Efficient Polymer Solar Cells Research Articles

Providing a Photovoltaic Performance Enhancement Relationship from Binary to Ternary Polymer Solar Cells via Machine Learning

Ternary polymer solar cells (PSCs) are currently the simplest and most efficient way to further improve the device performance in PSCs. To find high-performance organic photovoltaic materials, the established connection between the material structure and device performance before fabrication is of great significance. Herein, firstly, a database of the photovoltaic performance in 874 experimental PSCs reported in the literature is established, and three different fingerprint expressions of a molecular structure are explored as input features; the results show that long fingerprints of 2D atom pairs can contain more effective information and improve the accuracy of the models. Through supervised learning, five machine learning (ML) models were trained to build a mapping of the photovoltaic performance improvement relationship from binary to ternary PSCs. The GBDT model had the best predictive ability and generalization. Eighteen key structural features from a non-fullerene acceptor and the third components that affect the device’s PCE were screened based on this model, including a nitrile group with lone-pair electron, a halogen atom, an oxygen atom, etc. Interestingly, the structural features for the enhanced device’s PCE were essentially increased by the Jsc or FF. More importantly, the reliability of the ML model was further verified by preparing the highly efficient PSCs. Taking the PM6:BTP-eC9:PY-IT ternary PSC as an example, the PCE prediction (18.03%) by the model was in good agreement with the experimental results (17.78%), the relative prediction error was 1.41%, and the relative error between all experimental results and predicted results was less than 5%. These results indicate that ML is a useful tool for exploring the photovoltaic performance improvement of PSCs and accelerating the design and application with highly efficient non-fullerene materials.

Synthesis, Characterization and Photovoltaic Properties of Polyplatinaynes with Side Chain Functionalization by Different Electron-Accepting Group

AbstractFour new solution-processable platinum-containing polyynes functionalized with triphenylamine backbone and different acceptor fragment in the side chain were synthesized and characterized by spectroscopic, thermal and optical methods. The main- and side-chains show different absorption features in the solar spectrum, resulting in broad absorption coverage of the whole visible region. By changing the acceptor group in the side chain, the photophysical properties including energy levels, absorption wavelength and bandgap of the polymers were finely tuned. As the strength of electron acceptor is increased, the power conversion efficiency (PCE) of organic polymer solar cells fabricated with these polymers as electron donor and (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) as electron acceptor was increased. PCE of 1.35% can be obtained from solar cell based on the polyplatinayne with the dicyanovinyl side group under illumination of an AM 1.5 solar cell simulator in a 1:4 (polymer:PCBM) blend ratio. Graphical Abstract

A benzobisoxazole-based polymer assisting high efficiency polymer solar cells

Ternary strategy is an effective method to optimize photovoltaic process and improve device performance. In this work, a benzobisoxazole-based conjugated polymer PBBO was designed and employed as the guest component for PM6:BTP-eC9 based devices. The polymer PBBO shows a large band gap of 2.16 eV and strong photoluminescence property, with efficient energy transfer observed between PBBO and PM6. The ternary blends not only form a cascaded energy level distribution, but also an alloy-like structure, which can effectively promote the exciton dissociation, charge transfer and efficiently suppress charge recombination. As a result, the power conversion efficiency (PCE) of the ternary device is substantially improved from 17.50% to 18.66% with the incorporation of PBBO guest component. Meanwhile, the ternary device shows good stability with retaining 86% of initial efficiency after storage for 2000 hours. This research demonstrates that the polymer PBBO would be an excellent photovoltaic material to optimize the performance of polymer solar cells.

Improved efficiency of polymer solar cells using alcohol-soluble self-doped N-type polymers as cathode interface layer

Extensive research has been conducted on polymeric cathode interface substances, known for their self-doping features, for their application in organic solar cells (OSCs) to improve the ohmic interaction at the electrode with the active layer. In this paper, two novel polymers, PIIDN-F and PIIDN-FN, with self-doping effect, were successfully synthesized by combining isoindigo (IID), which contains an amino side chain, as an electrons-deficient group with fluorene, which contains different side chains. A thorough examination was conducted on the self-doping properties, electrical conductivity, work efficiency, and the angle of water contact between the two substances. Following this, PIIDN-F and PIIDN-FN were effectively utilized as cathode interface layers (CILs) within PTB7-Th:PC71BM OSCs. The PIIDN-F and PIIDN-FN achieve power conversion efficiencies (PCEs) of 8.97% and 9.04%, respectively. Findings indicate that the quantity of polar groups significantly influences the polymer's conductivity, adjustable work function, and the interaction at interfaces. These results show that by simply adjusting the number of polar groups, it is possible to provide efficient CILs for high-performance OSCs.

Cost-effective polymer donors based on pyridine for efficient nonfullerene polymer solar cells

Developing cost-effective polymer donors that can match nonfullerene acceptors is very important for practical applications of polymer solar cells (PSCs). In this work, low-cost 3-fluoropyridine and pyridine were employed as acceptor unit cores to construct cost-effective polymers PBDT-FPy, PBDT-Py and PBDF-Py by copolymerizing with commercially available donor units. PBDT-FPy, PBDT-Py and PBDF-Py show wide-bandgap of 2.08, 2.15 and 2.05 eV, respectively. Due to the strong electronegativity of nitrogen atom in pyridine and Nδ− … Hδ+ noncovalent dipole-dipole interactions, all polymers exhibit deep-lying highest-occupied molecular orbital (HOMO) energy levels, strong intermolecular π-π interaction and good planarity. The PBDT-FPy: Y6 based device exhibits a power conversion efficiency (PCE) of 8.34%, while the performance of PBDT-Py: Y6 and PBDF-Py: Y6 devices was significantly improved, with PCE of 10.02% and 10.00%. The results indicate that pyridine with simple structure and low synthetic cost is a promising building block to construct high-performance cost-effective polymer donors for application in PSCs.

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Bulk Heterojunction or Layer‐by‐Layer Structure PM6:L8‐BO Based Polymer Solar Cells Exhibiting an Efficiency of 17.84 % or 18.43 %

AbstractTwo kinds of polymer solar cells (PSCs) were fabricated with polymer donor PM6 and small molecule non‐fullerene acceptor L8‐BO as accepted based on bulk heterojunction (BHJ) or layer‐by‐layer (LbL) structure. The power conversion efficiency (PCE) of 18.43 % and 17.84 % can be achieved from the PSCs based on BHJ and LbL structure, respectively. Two kinds of PSCs exhibit the same open circuit voltage (VOC) of 0.88 V, which can be well explained from the same donor and acceptor materials and the same electrodes. The LbL based PSCs exhibit a relatively large short circuit current density (JSC) of 26.97 mA cm−2 and fill factor (FF) of 77.64 % in comparison with JSC of 26.64 mA cm−2 and FF of 76.07 % for BHJ based PSCs. The relatively high PCE of LbL based PSCs should be attributed to the sufficient exciton dissociation and charge collection efficiency, as well as the more balanced charge transport, which can be confirmed from the photogenerated current density dependence on the effective bias. This work demonstrates that layer‐by‐layer structure may have great potential in preparing highly efficient PSCs.

High-performance nonfullerene polymer solar cells based on chlorinated quinoxaline copolymer with a high short-circuit current density

In organic solar cells, the absorption range and extinction coefficient of the active layer not only affect the charge separation and carrier transfer efficiency of excitons, but also influence the JSC, and thus the device efficiency. Herein, an efficient nonfullerene polymer solar cells (NF–PSCs) based on a medium-bandgap (MBG) polymer donor PBDTTS-TClQx comprising chlorinethiophene quinoxaline (Qx) unit and a small molecule nonfullerene acceptor (SM-NFA) Y6 is developed. The PBDTTS-TClQx shows a strong absorption in the wavelength region of 330∼750 nm with an optical band gaps (Egopt) of 1.68 eV, which is well complementary with that of Y6 (1.33 eV) and facilitates achieving of high short-circuit current (JSC) in PSCs. As a result, the PBDTTS-TClQx:Y6-based PSCs achieved a power conversion efficiency (PCE) of 14.28% with a JSC of 25.9 mA cm−2. The JSC of 25.9 mA cm−2 achieved is among the highest reported for Qx-based polymer donors in PSCs.

Recent progress and prospects of dimer and multimer acceptors for efficient and stable polymer solar cells.

High power conversion efficiency (PCE) and long-term stability are essential prerequisites for the commercialization of polymer solar cells (PSCs). Small-molecule acceptors (SMAs) are core materials that have led to recent, rapid increases in the PCEs of the PSCs. However, a critical limitation of the resulting PSCs is their poor long-term stability. Blend morphology degradation from rapid diffusion of SMAs with low glass transition temperatures (Tgs) is considered the main cause of the poor long-term stability of the PSCs. The recent emergence of oligomerized SMAs (OSMAs), composed of two or more repeating SMA units (i.e., dimerized and trimerized SMAs), has shown great promise in overcoming these challenges. This innovation in material design has enabled OSMA-based PSCs to reach impressive PCEs near 19% and exceptional long-term stability. In this review, we summarize the evolution of OSMAs, including their research background and recent progress in molecular design. In particular, we discuss the mechanisms for high PCE and stability of OSMA-based PSCs and suggest useful design guidelines for high-performance OSMAs. Furthermore, we reflect on the existing hurdles and future directions for OSMA materials towards achieving commercially viable PSCs with high PCEs and operational stabilities.

19.32% Efficiency Polymer Solar Cells Enabled by Fine-Tuning Stacking Modes of Y-Type Molecule Acceptors: Synergistic Bromine and Fluorine Substitution of the End Groups.

The success of Y6-type nonfullerene small molecule acceptors (NF-SMAs) in polymer solar cells (PSCs) can be attributed to their unique honeycomb stacking style, which leads to favorable thin-film morphologies. The intermolecular interactions related to the crystallization tendency of these NF-SMAs is closely governed by their electron accepting end groups. For example, the high performance Y6 derivative L8-BO (BTP-4F) presents three types of stacking modes in contrast to two stacking modes of Y6. Hence, it is ultimately interesting to obtain more insight on the packing properties and the preferences influenced by chemical modifications such as end group engineering. This work designs and synthesizes asymmetric and symmetric L8-BO derivatives with brominated end groups and explores the stacking preferences in various modes. The asymmetric BTP-3FBr displays an optimized crystallization tendency and thin film morphology, leading to a decent power conversion efficiency (PCE) of 18.34% in binary devices and a top PCE of 19.32% in ternary devices containing 15 wt% IDIC as the second acceptor.

Effect of 1‐Fluoro‐2‐iodobenzene Solvent Additive on the Crystallization of Donors and Acceptors, and Ultrafast Carrier Dynamics in Polymer Solar Cells

AbstractControlled sequential crystallization of donors and acceptors is a critical factor for achieving enhanced phase separation and efficient charge transfer performance in polymer solar cells (PSCs). In this study, a comprehensive investigation of a structurally simple solvent additive, 1‐fluoro‐2‐iodobenzene (OFIB) is conducted, which efficiently controls the morphology of the active layer, resulting in fibrous assembly and significantly enhancing the power conversion efficiency from 16.34% to 18.38% based on the PM6:L8‐BO system. Density functional theory, molecular dynamics simulations, and grazing incidence small‐ and wide‐angle X‐ray scattering techniques reveal that the addition of OFIB to the processed blend aligns the orientation of the acceptor molecules, thereby enhancing the overall π–π stacking in the active layer. OFIB establishes nearly equal‐strength π–π interactions with the conjugated frameworks of both the donor and acceptor materials, benefiting from the multiple electron conjugation between its iodine atom and the conjugated framework in the active layer. Femtosecond‐timescale photophysical studies demonstrate that the OFIB‐optimized active layer shows reduced exciton losses at the donor–acceptor interface. This study offers a new perspective on the mechanism underlying the function of solvent additives and presents a comprehensive research methodology that will guide the development of next‐generation non‐fullerene acceptors for efficient PSCs.

Effect of diazine isomers on photovoltaic properties of simple and efficient wide band gap polymer donor materials

In this paper, we designed and synthesized six new wide band gap donor-acceptor (D-A) copolymers, PZ2-PZ7, with diazine isomers (pyrazine, pyridazine, pyrimidine) as the A unit and alkylthiophene- or alkylthiothienyl-substituted BDT as the D unit. The effect of diazine isomeric A units and side-chain substituents on molecular structure, optoelectronic properties and photovoltaic performances of the resulting D-A copolymers were investigated in details. Six low-cost polymers were easily obtained by minimal reaction steps and cheap raw materials. All the polymers exhibited wide band gaps (WBGs) (>1.9 eV) and deep-lying HOMO energy levels (<−5.48 eV), which is convenient for paring with low band gap nonfullerene acceptors (NFAs). Theoretical simulation calculation indicates that diazine isomeric A unit has great impact on the planarity of polymer backbone. Bulk heterojunction polymer solar cells (PSCs) were fabricated with these polymers as donor materials and representative NFAs (Y6 and ITIC) as acceptor materials. After optimization, pyrazine-based polymers PZ2 and PZ3 exhibited higher PCEs than those of pyridazine- and pyrimidine-based ones (PZ4-PZ7) regardless of the acceptors. Finally, the PZ2:Y6-based PSC achieved the highest power conversion efficiency (PCE) up to 11.21 %, which could be attributed to more balanced carrier mobility, increased charge dissociation probability, reduced charge recombination, and superior active layer morphology. This work suggests that diazine-based WBG polymers, especially for pyrazine, would become as very promising donor candidates for constructing low-cost and efficient NFA-based PSCs.

Optimization of Charge Management and Energy Loss in All-Small-Molecule Organic Solar Cells.

All-small-molecule organic solar cells (ASM-OSCs) have received tremendous attention in recent decades because of their advantages over their polymer counterparts. These advantages include well-defined chemical structures, easy purification, and negligible batch-to-batch variation. Remarkable progress with a power conversion efficiency (PCE) of over 17% has recently been achieved with improved charge management (FF × JSC) and reduced energy loss (Eloss). Morphology control is the key factor in the progress of ASM-OSCs, which remains a significant challenge because of the similarities in the molecular structures of the donors and acceptors. In this review, the effective strategies for charge management and/or Eloss reduction from the perspective of effective morphology control are summarized. The aim is to provide practical insights and guidance for material design and device optimization to promote further development of ASM-OSCs to a level where they can compete with or even surpass the efficiency of polymer solar cells.

What is the role of non-fullerene acceptor symmetry in polymer solar cell efficiency?

What is the role of non-fullerene acceptor symmetry in polymer solar cell efficiency?

Nonfused Ring Electron Acceptors for Ternary Polymer Solar Cells with Low Energy Loss and Efficiency Over 18.

Ternary polymer solar cells(PSCs) have been identified as an effective approach to improving power conversion efficiency (PCE) of binary PSCs. However, most of the third component, especially Y-series non-fullerene acceptors, is a fused ring acceptor which often requires a rather tedious synthesis and the use of hazardous organostannane reagents. In this work, two nonfused ring acceptors IOEH-4F and IOEH-N2F are synthesized by a green synthetic route and incorporated into PM6:Y6 blend. Encouragingly, the IOEH-4F and IOEH-N2F-based ternary PSCs exhibited more efficient charge transfer, exciton separation, and lower energy loss than PM6:Y6-based PSCs. And the IOEH-4F and IOEH-N2F-based ternary PSCs achieved an impressive PCE of 17.80% and 18.13%, respectively, which are higher than that of PM6:Y6 based PSCs (16.18%). Notably, these PCE values are also the highest PCEs for ternary PSCs including non-fused ring acceptors. Importantly, even when the IOEH-N2F:Y6 ratios increased from 0.05:1.2 to 0.50:1.2, the PCE of IOEH-N2F-based ternary PSCs (16.70%) are still higher than that of PM6:Y6 based PSCs, indicating the great potential for cost saving. It is believed that the findings will help the design of better nonfused ring acceptors and the optimization of corresponding ternary PSCs with cost-saving advantage.

Enhanced UV Absorption By 2D MoS2 Nanoparticles

MoS2 is one of the promising 2D materials that caught the interest of many research fields[1], [2] due to their size-dependent tunable bandgap and attractive magnetic, optical, and electrical properties[3]. Furthermore, recently there has been a growing interest in utilizing MoS2 for solar cell applications that demonstrated measurable device enhancements[4]–[6]. Hence, there is a great interest in understanding its potential for solar energy harvesting. In this study, we show a simple method to deposit a 2D layer of MoS2 nanoparticles (NPs) on top of Aluminum-doped Zinc oxide (AZO) layer (transparent conductive oxide) and investigate its spectral response and potential for application in optoelectronic systems.A thin film of 80 nm AZO layer was grown on a 4-inch quartz wafer using thermal Atomic Layer Deposition (ALD) with a 1:19 ratio which has shown good electrical and optical qualities for solar cell applications[7]. We deposited the MoS2 by spin-coating it on the AZO/quartz wafers for 40 sec at 1000 rpm. Incremental coating is carried on by dispersing seven layers with 500 μL of MoS2 in each step using a precise pipet to a cumulative dispersion volume of 3500 μL. The prepared samples were characterized using a UV-Vis-NIR spectrometer (Perkin Elmer Lambda) across a wide range of wavelengths (250-1200 nm) by measuring both transmittance and reflectance and calculating absorbance. Furthermore, the base AZO/quartz and quartz background signal were measured before spin-coating as reference.The obtained data shows a high absorbance effect due to MoS2 NPs at low wavelengths (<400 nm), where it peaks around 340 nm with an approximate absorbance of ~6.7%. Upon further examination, we notice that this behavior is not linear across the whole spectrum and instead is a function of (i) wavelength and (ii) MoS2 quantity which could be partially due to the quantum confinement effect of several layers of stacked 3D MoS2 nanoparticles[8]. This phenomenon could open the possibility of utilizing this material for low-wavelength filters or UV sensing applications[9]. Also, it can potentially be utilized for quantum down-conversion[10] of high-energy photons to re-emit photons at lower energies in order to enhance solar cells’ efficiencies and reduce thermal burden; however, further investigation is needed.[1] P. Zhou, C. Chen, X. Wang, B. Hu, and H. San, “2-Dimentional photoconductive MoS2 nanosheets using in surface acoustic wave resonators for ultraviolet light sensing,” Sensors and Actuators A: Physical, vol. 271, pp. 389–397, Mar. 2018, doi: 10.1016/j.sna.2017.12.007.[2] H. Dong et al., “Fluorescent MoS 2 Quantum Dots: Ultrasonic Preparation, Up-Conversion and Down-Conversion Bioimaging, and Photodynamic Therapy,” ACS Appl. Mater. Interfaces, vol. 8, no. 5, pp. 3107–3114, Feb. 2016, doi: 10.1021/acsami.5b10459.[3] K. F. Mak, C. Lee, J. Hone, J. Shan, and T. F. Heinz, “Atomically Thin MoS 2 : A New Direct-Gap Semiconductor,” Phys. Rev. Lett., vol. 105, no. 13, p. 136805, Sep. 2010, doi: 10.1103/PhysRevLett.105.136805.[4] Y. Tsuboi et al., “Enhanced photovoltaic performances of graphene/Si solar cells by insertion of a MoS 2 thin film,” Nanoscale, vol. 7, no. 34, pp. 14476–14482, 2015, doi: 10.1039/C5NR03046C.[5] N. A. Abd Malek et al., “Ultra-thin MoS2 nanosheet for electron transport layer of perovskite solar cells,” Optical Materials, vol. 104, p. 109933, Jun. 2020, doi: 10.1016/j.optmat.2020.109933.[6] Y.-J. Huang, H.-C. Chen, H.-K. Lin, and K.-H. Wei, “Doping ZnO Electron Transport Layers with MoS 2 Nanosheets Enhances the Efficiency of Polymer Solar Cells,” ACS Appl. Mater. Interfaces, vol. 10, no. 23, pp. 20196–20204, Jun. 2018, doi: 10.1021/acsami.8b06413.[7] S. Abdul Hadi, G. Dushaq, and A. Nayfeh, “Effect of atomic layer deposited Al 2 O 3 :ZnO alloys on thin-film silicon photovoltaic devices,” Journal of Applied Physics, vol. 122, no. 24, p. 245103, Dec. 2017, doi: 10.1063/1.4990871.[8] T. Li and G. Galli, “Electronic Properties of MoS 2 Nanoparticles,” J. Phys. Chem. C, vol. 111, no. 44, pp. 16192–16196, Nov. 2007, doi: 10.1021/jp075424v.[9] Z. Lou et al., “High-performance MoS_2/Si heterojunction broadband photodetectors from deep ultraviolet to near infrared,” Opt. Lett., vol. 42, no. 17, p. 3335, Sep. 2017, doi: 10.1364/OL.42.003335.[10] A. P. Sunitha, P. Praveen, M. K. Jayaraj, and K. J. Saji, “Upconversion and downconversion photoluminescence and optical limiting in colloidal MoS2 nanostructures prepared by ultrasonication,” Optical Materials, vol. 85, pp. 61–70, Nov. 2018, doi: 10.1016/j.optmat.2018.08.038.[11] Y. Wu et al., “Monolithic integration of MoS 2 -based visible detectors and GaN-based UV detectors,” Photon. Res., vol. 7, no. 10, p. 1127, Oct. 2019, doi: 10.1364/PRJ.7.001127. Figure 1

Enabling Highly Efficient and Thermal-Stable Polymer Solar Cells through Semi-Alloy Acceptors Composed of a Hinge-Like Dimer: A Versatile Doping Protocol.

The simultaneous improvement of power conversion efficiency (PCE) and thermal stability is a critical scientific challenge in advancing the commercial applications of polymer solar cells. To address this challenge, a dumbbell-shaped dimeric acceptor, DT19, is successfully designed and synthesized. It is incorporated as a third component into the PM1:BTP-eC9 system. This ternary strategy demonstrates a synergistic enhancement of the PCE and thermal stability of the host binary system. In particular, the PM1:BTP-eC9:DT19 system maintains a PCE of over 90% even after heating at 120°C for 200h. Additionally, the dimer-doping ternary strategy exhibits excellent generality for the other four Y-series systems and outperforms ternary systems containing alloy-like acceptors in terms of thermal stability. It is because DT19, with its hinge-like structure, can form a semi-alloy acceptor with the host acceptor, leading to strong interchain entanglement with the polymer donor, thus overcoming phase separation and excessive aggregation under thermal stress. This new type of dimeric material, which can synergistically enhance the device efficiency and thermal stability of active layers, presents promising application prospects.

Probing the Effect of Photovoltaic Material on Voc in Ternary Polymer Solar Cells with Non-Fullerene Acceptors by Machine Learning.

The power conversion efficiency (PCE) of ternary polymer solar cells (PSCs) with non-fullerene has a phenomenal increase in recent years. However, improving the open circuit voltage (Voc) of ternary PSCs with non-fullerene still remains a challenge. Therefore, in this work, machine learning (ML) algorithms are employed, including eXtreme gradient boosting, K-nearest neighbor and random forest, to quantitatively analyze the impact mechanism of Voc in ternary PSCs with the double acceptors from the two aspects of photovoltaic materials. In one aspect of photovoltaic materials, the doping concentration has the greatest impact on Voc in ternary PSCs. Furthermore, the addition of the third component affects the energy offset between the donor and acceptor for increasing Voc in ternary PSCs. More importantly, to obtain the maximum Voc in ternary PSCs with the double acceptors, the HOMO and LUMO energy levels of the third component should be around (-5.7 ± 0.1) eV and (-3.6 ± 0.1) eV, respectively. In the other aspect of molecular descriptors and molecular fingerprints in the third component of ternary PSCs with the double acceptors, the hydrogen bond strength and aromatic ring structure of the third component have high impact on the Voc of ternary PSCs. In partial dependence plot, it is clear that when the number of methyl groups is four and the number of carbonyl groups is two in the third component of acceptor, the Voc of ternary PSCs with the double acceptors can be maximized. All of these findings provide valuable insights into the development of materials with high Voc in ternary PSCs for saving time and cost.

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Fluorination strategy on π-bridge of polymer donor for efficient photovoltaic performance

Although fluorine-contained polymers have been adopted in efficient polymer solar cells, complicated reaction methods and costly fluorination reagents have impeded large-scale application. Here, a novel fluorinated polymer donor, PM6-F, was designed and synthesized via a newly developed 3-fluoro-2-iodithiophene to simplify synthesis procedures and minimise reaction costs from modest raw materials. Compared with the polymer analogue PM6 without any fluorine substituent on the main chain, it was found that PM6-F with a better configuration exhibited more orderly molecular packing, stronger and broader absorption, a narrower optical band gap, and a lower-lying HOMO energy level. The PM6-F:IT-4F-based PSCs obtained an excellent PCE of 14.90% with a VOC of 0.91 V, a JSC of 23.25 mA cm−2, and an FF of 70.42%. Notably, the value of 14.90% was among the highest recorded in the literature for IT-4F-based PSCs. This research demonstrated that modifying π-bridges with fluorine is a promising strategy for developing high-efficiency polymer donors.