Ethylenedioxythiophene-Based Small Molecular Donor with Multiple Conformation Locks for Organic Solar Cells with Efficiency of 19.3 .

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.

Carboxylating Elastomer via Thiol-Ene Click Reaction to Improve Miscibility with Conjugated Polymers for Mechanically Robust Organic Solar Cells with Efficiency of 19.

Incorporating flexible insulating polymers is a straightforward strategy to enhance the mechanical properties of rigid conjugated polymers, enabling their use in flexible electronic devices. However, maintaining electronic characteristics simultaneously is challenging due to the poor miscibility between insulating polymers and conjugated polymers. This study introduces the carboxylation of insulating polymers as an effective strategy to enhance miscibility with conjugated polymers via surface energy modulation and hydrogen bonding. The carboxylated elastomer, synthesized via a thiol-ene click reaction, closely matches the surface energy of the conjugated polymer. This significantly improves the mechanical properties, achieving a high crack-onset strain of 21.48%, surpassing that (5.93%) of the unmodified elastomer:conjugated polymer blend. Upon incorporating the carboxylated elastomer into PM6:L8-BO-based organic solar cells, an impressive power conversion efficiency of 19.04% is attained, which top-performs among insulating polymer-incorporated devices and outperforms devices with unmodified elastomer or neat PM6:L8-BO. The superior efficiency is attributed to the optimized microstructures and enhanced crystallinity for efficient and balanced charge transport, and suppressed charge recombination. Furthermore, flexible devices with 5% carboxylated elastomer exhibit superior mechanical stability, retaining ≈88.9% of the initial efficiency after 40 000 bending cycles at a 1 mm radius, surpassing ≈83.5% for devices with 5% unmodified elastomer.

NiOx Nanoparticles Hole-Transporting Layer Regulated by Ionic Radius-Controlled Doping and Reductive Agent for Organic Solar Cells with Efficiency of 19.18.

Nickel oxide (NiOx ) has garnered considerable attention as a prospective hole-transporting layer (HTL) in organic solar cells (OSCs), offering a potential solution to the stability challenges posed by traditional HTL, PEDOT:PSS, arising from acidity and hygroscopicity. Nevertheless, the lower work function (WF) of NiOx relative to donor polymers reduces charge injection efficiency in OSCs. Herein, NiOx nanoparticles are tailored through rare earth doping to optimize WF and the impact of ionic radius on their electronic properties is explored. Lanthanum (La3+ ) and yttrium (Y3+ ) ions, with larger ionic radii, are effectively doped at 1 and 3%, respectively, while scandium (Sc3+ ), with a smaller ion radius, allows enhanced 5% doping. Higher doping ratios significantly enhance WF of NiOx . A 5% Sc3+ doping raises WF to 4.99 eV from 4.77 eV for neat NiOx while maintaining high conductivity. Consequently, using 5% Sc-doped NiOx as HTL improves the power conversion efficiency (PCE) of OSCs to 17.13%, surpassing the 15.64% with the neat NiOx . Further enhancement to 18.42% is achieved by introducing the reductant catechol, outperforming the PEDOT:PSS-based devices. Additionally, when employed in a ternary blend system (D18:N3:F-BTA3), an impressive PCE of 19.18 % is realized, top-performing among reported OSCs utilizing solution-processed inorganic nanoparticles.

A Pyrene-Fused Dimerized Acceptor for Ternary Organic Solar Cells with 19% Efficiency and High Thermal Stability.

A pyrene-fused dimerized electron acceptor has been successfully synthesized and subsequently incorporated as the third component in ternary organic solar cells (OSCs). Diverging from the traditional dimerized acceptors with a linear configuration, this novel electron acceptor displays a distinctive "butterfly-like" structure, comprising two Y-acceptors as wings fused with a pyrene-based backbone. The extended π-conjugated backbone and the electron-donating nature of pyrene enable the new acceptor to show low solubility, elevated glass transition temperature (Tg ), and low-lying frontier energy levels. Consequently, the new dimerized acceptor seamlessly integrates as the third component into ternary OSCs, enhancing electron transporting properties, reducing non-radiative voltage loss, and elevating open-circuit voltage. These merits have enabled the ternary OSCs to show an exceptional efficiency of 19.07%, a marked improvement compared to the 17.6% attained in binary OSCs. More importantly, the high Tg exhibited by the pyrene-fused electron acceptor helps to stabilize the morphology of the photoactive layer thermal-treated at 70 °C, retaining 88.7% efficiency over 600 hours. For comparison, binary OSCs experience a decline to 73.7% efficiency after the same duration. These results indicate that the "butterfly-like" design and the incorporation of a pyrene unit is a promising strategy in the development of dimerized electron acceptors for OSCs.

Incorporating Naphthalene and Halogen into Near-Infrared Double-Cable Conjugated Polymers for Single-Component Organic Solar Cells with Low-Voltage Losses.

The invention of near-infrared pedant-based double-cable conjugated polymers has demonstrated remarkable efficacy in single-component organic solar cells (SCOSCs). This work focuses on the innovative double-cable conjugated polymers aimed at attaining good absorption and suitable energy levels. Specifically, in the aromatic side units, the electron-donating (D) part is designed using a thieno[3,4-c]pyrrole-4,6-dione (TPD) as a core unit, flanked by two cyclopentadithiophene groups on either side. The electron-deficient (A) terminal groups consist of 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene) malononitrile (NC), which can be further modified through fluorination to modulate the physical properties and packing modes of the acceptor material. The resulting double-cable conjugated polymers exhibit broad absorption spectra spanning 500-850 nm and possess lowered Frontier energy levels when incorporating fluorine elements, providing decreased voltage losses in SCOSCs. Therefore, SCOSCs fabricated using these polymers have demonstrated power conversion efficiencies ranging from 7.6 to 10.2%, in which fluorine-containing double-cable conjugated polymers showed higher PCEs due to more favorable crystalline packing, enhanced exciton dissociation probability, and charge-transporting ability.

Non-Covalent Interactions between Polyvinyl Chloride and Conjugated Polymers Enable Excellent Mechanical Properties and High Stability in Organic Solar Cells.

The incorporation of insulating polymers into conjugated polymers has been widely explored as a strategy to improve mechanical properties of flexible organic electronics. However, phase separation due to the immiscibility of these polymers has limited their effectiveness. In this study, we report the discovery of multiple non-covalent interactions that enhances the miscibility between insulating and conjugated polymers, resulting in improved mechanical properties. Specifically, we have added polyvinyl chloride (PVC) into the conjugated polymer PM6 and observed a significant increase in solution viscosity, indicative of favorable miscibility between these two polymers. This phenomenon has been rarely observed in other insulating/conjugated polymer composites. Thin films of PM6/PVC exhibit a much-improved crack-onset strain of 19.35 %, compared to 10.12 % for pristine PM6 films. Analysis reveal that a "cyclohexyl-like" structure formed through dipole-dipole interactions and hydrogen bonding between PVC and PM6 acted as a cross-linking site in the thin films, leading to improved mechanical properties. Moreover, PM6/PVC blend films have demonstrated excellent thermal and bending stability when applied as an electron donor in organic solar cells. These findings provide new insights into non-covalent interactions that can be utilized to enhance the properties of conjugated polymers and may have potential applications in flexible organic electronics.

Non-fused Polymerized Small-Molecule Acceptors with a Benzothiadiazole Core for All-Polymer Solar Cells.

Polymerized small-molecule acceptors (PSMAs) have made significant progress as the application in all-polymer solar cells (all-PSCs). Most PSMAs are constructed by near-infrared fused-ring electron acceptors via Stille polymerization, such as Y-series acceptors. However, very limited non-fused electron acceptors with simplified synthetic complexity have been used in PSMAs. In this work, two non-fused PSMAs with a benzothiadiazole (BT) core are developed for application in all-PSCs. The S-O non-covalent interaction and the regioregularity have been introduced to improve the crystallinity and charge transport properties. As a result, a high-power conversion efficiency (PCE) of 11.42% with an enhanced photocurrent has been obtained in these regioregular PBTO-γ-based solar cells, representing the highest PCEs based on non-fused PSMAs. The encouraging results will intrigue more design of non-fused PSMAs toward high-performance all-PSCs.

13% Single-Component Organic Solar Cells based on Double-Cable Conjugated Polymers with Pendent Y-Series Acceptors.

Double-cable conjugated polymers with pendent electron acceptors, including fullerene, rylene diimides, and nonfused acceptors, have been developed for application in single-component organic solar cells (SCOSCs) with efficiencies approaching 10%. In this work, Y-series electron acceptors have been firstly incorporated into double-cable polymers in order to further improve the efficiencies of SCOSCs. A highly crystalline Y-series acceptor based on quinoxaline core and the random copolymerized strategy are used to optimize the ambipolar charge transport and the nanophase separation of the double-cable polymers. As a result, an efficiency of 13.02% is obtained in the random double-cable polymer, representing the highest performance in SCOSCs, while the regular double-cable polymer only provides a low efficiency of 2.75%. The significantly enhanced efficiencies are attributed to higher charge carrier mobilities, better ordering conjugated backbones and Y-series acceptors in random double-cable polymers.

N-Annulated Perylene Bisimide-Based Double-Cable Polymers with Open-Circuit Voltage Approaching 1.20 V in Single-Component Organic Solar Cells.

In this work, we have introduced single/double-sided N-annulated perylene bisimide (PBI) with deep energy levels into double-cable polymers with poly[1-(5-(4,8-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)-6-methylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-5,7-bis(2-ethylhexyl)-3-(5-methylthiophen-2-yl)-4H,8H-benzo[1,2-c:4,5-c']dithiophene-4,8-dione] (PBDB-T-Cl) as a donor backbone, marking as s-PPNR and as-PPNR, according to the molecular symmetry. Both double-cable polymers displayed a high open-circuit voltage approaching 1.20 V in light of high energy level discrepancy between electron-donating and electron-withdrawing parts, which is the highest open-circuit voltage among double-cable-based single-component organic solar cell (SCOSC) devices. Additionally, the asymmetric polymer displayed improved absorption spectra, thereby promoting crystallization and phase separation. Consequently, the as-PPNR-based SCOSCs achieved a power conversion efficiency of 5.05% along with a higher short-circuit current density and fill factor than their s-PPNR-based counterparts. In this work, we have successfully incorporated N-annulated PBI into double-cable polymers and revealed the important effects on structural symmetry and phase separation of double-cable polymers for higher SCOSC performance.

Ultrathin Flexible Transparent Composite Electrode via Semi-embedding Silver Nanowires in a Colorless Polyimide for High-Performance Ultraflexible Organic Solar Cells.

Ultraflexible organic solar cells (OSCs) with both high power conversion efficiency (PCE) and good mechanical robustness are still challenging, in which flexible transparent composite electrodes (FTCEs, substrate-cum-electrodes) play critical roles. Here, an ultrathin FTCE (∼9 µm) via semi-embedding a silver nanowire electrode in a colorless polyimide (CPI) substrate was developed, which simultaneously possessed outstanding performance such as low square resistance (Rsq ∼ 12.7 Ω sq-1), high optical transmittance (T550 ∼ 86.3%), smooth surface (root-mean-square ∼ 0.32 nm), and excellent thermal, mechanical, and solution producing stability. Prior to the FTCE fabrication, four CPI samples with the number-average molecular weight ranging from 35.9 to 177.5 kDa were prepared and their optical, mechanical, and thermal properties were studied in detail. Moreover, the effect of the molecular weight on the minimum thickness that can withstand the following solution production of ultraflexible OSCs was investigated, which revealed that the molecular weight of CPI here should be above 81.4 kDa. Based on the FTCE, an ultraflexible OSC with a high PCE value of 14.37% and outstanding mechanical robustness was constructed, in which the PCE could still maintain above 96% of its initial value after 1000 bending cycles at a bending radius of 0.5 mm.

Enhancing the Performance of Small-Molecule Organic Solar Cells via Fused-Ring Design.

Organic solar cells (OSCs) as the promising green energy technology have drawn much attention in the last two decades. In comparison to polymer solar cells, small-molecule organic solar cells (SMOSCs) have the advantages of precise chemical structure and molecular weight, purification feasibility, batch reproducibility, etc. Despite of the recent advances in molecular design, the efficiencies of SMOSCs are still lagging behind those of polymer-based OSCs. In this work, a new small-molecule donor (SMD) with a fused-ring-connected bridge denoted F-MD has been designed and synthesized. When F-MD was applied into SMOSCs, the F-MD:N3 blends exhibited a power conversion efficiency (PCE) of over 13%, which is much higher than that of the linear π-bridged molecule L-MD based devices (8.12%). Further studies revealed that the fused-ring design promoted the planarity of the molecular conformation and facilitated charge transport in OSCs. More importantly, this strategy also lowered the crystallinity and self-aggregation of the films, and hence optimized the microstructure and phase separation in the corresponding blends. Thereby, the F-MD-based blends have been evidenced to have better exciton dissociation and reduced charge recombination in comparison with the L-MD counterparts, explaining the enhanced PCEs. Our work demonstrates that the fused-ring π-bridge strategy in small-molecule-donor design is an effective pathway to promote the efficiency of SMOSCs as well as enhance the diversity of SMD materials.

Insulating Polymers as Additives to Bulk-Heterojunction Organic Solar Cells: The Effect of Miscibility.

Adding insulating polymers to conjugated polymers is an efficient strategy to tailor their mechanical properties for flexible organic electronics. In this work, we selected two insulating polymers as additives for high-performance photoactive layers and investigated the mechanical and photovoltaic properties in organic solar cells (OSCs). The insulating polymers were found to reduce the electron mobilities in the photoactive layers, and hence the power conversion efficiencies were significantly decreased. More importantly, we found that the insulating polymers exhibited negative effect on the mechanical properties of the photoactive layers, with reduced Young's modulus and low crack onset strains. Further studies revealed that the insulating polymers had poor miscibility with the photoactive layers, providing large domains and more cavities in blend thin films, which act as negative effect for the tensile test. The studies indicate that rational selection of insulating polymers, especially enhancing the non-covalent interaction with the photoactive layers, will be critically important for the stretchable OSCs.

Mechanical Robust Flexible Single-Component Organic Solar Cells.

Owing to the advantages of being lightweight and compatible with surfaces with different deformations, flexible organic solar cells (OSCs) have broad scopes of applications, including wearable electronics and portable devices. Most flexible OSCs focus on the two-component bulk-heterojunction (BHJ) photo-active layers, but they usually suffer from degradation problems both in efficiency and mechanical durability derived from the limited phase stability under mechanical and thermal stress. Whereas, single-component organic solar cells (SCOSCs) based on the double-cable conjugated polymer are supposed to possess excellent mechanical robustness and long-term stability. Here, the first flexible SCOSCs based on a double-cable polymer are fabricated on a transparent silver nanowires (AgNWs) electrode on a plastic foil. Impressively, the obtained flexible SCOSCs exhibited a power conversion efficiency (PCE) of 7.21%. The flexible SCOSCs are further demonstrated to possess superior mechanical robustness (>95% retention after 1000 bending cycles) and storage stability (>97% retention after 430 h in nitrogen atmosphere) compared to several BHJ-type flexible OSCs. The pseudo-free-standing tensile test and morphology investigation are conducted to reveal the distinction in mechanical durability of the single-component polymer film and the BHJ-type films. Besides, ultraflexible SCOSCs are also fabricated, indicating the application prospect and superiority in flexible devices and wearable electronic products.

Near-Infrared Nonfullerene Acceptors Based on 4H-Cyclopenta[1,2-b:5,4-b']dithiophene for Organic Solar Cells and Organic Field-Effect Transistors.

The development of nonfullerene small molecular acceptors (NF-SMAs) has dominated the improvement of efficiencies for organic solar cells and the near-infrared (NIR) absorption is the primary feature of NF-SMAs compared with fullerene derivatives. In this article, a series of acceptor-donor-acceptor-structured NF-SMAs (named CPICs) containing 4H-cyclopenta[1,2-b : 5,4-b']dithiophene (CPDT) electron donor and F-substituted 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2FIC) as electron acceptor were designed and synthesized. With the increase of CPDT units, the elongated conjugations broadened the absorption range of the acceptors and tuned their energy levels sequentially. Therefore, their charge-transporting polarities switched from electron-only type to bipolar mode in organic field-effect transistors. Moreover, these changes also influenced the voltages, current densities, and eventual PCEs of their corresponding cells. When blending with PBDB-T, a champion efficiency of 10.01% was achieved in CPIC-2 based cells. This work demonstrated the importance of absorptions, suitable energy levels and charge transports in improving the efficiencies of organic solar cells.

Ti-Oxo Clusters with Peripheral Alkyl Groups as Cathode Interlayers for Efficient Organic Solar Cells.

Three independent Ti-oxo clusters (TOCs) that contain 6, 8, and 12 Ti atoms in the cores and alkyl groups on the surface were developed as cathode interlayers in bulk-heterojunction organic solar cells (OSCs). These TOCs have precise chemical structures with a single crystal, excellent solubility in methanol, and well-aligned work function. Smooth films can be facilely obtained by spin-casting their solution on top of the active layer. Therefore, they can be used as an interlayer in OSCs to provide a high power conversion efficiency (17.29%). Further studies reveal that these TOCs can not only reduce the work function of the silver electrode to provide better energy level alignment but also exhibit a significant n-doping effect with the non-fullerene acceptors to facilitate efficient electron extraction and transport. Our results demonstrate that TOCs as semiconductors have great potential application in OSCs.

Double-Cable Conjugated Polymers with Pendant Rylene Diimides for Single-Component Organic Solar Cells.

ConspectusConjugated polymers for application in organic solar cells (OSCs) have been developed from poly(phenylenevinylene) to poly(3-hexylthiophene) and then to "donor-acceptor" structures, providing power conversion efficiencies (PCEs) over 18% when blending with the electron acceptor as a two-component photoactive layer. Besides, graft-structural double-cable conjugated polymers that use an electron donor as conjugated backbones and an electron acceptor as pendant side units are one kind of conjugated polymer, in which charge carriers are generated in a single polymer. Therefore, double-cable conjugated polymers can be used as a single photoactive layer in single-component OSCs (SCOSCs). The covalently linked electron donor and acceptor enable double-cable polymers to maintain stable microstructures during long-term operation compared to two-component systems, which is very important for OSCs toward large-area applications. However, SCOSCs based on double-cable conjugated polymers provided PCEs below 3% in a long period, which is lagging far behind PCEs of two-component OSCs. The key reason for this is the limited number of chemical structures and the difficulty to tune the morphology in these polymers.In this Account, we provide an overview about our efforts on developing new double-cable conjugated polymers with rylene diimides as side units, and how to realize high PCEs in SCOSC devices. The studies start from developing a "functionalization-polymerization" method to synthesize the polymers containing rylene diimide acceptors, so that large amounts of double-cable conjugated polymers with distinct physical and electrochemical properties were obtained. Then, we will discuss how to control the nanophase separation in the crystalline region and optimize the miscibility in the amorphous region of double-cable polymers, simultaneously facilitating exciton dissociation and charge transport. With these efforts, a high PCE of 8.4% has been obtained, representing the record PCE in SCOSCs. In addition, the physical process and the stability of SCOSCs will be discussed. We hope that this account will inspire many innovative studies in this field and push the PCEs of SCOSCs to a new stage.

Chlorinated Spiroconjugated Fused Extended Aromatics for Multifunctional Organic Electronics.

The synthesis of a new molecule, SFIC-Cl, is reported, which features enhanced π-electron delocalization by spiroconjugation and narrowed bandgap by chlorination. SFIC-Cl is integrated into a single-crystal transistor (OFET) and organic light-emitting diode (OLED). The material demonstrates remarkable transport abilities across various solution-processed OFETs and retains efficient radiance in a near-infrared OLED emitting light at 700 nm. Furthermore, the intermolecular multi-dimensional connection of SFIC-Cl enables the fabrication of a single-component large-area (2 × 2 cm2 ) near-infrared OLED by spin-coating. The SFIC-Cl-acceptor-based solar cell shows excellent power conversion efficiency of 10.16% resulting from the broadened and strong absorption and well-matched energy levels. The study demonstrates that chlorinated spiroconjugated fused systems offer a novel direction toward the development of high-performance organic semiconductor materials for hybrid organic electronic devices.

An Organic-Inorganic Hybrid Electrolyte as a Cathode Interlayer for Efficient Organic Solar Cells.

An organic-inorganic hybrid electrolyte based on a cyclic Ti-oxo cluster as the inorganic core and naphthalene-based organic ammonium bromide salts as the electrolyte was developed with easy synthesis and low cost. The new hybrid electrolyte exhibits excellent solubility in methanol, aligned work function, good conductivity, and amorphous state in thin film, enabling its successful application as a cathode interlayer in organic solar cells with a high power conversion efficiency of 17.19 %. This work demonstrates that the hybrid electrolytes are a new kind of semiconductor, exhibiting promising applications in organic electronics.

Noncovalent π-stacked robust topological organic framework.

Organic frameworks (OFs) offer a novel strategy for assembling organic semiconductors into robust networks that facilitate transport, especially the covalent organic frameworks (COFs). However, poor electrical conductivity through covalent bonds and insolubility of COFs limit their practical applications in organic electronics. It is known that the two-dimensional intralayer π∙∙∙π transfer dominates transport in organic semiconductors. However, because of extremely labile inherent features of noncovalent π∙∙∙π interaction, direct construction of robust frameworks via noncovalent π∙∙∙π interaction is a difficult task. Toward this goal, we report a robust noncovalent π∙∙∙π interaction-stacked organic framework, namely πOF, consisting of a permanent three-dimensional porous structure that is held together by pure intralayer noncovalent π∙∙∙π interactions. The elaborate porous structure, with a 1.69-nm supramaximal micropore, is composed of fully conjugated rigid aromatic tetragonal-disphenoid-shaped molecules with four identical platforms. πOF shows excellent thermostability and high recyclability and exhibits self-healing properties by which the parent porosity is recovered upon solvent annealing at room temperature. Taking advantage of the long-range π∙∙∙π interaction, we demonstrate remarkable transport properties of πOF in an organic-field-effect transistor, and the mobility displays relative superiority over the traditional COFs. These promising results position πOF in a direction toward porous and yet conductive materials for high-performance organic electronics.

Miscibility-Controlled Phase Separation in Double-Cable Conjugated Polymers for Single-Component Organic Solar Cells with Efficiencies over 8 .

A record power conversion efficiency of 8.40 % was obtained in single-component organic solar cells (SCOSCs) based on double-cable conjugated polymers. This is realized based on exciton separation playing the same role as charge transport in SCOSCs. Two double-cable conjugated polymers were designed with almost identical conjugated backbones and electron-withdrawing side units, but extra Cl atoms had different positions on the conjugated backbones. When Cl atoms were positioned at the main chains, the polymer formed the twist backbones, enabling better miscibility with the naphthalene diimide side units. This improves the interface contact between conjugated backbones and side units, resulting in efficient conversion of excitons into free charges. These findings reveal the importance of charge generation process in SCOSCs and suggest a strategy to improve this process: controlling miscibility between conjugated backbones and aromatic side units in double-cable conjugated polymers.