Journal Pre-proof

Guest-oriented non-fullerene acceptors for ternary organic solar cells with over 16.0%
and 22.7% efficiencies under one-sun and indoor light

Yongjoon Cho, Tanya Kumari, Seonghun Jeong, Sang Myeon Lee, Mingyu Jeong,
Byongkyu Lee, Jiyeon Oh, Youdi Zhang, Bin Huang, Lie Chen, Changduk Yang
PII: S2211-2855(20)30453-5
DOI: https://doi.org/10.1016/j.nanoen.2020.104896
Reference: NANOEN 104896

To appear in: Nano Energy

Received Date: 19 March 2020

Revised Date: 21 April 2020
Accepted Date: 26 April 2020

Please cite this article as: Y. Cho, T. Kumari, S. Jeong, S.M. Lee, M. Jeong, B. Lee, J. Oh, Y. Zhang,
B. Huang, L. Chen, C. Yang, Guest-oriented non-fullerene acceptors for ternary organic solar cells with
over 16.0% and 22.7% efficiencies under one-sun and indoor light, Nano Energy (2020), doi: https://
doi.org/10.1016/j.nanoen.2020.104896.

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Article type: Full Paper

Guest-Oriented Non-Fullerene Acceptors for Ternary

Organic Solar Cells with over 16.0% and 22.7% Efficiencies
under One-Sun and Indoor Light

Yongjoon Cho,†,§ Tanya Kumari,†,§ Seonghun Jeong,† Sang Myeon Lee,† Mingyu Jeong,† Byongkyu Lee,† Jiyeon Oh,†
Youdi Zhang,† Bin Huang,†,‡ Lie Chen,‡ and Changduk Yang*,†
†
Department of Energy Engineering, School of Energy and Chemical Engineering, Perovtronics Research Center,
Low Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology (UNIST), 50
UNIST-gil, Ulju-gun, Ulsan 44919, Republic of Korea.
‡
Institute of Polymers and Energy Chemistry (IPEC), Nanchang University, 999 Xuefu Avenue, Nanchang 330031,
China
E-mail: yang@unist.ac.kr

Yongjoon Cho: Methodology, Validation, Formal analysis, Investigation, Data Curation,

Writing - Original Draft, Visualization. Tanya Kumari: Methodology, Validation, Formal

analysis, Investigation, Writing - Review & Editing. Seonghun Jeong: Investigation, Resources,

Validation.

Sang Myeon Lee: Investigation, Resources, Validation. Mingyu Jeong: Investigation,

Resources, Validation. Byongkyu Lee: Investigation, Resources. Jiyeon Oh: Investigation,

Resources. Youdi Zhang: Investigation, Resources. Bin Huang: Investigation, Resources. Lie

Chen: Validation. Changduk Yang: Conceptualization, Writing - Original Draft, Writing -

Review & Editing, Supervision, Project administration, Funding acquisition.

1
Article type: Full Paper

Guest-Oriented Non-Fullerene Acceptors for Ternary

Organic Solar Cells with over 16.0% and 22.7%
Efficiencies under One-Sun and Indoor Light

Yongjoon Cho,†,§ Tanya Kumari,†,§ Seonghun Jeong,† Sang Myeon Lee,† Mingyu Jeong,† Byongkyu Lee,† Jiyeon
Oh,† Youdi Zhang,† Bin Huang,†,‡ Lie Chen,‡ and Changduk Yang*,†
†
Department of Energy Engineering, School of Energy and Chemical Engineering, Perovtronics Research
Center, Low Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology
(UNIST), 50 UNIST-gil, Ulju-gun, Ulsan 44919, Republic of Korea.
‡
Institute of Polymers and Energy Chemistry (IPEC), Nanchang University, 999 Xuefu Avenue, Nanchang
330031, China
E-mail: yang@unist.ac.kr

Abstract

Given that the ring-fusion strategy can effectively tail the electrical, optical, and structural

properties of π-conjugated materials, we have herein developed Y-series non-fullerene

acceptors with a dual acceptor–donor–dual acceptor-type structure, bearing non-fused bare

bithiophene (Y-Th2), hexagonal ring-fused bithiophene (Y-BDT), or pentagonal ring-fused

bithiophene (Y-CDT) central donor units. Several characterization techniques were applied to

perform a comparative investigation of their optical and physical properties and frontier

energy levels with respect to the different ring-fusion of the central units. Moreover, for the

cascade energy level alignment, the synthesized acceptors were employed as a third

component in the PM6:Y6 that served as a binary host platform. The introduction of the

optimal amount of Y-Th2 or Y-BDT into the host system improved the device performance.

Specifically, Y-Th2 exhibited the best power conversion efficiency (PCE) (16.01%) along

with improved photovoltaic parameters, whereas the addition of Y-CDT impaired the PCE.

Moreover, the optimized Y-Th2-based ternary organic solar cell achieved a PCE of 22.72%
1
under indoor illumination at 1000 lux. Thus, the in-depth structural, morphological, and

electrical analyses not only established a structure–property correlation, but also provided

better design criteria for the guest-oriented non-fullerene acceptors for ternary photovoltaic

applications, especially for Y6-containing systems.

Keywords: guest-oriented non-fullerene acceptors, indoor application, ring-fusion strategy,

structure−property correlation, ternary organic solar cell

Graphical Abstract

Research highlights

• Ring-fusion strategy effectively tune the electrical, optical, and structural properties of

conjugated materials.

• The guest-oriented non-fullerene acceptors with a dual acceptor–donor–dual acceptor-

type structure, containing non-fused, hexagonal ring-fused, or pentagonal ring-fused

bithiophene central donor units are synthesized.

• The cascade energy level alignment and complementary absorption improve

photovoltaic properties of ternary orgainc solar cells.

• High efficiencies of 16.01% and 22.72% are achieved under one-sun and indoor light,

2
 respectively.

1. Introduction

The solution-processed bulk heterojunction organic solar cells (OSCs) have become a

promising renewable energy for the future, due to their various advantages such as the low

weight, flexibility, transparency, and potential low-cost production [1-8]. In the last five

years, the development of non-fullerene acceptors along with properly selected counterpart

donor molecules has significantly improved the power conversion efficiencies (PCEs) [9-17].

For example, Y6 has been recently reported as a narrow bandgap non-fullerene acceptor with

an outstanding PCE of over 15%, which is among the highest values that can be achieved in

single junction binary devices when mixing wide bandgap donor polymers such as PM6 [18].

The development of ternary OSCs by introducing a third component into the binary host

matrix has proven to be an easy and efficient strategy to enhance their performance by

incorporating the advantages of the three components [19,20]. Recent research efforts aimed

at further improving the PCEs of the PM6:Y6, which is considered as the archetype of high-

performing binary systems, by generating ternary OSCs. For example, the incorporation of

fullerene acceptor derivatives (PC61MB and PC71BM) into the PM6:Y6 enhanced the PCE,

owing to the improved charge transport and the reduced non-radiative energy loss [21-24].

Nevertheless, the PCE improvement of ternary OSCs made by the addition of fullerene

derivatives is limited, because of their intrinsic disadvantages such as the small optical

absorption, poor absorption coefficient, and fixed energetic/band alignment [16,25].

Therefore, the use of two non-fullerene acceptors with diverse molecular structures in the

ternary OSCs can be proven beneficial, because (i) an absorption complementarity and a

broad visible light absorption can be achieved, thus maximizing the photon flux; (ii) the

3
adjustment of the energy levels can positively affect the charge and energy dynamics; (iii) the

optimization of the blend compatibility can favor the charge transportation and recombination

mechanisms [19]. To that end, recent studies have begun to focus on the development of

guest-oriented non-fullerene acceptors for the PM6:Y6 system. However, only few PM6:Y6-

based ternary OSCs bearing additional non-fullerene acceptors with higher PCEs than that of

the PM6:Y6 binary OSCs have been reported so far, because, currently, only few suitable

acceptors of this type are available [25-28].

In this study, in order to develop ternary OSCs based on high-performance PM6:Y6, we

designed and synthesized Y-series non-fullerene acceptors (Y-Th2, Y-BDT, and Y-CDT)

with a dual acceptor–donor–dual acceptor (A'–A–D–A–A')-type structure using non-fused

bare bithiophene, hexagonal ring-fused bithiophene, and pentagonal ring-fused bithiophene

central donor units. Th2, BDT, and CDT indicate the 2,2'-bithiophene, benzo[1,2-b:4,5-

b']dithiophene, and cyclopenta[1,2-b:5,4-b']dithiophene building donor units. In a

comparative study, we presented how the optical properties, the energetics, and the

crystalline nature of the Y-series non-fullerene acceptors may vary depending on the different

ring-fusion of the central donor units. Herein, an optimal amount of Y-series non-fullerene

acceptors was incorporated as a guest acceptor to fabricate the PM6:Y6-based ternary OSCs,

while PCEs of 16.01% and 22.72% were obtained for the Y-Th2-based ternary OSC, under

one-sun and indoor illumination at 1000 lux, respectively. This work highlights the

importance of controlling the ring-fusion of central oligothiophene donor units for the design

of guest non-fullerene acceptors and the subsequent development of high-performance, Y6-

based ternary OSCs.

2. Results and Discussion

4
2.1. Material synthesis and characterizations

To assess the structural difference between the central building blocks, the conjugation

lengths, electrostatic potentials, net dipole moments, highest occupied molecular orbital

(HOMO) energy levels, and ionization potentials (IPs) of the Th2, BDT, and CDT units were

first calculated by the density functional theory (DFT at B3LYP/6-31G*) (Figure 1, Table

S1). The hexagonal ring-fused BDT skeleton had a slightly extended π-conjugation length

compared to the non-fused bare Th2 and pentagonal ring-fused CDT central units. In

contrast, both Th2 and BDT had an almost zero net dipole moment, because the two sulfur

atoms in the thiophene units are symmetrically located on opposite sides, while a net dipole

moment of 1.81 D along the y-axis was observed in CDT, due to the unidirectionally aligned

sulfur atoms. Besides, the calculated HOMO/IP values of Th2, BDT, and CDT were

−5.62/7.10, −5.68/7.11, and −5.35/6.84 eV, respectively, indicating a stronger electron-

donating strength of CDT. The overall DFT data are summarized and analyzed by a radar

chart in Figure 1e.

The synthetic routes of the Y-series non-fullerene acceptors are described in Scheme 1. First,

bis-stannylated central donor moieties [(3,3'-dioctyl-[2,2'-bithiophene]-5,5'-

diyl)bis(trimethylstannane) (1), (4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-

b']dithiophene-2,6-diyl)bis(trimethylstannane) (2), and (4,4-dihexadecyl-4H-cyclopenta[1,2-

b:5,4-b']dithiophene-2,6-diyl)bis(trimethylstannane) (3)] were prepared based on previously

established procedures [29-31]. Afterwards, each of them reacted via a palladium-catalyzed

Stille coupling with 7-bromobenzo[c][1,2,5]thiadiazole-4-carbaldehyde (4), affording the

dialdehyde intermediates 7,7'-(3,3'-dioctyl-[2,2'-bithiophene]-5,5'-

diyl)bis(benzo[c][1,2,5]thiadiazole-4-carbaldehyde (1a), 7,7'-(4,8-bis(5-(2-

ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-

5
diyl)bis(benzo[c][1,2,5]thiadiazole-4-carbaldehyde) (2a), and 7,7'-(4,4-dihexadecyl-4H-

cyclopenta[1,2-b:5,4-b']dithiophene-2,6-diyl)bis(benzo[c][1,2,5]thiadiazole-4-carbaldehyde)

(3a), respectively. A Knoevenagel condensation of the obtained dialdehydes with 3-

ethylrhodanine in the presence of piperidine as a catalyst yielded the target guest-oriented Y-

series non-fullerene acceptors (Y-Th2, Y-BDT, and Y-CDT) with the A'–A–D–A–A'-type

structure. The structures and purity of the final products were verified through 1H and 13
C

nuclear magnetic resonance (NMR) spectroscopy and high-resolution mass spectrometry

(HR-MS) (See the Experimental Section and Figure S17–19). All the Y-series acceptors

were well dissolved in various organic solvents at room temperature, such as chloroform (CF)

and chlorobenzene, implying their effective application in the facile preparation of devices.

The electrochemical behavior of the Y-series acceptors was evaluated by cyclic voltammetry

(CV). Thin films of the molecules were deposited on a platinum working electrode and

measured in acetonitrile (CH3CN) using ferrocene/ferrocenium (Fc/Fc+) as the internal

standard and tetra-n-butylammonium hexafluorophosphate (n-Bu4NPF6, 0.1 M/CH3CN) as

the supporting electrolyte. An absolute energy of −4.8 eV versus the vacuum level was

assigned to Fc/Fc+. As shown in Figure S1, all three molecules displayed irreversible strong

reduction and oxidation waves. Based on the onset values of the first oxidation and reduction

potentials, the HOMO and lowest unoccupied molecular orbital (LUMO) energy levels were

determined according to the equations EHOMO = −(Eoxonset – EFconset + 4.8) (eV) and ELUMO =

−(Eredonset – EFconset + 4.8) (eV). The CV-derived HOMO/LUMO energy levels of Y-Th2, Y-

BDT, and Y-CDT were −5.63/−3.63, −5.51/−3.66, and −5.51/−3.72, respectively, as

described in Figure 2a and Table 1. Moreover, the HOMO and LUMO levels of all the Y-

acceptors were located between those of the PM6 donor and Y6 acceptor hosts, indicating the

6
formation of a cascade energy level alignment, which may allow for an efficient charge-

carrier transport in the ternary active layer [32-34].

The optical properties of the synthesized acceptors were investigated by ultraviolet–visible

(UV–Vis) absorption spectroscopy in CF and thin films, as shown in Figure 2b, 2c, S2, and

Table 1. As commonly observed for conjugated materials, the absorption spectra of the Y-

series non-fullerene acceptors films exhibited an obvious redshift relative to those of their

solutions [35,36]. Y-CDT showed a larger redshift at the maximum (λmax) and onset (λonset)

absorption wavelengths than the others, due to the enhanced intramolecular charge transfer

characteristics along the backbone that were induced by the stronger electron-donating

strength of the CDT core. It is worth mentioning that, despite the similar λmax values of Y-

Th2 and Y-BDT, Y-BDT exhibited an additional vibronic shoulder at around 600 nm, leading

to a widened absorption feature and a higher λonset value. This may be due to the more

effective intermolecular π–π overlapping induced by the increased numbers of π–orbitals and

extended conjugated length of BDT core [37,38]. Moreover, compared to the binary host

platforms (PM6 donor and Y6 acceptor) that mainly covered the currently used large visible

wavelength regions, both Y-Th2 and Y-BDT exhibited good complementary absorption

characteristics in the short-wavelength region, while the Y-CDT possessed a weak

complementary absorption range (Figure 2b, S2). It is also interesting to note that the Y-Th2

film exhibited more than one order of magnitude higher absorption coefficient than the other

films (Figure 2c).

As shown in Figure S3 and Table S2, HOMO/LUMO energy levels of Y-Th2, Y-BDT, and

Y-CDT evalutated by DFT calculation, were −5.68/−3.76, −5.50/−3.77, and −5.48/−3.80 eV,

respectively, showing the similar trend with the CV results. Compared to the core units, the

7
HOMO levels of Y-series acceptors have a different tendency, implying that HOMO and

LUMO can be simultaneously tuned when forming their final push-pull architectures [39].

On the other hand, the DFT-derived optimized geometries of the Y-series non-fullerene

acceptors indicated that Y-Th2 possessed a very planar configuration with smaller dihedral

angles of the A–D and A'–A blocks compared to Y-BDT and Y-CDT (Figure 2d). Like the

above results, relative to the others, Y-CDT exhibited a larger dipole moment due to the non-

offset configuration of the segments (Figure 2e and Table S2).

2.2. Photovoltaic properties

As depicted in Figure 3a, the OSCs were fabricated with the conventional architecture of

indium-tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)

(PEDOT:PSS)/active layer/ perylene diimide amino N-oxide (PDINO)/Al. The binary host

system (PM6:Y6) was optimized at a 1:1.2 wt% ratio and was spin-coated using a CF

solution containing 0.5 vol% of 1-chloronapthalene (CN). The effect of various amounts of

the developed acceptors (0, 5, 10, 15, and 20 wt% relative to Y6) as third components was

also investigated, while maintaining the optimized PM6:Y6 ratio (1:1.2 wt%). The

performance of the OSCs was examined under simulated AM 1.5G one-sun illumination (100

mW cm−2). The representative current density–voltage (J–V) characteristics of the best

ternary OSCs are shown in Figure 3b, and the corresponding device parameters are

summarized in Table 2. The results obtained for all the tested ternary OSCs by the

application of various amounts of guest-oriented Y-series non-fullerene acceptors are

presented in Figure S4–6 and Table S3–5. Under the optimum conditions, the PM6:Y6

binary OSC demonstrated a PCE up to 15.04% with a JSC of 24.69 ± 0.51 mA cm−2, a VOC of

0.840 ± 0.001 V, and an FF of 70.10 ± 0.54%. The performance of all the ternary OSCs with

different Y-Th2 contents were enhanced, while the incorporation of 15 wt% Y-Th2 resulted

8
in a PCE of 16.01% (average PCE = 15.70 ± 0.31%) and enhanced the photovoltaic

parameters. Furthermore, the Y-Th2-based ternary OSCs exhibited low leakage currents

(~10−3 mA cm−2) under reverse bias and high rectification ratios (~105) in the dark J–V

characteristics (Figure S7), indicating their superior charge extraction efficacy [40].

The PCE of the Y-BDT-based ternary OSCs was slightly improved up to 15.18% when a Y-

BDT loading of 5 wt% was used. However, further increase of the loading ratios resulted in a

gradual drop in both JSC and FF that consequently impaired the overall PCEs. Moreover, the

VOC values were linearly improved by higher Y-Th2 or Y-BDT contents, which could be

explained by the possibility of up-shifted LUMO levels induced by their average

composition, if there could form a proper alloy-like structure of two acceptors [19,25,41]. In

contrast, higher Y-CDT concentrations deteriorated all the photovoltaic parameters, including

VOC.

As shown in Figure 3c, the external quantum efficiency results of the optimized binary and

ternary devices were consistent with the results obtained from the J–V measurements, within

a 4.5% deviation. The Y-Th2-based ternary OSC showed a higher photoresponse than the

other synthesized OSCs, indicating a more efficient photon utilization, which was attributed

to the complementary absorption of Y-Th2 with a higher absorption coefficient. Moreover,

the PM6:Y6:Y-Th2 ternary blend film displayed the strongest absorption in the short-

wavelength range of 350–620 nm (Figure S8). Besides, CV measurements of the Y6-based

acceptor films mixed with different contents of Y-series non-fullerene acceptors (0, 10, and

20%) were performed to understand the mesophase as a function of two acceptor components

(Figure S9, Table S6). The increase in the Y-Th2 and Y-BDT content gradually reduced the

onset reduction and oxidation potentials, resulting in higher HOMO and LUMO values, while

there was no significant change in the onset potentials upon the addition of Y-CDT, where

9
the HOMO and LUMO values were similar. It was thus demonstrated that the Y-Th2 and Y-

BDT acceptors can effectively form an alloy state with Y6, which can further explain the

change in the VOC trend for the Y-Th2- and Y-BDT-based ternary OSCs [25,36,42]. It was

also proven that the formation of such alloy-like domains with Y-CDT and Y6 is not favored.

The surface energies of all the materials and the interfacial energies of the Y-series acceptors

with each host material were calculated via the Owens-Wendt model (Figure S10, S11 and

Table S7). The similar interfacial energies of 1.13−3.50 mN m-1 were observed between Y-

series acceptors and PM6 host donor; on the other hand, the interfacial energies with Y6 host

acceptor are 0.028 mN m-1 for Y-Th2:Y6, 0.98 mN m-1 for Y-BDT:Y6, and 9.97 mN m-1 for

Y-CDT:Y6. These results prove that the Y-BDT and especially Y-Th2 have great

compatibility and miscibility with host materials in the corresponding ternary systems, which

satisfies the prerequisites for the formation of the alloy structures of Y-Th2 and Y-BDT

demonstrated in the above CV results [43,44].

2.3 Charge-carrier transport and recombination dynamics

Photoluminescence (PL) spectra of neat PM6, Y-Th2, Y-BDT, Y-CDT, and Y6, and their

ternary blend films with binary host film were recorded to assess the charge transfer status

(Figure S12, S13). All the films were excited at the same wavelength of 565 nm except for

the neat Y6 film (excited at 635 nm), and PM6, Y-Th2, Y-BDT, Y-CDT, and Y6 exhibited

strong PL emissions centered at 681, 764, 794, 827, and 908 nm, respectively. The PL

intensities were effectively quenched in the binary host film and all the ternary blend films

with each optimized composition relative to the PM6 and Y-acceptor pristine films as

summarized in Table S8; especially, the Y-Th2-based ternary blend film had higher

quenching efficiencies of 97.63 and 99.32% of each pristine PM6 and Y-Th2 PL emission

than the other ternary films, demonstrating a more efficient charge transfer process [25,45].

10
The charge transport properties and recombination dynamics were also examined. The

charge-carrier mobilities of the hole- and electron-only devices were estimated using a space-

charge limited curve (Figure S14). The electron (µe) and hole (µh) mobilities of the

corresponding cells are outlined in Table S9. The µe and µh values of the control binary cell

were calculated to be 5.38 × 10−4 cm2 V−1 s−1 and 4.01 × 10−4 cm2 V−1 s−1, respectively, with

an µh/µe ratio of 0.76 (Figure S14, Table S9). Moreover, both values were increased to 6.55

× 10−4 cm2 V−1 s−1 and 5.00 × 10−4 cm2 V−1 s−1, respectively, in the Y-Th2-based ternary cell,

while they were negatively affected by the addition of Y-BDT and Y-CDT.

The net photocurrent (Jph) was also calculated versus the effective applied voltage (Veff) to

quantify the charge generation and the extraction properties (Figure 4a, Table S10) using the

equations Jph = JL − JD, where JL indicates the current under illumination and JD the dark

current, and Veff = V0−V, where V0 is the voltage at Jph = 0 and V is the applied bias voltage.

The Jph values of all the cells were fully saturated at high Veff, thus achieving the saturation

current density (Jsat). The calculated Jsat values for the control binary and ternary Y-Th2-, Y-

BDT-, and Y-CDT-based cells were 25.1, 26.2, 25.9, and 24.7 mA cm−2, respectively,

suggesting that the most efficient charge generation occurred in the Y-Th2-based ternary cell.

Furthermore, relative to the Y-BDT- and Y-CDT-based ternary cells, the control binary and

Y-Th2-based ternary cells exhibited higher Jph/Jsat ratios under short-circuit conditions,

indicating the improved exciton dissociation efficiency [46,47]. The dependence of the J–V

characteristics of the devices on the light intensity (I) was also examined to investigate the

recombination properties in the devices (Figure 4b, 4c). It is well-known that JSC is directly

proportional to Iα, where α represents the unity when all the carriers are swept out prior to the

bimolecular recombination process. The calculated α value of all the cells was almost equal

to 1. Additionally, VOC is directly proportional to S(kT/q)ln(I), where k, T, and q represent the

11
Boltzmann’s constant, the temperature (K), and the elementary charge, respectively. The

fitted S value would be closer to 1 if the monomolecular recombination (trap-assisted) in the

OSCs was negligible. However, all the cells had similar S values of 1.75 ± 0.15. The obtained

results demonstrated that the monomolecular recombination was dominant, while the

bimolecular recombination was effectively suppressed in the highly optimized cells,

regardless of the presence of the guest-oriented Y-series non-fullerene acceptors [48,49].

12
2.4. Film morphology and microstructure

To understand the effect of the Y-acceptors as a third component on the morphological

feature of the active layer, tapping-mode atomic force microscopy (AFM) and transmission

electron microscopy (TEM) were applied for the ternary films containing 5 wt% and 15 wt%

of the Y-acceptors (Figure 5, S15). The AFM height images for all the ternary films with the

each optimal amount of third acceptors exhibited smooth and uniform surface morphologies

with similar root-mean-square roughness (RMS) of 0.97–1.12 nm. Note that the ternary films

containing 15 wt% of Y-BDT and Y-CDT showed slightly increased RMS values (1.33 and

1.31 nm, respectively). Note also that a strong phase separation with well-distributed fiber

textures was also observed in the Y-Th2-based ternary films. In addition, the TEM images of

the Y-BDT- and Y-CDT-based ternary films were not significantly change from the binary

host blend, while the introduction of the Y-Th2 led to a uniformly distributed flower-like

phase separation in the corresponding film. Taken together, one can conclude that more bi-

continues interpenetrating network structure after introducing Y-Th2 is favorable for efficient

charge transport and extraction, supporting the above-observed higher JSC and FF values

[50,51].

Grazing-incidence wide-angle X-ray scattering (GIWAXS) analysis was also performed to

further investigate the crystallinity and the molecular orientation of the neat Y-series non-

fullerene acceptors and blend films (Figure 6, S16), and the corresponding GIWAXS

parameters are included in Table S11. Numerous diffraction spots with a series of multiple

sharp, out-of-plane diffraction peaks were observed for the neat Y-BDT and especially neat

Y-Th2 films, indicating strongly oriented polycrystalline structures, whereas no diffraction

peaks were observed for the neat Y-CDT film, reflecting its amorphous features. All the

blend films exhibited a preferential face-on orientation, as confirmed by a strong (010) π–π

13
diffraction peak at the out-of-plane direction and (100) lamellar peaks at the out-of-plane and

in-plane directions. It has been previously reported that the (010) diffraction peak for the

PM6:Y6 binary host system is dominated by the Y6 acceptor [18,26].

It was also noted that, compared to the other blend films, the Y-Th2-based ternary film

exhibited smaller π–π and lamellar d-spacing values (d(010) = 3.572 Å and d(100) = 21.080 Å),

suggesting a tighter molecular packing structure. This could be attributed to the superior

crystalline nature of Y-Th2 within the ternary blends, allowing the host materials to pack

more efficiently together with good miscibility [52,53]. Therefore, the increased packing in

the face-on orientation could be beneficial for the intermolecular charge transport along the

vertical direction to the electrode, which complied with the above observed higher µe and µh

values of the Y-Th2-based cell. Additionally, the π–π stacking crystallite coherence length

(CCL010), calculated by the Scherrer equation, was almost the same in the binary and ternary

host blends, indicating that the addition of Y-series non-fullerene acceptors had a negligible

effect on the molecular ordering of the Y6 host acceptor. In addition, relative to the others,

the Y-Th2-based ternary film exhibited a larger CCL100 value associated with the (100) peak,

implying the increased lamellar crystalline size.

2.5 Indoor application

Among the potential photovoltaic technologies, the OSCs have unique advantageous

properties (e.g., highly tunable light-absorption and roll-to-roll processability) for

applications to indoor energy harvesting materials [54,55]. Therefore, the potential

applications of the developed OSCs in indoor light environments were studied using the Y-

Th2-based ternary OSC that exhibited the best performance. The indoor performance of the

optimized Y-Th2-based ternary device was investigated under solar light-emitting diode

(LED) lamps with 1000, 3000, and 5000 lux illumination intensities, using the ORIEL LED

14
Solar Simulator (LSH7320 ABA) (Figure 7a). Figure 7b depicts the J–V characteristics of

the best performed devices at each illumination condition, while the corresponding

photovoltaic parameters are summarized in Table S12. The change in the light intensity from

1000 to 5000 lux led to gradual increased JSC and VOC values, due to the increased number of

input photons, but negatively affected the FF, because of the increased non-germinate charge

recombination under high illumination [56-58]. The PCE histograms obtained from 120

devices are visualized in the inset of Figure 7b, where relatively higher PCEs with a

narrower distribution were observed under 1000 lux. Herein, a PCE of up to 22.72% with JSC

of 32.01 ± 0.28 ×10 µA cm−2, VOC of 0.701 ± 0.002 V, and FF of 74.48 ± 0.64% could be

achieved using the indoor LED light.

3. Conclusions

In summary, A'–A–D–A–A'-type guest-oriented Y-series non-fullerene acceptors (Y-Th2, Y-

BDT, and Y-CDT) with different central donor blocks were synthesized and characterized in

order to be employed in the binary PM6:Y6 host to generate ternary OSCs. Tuning the ring-

fusion mode of the central donor units within the Y-series non-fullerene acceptors

significantly affected their energy levels, optical properties, and crystallinity. All the

synthesized acceptors sufficiently formed energy cascades relative to the HOMO/LUMO

levels of the host materials. Among the tested acceptors, Y-Th2 and Y-BDT exhibited better

complementary absorption overlapping with the host materials. Especially Y-Th2 showed the

optimum absorption coefficient and crystallinity, and consequently, the Y-Th2-based ternary

OSC exhibited the best PCE (16.01%), which was greater than that of the optimized control

device based on PM6:Y6. Moreover, the application of the Y-Th2-based ternary OSC in

indoor LED light was explored, demonstrating a PCE of 22.72% under an indoor illumination

15
of 1000 lux. Therefore, the current study demonstrated the feasibility of controlling the ring-

fusion of oligothiophene central donor units to new, superior guest-oriented non-fullerene

acceptors with tailored intrinsic properties for their application to high-performance ternary

OSCs.

4. Experimental Section

Materials and characterization: All starting materials were purchased from Sigma-Aldrich

and Acros and used without further purification. All solvents were of ACS grade unless

otherwise noted. (3,3'-dioctyl-[2,2'-bithiophene]-5,5'-diyl)bis(trimethylstannane) (1), (4,8-

bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-

diyl)bis(trimethylstannane) (2), (4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophene-

2,6-diyl)bis(trimethylstannane) (3), 7-bromobenzo[c][1,2,5]thiadiazole-4-carbaldehyde (4),

PM6 and Y6 were synthesized according to the previously reported methods [29-31]. 1H

NMR and 13C NMR spectra were recorded on a VNMRS 400 MHz spectrophotometer using

deutrated chloroform (CDCl3) as solvent and tetramethylsilane (TMS) as the internal standard.

HRMS spectra were measured using AccuTOF 4G+ DART. UV-Vis-NIR spectra were

recorded on a UV-1800 (SHIMADZU) spectrophotometer. For UV-vis-NIR spectra of Y-

acceptors, their solutions (4.00 mg mL-1 in CF) were used and the films were prepared by

deposition from the 8.00 mg mL-1 concentrated CF solution via the spin-casting method at

1000 rpm. The optical bandgaps were estimated from the absorption onset of the as-cast thin

films. CV measurements were performed on a Solartron electrochemical station (METEK,

Versa STAT3) with a three-electrode cell in a 0.1 M n-Bu4NPF6 solution in CH3CN at a scan

rate of 100 mV s−1 at room temperature. An Ag/Ag+ (0.01 M AgNO3 in CH3CN) electrode, a

platinum wire, and a material-coated platinum electrode were used as the reference electrode,

16
the counter electrode, and the working electrode, respectively. The Ag/Ag+ reference

electrode was calibrated using a Fc/Fc+ redox couple as an internal standard, whose oxidation

potential is set at − 4.8 eV with respect to the zero vacuum level. HOMO and LUMO energy

levels were determined according to the equations (EHOMO = −( Eoxonset − EFconset + 4.8) (eV))

and (ELUMO = −(Eredonset − EFconset + 4.8) (eV)). DFT calculations were performed using the

Gaussian 09 package at B3LYP function and the 6-31G* basis set to elucidate the

conjugation lengths, electrostatic potentials, net dipole moments, HOMO and LUMO energy

levels, and IPs after optimizing the geometry of materials. The contact angles of all the

materials were obtained using the Phoenix 300 Model instrument. The surface energy was

calculated via measuring the contact angles of two different solvents, distilled water (DI) and

ethylene glycol (EG) on each film. The surface energy of film was calculated via the Owens-

Wendt model and the interfacial energy between each component was estimated via Wu

model. PL spectra were obtained using a Varian Cary Eclipse fluorescence spectrometer.

For morphological characterization, the optimized device fabrication processing condition

were used to prepare thin films and all the characterizations otherwise mentioned were

performed in ambient atmospheric condition. Glass substrate was used to fabricate samples

for the absorption, optical fluorescence microscopy, and thickness measurement while for all

other characterizations, samples were fabricated on a silicon substrate. AFM was performed

using a Bruker Dimension Icon Atomic Force Microscope with an RTESP-150 probe in the

standard tapping mode. The thickness of the films was measured using a stylus profilometer

of P6, KLA Tencor. TEM analysis was performed using a JEOL USA JEM-2100F (Cs

corrector) transmission electron microscope equipped with an energy dispersive X-ray

analysis at an acceleration voltage of 200 kV. GIWAXS measurements were conducted at

PLS-II 6D and 9A U-SAXS beamline in Pohang Accelerator Laboratory (South Korea). The

17
X-rays coming from the in-vacuum undulator (IVU) were monochromated at 11.05 keV

(wavelength of 1.12199 Å). The incidence angle (≈ 0.12-14 °) of X-ray beam was chosen to

allow for complete penetration into the film. GIXD patterns were recorded with a 2D CCD

detector.

Synthesis of 7,7'-(3,3'-dioctyl-[2,2'-bithiophene]-5,5'-diyl)bis(benzo[c][1,2,5]thiadiazole-4-

carbaldehyde) (1a): To a two-neck round-bottom flask of 1 (1 g, 1.40 mmol), 4 (0.85 g, 3.50

mmol), and tetrakis(triphenylphosphine)palladium(0) in toluene (100 ml) were added under

inert atmosphere. The reaction mixture was refluxed overnight with vigorous stirring. After

cooling to room temperature, the volatile was removed under reduced pressure. The resulting

crude mixture was purified by column chromatography using hexane/dichloromethane

(DCM) as an eluent, obtaining a red solid (0.72 g, 72%). 1H NMR (CDCl3, 400 MHz) δ ppm

10.75 (s, 2H), 8.24-8.27 (m, 4H), 8.02 (d, J = 7.5 Hz, 2H), 2.71 (m, 4H), 1.74-1.66 (m, 4H),

1.38-1.19 (m, 20H), 0.81 (m, 6H). HRMS (ESI) m/z 714.2221 (C38H42N4O2S4 calcd. for m/z

714.2191).

Synthesis of 7,7'-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-

diyl)bis(benzo[c][1,2,5]thiadiazole-4-carbaldehyde) (2a): 2a was synthesized through the

same synthetic route as 1a, and 2 was used instead of 1, yielding a purple solid (0.46 g, 41%).
1
H NMR (CDCl3, 400 MHz) δ ppm 10.78 (s, 2H), 9.12 (s, 2H), 8.26 (d, J = 7.5 Hz, 2H), 8.10

(d, J = 7.5 Hz, 2H), 7.50 (d, J = 3.5 Hz, 2H), 7.03 (d, J = 3.5 Hz, 2H), 2.96 (d, J = 6.7 Hz,

4H), 1.76-1.70 (m, 2H), 1.50-1.20 (m, 16H), 0.99-0.88 (m, 12H). HRMS (ESI) m/z 902.1997

(C48H46N4O2S6 calcd. for m/z 902.1945).

Synthesis of 7,7'-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophene-2,6-

diyl)bis(benzo[c][1,2,5]thiadiazole-4-carbaldehyde) (3a): 3a was synthesized through the

same synthetic route as 1a, and 3 was used instead of 1, yielding a blue solid (0.64 g, 60%). δ

18
ppm 10.72 (s, 2H), 8.27 (s, 2H), 8.24 (d, J = 7.5 Hz, 2H), 8.03 (d, J = 7.5 Hz, 2H), 2.04 (m,

4H), 1.34-1.04 (m, 56H), 0.86 (t, J = 6.8 Hz, 6H). HRMS (ESI) m/z 950.4741 (C55H74N4O2S4

calcd. for m/z 950.4695).

Synthesis of Y-Th2: To a two-neck round-bottom flask of 1a (0.50 g, 0.70 mmol) in CF (50

ml) with piperidine (0.5 ml) were added. The reaction mixture was stirred at 80 °C overnight.

After cooling to room temperature, the mixture quenched by water was extracted with DCM.

After dried over anhydrous magnesium sulfate and the volatile was removed under reduced

pressure. The residue was purified by column chromatography using hexane/DCM as an

eluent, yielding a red solid (0.60 g, 86%). 1H NMR (CDCl3, 400 MHz) δ ppm 8.48 (s, 2H),

8.18 (s, 2H), 7.94 (d, J = 7.6 Hz, 2H), 7.68 (d, J = 7.6 Hz, 2H), 4.28-4.20 (q, J = 7.1 Hz, 4H),

2.74-2.66 (t, J = 7.7 Hz, 4H), 1.75-1.64 (m, 4H), 1.40-1.16 (m, 26H), 0.82 (m, 6H). 13C NMR

(CDCl3, 100 MHz) δ ppm 192.96, 167.49, 154.42, 151.81, 144.21, 138.59, 132.15, 131.25,

131.07, 129.09, 126.97, 125.26, 125.14, 124.79, 39.96, 31.90, 30.77, 29.48, 29.41, 29.28,

29.25, 22.68, 14.11, 12.34. HRMS (ESI) m/z 1000.1954 (C48H52N6O2S8 calcd. for m/z

1000.1917).

Synthesis of Y-BDT: Y-BDT was synthesized through the same synthetic route as Y-Th2,

yielding a purple solid (0.50 g, 82%). 1H NMR (CDCl3, 400 MHz) δ ppm 8.95 (s, 2H), 8.37

(s, 2H), 7.92(d, J = 7.7 Hz, 2H), 7.63 (d, J = 7.7 Hz, 2H), 7.46 (d, J = 3.4 Hz, 2H), 7.03 (d, J

= 3.4 Hz, 2H), 4.25-4.17 (q, J = 6.8 Hz, 4H), 2.98 (d, J = 6.9 Hz, 4H), 1.86-1.76 (m, 2H),

1.50-1.19 (m, 22H), 1.03-0.88 (m, 12H). 13C NMR (CDCl3, 100 MHz) δ ppm 192.93, 167.48,

154.31, 151.08, 145.85, 139.46, 139.20, 137.48, 136.05, 131.27, 130.55, 129.66, 129.41,

129.12, 126.91, 125.72, 125.32, 124.58, 124.51, 41.54, 39.96, 34.33, 32.53, 29.41, 25.83,

23.04, 15.66, 12.34, 11.01. HRMS (ESI) m/z 1188.1711 (C58H56N6O2S10 calcd. for m/z

1188.1672).

19
Synthesis of Y-CDT: Y-CDT was synthesized through the same synthetic route as Y-Th2,

yielding a blue solid (0.69 g, 88%). 1H NMR (CDCl3, 400 MHz) δ ppm 8.39 (s, 2H), 8.18 (s,

2H), 7.83 (d, J = 7.7 Hz, 2H), 7.56 (d, J = 7.7 Hz, 2H), 4.28-4.20 (q, J = 7.1 Hz, 4H), 2.09-

2.00 (m, 4H), 1.38-1.05 (m, 62H), 0.89-0.80 (t, J = 6.9 Hz, 6H). 13C NMR (CDCl3, 100 MHz)

δ ppm 192.89, 167.48, 160.98, 154.41, 151.42, 141.18, 141.05, 131.12, 129.98, 126.88,

124.52, 124.20, 123.67, 123.45, 54.46, 39.97, 37.85, 31.91, 30.04, 29.67, 29.69, 29.63, 29.44,

29.35, 24.81, 22.69, 14.13, 12.34. HRMS (ESI) m/z 1236.4501 (C65H84N6O2S8 calcd. for m/z

1236.4421).

Device fabrication and measurement: Binary and ternary devices were fabricated in the

conventional device structure of glass/ITO/PEDOT:PSS/active layer/PDINO/Al. The pre-

patterned ITO glass substrates were cleaned by subsequent sonication in detergent, deionized

water, acetone, and isopropanol for 15 min respectively. The substrates were dried overnight

at 40 °C and then plasma surface treatment is done for 5 min prior to use. For active layer

preparation, PM6:Y6 (1:1.2 ratio) were dissolved in anhydrous CF with total concentration of

16 mg ml-1. 0.5 vol% of CN is added to the solution and stirred at 40 °C for 2-3 hrs. Each

small molecule (SM) acting as third component (Y-Th2, Y-BDT, and Y-CDT) was dissolved

separately in CF and stirred at 40 °C for 2-3 hrs. Different wt% of SM with respect to the

Y6’s concentration were added separately in the active layer solution and again stirred at

45 °C for 1 hr. For device fabrication, PEDOT:PSS layer (Clevios P VP AI 4083) was spin-

coated at 5000 rpm for 30s on the pre-cleaned ITO substrate, and then thermally annealed at

140 °C for 20 min. The substrates were subsequently transferred to the glovebox and the

active layer was spin-coated for binary and ternary device fabrication and the films were

subsequently treated by thermal annealing for 10 min at 110 °C. After cooling, a thin PDINO

layer (0.75 mg mL-1 in methanol) as electron transporting layer is spin coated at 3000 rpm for

20
30s. Finally, an 80 nm thick layer of Al was deposited using a shadow mask (device area:

0.477 mm2) under high vacuum (< 3 × 10−6 Pa).

For the photovoltaic device characterization, the J–V measurements were carried out using a

Keithley 2365A source measurement unit under simulated sunlight (AM 1.5G) at an intensity

of 100 mW cm-2. Xenon arc lamp solar simulator and Si reference cell (Oriel SRC-1000-TC-

K-KG5-N), which was calibrated and certified by VLSI Standards Inc. were used. Solar cell

zig with a rectangular opening (window size: 9 mm × 15 mm) were used to evaluate the

device performance, no additional mask/aperture was used for the measurement. The

standard silicon photodiode was used to calibrate the irradiance, prior to the device

measurement. For indoor application measurement, the illumination intensity was calibrated

using irradiance calibrator (Newport Inc.) and a standard silicon reference cell. QEX7

quantum efficiency measurement system (PV Measurements, Inc.) was used for EQE

measurements under an ambient atmosphere. The integrated Jsc values differ no more than

4.5% from the measured values. For mobility measurements, the hole- and electron-only

devices were fabricated using a device architecture of ITO/Au/active layer/Au and

ITO/Ag/active layer/Ag, respectively. The µ h and µ e were measured using the SCLC method,

which is described by the Mott–Gurney square law as

JSCLC = (9/8)ε0εrµ((V2)/(L3))

where, JSCLC is the current density, ε0 is the dielectric constant of free space, εr is the relative

permittivity of the transport medium, µ is the µ h or µ e, V is the applied voltage across the

device, and L is the thickness of the active layer.

Supplementary Information

Supplementary Information is available from the Elsevier or from the author.

21
Acknowledgements

C. Y. conceptualized the project. Y. C. Synthesized and characterized guest-oriented Y-

acceptors, as well as analyzed the data. T. K. carried out the device fabrication and

measurement. Y. C. and T. K. contributed equally to this work. S. J. and Y. Z. synthesized

Y6. S. L., M. J. and B. H. synthesized PM6. B. L. measured TEM. J. O. measured AFM. Y. C.

and C. Y. wrote the manuscript. This work was supported by the National Research

Foundation of Korea (NRF) grant funded by the Korea government (MSIP)

(2018R1A2A1A05077194), Center for Advanced Soft-Electronics funded by the Ministry of

Science and ICT as Global Frontier Project (2012M3A6A5055225), Wearable platform

Materials Technology Center (2016R1A5A1009926) funded by the Ministry of Science, ICT

and future Planning, and the Research Project Funded by Ulsan City (1.200042) of UNIST

(Ulsan National Institute of Science & Technology). GIXD measurements at PLS-II 6D

UNIST-PAL beamline and 9A beamline were supported in part by MEST, POSTECH, and

UNIST UCRF. The authors declare no competing financial interests. Correspondence and

requests for materials should be addressed to C. Y.

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Figures and Table

Figure 1. Comparison of different ring-fused central donor units through theoretical

simulation. (a) Optimized geometries with conjugation length, (b) electrostatic potential with
electron density and dipole moment, (c) simulated HOMO orbitals and energy levels of Th2,
BDT, and CDT units by DFT calculation, (d) comparison of electron donating strength by
order of IPs, and (e) a radar chart for a summary of conjugation lengths, HOMO levels, and
IPs of Th2, BDT, and CDT units.

27
Scheme 1. Synthetic routes of Y-Th2, Y-BDT, and Y-CDT.

Figure 2. Optoelectrical properties and optimized structures of Y-series acceptors. (a)

Energy level diagram of materials utilized for the photovoltaic devices, (b) normalized UV-
Vis absorption spectra of active layer components in thin films, (c) absorption coefficients of
Y-acceptors in thin films, and (d) optimized geometries and (e) dipole moments of Y-Th2, Y-
BDT, and Y-CDT by DFT calculation.

28
Table 1. Optical and electrophysical properties of Y-Th2, Y-BDT, and Y-CDT.
λsolmax λfilmmax λonset Egopt EgCV ELUMO EHOMO
[nm]a [nm]a [nm]b [eV]b [eV]c [eV]c [eV]c

Y-Th2 323, 382, 522 335, 387, 547 712 1.74 2.00 -3.63 -5.63

325, 379,
Y-BDT 335, 529 762 1.63 1.85 -3.66 -5.51
500, 576

Y-CDT 327, 402, 657 338, 411, 653 821 1.51 1.79 -3.72 5.51
a
Taken from the material solutions in CF and the corresponding films on glass substrates;
b
determined from the onset of the UV-vis absorption plots in the films; cestimated from the
oxidation and the reduction onsets (Eoxonset and Eredonset) by the equations of EHOMO =
−( Eoxonset − EFconset + 4.8) eV, ELUMO = −(Eredonset − EFconset + 4.8) eV, and EgCV = EHOMO −
ELUMO;

Figure 3. Device performance. (a) The schematic illustration of conventional device

architecture used in this study, (b) J–V characteristics under illumination of AM 1.5G (100
mW cm-2), and (c) the corresponding EQE spectra from the optimized ternary devices and
binary host one.

Table 2. Photovoltaic parameters of the ternary devices with the optimized amounts of Y-
acceptors as the third component under illumination of AM 1.5G (100 mW cm-2).
Jsc Jcal Voc FF PCE Rs Rsh
[mA cm-2] [mA cm-2] [V] [%] [%] [Ω] [Ω]
14.77 ± 0.27 (1.10 ± 0.83)
Binary 24.69 ± 0.51 23.63 0.840 ± 0.001 70.10 ± 0.54 22.9 ± 2.8
(15.04) × 104
Ternary
15.70 ± 0.31 (1.35 ± 0.51)
w/ Y-Th2 25.35 ± 0.77 24.32 0.851 ± 0.002 71.44 ± 0.41 23.3 ± 2.9
(16.01) × 104
(15 wt%)
Ternary
14.85 ± 0.33 (1.46 ± 0.59)
w/ Y-BDT 25.03 ± 0.37 23.95 0.851 ± 0.001 70.04 ± 0.16 22.3 ± 2.5
(15.18) × 104
(5 wt%)
Ternary
14.11 ± 0.32 (1.27 ± 0.27)
w/ Y-CDT 24.68 ± 0.36 23.58 0.833 ± 0.002 68.81 ± 0.23 20.8 ± 2.0
(14.43) × 104
(5 wt%)

29
Figure 4. Charge-carrier transport and recombination dynamics. (a) Jph versus Veff
characteristics, and (b) Jsc and (c) Voc versus light intensity characteristics of the optimized
ternary devices with the binary host one.

Figure 5. Morphologies of blend films. 1 µm × 1 µm scaled AFM height images (a-d) and
magnified TEM images (e-f) of the PM6:Y6 binary host film (a and e) and the ternary films
with Y-Th2 (15 wt%, b and f), Y-BDT (5 wt%, c and g), and Y-CDT (5 wt%, d and h),
respectively.

30
Figure 6. Crystalline properties of blend films. The 2D GIWAXD pictures (a-d) and the
line cut profiles (e-f) of the PM6:Y6 binary host film (a and e) and the ternary films with Y-
Th2 (15 wt%, b and f), Y-BDT (5 wt%, c and g), and Y-CDT (5 wt%, d and h), respectively.

Figure 7. Device performance under indoor light. (a) The images of indoor measurement
system and (b) J–V characteristics of PM6:Y6:Y-Th2 device under illuminations of 1000,
3000, and 5000 lux for the indoor application.

31
Yongjoon Cho is in the combined master’s and doctorate course for department of energy
engineering in Ulsan National Institute of Science and Technology (UNIST). He received his
BS in 2016 in Energy Conversion & Storage and Nanochemistry from UNIST. He joined
Professor Changduk Yang’s group in 2016 and his main research interest is focusing on
synthesizing novel organic materials for organic photovoltaics, organic field-effect transistors
and organic photocatalysts.

Tanya Kumari received her Ph.D. from Ulsan National Institute of Science and Technology
(UNIST, South Korea) in Energy Engineering in 2019 under the supervision of Prof.
Changduk Yang. She is currently working as a postdoctoral research associate in UNIST. Her
main research focus is on device physics of organic solar cells for the development of
stretchable devices with high performance.

Seonghun Jeong is enrolled in a combined master’s and doctorate course in department of energy
engineering at the Ulsan National Institute of Science and Technology (UNIST, South Korea). He
received his B.S. in 2019 in department of chemical engineering from UNIST. He joined Professor
Changduk Yang’s group in the same year and his main research focus is on synthesizing novel
organic materials for organic photovoltaics and organic field-effect transistors.

32
Sang Myeon Lee is enrolled in the combined master's and doctorate course in Department of
Energy Engineering at Ulsan National Institute of Science and Technology (UNIST, South
Korea). He received his B.S. in 2014 in Department of Energy Engineering from UNIST. In
the same year, he has joined Prof. Changduk Yang's group, and his main research focus is on
the synthesis of conjugated organic semiconductors for electronic applications.

Mingyu Jeong received his B.S. degree in Nano-Bioscience and Chemical Engineering in
2015 from Ulsan National Institute of Science (UNIST). Currently, he is in the combined
master's and Ph.D program in Prof. Changduk Yang’s group and his main research focus is
synthesis of organic materials for organic photovoltaics and perovskite solar cells.

Byongkyu Lee is enrolled in the combined master's and doctorate course in Energy
Engineering at the Ulsan National Institute of Science and Technology (UNIST, South
Korea). He received his B.S. in 2015 in Energy Conversion & Storage and Nanochemisty
from UNIST. Then, he has joined Prof. Changduk Yang's group. His main research focus is
on the development of optoelectric materials and the device physics of OSCs.

33
Jiyeon Oh is in the combined master's and doctorate course for Energy Engineering in Ulsan
National Institute of Science and Technology (UNIST, south Korea). Before coming to
UNIST, she received BS in 2016 in Advanced Materials Chemistry at Korea University. She
joined Professor Changduk Yangs group in 2017. Her main research is device physics of
organic solar cells.

Youdi Zhang received his Ph.D. degree from Dalian University of Technology in 2014. He
joined the group of Prof. Yongfang Li at Soochow University as a postdoctoral fellow (2014-
2016). He then joined the group of Prof. Changduk Yang at Korea Ulsan National Institute of
Science and Technology (UNIST) as a research assistant professor in 2019-2020. He is
currently an associate professor in the College of Chemistry at Nanchang University. His
main research interests focus on the synthesis and application of organic photovoltaic
materials.

Bin Huang is a Ph.D. candidate under the supervision of Professor Lie Chen at College of
Chemistry, Nanchang University. His researches focus on developing novel polymers and
small molecules for organic solar cells and perovskite solar cells.

34
Lie Chen received her Ph. D from Nanchang University, China in 2009 and worked as a
postdoctor in Max-Plank institute for polymer research, Germany in 2012-2013. She
currently is a full professor of Chemistry at Nanchang University. She has published more
than 100 research papers. Her research interests are the molecular design and interfacial
modulation for organic solar cells and perovskite solar cells.

Changduk Yang obtained his Ph.D. degree from the Max Planck Institute for Polymer
Research (Germany) in 2006 under Prof. Klaus Müllen. He finished his postdoctoral training
in 2009 at the University of California Santa Barbara (U.S.) with Prof. Fred Wudl. In March
2009, he has joined UNIST. He serves on the editorial board for Polymer (South Korea) and
works as a fulltime professor at UNIST. His research focus is on the development of organic
semiconducting materials and multifunctional molecule-related self-assembly for various
applications, including organic optoelectronics, triboelectric generators, and secondary
batteries.

35
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: