance at the (PM6:Y6:PCBM) is provided in Fig. S12. The PM6 layer is mainly
interface, which signifies the effect of the FF and JSC enhancement of the responsible for absorption in the visible light region (with a maximum
device [37]. absorption peak at 620 nm), the Y6 (BTP-4 F) layer is the complemen­
tary absorption in the long wavelength region (600 – 1000 nm with a
peak at 829 nm), and the PCBM is in the UV region (peak at 340 nm).
2.5. Photovoltaic performance of semi-transparent OSCs Since the visible wavelength transmittance (380 – 780 nm) is important
for the AVT of ST-OSCs [7], a small amount of PCBM was used, which is
The concept proposed in this study can be a very effective and sufficient for UV absorption while reducing the parasitic absorption in
valuable new strategy in the development of translucent solar cells as the visible region. We note that 51% of the solar photon flux resides in
well as opaque solar cells. To demonstrate the successful outcomes of a the near-infrared (NIR) region, and 2% also resides in the ultraviolet
bilateral SAM strategy on the overall performance of organic photo­ (UV) region; an ideal active layer for ST-OSCs should have a high
voltaics, we used EDT/ZnO/2-ATP as the cathode interlayer and fabri­ transmittance in the visible region and high absorbance in UV and NIR
cated both rigid and flexible ST-OSCs. Fig. 5a depicts the device regions [42]. Consequently, the increased efficiency while keeping a
architecture of the ST-OSCs. Herein, we employed the OMO multilayer high light transmittance is based on optimizing the OMO top electrode,
electrode composed of MoO3 and Ag for the top electrode. The OMO photoactive layer material selection, and enhanced overall device per­
(MoO3/Ag/MoO3) multilayer electrodes can offer high transmittance by formance through optoelectrical response due to bilateral SAMs inter­
destructive interference reflection and suppression of surface plasmon facial modification. The proposed strategy of bilateral SAMs was also
resonance (SPR) [38]. It is noteworthy that the thickness of the bottom applied in different active layer materials with fullerene and
MoO3 layer is fixed at 15 nm to ensure effective charge extraction from non-fullerene-based acceptors, as revealed in Table S9 for
the active layer. In addition, the top MoO3 layer is 25 nm, which can non-transparent and Table S10 for transparent devices. The results show
exhibit the optimal performance based on previous optical calculations a consistent pattern where adding bilateral SAMs can improve the per­
[39]. Hence, in this study, we optimize the thickness of the intermediate formance of both rigid and semitransparent devices.
Ag layer considering the AVT and PV performances.
The transmittance spectra of the devices for the different thicknesses 2.6. Optical simulations of OSCs
of Ag electrodes in OMO electrodes were measured and represented in
Fig. 5b, where the overall transparency increases with the decrease of Ag The optical properties of OSCs are investigated by using optical
thickness. Preliminary experiments showed that when the Ag layer was simulations. First, we set the optical parameters (refractive index and
thinner than 10 nm, it did not achieve sufficient conductivity for the extinction coefficient) of the EDT/ZnO/2-ATP cathode interlayer and
electrodes in general OSCs. Note that high transmittance in the visible PM6:Y6:PCBM active layer. For the optical model of OSCs, samples of
light range (400 – 550 nm) and low transmittance in the long EDT/ZnO/2-ATP (~60 nm) and PM6:Y6:PCBM (~120 nm) were pre­
pared on a glass substrate, and their transmittance and reflectance were
Table 3 measured. The optical parameters of the cathode and active layers are
Shunt resistance (Rsh) and ideality factor (n) were obtained from dark J-V extracted based on the measured transmittance and reflectance
curves with a different ETL modification. (Fig. S13) of these samples [33,43]. Next, using the obtained optical
ETL Material RSH n parameters, we conducted optical simulations for semi-transparent and
(Ω cm2) non-transparent OSCs using a finite-difference time-domain method.
ZnO 5.52 × 105 1.40 The absorbance of each layer in the opaque OSCs, and the optical
ZnO /2-ATP 6.53 × 105 1.35 transmittance and transmitted color of the semi-transparent OSCs were
EDT/ZnO 8.56 × 105 1.32 calculated. For the opaque OSCs, the external quantum efficiency (EQE)
EDT/ZnO/2-ATP 4.80 × 106 1.25
was evaluated by analyzing the optical absorption spectrum of the

7
M.F. Albab et al. Nano Energy 121 (2024) 109219

Fig. 5. Results of ST-OSCs: a) schematic representation of a device structure with the oxide-metal-oxide (OMO) top electrode, b) transmittance spectra with different
thicknesses of the Ag intermediate layer, c) fabricated semi-transparent organic solar cell (ST-OSC) with a 10 nm intermediate Ag layer, d) color coordinates for
transmitting colors of ST-OSCs on the CIE 1931 xy chromaticity diagram. e) J-V curves of small-area ST-OSCs with various Ag layer thicknesses, and f) comparison of
PCE and average visible transmittance (AVT) for this work and some representative small areas (less than 1 cm2) of inverted ST-OSCs.

device. In Fig. 3b, overall EQE values in the range of 400 – 800 nm are contributes to the EQE. Therefore, a clear increase in EQE can be seen at
enhanced with the 2-ATP SAM, and the EQE in the short wavelengths the 300 – 800 nm wavelength range is observed in Fig. 3b. For semi-
below 400 nm are also improved. Fig. 6a shows the calculated EQE transparent OSCs, the transmittance spectrum and color coordinates
absorbance spectra in the ZnO and PM6:Y6:PCBM active layers and the were analyzed depending on the Ag thickness of the OMO multilayer
calculated EQE of the device. The calculated EQE of the device is very electrode. As can be seen in Fig. 6b, the simulated transmittance is
similar to the EQE observed in the OSC using the 2-ATP SAM (Fig. 3b), consistent with the actual measurement results, and Fig. 6c shows
which shows that most of the generated carriers in the 400 – 800 nm similar trends in color coordinates for the thickness of the OMO
wavelength range are successfully transferred via 2-ATP SAMs. In electrodes.
addition, comparing Fig. 3b and Fig. 6a in 300 – 400 nm it shows the 2-
ATP SAMs are advantageous for transferring the generated carriers. The
OSCs without 2-ATP exhibit EQE curves similar to the calculated EQE 2.7. Large area OPV modules
only in the active layer; it implies that only the absorbance in the PM6:
Y6:PCBM active layer contributes to the EQE when without 2-ATP SAM. Enhancing the efficiency of large-area organic solar cells (OSCs) re­
However, in SAMs-modified OSCs, the absorbance in the ZnO layer also mains a significant obstacle, influenced by various factors such as the
mechanism of film formation, substrate properties, coating methods,

Fig. 6. Optical simulation results: a) EQE for the opaque OSC, b) transmittance spectra with different thicknesses of the Ag intermediate layer, and c) color co­
ordinates for transmitting colors of ST-OSCs on the CIE 1931 xy chromaticity diagram.

8
M.F. Albab et al. Nano Energy 121 (2024) 109219

materials used in the photoactive layer, and the interface layer (specif­ CRediT authorship contribution statement
ically the cathode interface layer). These factors, in turn, impact the
device’s overall performance, leading to reduced efficiency [44,45]. Lim Dong Chan: Conceptualization, Methodology, Project admin­
Therefore, in order to assess the potential of the bilateral SAMs strategy istration, Resources, Supervision, Visualization, Writing – original draft,
in various practical applications, we fabricated large-area OPV modules Writing – review & editing. Kim Yong-Ki: Investigation, Writing – re­
with a size of 10 × 10 cm2 (active area of 54 cm2) on both rigid view & editing. Kim Yong Hyun: Conceptualization, Methodology,
glass/ITO and PET/ITO substrates. The J-V characteristics of the Writing – review & editing. Jahandar Muhammad: Formal analysis,
semi-transparent OPV modules are presented in Fig. S14, and the cor­ Investigation, Writing – original draft, Writing – review & editing. Albab
responding device parameters are summarized in Table S11. The rigid Muh Fadhil: Formal analysis, Investigation, Writing – original draft,
and opaque module with a MoO3/Ag (15/100 nm) top electrode exhibits Writing – review & editing. Kim Soyeon: Conceptualization, Method­
the highest PCE of 13.88% (VOC of 9.11 V, JSC of 2.43 mA/cm2, and FF of ology, Supervision, Visualization, Writing – review & editing, Resources,
0.62). The PCE of flexible and opaque modules is 10.66% (VOC of Validation. Prasetio Adi: Investigation, Writing – review & editing.
8.86.11 V, JSC of 2.43 mA/cm2, and FF of 0.62). Shin Myunghun: Conceptualization, Methodology, Supervision,
By using bilateral SAM modifications and OMO (MoO3/Ag/MoO3 = Writing – review & editing, Data curation, Visualization.
15/20/25 nm) electrodes, the ST-OSCs achieved remarkable PCEs:
10.75% and 7.85% for rigid- and flexible-type transparent modules,
respectively. In addition, when using a very thin Ag interlayer in the Declaration of Competing Interest
OMO (15/10/25 nm), the OSCs showed a PCE of 8.17% and 5.12%,
respectively. Note that all devices were prepared and fabricated under The authors declare the following financial interests/personal re­
the same conditions. From a LUE perspective, to our best knowledge, a lationships which may be considered as potential competing interests:
PCE of 8.17% is the highest efficiency for the large-area (> 1 cm2) semi- Dong Chan Lim reports financial support was provided by National
transparent modules with an AVT value higher than 35% and a LUE of Research Foundation of Korea. If there are other authors, they declare
2.5% (Fig. S15 and Table S12). The JSC value was found to be the most that they have no known competing financial interests or personal re­
distinguishing parameter for both types (opaque and ST-OSCs), with the lationships that could have appeared to influence the work reported in
opaque structure exhibiting a larger JSC value due to the re-absorption of this paper.
photons reflected by the opaque Ag that entered the glass but were not
absorbed in the active layer. Thus, we suggest that the optimum Ag Data availability
intermediate thickness that can deliver overall good transmittance and
efficiency for ST-OSCs was 10 - 20 nm, with an average transmittance of Data will be made available on request.
≥ 25%.
Acknowledgements
3. Conclusions
This research was supported by the Fundamental Research Program
We have successfully demonstrated a novel approach of bilateral of the National Research Foundation of Korea (Grant NRF-
SAMs to improve the performance of opaque/translucent and rigid/ 2020M3H4A3081820).
flexible OSCs for advanced BIPV and VIPV applications. The developed
SAM treatment (EDT in the ITO/ZnO interface, and 2-ATP in the ZnO/ Appendix A. Supporting information
photoactive layer interface) increased hydrophobicity without signifi­
cantly changing the surface roughness. The bilateral SAMs have dipoles Supplementary data associated with this article can be found in the
pointing from the cathode to the photoactive layer at the bilateral in­ online version at doi:10.1016/j.nanoen.2023.109219.
terfaces of the ZnO layer, which reduces the WF of the ZnO layer. The
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M.F. Albab et al. Nano Energy 121 (2024) 109219

Muhammad Jahandar received his Ph.D. in Advanced Mate­ Adi Prasetio obtained his BS from Diponegoro University and
rials and Chemical Engineering from the University of Science MEng from Pukyong National University in South Korea, where
and Technology, Korea, in 2018. He is a senior researcher at the he conducted research on polymeric electron selective layers
Energy and Electronic Materials Center at the Korea Institute of for flexible organic solar cells at the Korea Institute of Materials
Materials Science (KIMS), Korea. His current research focuses Science (KIMS). His areas of interest include organic solar cells,
on device engineering of solution-processed organic perovskite solar cells, silicon heterojunction solar cells, and
photovoltaics. silicon/perovskite tandem solar cells.

Yong Hyun Kim received his Ph.D. in Physics from the Dres­ Soyeon Kim received her Ph.D. degree in Chemical & Bio­
den University of Technology, Germany in 2013. He is molecular Engineering from Yonsei University, Korea in 2017.
currently a Professor of Electronic Engineering at Pukyong She is a senior researcher of the Energy and Electronic Mate­
National University. His areas of interest include alternative rials Center at the Korea Institute of Materials Science (KIMS),
electrodes and stretchable devices, light extraction systems, Korea. Her main research interests are in organic materials,
and interface engineering by doping technology. including synthesis and applications for energy and electronic
devices.

Yong-Ki Kim received his B.S. in the School of Electronics and Dong Chan Lim received his Ph.D. degree in Cluster Physics
Information Engineering at Korea Aerospace University in from Konstanz University, Germany in 2007. He is a principal
2017. He is currently taking a joint Master’s and doctoral De­ researcher at the Energy and Electronic Materials Center at the
gree Course at the School of Electronics and Information En­ Korea Institute of Materials Science (KIMS), Korea. His main
gineering, Korea Aerospace University. His research interests research interests are in photovoltaics and related materials,
include thin film photovoltaic and photonic devices and opto­ such as quantum clusters and transparent electrodes. In addi­
electronic synaptic devices for neuromorphic computing. tion, his research interests include photo-electrochemical de­
vices and hybrid energy conversion materials to create clean
and sustainable energy and water.

Myunghun Shin received his Ph.D in Electrical Engineering at

Korea Advanced Institute of Science and Technology (KAIST),
Korea in 2000. He is now an associate professor at the School of
Electronics, Telecommunications and Computer Engineering,
Korea Aerospace Engineering. His research interests are thin
film photovoltaic devices, high-speed photonics and systems,
microwave photonic devices and applications, and new inter­
disciplinary fields with optical/display devices.

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