Impact of the Molecular Structure of Oligo(ethylene glycol)-Incorporated Y-Series Acceptors on the Formation of Alloy-like Acceptors and Performance of Non-Halogenated Solvent-Processable Organic Solar Cells.

To realize efficient, green solvent-processable organic solar cells (OSCs), considerable effort has been expended on the development of conjugated materials with both superior optoelectrical properties and processability. However, molecular design strategies that enhance solubility often reduce crystalline/electrical properties of the materials. In this study, we develop three new guest small-molecule acceptors (SMAs) (Y-4C-4O, Y-6C-4O, and Y-12C-4O) featuring inner side chains consisting of terminal oligo(ethylene glycol) (OEG) groups and alkyl spacers of different lengths. When a host SMA (Y6) and guest SMA (Y-nC-4O) are mixed, favorable interactions between these materials lead to the formation of "alloy-like" composites. The alloy-like SMA composites enable sufficient processing in o-xylene to afford suitable blend-film morphologies. It is also found that the lengths of the alkyl spacers in guest SMAs have a significant impact on the performance of the o-xylene-processed OSCs. The PM6:Y6:Y-4C-4O blend achieves a maximum power conversion efficiency (PCE) of 17.03%, outperforming PM6:Y6:Y-6C-4O (PCE = 15.85%) and PM6:Y6:Y-12C-4O (PCE = 12.12%) OSCs. The high PCE of the PM6:Y6:Y-4C-4O device is mainly attributed to the well-intermixed morphology and superior crystalline/electrical properties, which result from the high compatibility of the Y6:Y-4C-4O composites with PM6. Thus, we demonstrate that an alloy-like SMA composite based on well-designed OEG-incorporated Y-series SMAs can afford green solvent-processable, high-performance OSCs.

Poly(dimethylsiloxane)-block-PM6 Polymer Donors for High-Performance and Mechanically Robust Polymer Solar Cells.

High power conversion efficiency (PCE) and stretchability are the dual requirements for the wearable application of polymer solar cells (PSCs). However, most efficient photoactive films are mechanically brittle. In this work, highly efficient (PCE = 18%) and mechanically robust (crack-onset strain (COS) = 18%) PSCs are acheived by designing block copolymer (BCP) donors, PM6-b-PDMSx (x = 5k, 12k, and 19k). In these BCP donors, stretchable poly(dimethylsiloxane) (PDMS) blocks are covalently linked with the PM6 blocks to effectively increase the stretchability. The stretchability of the BCP donors increases with a longer PDMS block, and PM6-b-PDMS19k :L8-BO PSC exhibits a high PCE (18%) and 9-times higher COS value (18%) compared to that (COS = 2%) of the PM6:L8-BO-based PSC. However, the PM6:L8-BO:PDMS12k ternary blend shows inferior PCE (5%) and COS (1%) due to the macrophase separation between PDMS and active components. In the intrinsically stretchable PSC, the PM6-b-PDMS19k :L8-BO blend exhibits significantly greater mechanical stability PCE80% ((80% of the initial PCE) at 36% strain) than those of the PM6:L8-BO blend (PCE80% at 12% strain) and the PM6:L8-BO:PDMS ternary blend (PCE80% at 4% strain). This study suggests an effective design strategy of BCP PD to achieve stretchable and efficient PSCs.

Efficient and Nonhalogenated Solvent-Processed Organic Solar Cells Enabled by Conjugated Donor-Acceptor Block Copolymers Containing the Same Benzodithiophene Unit.

Organic solar cells (OSCs) based on conjugated block copolymers (CBCs) have gained considerable attention owing to their simple one-pot solution process. However, their power conversion efficiencies (PCEs) require significant improvement. Furthermore, the majority of efficient CBC-based OSCs are processed using environmentally toxic halogenated solvents. Herein, we develop a new CBC (PBDB-T-b-PY5BDT) and demonstrate efficient and stable OSCs achieved by a halogen-free solution process. We design a (D1-A1)-b-(D1-A2)-type CBC (PBDB-T-b-PY5BDT) that shares the same benzodithiophene (BDT) units in donor and acceptor blocks. This alleviates unfavorable molecular interactions between the blocks at their interfaces. The PBDB-T-b-PY5BDT-based devices exhibit a high PCE (10.55%), and they show good mechanical, thermal, and storage stabilities. Importantly, we discuss the potential of our OSCs by preparing two different control systems: one based on a binary polymer blend (PBDB-T:PY5BDT) and another based on a conjugated random copolymer (CRC, PBDB-T-r-PY5BDT). We demonstrate that the photovoltaic performance, device stability, and mechanical robustness of the CBC-based OSCs exceed those of the binary all-polymer solar cells and CRC-based OSCs.

Intrinsically Stretchable, Highly Efficient Organic Solar Cells Enabled by Polymer Donors Featuring Hydrogen-Bonding Spacers.

Intrinsically stretchable organic solar cells (IS-OSCs), consisting of all stretchable layers, are attracting significant attention as a future power source for wearable electronics. However, most of the efficient active layers for OSCs are mechanically brittle due to their rigid molecular structures designed for high electrical and optical properties. Here, a series of new polymer donors (PD s, PhAmX) featuring phenyl amide (N1 ,N3 -bis((5-bromothiophen-2-yl)methyl)isophthalamide, PhAm)-based flexible spacer (FS) inducing hydrogen-bonding (H-bonding) interactions is developed. These PD s enable IS-OSCs with a high power conversion efficiency (PCE) of 12.73% and excellent stretchability (PCE retention of >80% of the initial value at 32% strain), representing the best performances among the reported IS-OSCs to date. The incorporation of PhAm-based FS enhances the molecular ordering of PD s as well as their interactions with a Y7 acceptor, enhancing the mechanical stretchability and electrical properties simultaneously. It is also found that in rigid OSCs, the PhAm5:Y7 blend achieves a much higher PCE of 17.5% compared to that of the reference PM6:Y7 blend. The impact of the PhAm-FS linker on the mechanical and photovoltaic properties of OSCs is thoroughly investigated.

Benzotriazole-Based Nonfused Ring Acceptors for Efficient and Thermally Stable Organic Solar Cells.

Nonfused ring acceptors (NFRAs) have attracted significant attention for nonfullerene organic solar cells (OSCs) owing to their chemical tunability and facile synthesis. In this study, a benzotriazole-based NFRA with chlorinated end groups (Triazole-4Cl) is developed to realize highly efficient and thermally stable NFRA-based OSCs; an analogous NFRA with nonchlorinated end groups (Triazole-H) is synthesized for comparison. Triazole-4Cl film exhibits the high-order packing structure and the near-infrared absorption capability, which are advantageous in charge transport and light harvesting of the resulting OSCs. In particular, the strong crystalline behavior of Triazole-4Cl results in enhanced self-aggregation, leading to high charge carrier mobility. Owing to these properties, a PBDB-T (polymer donor):Triazole-4Cl OSC demonstrates a high short-circuit current, fill factor, and power conversion efficiency (PCE = 10.46%), outperforming a PBDB-T:Triazole-H OSC (PCE = 7.65%). In addition, the thermal stability of a PBDB-T:Triazole-4Cl OSC at an elevated temperature of 120 °C exceeds that of a PBDB-T:Triazole-H OSC. This is mainly attributed to the significantly higher cold crystallization temperature of Triazole-4Cl (205.9 °C). This work provides useful guidelines for the design of NFRAs to achieve efficient and thermally stable NFRA-based OSCs.