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Non-radiative recombination losses limit the property of perovskite solar cells (PSCs). Here, a synergistic strategy of SnSe2QDs doping into SnO2 and chlorhexidine acetate (CA) coating on the surface of perovskite is proposed. The introduction of 2D SnSe2QDs reduces the oxygen vacancy defects and increases the carrier mobility of SnO2. The optimized SnO2 as a buried interface obviously improves the crystallization quality of perovskite. The CA containing abundant active sites of âNH2/âNHâ, âCâN, CO, âCl groups passivate the defects on the surface and grain boundary of perovskite. The alkyl chain of CA also improves the hydrophobicity of perovskite. Moreover, the synergism of SnSe2QDs and CA releases the residual stress and regulates the energy level arrangement at the top and bottom interface of perovskite. Benefiting from these advantages, the bulk and interface non-radiative recombination loss is greatly suppressed and thereby increases the carrier transport and extraction in devices. As a result, the best power conversion efficiency (PCE) of 23.41% for rigid PSCs and the best PCE of 21.84% for flexible PSCs are reached. The rigid PSC maintains 89% of initial efficiency after storing nitrogen for 3100 h. The flexible PSCs retain 87% of the initial PCE after 5000 bending cycles at a bending radius of 5 mm.
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Developing a new end group for synthesizing asymmetric small molecule acceptors (SMAs) is crucial for achieving high-performance organic photovoltaics (OPVs). Herein, an asymmetric small molecule acceptor, BTP-BO-4FO, featuring a new difluoro-methoxylated end-group is reported. Compared to its symmetric counterpart L8-BO, BTP-BO-4FO exhibits an upshifted energy level, larger dipole moment, and more sequential crystallinity. By adopting two representative and widely available solvent additives (1-chloronaphthalene (CN) and 1,8-diiodooctane (DIO)), the device based on PM6:BTP-BO-4FO (CN) photovoltaic blend demonstrates a power conversion efficiency (PCE) of 18.62% with an excellent open-circuit voltage (VOC) of 0.933 V, which surpasses the optimal result of L8-BO. The PCE of 18.62% realizes the best efficiencies for binary OPVs based on SMAs with asymmetric end groups. A series of investigations reveal that optimized PM6:BTP-BO-4FO film demonstrates similar molecular packing motif and fibrillar phase distribution as PM6:L8-BO (DIO) does, resulting in comparable recombination dynamics, thus, similar fill factor. Besides, it is found PM6:BTP-BO-4FO possesses more efficient charge generation, which yields better VOC-JSC balance. This study provides a new ending group that enables a cutting-edge efficiency in asymmetric SMA-based OPVs, enriching the material library and shed light on further design ideas.
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Interface modification plays an important role in improving the power conversion efficiency (PCE) of organic solar cells (OSCs). However, the low non-covalent interaction between the cathode interface layer (CIL) and nonfullerene acceptor (NFA) directly affects the charge collection of OSCs. Here, the non-covalent interaction between the CIL and NFA is enhanced by introducing the 2D vermiculite (VML) in the poly(9,9-bis(3'-(N,N-dimethyl)-Nethylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)) dibromide (PFN-Br) interface layer to form an efficient electron transport channel. As a result, the electron extraction efficiency from the active layer to the CIL is increased, and the PCE of OSCs based on PBDB-T:ITIC is boosted from 10.87% to 12.89%. In addition, the strategy of CIL doping VML is proven to be universal in different CIL materials, for which the PCE is boosted from 10.21% to 11.57% for OSCs based on PDINN and from 9.82% to 11.27% for OSCs based on PNDIT-F3N. The results provide a viable option for designing efficient CIL for high-performance non-fullerene OSCs, which may promote the commercialization of OSCs.
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Incorporating a third component into binary organic solar cells (b-OSCs) has provided a potential platform to boost power conversion efficiency (PCEs). However, gaining control over the non-equilibrium blend morphology via the molecular design of the perylene diimide (PDI)-based third component toward efficient ternary organic solar cells (t-OSCs) still remains challenging. Herein, two novel PDI derivatives are developed with tailored molecular planarity, namely ufBTz-2PDI and fBTz-2PDI, as the third component for t-OSCs. Notably, after performing a cyclization reaction, the twisted ufBTz-2PDI with an amorphous character transferred to the highly planar fBTz-2PDI followed by a semi-crystalline character. When incorporating the semi-crystalline fBTz-2PDI into the D18:L8-BO system, the resultant t-OSC achieved an impressive PCE of 18.56%, surpassing the 17.88% attained in b-OSCs. In comparison, the addition of amorphous ufBTz-2PDI into the binary system facilitates additional charge trap sites and results in a deteriorative PCE of 14.37%. Additionally, The third component fBTz-2PDI possesses a good generality in optimizing the PCEs of several b-OSCs systems are demonstrated. The results not only provided a novel A-DA'D-A motif for further designing efficient third component but also demonstrated the crucial role of modulated crystallinity of the PDI-based third component in optimizing PCEs of t-OSCs.
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The high-performance hole transporting material (HTM) is one of the most important components for the perovskite solar cells (PSCs) in promoting power conversion efficiency (PCE). However, the low conductivity of HTMs and their additional requirements for doping and post-oxidation greatly limits the device performance. In this work, three novel pyrene-based derivatives containing methoxy-substituted triphenylamines units (PyTPA, PyTPA-OH and PyTPA-2OH) are designed and synthesized, where different numbers of hydroxyl groups are connected at the 2- or 2,7-positions of the pyrene core. These hydroxyl groups at the 2- or 2,7-positions of pyrene play a significantly role to enhance the intermolecular interactions that are able to generate in situ radicals with the assistance of visible light irradiation, resulting in enhanced hole transferring ability, as well as an enhanced conductivity and suppressed recombination. These pyrene-core based HTMs exhibit excellent performance in PSCs, which possess a higher PCE than those control devices using the traditional spiro-OMeTAD as the HTM. The best performance can be found in the devices with PyTPA-2OH. It has an average PCE of 23.44% (PCEmax = 23.50%), which is the highest PCE among the reported PSCs with the pyrene-core based HTMs up to date. This research offers a novel avenue to design a dopant-free HTM by the combination of the pyrene core, methoxy triphenylamines, and hydroxy groups.
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Volatile solid additives have emerged as a promising strategy for enhancing film morphology and promoting the power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, a series of novel polycyclic aromatic additives with analogous chemical structures, including fluorene (FL), dibenzothiophene (DBT), and dibenzofuran (DBF) derived from crude oils, are presented and incorporated into OSCs. All these additives exhibit strong interactions with the electron-deficient terminal groups of L8-BO within the bulk-heterojunction OSCs. Moreover, they demonstrate significant sublimation during thermal annealing, leading to increase free volumes for the rearrangement and recrystallization of L8-BO. This phenomenon leads to an improved film morphology and an elevated glass-transition temperature of the photoactive layers. Consequently, the PCE of the PM6:L8-BO blend has been boosted from 16.60% to 18.60% with 40 wt% DBF additives, with a champion PCE of 19.11% achieved for ternary PM6:L8-BO:BTP-eC9 OSCs. Furthermore, the prolonged shelf and thermal stability have been observed in OSCs with these additives. This study emphasizes the synergic effect of volatile solid additives on the performance and thermal stability of OSCs, highlighting their potential for advancing the field of photovoltaics.
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The advancement of acceptors plays a pivotal role in determining photovoltaic performance. While previous efforts have focused on optimizing acceptor-donor-acceptor1-donor-acceptor (A-DA1-D-A)-typed acceptors by adjusting side chains, end groups, and conjugated extension of the electron-deficient central A1 unit, the systematic exploration of the impact of peripheral aryl substitutions, particularly with different electron groups, on the A1 unit and its influence on device performance is still lacking. In this study, three novel acceptors - QxTh, QxPh, and QxPy - with distinct substitutions on the quinoxaline (Qx) are designed and synthesized. Density functional theory (DFT) analyses reveal that QxPh, featuring a phenyl-substituted Qx, exhibits the smallest molecular binding energies and a tightest π···π stacking distance. Consequently, the PM6:QxPh device demonstrates a better power conversion efficiency (PCE) of 17.1% compared to the blends incorporating QxTh (16.4%) and QxPy (15.7%). This enhancement is primarily attributed to suppressed charge recombination, improved charge extraction, and more favorable molecular stacking and morphology. Importantly, introducing QxPh as a guest acceptor into the PM6:BTP-eC9 binary system yields an outstanding PCE of 19.5%, indicating the substantial potential of QxPh in advancing ternary device performance. The work provides deep insights into the expansion of high-performance organic photovoltaic materials through peripheral aryl substitution strategy.
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Ionic liquids have been widely used to improve the efficiency and stability of perovskite solar cells (PSCs), and are generally believed to passivate defects on the grain boundaries of perovskites. However, few studies have focused on the relevant effects of ionic liquids on intragrain defects in perovskites which have been shown to be critical for the performance of PSCs. In this work, the effect of ionic liquid 1-hexyl-3-methylimidazolium iodide (HMII) on intragrain defects of formamidinium lead iodide (FAPbI3) perovskite is investigated. Abundant {111}c intragrain planar defects in pure FAPbI3 grains are found to be significantly reduced by the addition of the ionic liquid HMII, shown by using ultra-low-dose selected area electron diffraction. As a result, longer charge carrier lifetimes, higher photoluminescence quantum yield, better charge carrier transport properties, lower Urbach energy, and current-voltage hysteresis are achieved, and the champion power conversion efficiency of 24.09% is demonstrated. These observations suggest that ionic liquids significantly improve device performance resulting from the elimination of {111}c intragrain planar defects.
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In this study, two novel donor-acceptor (D-A) copolymers are designed and synthesized, DTBT-2T and DTBT-2T2F with 2,2'-bithiophene or 3,3'-difluoro-2,2'-bithiophene as the donor unit and dithienobenzothiadiazole as the acceptor unit, and used them as donor materials in non-fullerene organic solar cells (OSCs). Due to enhanced planarity of polymer chains resulted by the intramolecular F···S noncovalent interactions, the incorporation of 3,3'-difluoro-2,2'-bithiophene unit instead of 2,2'-bithiophene into the polymers can enhance their molecular packing, crystallinity and hole mobility. The DTBT-2T:L8-BO based binary OSCs deliver a power conversion efficiency (PCE) of only 9.71% with a Voc of 0.78 V, a Jsc of 20.69 mA cm-2 , and an FF of 59.67%. Moreover, the introduction of fluoro atoms can lower the highest occupied molecular orbital levels. As a result, DTBT-2T2F:L8-BO based single-junction binary OSCs exhibited less recombination loss, more balanced charge mobility, and more favorable morphology, resulting in an impressive PCE of 17.03% with a higher Voc of 0.89 V, a Jsc of 25.40 mA cm-2, and an FF of 75.74%. These results indicate that 3,3'-difluoro-2,2'-bithiophene unit can be used as an effective building block to synthesize high performance polymer donor materials. This work greatly expands the selection range of donor units for constructing high-performance polymers.
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Non-fullerene acceptors (NFAs) significantly enhance photovoltaic performance in organic solar cells (OSCs) using halogenated solvents and additives. However, these solvents are environmentally detrimental and unsuitable for industrial-scale production, and the issue of OSCs' poor long-term stability persists. This report introduces eight asymmetric NFAs (IPCnF-BBO-IC2F, IPCnF-BBO-IC2Cl, IPCnCl-BBO-IC2F, and IPCnCl-BBO-IC2Cl, where n = 1 and 2). These NFAs comprise a 12,13-bis(2-butyloctyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno-[3,2-b]indole (BBO) core. One end of the core attaches to a mono- or di-halogenated 9H-indeno[1,2-b]pyrazine-2,3-dicarbonitrile (IPC) end group (IPC1F, IPC1Cl, IPC2F, or IPC2Cl), while the other end connects to a 2-(5,6-dihalo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC) end group (IC2F or IC2Cl). The optical and electronic properties of these NFAs can be finely tuned by controlling the number of halogen atoms. Crucially, these NFAs demonstrate excellent compatibility with PM6 even in o-xylene, facilitating the production of additive-free OSCs. The di-halogenated IPC-based NFAs outperform their mono-halogenated counterparts in photovoltaic performance within OSCs. Remarkably, the di-halogenated IPC-based NFAs maintain 94â98% of their initial PCEs over 2000 h in air without encapsulation, indicating superior long-term device stability. These findings imply that the integration of di-halogenated IPCs in asymmetric NFA design offers a promising route to efficient, stable OSCs manufactured through environmentally friendly processes.
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CsPbBr3quantum dots (QDs) have excellent optical properties and good phase stability, but the long-chain ligands on their surfaces affect the charge transfer between QDs. Here, we propose a simple ligand exchange strategy: solution-phase ligand exchange. By adding an acetone solution of phenylethylammonium bromide to the purification process of CsPbBr3QDs, the long-chain ligands were effectively replaced and the electric coupling between QDs was improved. As a result, the power conversion efficiency of the solar cell was increased from 1.95% to 2.83%. Meanwhile, the stability of the devices was significantly improved in the unencapsulated case.
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New ß-amino-substituted porphyrin derivatives bearing carboxy groups were synthesized and their performance as sensitizers in dye-sensitized solar cells (DSSC) was evaluated. The new compounds were obtained in good yields (63-74%) through nucleophilic aromatic substitution reactions with 3-sulfanyl- and 4-sulfanylbenzoic acids. Although the electrochemical studies indicated suitable HOMO and LUMO energy levels for use in DSSC, the devices fabricated with these compounds revealed a low power conversion efficiency (PCE) that is primarily due to the low open-circuit voltage (Voc) and short-circuit current density (Jsc) values.
Assuntos
Porfirinas , Energia Solar , Porfirinas/química , Porfirinas/síntese químicaRESUMO
Although much promising synthetic progress in conjugated polymer-based organic solar cells (OSCs) has resulted in significant improvement in power conversion efficiencies (PCEs) of from over 15 to >19.0% in the last five years, the sophisticated and complex reactions from at least two families' monomers with remarkably different electron push-pull effects could still pose an unavoidable material burden for the commercialization of OSCs in the coming future. Therefore, the method of preparing a homopolymer from a sole monomer would significantly reduce the synthetic steps and costs in order to pave the way for the large-scale production of OSC materials. Therefore, alkylthio-thiophenyl-substituted benzo[1,2-b;4,5-b']dithiophene (BDTTS) as the sole and key structural moiety with dihalogen and distannyl functional groups was designed and synthesized, respectively, in this study, for facile monomer syntheses and polymerizations to achieve three wide-bandgap homopolymer donors of BDTTS-alt-BDTT-Cl (P13), BDTTS-alt-BDTT (P15), and BDTTS (P14), respectively. The structural symmetry dependency on their physical, electrochemical, and optical properties, thin-film morphologies, and photovoltaic (PV) performance was investigated in detail. As a result, OSCs based on the asymmetric polymer P15, paired with BTP-eC9 as the electron acceptor, presented the best PV performance, with a PCE of 11.5%, a fill factor (FF) of 65.87%, and a short-circuit current (JSC) of 22.04 mA·cm-2, respectively. This PCE value is among the highest ones reported for BDT-type homopolymer donor-based OPVs, providing us with knowledge for obtaining promising PV performance from devices made of P15-like materials.
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Solar cells represent a promising innovation in energy storage, offering not only exceptional cleanliness and low cost but also a high degree of flexibility, rendering them widely applicable. In recent years, scientists have dedicated substantial efforts to enhancing the performance of solar cells, aiming to drive sustainable development and promote clean energy applications. One approach that has garnered significant attention is strain engineering, which involves the adjustment of material microstructure and organization through mechanical tensile or compressive strain, ultimately serving to enhance the mechanical properties and performance stability of materials. This paper aims to provide a comprehensive review of the latest advancements in the application of strain engineering in solar cells, focused on the current hot research area-perovskite solar cells. Specifically, it delves into the origins and characterization of strain in solar cells, the impact of strain on solar cell performance, and the methods for regulating stable strain. Furthermore, it outlines strategies for enhancing the power conversion efficiency (PCE) and stability of solar cells through strain engineering. Finally, the paper conducts an analysis of the challenges encountered in the development process and presents a forward-looking perspective on further enhancing the performance of solar cells through strain engineering.
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Ternary organic solar cells (T-OSCs) represent an efficient strategy for enhancing the performance of OSCs. Presently, the majority of high-performance T-OSCs incorporates well-established Y-acceptors or donor polymers as the third component. In this study, a novel class of conjugated small molecules has been introduced as the third component, demonstrating exceptional photovoltaic performance in T-OSCs. This innovative molecule comprises ethylenedioxythiophene (EDOT) bridge and 3-ethylrhodanine as the end group, with the EDOT unit facilitating the creation of multiple conformation locks. Consequently, the EDOT-based molecule exhibits two-dimensional charge transport, distinguishing it from the thiophene-bridged small molecule, which displays fewer conformation locks and provides one-dimensional charge transport. Furthermore, the robust electron-donating nature of EDOT imparts the small molecule with cascade energy levels relative to the electron donor and acceptor. As a result, OSCs incorporating the EDOT-based small molecule as the third component demonstrate enhanced mobilities, yielding a remarkable efficiency of 19.3 %, surpassing the efficiency of 18.7 % observed for OSCs incorporating thiophene-based small molecule as the third component. The investigations in this study underscore the excellence of EDOT as a building block for constructing conjugated materials with multiple conformation locks and high charge carrier mobilities, thereby contributing to elevated photovoltaic performance in OSCs.
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The blend nanomorphology of electron-donor (D) and -acceptor (A) materials is of vital importance to achieving highly efficient organic solar cells. Exogenous additives especially aromatic additives are always needed to further optimize the nanomorphology of blend films, which is hardly compatible with industrial manufacture. Herein, we proposed a unique approach to meticulously modulate the aggregation behavior of NFAs in both crystal and thin film nanomorphology via self-regulation effect. Nonfullerene acceptor Z9 was designed and synthesized by tethering phenyl groups on the inner side chains of the Y6 backbone. Compared with Y6, the tethered phenyl groups participated in the molecular aggregation via the π-π stacking of phenyl-phenyl and phenyl-2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (IC-2F) groups, which induced 3D charge transport with phenyl-mediated super-exchange electron coupling. Moreover, ordered molecular packing with suitable phase separation was observed in Z9-based blend films. High power conversion efficiencies (PCEs) of 19.0 % (certified PCE of 18.6 %) for Z9-based devices were achieved without additives, indicating the great potential of the self-regulation strategy in NFA design.
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Organic solar cells (OSCs) are still suffering from the low light utilization and unstable under ultraviolet irradiation. To tackle these challenges, we design and synthesize a non-fused acceptor based on 1-(2-butyloctyl)-1H-pyrrole as π-bridge unit, denoted as GS70, which serves as active layer in the front-cell for constructing tandem OSCs with a parallel configuration. Benefiting from the well-complementary absorption spectra with the rear-cell, GS70-based parallel tandem OSCs exhibit an improved photoelectron response over the range between 600-700â nm, yielding a high short-circuit current density of 28.4â mA cm-2. The improvement in light utilization translates to a power conversion efficiency of 19.4 %, the highest value among all parallel tandem OSCs. Notably, owing to the intrinsic stability of GS70, the manufactured parallel tandem OSCs retain 84.9 % of their initial PCE after continuous illumination for 1000â hours. Overall, this work offers novel insight into the molecular design of low-cost and stability non-fused acceptors, emphasizing the importance of adopting a parallel tandem configuration for achieving efficient light harvesting and improved photostability in OSCs.
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Achieving both high power conversion efficiency (PCE) and device stability is a major challenge for the practical development of organic solar cells (OSCs). Herein, three non-fully conjugated dimerized giant acceptors (named 2Y-sites, including wing-site-linked 2Y-wing, core-site-linked 2Y-core, and end-site-linked 2Y-end) are developed. They share the similar monomer precursors but have different alkyl-linked sites, offering the fine-tuned molecular absorption, packing, glass transition temperature, and carrier mobility. Among their binary active layers, D18/2Y-wing has better miscibility, leading to optimized morphology and more efficient charge transfer compared to D18/2Y-core and D18/2Y-end. Therefore, the D18/2Y-wing-based OSCs achieve a superior PCE of 17.73 %, attributed to enhanced photocurrent and fill factor. Furthermore, the D18/2Y-wing-based OSCs exhibit a balance of high PCE and improved stability, distinguishing them within the 2Y-sites. Building on the success of 2Y-wing in binary systems, we extend its application to ternary OSCs by pairing it with the near-infrared absorbing D18/BS3TSe-4F host. Thanks to the complementary absorption within 300-970â nm and further optimized morphology, ternary OSCs obtain a higher PCE of 19.13 %, setting a new efficiency benchmark for the dimer-derived OSCs. This approach of alkyl-linked site engineering for constructing dimerized giant acceptors presents a promising pathway to improve both PCE and stability of OSCs.
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The passivation of the defects derived from rapid-crystallization with electron-donating molecules is always a prerequisite to obtain desirable perovskite films for efficient and stable solar cells, thus, the in-depth understanding on the correlations between molecular structure and passivation capacity is of great importance for screening passivators. Here, we introduce the double-ended amide molecule into perovskite precursor solution to modulate crystallization process and passivate defects. By regulating the intermediate bridging skeletons with alkyl, alkenyl and benzene groups, the results show the passivation strength highly depends on the spin-state electronic structure that serves as an intrinsic descriptor to determine the intramolecular charge distribution by controlling orbital electron transfer from the donor segment to acceptor segment. Upon careful optimization, the benzene-bridged amide molecule demonstrates superior efficacy on improving perovskite film quality. As a physical proof-of-concept, the carbon-based, all-inorganic CsPbI2Br solar cell delivers a significantly increased efficiency of 15.51 % with a remarkably improved stability. Based on the same principle, a champion efficiency of 24.20 % is further obtained on the inverted (Cs0.05MA0.05FA0.9)Pb(I0.93Br0.07)3 solar cell. These findings provide new fundamental insights into the influence of spin-state modulation on effective perovskite solar cells.
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To meet the industrial requirements of organic photovoltaic (OPV) cells, it is imperative to accelerate the development of cost-effective materials. Thiophene-benzene-thiophene central unit-based acceptors possess the advantage of low synthetic cost, while their power conversion efficiency (PCE) is relatively low. Here, by incorporating a para-substituted benzene unit and 1st-position branched alkoxy chains with large steric hindrance, a completely non-fused non-fullerene acceptor, TBT-26, was designed and synthesized. The narrow band gap of 1.38â eV ensures the effective utilization of sunlight. The favorable phase separation morphology of TBT-26-based blend film facilitates the efficient exciton dissociation and charge transport in corresponding OPV cell. Therefore, the TBT-26-based small-area cell achieves an impressive PCE of 17.0 %, which is the highest value of completely non-fused OPV cells. Additionally, we successfully demonstrated the scalability of this design by fabricating a 28.8â cm2 module with a high PCE of 14.3 %. Overall, our work provides a practical molecular design strategy for developing high-performance and low-cost acceptors, paving the way for industrial applications of OPV technology.