Constructing Multiscale Fibrous Morphology to Achieve 20% Efficiency Organic Solar Cells by Mixing High and Low Molecular Weight D18.

This study underscores the significance of precisely manipulating the morphology of the active layer in organic solar cells (OSCs). By blending polymer donors of D18 with varying molecular weights, a multiscale interpenetrating fiber network structure within the active layer is successfully created. The introduction of 10% low molecular weight D18 (LW-D18) into high molecular weight D18 (HW-D18) produces MIX-D18, which exhibits an extended exciton diffusion distance and orderly molecular stacking. Devices utilizing MIX-D18 demonstrate superior electron and hole transport, improves exciton dissociation, enhances charge collection efficiency, and reduces trap-assisted recombination compared to the other two materials. Through the use of the nonfullerene acceptor L8-BO, a remarkable power conversion efficiency (PCE) of 20.0% is achieved. This methodology, which integrates the favorable attributes of high and low molecular weight polymers, opens a new avenue for enhancing the performance of OSCs.

The superiority of isomeric, fluorination and curtailed π-conjunction on A-D-A type acceptors for organic photovoltaics.

The performance of organic solar cell (OSC) devices has been significantly enhanced by the dramatic evolution of A-D-A type non-fullerene acceptors (NFAs). Nevertheless, the structure-property-performance relationship of NFAs in the OSC device is unclear. Here, the intrinsic design factors of isomeric, fluorination and π-conjunction curtailing on the photophysical properties of benzodi (thienopyran) (BDTP) (named NBDTP-M, NBDTTP-M, NBDTP-Fin, and NBDTP-Fout)-based NFAs are discussed. The results show that fluorination on the terminal group of NBDTP-Fout could effectively decrease the highest occupied orbital (HOMO) energy level and the lowest unoccupied orbital (LUMO) energy level. And the long π-conjugated donor unit for NBDTTP-M could increase the HOMO energy level and bring a small HOMO-LUMO energy bandgap. Meanwhile, the substitution of external oxygen atoms and the fluorine atoms in the terminal group could introduce positive changes to the electrostatic potential of the NBDTP-Fout, favouring the charge separation at the donor/acceptor interface. Moreover, the structural design of external oxygen atom substitution, fluorination on the terminal group and curtailed π-conjugated donor unit could decrease the electron vibration-coupling of exciton diffusion, exciton dissociation and electronic transfer processes. The suppression of the exciton decay and charge recombination in those high-performance NFAs indicate that the investigated molecular designs could be effective for further improvement of OSCs.

Organic Heterostructures with Dendrimer Based Mixed Layer for Electronic Applications.

Recently, much research has focused on the search for new mixed donor-acceptor layers for applications in organic electronics. Organic heterostructures with layers based on the generation 1 poly(propylene thiophenoimine) (G1PPT) dendrimer, N,N'-diisopropylnaphthalene diimide (MNDI), and a combination of the two were prepared and their electrical properties were investigated. Single layers of G1PPT and MNDI and a mixed layer (G1PPT:MNDI) were obtained via spin coating on quartz glass, silicon, and glass/ITO substrates, using chloroform as a solvent. The absorption mechanism was investigated, the degree of disorder was estimated, and the emission properties of the layers were highlighted using spectroscopic methods (UV-Vis transmission and photoluminescence). The effects of the concentration and surface topographical particularities on the properties of the layers were analyzed via atomic force microscopy. All of the heterostructures realized with ITO and Au electrodes showed good conduction, with currents of the order of mA. Additionally, the heterostructure with a mixed layer exhibited asymmetry in the current-voltage curve between forward and reverse polarization in the lower range of the applied voltages, which was more significant at increased concentrations and could be correlated with rectifier diode behavior. Consequently, the mixed-layer generation 1 poly(propylene thiophenoimine) dendrimer with N,N'-diisopropylnaphthalene diimide can be considered promising for electronic applications.

Sensitive SWIR Organic Photodetectors with Spectral Response Reaching 1.5 µm.

The performance of organic photodetectors (OPDs) sensitive to the short-wavelength infrared (SWIR) light lags behind commercial indium gallium arsenide (InGaAs) photodetectors primarily due to the scarcity of organic semiconductors with efficient photoelectric responses exceeding 1.3 µm. Limited by the Energy-gap law, ultralow-bandgap organic semiconductors usually suffer from severe non-radiative transitions, resulting in low external quantum efficiency (EQE). Herein, a difluoro-substituted quinoid terminal group (QC-2F) with exceptionally strong electron-negativity is developed for constructing a new non-fullerene acceptor (NFA), Y-QC4F with an ultralow bandgap of 0.83 eV. This subtle structural modification significantly enhances intermolecular packing order and density, enabling an absorption onset up to 1.5 µm while suppressing non-radiation recombination in Y-QC4F films. SWIR OPDs based on Y-QC4F achieve an impressive detectivity (D*) over 1011 Jones from 0.4 to 1.5 µm under 0 V bias, with a maximum of 1.68 × 1012 Jones at 1.16 µm. Furthermore, the resulting OPDs demonstrate competitive performance with commercial photodetectors for high-quality SWIR imaging even under 1.4 µm irradiation.

Unraveling the Solution Aggregation Structures and Processing Resiliency of High-Efficiency Organic Photovoltaic Blends.

The solution aggregation structure of conjugated polymers is crucial to the morphology and resultant optoelectronic properties of organic electronics and is of considerable interest in the field. Precise characterizations of the solution aggregation structures of organic photovoltaic (OPV) blends and their temperature-dependent variations remain challenging. In this work, the temperature-dependent solution aggregation structures of three representative high-efficiency OPV blends using small-angle X-ray/neutron scattering are systematically probed. Three cases of solution processing resiliency are elucidated in state-of-the-art OPV blends. The exceptional processing resiliency of high-efficiency PBQx-TF blends can be attributed to the minimal changes in the multiscale solution aggregation structure at elevated temperatures. Importantly, a new parameter, the percentage of acceptors distributed within polymer aggregates (Ф), for the first time in OPV blend solution, establishes a direct correlation between Ф and performance is quantified. The device performance is well correlated with the Kuhn length of the cylinder related to polymer aggregates L1 at the small scale and the Ф at the large scale. Optimal device performance is achieved with L1 at ≈30 nm and Ф within the range of 60 ± 5%. This study represents a significant advancement in the aggregation structure research of organic electronics.

Nonfullerene Acceptors Bearing Spiro-Substituted Bithiophene Units in Organic Solar Cells: Tuning the Frontier Molecular Orbital Distribution to Reduce Exciton Binding Energy.

The development of nonfullerene acceptors (NFAs), represented by ITIC, has contributed to improving the power conversion efficiency (PCE) of organic solar cells (OSCs). Although tuning the electronic structures to reduce the exciton binding energy (Eb) is considered to promote photocharge generation, a rational molecular design for NFAs has not been established. In this study, we designed and developed two ITIC-based NFAs bearing spiro-substituted bithiophene or biphenyl units (named SpiroT-DCI and SpiroF-DCI) to tune the frontier molecular orbital (FMO) distribution of NFAs. While the highest occupied molecular orbitals (HOMOs) of SpiroF-DCI and ITIC are delocalized in the main π-conjugated framework, the HOMO of SpiroT-DCI is distributed on the bithiophene unit. Reflecting this difference, SpiroT-DCI exhibits a smaller Eb than either SpiroF-DCI or ITIC, and exhibits greater external quantum efficiency in single-component OSCs. Furthermore, SpiroT-DCI shows improved PCEs for bulk-heterojunction OSCs with a donor of PBDB-T, compared with that of either SpiroT-DCI or ITIC. Time-resolved spectroscopy measurements show that the photo-induced intermolecular charge separation is effective even in pristine SpiroT-DCI films. This study highlights the introduction of spiro-substituted bithiophene units that are effective in tuning the FMOs of ITIC, which is desirable for reducing the Eb and improving the PCE in OSCs.

Halogenation Strategy: Simple Wide Band Gap Nonfullerene Acceptors with the BODIPY-Thiophene-Backboned Polymer Donor for Enhanced Outdoor and Indoor Photovoltaics.

Researchers have been motivated to develop photovoltaic systems that can efficiently convert artificial light into power with the growing use of indoor electrical devices for the Internet of Things. Understanding the impact of molecular design strategies involving morphological optimization through the terminal group of the non-fullerene acceptors (NFAs) is crucial. This is critically important to enhancing the photovoltaic efficiency of organic photovoltaic devices under diverse irradiation conditions. Halogenation of terminal groups proves to be a standout approach for adjusting energy levels, refining light-harvesting capabilities, crystallinity, and bolstering the intermolecular stacking in NFAs. Herein, we have designed two simple NFAs, DICTF-4F and DICTF-4Cl, to explore the dihalogenation (F and Cl) effect on the terminal group on the optical and electrochemical properties. After combining with the BODIPY-thiophene-backboned donor polymer P(BdP-HT), the organic solar cells (OSCs) using an optimized active layer with P(BdP-HT):DICTF-4F and P(BdP-HT):DICTF-4Cl attained a power conversion efficiency (PCE) of about 8.03 and 14.16%, respectively, under 1 sun illumination. Moreover, the OSC-based P(BdP-HT):DICTF-4Cl active layer showed a PCE approaching 24% under 1000 lx indoor conditions.

Exploration of the effect of multiple acceptor and π-spacer moieties coupled to indolonaphthyridine core for promising organic photovoltaic properties: a first principles framework.

Herein, the indolonaphthyridine-based molecules (INDTD1-INDTD8) with A1-π-A2-π-A1 configuration were designed by the end-capped modification of INDTR reference with various acceptors. The density functional theory (DFT) and time-dependent DFT (TD-DFT) analyses at M06/6-31G(d,p) level were reported in this research to explore their optoelectronic and photovoltaic features. Their geometrical structures were initially optimized at the afore-said level and followed by various calculations such as the frontier molecular orbitals (FMOs), UV-Visible, density of states (DOS), transition density matrix (TDM), binding energy (Eb), open circuit voltage (Voc) and fill factor (FF). Moreover, their global reactivity parameters (GRPs) were depicted by using the HOMO-LUMO band gaps obtained from the FMOs study. The tailored molecules demonstrated lower band gaps (2.183-2.269 eV) than INDTR (2.288 eV). They also showed bathochromic shifts in the visible region in chloroform (735.937-762.318 nm) and gas phase (710.384-729.571 nm) as compared to INDTR (724.710 and 698.498 nm, respectively). Further, intramolecular charge transfer (ICT) was demonstrated via the DOS and TDM graphical maps. Among all the entitled chromophores, INDTD7 showed significantly reduced band gap (2.183 eV), red-shifted absorption value (760.914 nm) in chloroform solvent and minimal Eb value (0.554 eV). The presence of -SO3H groups on the terminal acceptors of INDTD7  may enhance the mobility of charges. The results suggested that the newly designed chromophores can be effective candidates for the future organic solar cell applications. Moreover, this study may encourage the experimentalists to develop photovoltaic materials.

Progress in Non-Fullerene Acceptors: Evolution from Small to Giant Molecules.

With the rapid development of non-fullerene acceptors (NFAs), the power conversion efficiency (PCE) of organic solar cells (OSCs) is increasing. According to their different chemical structures, NFAs can initially be divided into two categories: small molecule acceptors (SMAs) and polymerized small molecule acceptors (PSMAs). Due to the strong absorption capacity and controllable energy levels, the PCE of devices based on SMAs has approached 20%. Compared with SMAs, PSMAs have advantages in stability and flexibility, and the PCE of PSMA-based devices has exceeded 18%. However, the higher synthesis cost and lower batch repeatability hinder its further development. Recently, the concept of giant molecule acceptors (GMAs) has been proposed. These materials have a clear molecular structure and are considered novel acceptor materials that combine the advantages of SMAs and PSMAs. Currently, the PCE of devices based on GMAs has exceeded 19%. In this review, we will introduce the latest developments in SMAs, PSMAs, and GMAs. Then, the advantages of GMAs and the relationship between their structure and performance will be analyzed. In the end, perspectives on the opportunities and challenges of these materials are provided, which could inspire further development of NFAs for advanced OSCs.

Accomplishing High-Performance Organic Solar Sub-Modules (≈55 cm2) with >16% Efficiency by Controlling the Aggregation of an Engineered Non-Fullerene Acceptor.

The fabrication of environmentally benign, solvent-processed, efficient, organic photovoltaic sub-modules remains challenging due to the rapid aggregation of the current high performance non-fullerene acceptors (NFAs). In this regard, design of new NFAs capable of achieving optimal aggregation in large-area organic photovoltaic modules has not been realized. Here, an NFA named BTA-HD-Rh is synthesized with longer (hexyl-decyl) side chains that exhibit good solubility and optimal aggregation. Interestingly, integrating a minute amount of new NFA (BTA-HD-Rh) into the PM6:L8-BO system enables the improved solubility in halogen-free solvents (o-xylene:carbon disulfide (O-XY:CS2)) with controlled aggregation is found. Then solar sub-modules are fabricated at ambient condition (temperature at 25 ± 3 °C and humidity: 30-45%). Ultimately, the champion 55 cm2 sub-modules achieve exciting efficiency of >16% in O-XY:CS2 solvents, which is the highest PCE reported for sub-modules. Notably, the highest efficiency of BTA-HD-Rh doped PM6:L8-BO is very well correlated with high miscibility with low Flory-Huggins parameter (0.372), well-defined nanoscale morphology, and high charge transport. This study demonstrates that a careful choice of side chain engineering for an NFA offers fascinating features that control the overall aggregation of active layer, which results in superior sub-module performance with environmental-friendly solvents.

The Development of Quinoxaline-Based Electron Acceptors for High Performance Organic Solar Cells.

In the recent advances of organic solar cells (OSCs), quinoxaline (Qx)-based nonfullerene acceptors (QxNFAs) have attracted lots of attention and enabled the recorded power conversion efficiency approaching 20%. As an excellent electron-withdrawing unit, Qx possesses advantages of many modifiable sites, wide absorption range, low reorganization energy, and so on. To develop promising QxNFAs to further enhance the photovoltaic performance of OSCs, it is necessary to systematically summarize the QxNFAs reported so far. In this review, all the focused QxNFAs are classified into five categories as following: SM-Qx, YQx, fused-YQx, giant-YQx, and polymer-Qx according to the molecular skeletons. The molecular design concepts, relationships between the molecular structure and optoelectronic properties, intrinsic mechanisms of device performance are discussed in detail. At the end, the advantages of this kind of materials are summed up, the molecular develop direction is prospected, the challenges faced by QxNFAs are given, and constructive solutions to the existing problems are advised. Overall, this review presents unique viewpoints to conquer the challenge of QxNFAs and thus boost OSCs development further toward commercial applications.

Non-Fullerene Organic Electron Transport Materials toward Stable and Efficient Inverted Perovskite Photovoltaics.

Inverted perovskite solar cells (PSCs) attract continuing interest due to their low processing temperature, suppressed hysteresis, and compatibility with tandem cells. Considerable progress has been made with reported power conversion efficiency (PCE) surpassing 26%. Electron transport Materials (ETMs) play a critical role in achieving high-performance PSCs because they not only govern electron extraction and transport from the perovskite layer to the cathode, but also protect the perovskite from contact with ambient environment. On the other hand, the non-radiative recombination losses at the perovskite/ETM interface also limits the future development of PSCs. Compared with fullerene derivatives, non-fullerene n-type organic semiconductors feature advantages like molecular structure diversity, adjustable energy level, and easy modification. Herein, the non-fullerene ETM is systematically summarized based on the molecular functionalization strategy. Various types of molecular design approaches for producing non-fullerene ETM are presented, and the insight on relationship of chemical structure and device performance is discussed. Meantime, the future trend of non-fullerene ETM is analyzed. It is hoped that this review provides insightful perspective for the innovation of new non-fullerene ETMs toward more efficient and stable PSCs.

Wide Bandgap Polymer Donors Based on Succinimide-Substituted Thiophene for Nonfullerene Organic Solar Cells.

The advent of nonfullerene acceptors (NFAs) has greatly improved the photovoltaic performance of organic solar cells (OSCs). However, to compete with other solar cell technologies, there is a pressing need for accelerated research and development of improved NFAs as well as their compatible wide bandgap polymer donors. In this study, a novel electron-withdrawing building block, succinimide-substituted thiophene (TS), is utilized for the first time to synthesize three wide bandgap polymer donors: PBDT-TS-C5, PBDT-TSBT-C12, and PBDTF-TSBT-C16. These polymers exhibit complementary bandgaps for efficient sunlight harvesting and suitable frontier energy levels for exciton dissociation when paired with the extensively studied NFA, Y6. Among these donors, PBDTF-TSBT-C16 demonstrates the highest hole mobility and a relatively low highest occupied molecular orbital (HOMO) energy level, attributed to the incorporation of thiophene spacers and electron-withdrawing fluorine substituents. OSC devices based on the blend of PBDTF-TSBT-C16:Y6 achieve the highest power conversion efficiency of 13.21%, with a short circuit current density (Jsc) of 26.83 mA cm-2, an open circuit voltage (Voc) of 0.80 V, and a fill factor of 0.62. Notably, the Voc × Jsc product reaches 21.46 mW cm-2, demonstrating the potential of TS as an electron acceptor building block for the development of high-performance wide bandgap polymer donors in OSCs.

Machine learning assisted designing of non-fullerene electron acceptors: A quest for lower exciton binding energy.

The designing of acceptors materials for the organic solar cells is a hot topic. The normal experimental methods are tedious and expensive for large screening. Machine learning guided exploration is more suitable solution. Bagging regression, random forest regression, gradient boosting regression, and linear regression are trained to predict exciton binding energy. Breaking Retrosynthetically Interesting Chemical Substructures (BRICS) methodology has utilized for designing of new non-fullerene acceptors (NFAs). The predicted values were used to select the designed NFAs. On the selected NFAs, clustering and chemical similarity analyses are also performed. Chemical fingerprints are used for this purpose, and the synthetic accessibility score of the new NFAs is also investigated.30 NFAs have selected with low exciton binding energy values. This approach will allow for the rapid screening of NFAs for organic solar cells. Our proposed framework stands out as a valuable tool for strategically selecting the most effective NFAs for organic solar cells and offers a streamlined approach for material discovery.

Dilute Donor Organic Solar Cells Based on Non-fullerene Acceptors.

The advent of small molecule non-fullerene acceptor (NFA) materials for organic photovoltaic (OPV) devices has led to a series of breakthroughs in performance and device lifetime. The most efficient OPV devices have a combination of electron donor and acceptor materials that constitute the light absorbing layer in a bulk heterojunction (BHJ) structure. For many BHJ-based devices reported to date, the weight ratio of donor to acceptor is near equal. However, the morphology of such films can be difficult to reproduce and manufacture at scale. There would be an advantage in developing a light harvesting layer for efficient OPV devices that contains only a small amount of either the donor or acceptor. In this work we explore low donor content OPV devices composed of the polymeric donor PM6 blended with high performance NFA materials, Y6 or ITIC-4F. We found that even when the donor:acceptor weight ratio was only 1:10, the OPV devices still have good photoconversion efficiencies of around 6% and 5% for Y6 and ITIC-4F, respectively. It was found that neither charge mobility nor recombination rates had a strong effect on the efficiency of the devices. Rather, the overall efficiency was strongly related to the film absorption coefficient and maintaining adequate interfacial surface area between donor and acceptor molecules/phases for efficient exciton dissociation.

A theoretical investigation for improving the performance of non-fullerene organic solar cells through side-chain engineering of BTR non-fused-ring electron acceptors.

In the current quantum chemical study, indacenodithiophene donor core-based the end-capped alterations of the reference chromophore BTR drafted eight A2-A1-D-A1-A2 type small non-fullerene acceptors. All the computational simulations were executed under MPW1PW91/6-31G (d, p) level of DFT. The UV-Vis absorption, open circuit voltage, electron affinity, ionization potential, the density of states, reorganization energy, orbital analysis, and non-covalent interactions were studied and compared with BTR. Several molecules of our modeled series BT1-BT8 have shown distinctive features that are better than those of the BTR. The open circuit voltage (VOC) of BT5 has a favorable impact, allowing it to replace BTR in the field of organic solar cells. The charge carrier motilities for proposed molecules generated extraordinary findings when matched to the reference one (BTR). Further charge transmission was confirmed by creating the complex with a PM6 donor molecule. The remarkable dipole moment contributes to the formation of non-covalent bond interactions with chloroform, resulting in superior charge mobility. Based on these findings, it can be said that every tailored molecule has the potential to surpass chromophore molecule (BTR) in OSCs. So, all tailored molecules may enhance the efficiency of photovoltaic cells due to the involvement of potent terminal electron-capturing acceptor2 moieties. Considering these obtained results, these newly presented molecules can be regarded for developing efficient solar devices in the future.

Optimizing Alkyl Side Chains in Difluorobenzene-Rhodanine Small-Molecule Acceptors for Organic Solar Cells.

A series of small molecules, T-2FB-T-ORH, T-2FB-T-BORH, and T-2FB-T-HDRH, were synthesized to have a thiophene-flanked difluorobenzene (T-2FB-T) core and alkyl-substituted rhodanine (RH) end groups for their use as nonfullerene acceptors (NFAs) in organic solar cells (OSCs). Octyl, 2-butyloctyl (BO), and 2-hexyldecyl (HD) alkyl side chains were introduced into RHs to control the material's physical properties based on the length and size of the alkyl chains. The optical properties of the three NFAs were found to be almost the same, irrespective of the alkyl chain length, whereas the molecular crystallinity and material solubility significantly differed depending on the alkyl side chains. Owing to the sufficient solubility of T-2FB-T-HDRH, OSCs based on PTB7-Th and T-2FB-T-HDRH were fabricated. A power conversion efficiency of up to 4.49% was obtained by solvent vapor annealing (SVA). The AFM study revealed that improved charge mobility and a smooth and homogeneous film morphology without excessive aggregation could be obtained in the SVA-treated film.

Recent Progress in Semitransparent Organic Solar Cells: Photoabsorbent Materials and Design Strategies.

The increasing energy demands of the global community can be met with solar energy. Solution-processed organic solar cells have seen great progress in power conversion efficiencies (PCEs). Semitransparent organic solar cells (ST-OSCs) have made enormous progress in recent years and have been considered one of the most promising solar cell technologies for applications in building-integrated windows, agricultural greenhouses, and wearable energy resources. Therefore, through the synergistic efforts of transparent electrodes, engineering in near-infrared photoabsorbent materials, and device engineering, high-performance ST-OSCs have developed, and PCE and average visible transmittance reach over 10% and 40%, respectively. In this review, we present the recent progress in photoabsorbent material engineering and strategies for enhancing the performance of ST-OSCs to help researchers gain a better understanding of structure-property-performance relationships. To conclude, new design concepts in material engineering and outlook are proposed to facilitate the further development of high-performance ST-OSCs.

The Role of Solution Aggregation Property toward High-Efficiency Non-Fullerene Organic Photovoltaic Cells.

In organic photovoltaic cells, the solution-aggregation effect (SAE) is long considered a critical factor in achieving high power-conversion efficiencies for polymer donor (PD)/non-fullerene acceptor (NFA) blend systems. However, the underlying mechanism has yet to be fully understood. Herein, based on an extensive study of blends consisting of the representative 2D-benzodithiophene-based PDs and acceptor-donor-acceptor-type NFAs, it is demonstrated that SAE shows a strong correlation with the aggregation kinetics during solidification, and the aggregation competition between PD and NFA determines the phase separation of blend film and thus the photovoltaic performance. PDs with strong SAEs enable earlier aggregation evolutions than NFAs, resulting in well-known polymer-templated fibrillar network structures and superior PCEs. With the weakening of PDs' aggregation effects, NFAs, showing stronger tendencies to aggregate, tend to form oversized domains, leading to significantly reduced external quantum efficiencies and fill factors. These trends reveal the importance of matching SAE between PD and NFA. The aggregation abilities of various materials are further evaluated and the aggregation ability/photovoltaic parameter diagrams of 64 PD/NFA combinations are provided. This work proposes a guiding criteria and facile approach to match efficient PD/NFA systems.

Halogenated 9H-Indeno[1,2-b]Pyrazine-2,3-Dicarbonitrile End Groups Based Asymmetric Non-Fullerene Acceptors for Green Solvent-Processable, Additive-Free, and Stable Organic Solar Cells.

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 94‒98% 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.