Molecular Packing Research Articles

Boosting the performance of polymer field-effect transistors through fluorine atom substitutions and comparing the effect of various acceptor units and channel mobilities

Three conjugated copolymers, PDPP-2FTVT, PIID-2FTVT, and PNDI-2FTVT based on the 2,2′-(1E)-1,2-ethenediylbis[3-fluorothiophene] (2FTVT) core with varying acceptor units, diketopyrrolopyrrole (DPP), isoindigo (IID), and naphthalenediimide (NDI) were developed for organic field-effect transistors (OFETs). Combined electron-withdrawing fluorine atoms and vinyl linkage in the 2FTVT unit not only reduce the frontier molecular orbital energies but also extended the absorption profile and planarize the polymer backbone, manifesting synergetic effect on the strengthened molecular interactions and charge-carrier properties. The resulted copolymer, PDPP-2FTVT show highly reliable thin film transistor properties with highest hole mobility of 1.93 cm2 V−1 s−1 compared to PIID-2FTV and PNDI-2FTVT. PIID-2FTV copolymer show ambipolar characteristic with hole and electron mobilities of 0.71 and 0.03 cm2 V−1 s−1 respectively while PNDI-2FTVT exhibited the highest electron mobility of 0.20 cm2 V−1 s−1 among three copolymers. Thin film micro-structure characterization reveal that the three copolymers formed lamellar, edge-on molecular packing (for PDPP-2FTVT and PIID-2FTV), increased crystallinity with smaller π-π stacking distances, and strengthen the planarity after thermal annealing. These results contribute important progresses in solution-processed OFET and could provide a greater possibility of 2FTVT based copolymers for commercial application.

Hierarchical Self-Assembly of Multidimensional Functional Materials from Sequence-Defined Peptoids.

Hierarchical self-assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular-level understanding of the hierarchical assembly of sequence-defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron-based powder X-ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence-defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Self‐Assembled Cyclotriguaiacyclene‐Integrated Supramolecular Systems for Liquid Crystal and Self‐Assembly Behavior

AbstractAn advanced tri‐substituted supramolecular material was synthesized via conversion of cyclotriveratrylene to cyclotriguaiacyclene with further esterification reaction with fluorescein unit embedded with side‐arms. All four luminescent materials exhibited columnar hexagonal type mesophase on both heating and cooling conditions. The materials with hexadecyloxy and octadecyloxy tail group exhibit liquid crystalline behavior at room temperature indicating the presence of a mesophase even under ambient conditions. By combining polarizing optical microscopy, differential scanning calorimetry, and high‐temperature X‐Ray diffraction techniques to understanding the optical, thermal, and molecular packing behavior of the compounds in the liquid crystalline state. The cyclotriguaiacyclene core with high fluorescent nature displayed columnar hexagonal type self‐assembly at room temperature. All four supramolecular mesogens showed higher thermal stability of mesophase. The computational study provides the importance of the electronic nature of the compounds.

Hierarchical Self‐Assembly of Multidimensional Functional Materials from Sequence‐Defined Peptoids

AbstractHierarchical self‐assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular‐level understanding of the hierarchical assembly of sequence‐defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron‐based powder X‐ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence‐defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Unraveling the influence of surface functionalities on gas Physisorption: A comprehensive study on SBA-15 nanoporous material from Monte Carlo simulation for improved Textural-Energetic characterization

In this study, we conducted experimental and Monte Carlo simulation studies in the grand canonical ensemble (GCMC) to investigate the role of molecular orientation and surface heterogeneity on the adsorption of N2 at 77 K. Our research focused on a series of ordered nanoporous materials (SBA-15) with varying degrees of oxygen functionalities. Specifically, we examined the effects of surface heterogeneity on the calculation of pore size distribution (PSD) and the Brunauer-Emmett-Teller (BET) area of porous materials. To provide a comprehensive perspective, we compared our results with three levels of surface oxidation, including a pristine case without any surface oxidation.The results from both our experimental and simulation data reveal the importance of chemical heterogeneity in determining equilibrium properties such as molecular packing within the pores, differential enthalpies of adsorption, and N2 orientation distribution. Our findings suggest that accurate characterization of surface heterogeneity is crucial for understanding gas adsorption in nanoporous materials and for developing better models for predicting their performance in various applications. Moreover, our simulations revealed substantial changes in the molecular orientation of adsorbate particles with increasing surface heterogeneity. This insight provides valuable information about the behavior of molecules within the nanoporous materials, further enhancing our understanding of the complex adsorption processes in these systems.

Insights on molecular modeling and supramolecular arrangement of bilastine polymorphs.

The advancement in the development of second-generation drugs in the field of antihistamines represents a significant milestone in the management of allergic diseases, targeting the effects of histamine. The efficacy of bilastine in treating allergic disorders has sparked interest in investigating its polymorphism, a crucial property that impacts quality, safety, and effectiveness as per regulatory guidelines. This study examines the polymorphism of bilastine, focusing on two crystalline forms labeled as Form I and Form II. Utilizing advanced analytical techniques, the research explores the structural characteristics and molecular interactions within these forms. Geometric parameters, such as bond lengths, bond angles, and torsion angles, are examined to comprehend molecular conformations and crystal packing arrangements. Hydrogen bonding, covalent bonds, and van der Waals forces contribute to the unique supramolecular arrangements in these forms.This study provides a significant contribution to understanding bilastine's polymorphism, offering critical insights to researchers and regulatory bodies to ensure the quality, efficacy, and safety of antihistamine products. The molecular conformation of two bilastine forms was obtained through DFT with the exchange-correlation functional M06-2X and the 6-311 + + G(d,p) basis set, and the results were compared with the experimental X-ray. The atomic coordinates were obtained directly from the crystalline structures, and charge transfer was also investigated using frontier molecular orbitals (HOMO and LUMO), and MEP map in order to evaluate the energies associated with charge transfers and regions of high electron affinity. The geometric and topological parameters and intermolecular interactions in the crystals were analyzed using Hirshfeld Surface.

Long-range polymer ordering by directional coating to remarkably enhance the charge carrier mobility in PCDTPT-based organic field-effect transistors.

With the wide potential of organic field-effect transistors in all the modern electronic circuitries, researchers are grappling with the challenge of poor charge transport and hence lower mobility in organic polymers. Low-charge carrier mobility is mainly due to disorder in the molecular packing of organic semiconductors along with other factors, such as impurities, defects and interactions between molecules. The current research work has been conducted to align the molecular chains of poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-‌‌‌b:5,4-‌b']‌dithiophen-2-yl)-alt-[1,2,5]thiadiazolo-[3,4-c]pyridine] (PCDTPT) using directional coating techniques such as dip coating and brush coating on nano-grooved substrates. Long-range order of polymer chains was clearly observed along the direction of brush coating and nanogrooves in optical and atomic force microscope (AFM) images while transmission spectra confirmed decreased pi-pi stacking for the polymer films deposited by this technique. By comparing the mobility performance of brush-coated devices with other techniques, we found a remarkable mobility enhancement of 90 times that of conventional spin-coated device and 24 times enhancement compared with the dip-coated device for the case when the alignment of polymer chains was parallel to the channel. All the fabrication and characterizations were performed in the ambient environment. This study demonstrates a potential approach to align the polymers on long and short ranges hence providing a route for high-performing devices in ambient conditions.

Disorder-Induced Transition from Transient Quantum Delocalization to Charge Carrier Hopping Conduction in a Nonfullerene Acceptor Material

Nonfullerene acceptors have caused a step change in organic optoelectronics research but little is known about the mechanism and factors limiting charge transport in these molecular materials. Here a joint computational-experimental investigation is presented to understand the impact of various sources of disorder on the electron transport in the nonfullerene acceptor O-IDTBR. We find that in single crystals of this material, electron transport occurs in the transient quantum delocalization regime with the excess charge delocalized over about three molecules on average, according to quantum-classical nonadiabatic molecular-dynamics simulations. In this regime, carrier delocalization and charge mobility (μa=7 cm2 V−1 s−1) are limited by dynamical disorder of off-diagonal and diagonal electron-phonon coupling. In molecular assemblies representing disordered thin films, the additional static disorder of off-diagonal electron-phonon coupling is sufficient to fully localize the excess electron on single molecules, concomitant with a transition of transport mechanism from transient quantum delocalization to small polaron hopping and a drop in electron mobility by about 1 order of magnitude. Yet, inclusion of static diagonal disorder resulting from electrostatic interactions arising from the acceptor-donor-acceptor (A-D-A) structure of O-IDTBR, are found to have the most dramatic impact on carrier mobility, resulting in a further drop of electron mobility by about 4–5 orders of magnitude to 10−5 cm2 V−1 s−1, in good agreement with thin-film electron mobility estimated from space-charge-limited-current measurements. Limitations due to diagonal disorder caused by electrostatic interactions are likely to apply to most nonfullerene acceptors. They imply that while A-D-A or A-DAD-A motifs are beneficial for photoabsorption and exciton transport, the electrostatic disorder they create can limit carrier transport in thin-film optoelectronic applications. This work shows the value of computational methods, in particular, nonadiabatic molecular-dynamics propagation of charge carriers, to distinguish different regimes of transport for different types of molecular packing. Published by the American Physical Society 2024

Thermal Radiation Annealing for Overcoming Processing Temperature Limitation of Flexible Perovskite Solar Cells.

Common polymeric conductive electrodes, such as polyethylene terephthalate (PET) coated with indium tin oxide, face a major challenge due to their low processing-temperature limits, attributed to PET's low glass transition temperature (Tg) of (70-80°C). This limitation significantly narrows the scope of material selection, limits the processing techniques applicable to the low Tg, and hinders the ripened technology transfer from glass substrates to them. Addressing the temperature constraints of the flexible substrates is impactful yet underexplored, with broader implications for fields beyond photovoltaics. Here, a new thermal radiation annealing methodology is introduced to address this issue. By applying the above Tg radiation annealing in conjunction with thermoelectric cooling, highly ordered molecular packing on PET substrates is successfully created, which is exclusively unachievable due to PET's low thermal tolerance. As a result, in the context of perovskite solar cells, this approach enables the circumvention of high-temperature annealing limitations of PET substrates, leading to a remarkable flexible device efficiency of 22.61% and a record fill factor of 83.42%. This approach proves especially advantageous for advancing the field of flexible optoelectronic devices.

Crystal structure and Hirshfeld surface analysis of (Z)-4-({[2-(benzo[b]thio-phen-3-yl)cyclo-pent-1-en-1-yl]meth-yl}(phen-yl)amino)-4-oxobut-2-enoic acid.

In the title compound, C24H21NO3S, the cyclopentene ring adopts an envelope conformation. In the crystal, mol-ecules are linked by C-H⋯π inter-actions, forming ribbons along the a axis. Inter-molecular C-H⋯O hydrogen bonds connect these ribbons to each other, forming layers parallel to the (01) plane. The mol-ecular packing is strengthened by van der Waals inter-actions between the layers. The inter-molecular contacts were qu-anti-fied using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H⋯H 46.0%, C⋯H/H⋯C 21.1%, O⋯H/H⋯O 20.6% and S⋯H/H⋯S 9.0%.

Molecularly Thin 2D Organic Single Crystals: A New Platform for High-Performance Polarization-Sensitive Phototransistors.

The inherent linear dichroism (LD), high absorption, and solution processability of organic semiconductors hold immense potential to revolutionize polarized light detection. However, the disordered molecular packing inherent to polycrystalline thin films obscures their intrinsic diattenuation, resulting in diminished polarization sensitivity. In this study, we develop filter-free organic polarization-sensitive phototransistors (PSPs) with both a high linear dichroic ratio (LDR) and exceptional photosensitivity utilizing molecularly thin dithieno[3,2-b:2',3'-d]thiophene derivatives (DTT-8) two-dimensional molecular crystals (2DMCs) as the active layer. The orderly molecular packing in 2DMCs amplifies the inherent LD, and their molecular-scale thickness enables complete channel depletion, significantly reducing the dark current. As a result, PSPs with an impressive LDR of 3.15 and a photosensitivity reaching 3.02 × 106 are obtained. These findings present a practical demonstration of using the polarization angle as an encryption key in optical communication, showcasing the potential of 2DMCs as a viable and promising category of semiconductors for filter-free, polarization-sensitive photodetectors.

A 3,3'-Difluoro-2,2'-Bithiophene Based Donor Polymer Realizing High Efficiency (>17%) Single Junction Binary Organic Solar Cells.

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 0.78V, a Jsc of 20.69mAcm-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 0.89V, a Jsc of 25.40mAcm-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.

Intrinsically Stretchable Polymer Semiconductor with Regional Conjugation for Stretchable Electronics

AbstractThe development of intrinsically stretchable polymer semiconductor holds substantial promise in the field of wearable electronics. However, charge transport mobility is typically compromised in existing stretchable semiconductors to achieve the desired stretchability. Herein, a novel “regional conjugation” strategy is proposed to design an intrinsically stretchable polymer semiconductor oligo‐diketopyrrolopyrrole‐thieno[3,2‐b]thiophene (DPPTT)–urethane, in which oligo‐DPPTT conjugated units and alkyl urethane nonconjugated units are introduced. The regional conjugation of oligo‐DPPTT in the polymer backbone endows DPPTT–urethane with good molecular packing, leading to a high mobility of up to 1.7 cm2 V−1 s−1. Additionally, incorporating alkyl urethane nonconjugated units in the backbone can reduce film crystallinity and chain aggregation, which contribute to the stretchability of the polymer thin film. Consequently, fully stretchable transistors retain carrier mobility even at 100% biaxial tensile strain. Furthermore, the fully stretchable organic field‐effect transistor arrays show remarkable charge transport reversibility and durability after 1000 stretch–release cycles at 25% strain. Additionally, the device exhibits extraordinary electrical stability in air atmosphere. Overall, these results indicate that the “regional conjugation” strategy provides an effective and promising methodology to design intrinsically stretchable and high‐performance polymer semiconductor that can advance the development of soft and wearable electronics.

Unraveling the influence of aromatic endcaps in peptide self-assembly

Aromatic peptides are an emerging class of building units for molecular self-assembly and creation of functional biomaterials. The strength of aromatic association plays an essential role in the self-assembly of aromatic peptides. Here, we design a series of aromatic peptides with different hydrophobic domains but the same peptide sequence. The hydrophobicity and aromaticity can be carefully regulated by the number of benzene rings and the alkyl spacer between the benzene and peptide regions. Upon the continuous enhancement of aromaticity, diverse supramolecular nanostructures, including nanotubes, nanofibers, and short helical ribbons, were clearly observed. The peptide with diphenyl groups exhibits the highest regularity of molecular packing, due to the synergy of force balance between hydrogen bonding and π–π interactions. In addition, the incorporation of a spacer in between the aromatic and peptide regions facilitates the self-assembly capability, as the interference between aromatic association and hydrogen bonding is hindered. These dramatic results demonstrate that aromaticity serves as an effective and robust parameter in the molecular arrangement, providing a new perspective into the formation and evolution of supramolecular assembly.

Heliconical nematic and smectic phases: the synthesis and characterisation of the CB4O.m and CB8O.m series

ABSTRACT The synthesis and characterisation of two series of nonsymmetric dimers belonging to the family of compounds, the 1-(4-cyanobiphenyl-4′-yl)-ω-(4-alkylanilinebenzylidene-4′-oxy)alkanes (CBnO.m) is reported; in the acronym, n refers to the number of carbon atoms in the spacer, and m in the terminal alkyl chain. The two series reported, CB4O.m and CB8O.m, both show twist-bend nematic (NTB) and smectic phases (SmCTB-SH and SmCTB-DH). Their phase behaviour is compared to that of the CB6O.m and CB10O.m series. For each series, locally intercalated molecular packing is observed for short terminal chains and interdigitated packing for long terminal chains. The intercalated anticlinic smectic CA phase is observed for the CB8O.m and CB10O.m series. All four series exhibit the SmCTB-SH and SmCTB-DH phases for the longer terminal chains and all have an interdigitated molecular arrangement. The absence of an intercalated heliconical phase is attributed to the high viscosity associated with the network intercalated structure.

Structure and piezochromism of chrysene at high pressures

Fluorescence materials have attracted great attention in the last decades because of their modulable fluorescence properties and broad applications. Molecular packing is one of the most important factors that determines organic molecular piezochromic fluorescence behavior. Herein, we systematically investigated the fluorescence, vibrational, and structural properties of chrysene up to 20 GPa by using multiple experimental techniques and ab-initio calculations. We find the obvious color-changing with increasing pressure. Meanwhile, the phase transition at a pressure of about 6.6 GPa has been identified from both the frequency shifts and the changes in intensity of the Raman modes. However, the structure of chrysene at ambient pressure remains stable to at least P∼20.2 GPa from both experimental and theoretical x-ray diffraction results. Further structural analysis indicates that the angle between two molecular planes decreases with pressure, resulting in the packing alteration. The combined results from the experiments and computations demonstrated that the observed phase transition at 6.6 GPa is probably a result of the change of molecular packing. Furthermore, the intermolecular interactions have changed correspondingly due to the change of the molecular packing, which results in the color-changing of chrysene under pressure. These results provide further evidence that the intermolecular interactions play the important role in tuning the photo-physical properties, and this work will contribute to understanding the relationship between molecular packing and piezochromism in fluorescence materials.

π-Extended Nonfullerene Acceptor for Compressed Molecular Packing in Organic Solar Cells To Achieve over 20% Efficiency.

Organic photovoltaics (OPVs) suffer from a trade-off between efficient charge transport and suppressed nonradiative recombination due to the aggregation-induced luminance quenching of organic semiconductors. To resolve this grand challenge, a π-extended nonfullerene acceptor (NFA) B6Cl with large voids among the honeycomb network is designed and introduced into photovoltaic systems. We find that the presence of a small amount of (i.e., 0.5 or 1 wt %) B6Cl can compress the molecular packing of the host acceptor L8-BO, leading to shortened π-π stacking distance from 3.59 to 3.50 Å (that will improve charge transport) together with ordered alkyl chain packing (that will inhibit nonradiative energy loss due to the suppressed C-C and C-H bonds vibrations), as validated by high-energy X-ray scattering measurements. This morphology transformation ultimately results in simultaneously improved JSC, FF, and VOC of OPVs. As a result, the maximum PCEs of PM6:L8-BO and D18:L8-BO are increased from 19.1 and 19.3% to 19.8 and 20.2%, respectively, which are among the highest values for single-junction OPVs. The university of B6Cl to increase the performance of OPVs is further evidenced in a range of polymer:NFA OPVs.

Synthesis, crystallographic structure, Hirshfeld surface analysis and DFT calculations of Schiff base (Z)-4-methyl-2-(((3-nitrophenyl)imino)methyl)phenol

The (Z)-4-methyl-2-(((3-nitrophenyl)imino)methyl)phenol (C15H14N2O3) (MNIMP) was prepared by condensation of 2-hydroxy-5-methyl-benzaldehyde and 2-methyl-4-nitro-phenylamine in ethanol and characterized by NMR (1H and 13C), IR and UV–Visible spectroscopy. The molecular crystal packing has been quantitatively explored via Hirshfeld surface analysis, where the intramolecular C−H⋯O bonding represents the principle contribution that stabilizes the crystal packing, with an overall 27.5 % for O⋯H interactions. The outcomes of a theoretical investigation conducted at the B3LYP/6–311++G(d,p) level using the DFT approach are in strong agreement with the results of the experiment. The experimental outcome is compatible with the optimized structure. Z)-4-methyl-2-(((3-nitrophenyl)imino)methyl)phenol vibrational spectrum is calculated at the same theoretical level (DFT/ B3LYP/6–311++G(d,p)), and it is discovered that the theoretically estimated vibrational frequencies and assignments accord well with experimental FT-IR values.

Non-halogenated Solvent-Processed Organic Solar Cells with Approaching 20 % Efficiency and Improved Photostability.

The development of high-efficiency organic solar cells (OSCs) processed from non-halogenated solvents is crucially important for their scale-up industry production. However, owing to the difficulty of regulating molecular aggregation, there is a huge efficiency gap between non-halogenated and halogenated solvent processed OSCs. Herein, we fabricate o-xylene processed OSCs with approaching 20 % efficiency by incorporating a trimeric guest acceptor named Tri-V into the PM6:L8-BO-X host blend. The incorporation of Tri-V effectively restricts the excessive aggregation of L8-BO-X, regulates the molecular packing and optimizes the phase-separation morphology, which leads to mitigated trap density states, reduced energy loss and suppressed charge recombination. Consequently, the PM6:L8-BO-X:Tri-V-based device achieves an efficiency of 19.82 %, representing the highest efficiency for non-halogenated solvent-processed OSCs reported to date. Noticeably, with the addition of Tri-V, the ternary device shows an improved photostability than binary PM6:L8-BO-X-based device, and maintains 80 % of the initial efficiency after continuous illumination for 1380 h. This work provides a feasible approach for fabricating high-efficiency, stable, eco-friendly OSCs, and sheds new light on the large-scale industrial production of OSCs.

Non‐halogenated Solvent‐Processed Organic Solar Cells with Approaching 20 % Efficiency and Improved Photostability

AbstractThe development of high‐efficiency organic solar cells (OSCs) processed from non‐halogenated solvents is crucially important for their scale‐up industry production. However, owing to the difficulty of regulating molecular aggregation, there is a huge efficiency gap between non‐halogenated and halogenated solvent processed OSCs. Herein, we fabricate o‐xylene processed OSCs with approaching 20 % efficiency by incorporating a trimeric guest acceptor named Tri‐V into the PM6:L8‐BO‐X host blend. The incorporation of Tri‐V effectively restricts the excessive aggregation of L8‐BO‐X, regulates the molecular packing and optimizes the phase‐separation morphology, which leads to mitigated trap density states, reduced energy loss and suppressed charge recombination. Consequently, the PM6:L8‐BO‐X:Tri‐V‐based device achieves an efficiency of 19.82 %, representing the highest efficiency for non‐halogenated solvent‐processed OSCs reported to date. Noticeably, with the addition of Tri‐V, the ternary device shows an improved photostability than binary PM6:L8‐BO‐X‐based device, and maintains 80 % of the initial efficiency after continuous illumination for 1380 h. This work provides a feasible approach for fabricating high‐efficiency, stable, eco‐friendly OSCs, and sheds new light on the large‐scale industrial production of OSCs.