The hole-transporting layer is an essential component in a perovskite solar cell (PSC) and plays a key role in controlling both power conversion efficiency (PCE) and stability. Here, we report a new hole-transporting material (HTM), methoxy groupcontaining poly(triarylamine) (PTAA) (CH 3 O-PTAA), for efficient PSCs with improved thermal stability. As compared to commonly used PTAA (CH 3 -PTAA), CH 3 O-PTAA exhibits enhanced doping ability and stability under thermal stress. With CH 3 O-PTAA, (FAPbI 3 ) 0.85 (MAPbBr 3 ) 0.15 -based PSCs show high PCEs over 20%, comparable to those of CH 3 -PTAA devices. More importantly, better long-term thermal stability with only 3% reduction from the initial PCE (6.1% reduction on average) has been achieved for encapsulated PSCs with CH 3 O-PTAA than that of PSCs with CH 3 -PTAA under dark storage conditions (ISOS-D-3) of 85 °C and 85% relative humidity (RH) over 1000 h. Detailed studies have been conducted to reveal the strong correlation between the doping behavior of HTMs and the performance of PSCs, which provide useful guidelines for the design of new HTMs for efficient and stable PSCs.

All‐polymer solar cells (all‐PSCs) are a highly attractive class of photovoltaics for wearable and portable electronics due to their excellent morphological and mechanical stabilities. Recently, new types of polymer acceptors (PAs) consisting of non‐fullerene small molecule acceptors (NFSMAs) with strong light absorption have been proposed to enhance the power conversion efficiency (PCE) of all‐PSCs. However, polymerization of NFSMAs often reduces entropy of mixing in PSC blends and prevents the formation of intermixed blend domains required for efficient charge generation and morphological stability. One approach to increase compatibility in these systems is to design PAs that contain the same building blocks as their polymer donor (PD) counterparts. Here, a series of NFSMA‐based PAs [P(BDT2BOY5‐X), (X = H, F, Cl)] are reported, by copolymerizing NFSMA (Y5‐2BO) with benzodithiophene (BDT), a common donating unit in high‐performance PDs such as PBDB‐T. All‐PSC blends composed of PBDB‐T PD and P(BDT2BOY5‐X) PA show enhanced molecular compatibility, resulting in excellent morphological and electronic properties. Specifically, PBDB‐T:P(BDT2BOY5‐Cl) all‐PSC has a PCE of 11.12%, which is significantly higher than previous PBDB‐T:Y5‐2BO (7.02%) and PBDB‐T:P(NDI2OD‐T2) (6.00%) PSCs. Additionally, the increased compatibility of these all‐PSCs greatly improves their thermal stability and mechanical robustness. For example, the crack onset strain (COS) and toughness of the PBDB‐T:P(BDT2BOY5‐Cl) blend are 15.9% and 3.24 MJ m–3, respectively, in comparison to the PBDB‐T:Y5‐2BO blends at 2.21% and 0.32 MJ m–3.

Blends of polymer donors (PDs) and small molecule acceptors (SMAs) have afforded highly efficient polymer solar cells (PSCs). However, most of the efficient PSCs are processed using toxic halogenated solvents, and they are mechanically fragile. Here, a new series of PDs by incorporating a hydrophilic oligo(ethylene glycol) flexible spacer (OEG‐FS) is developed, and efficient PSCs with a high power conversion efficiency (PCE) of 17.74% processed by a non‐halogenated solvent are demonstrated. Importantly, the incorporation of these OEG‐FSs into the PDs significantly increases the mechanical robustness and ductility of resulting PSCs, making them suitable for application as stretchable devices. The OEG‐FS alleviates excessive backbone rigidity of the PDs while enhancing their pre‐aggregation in the non‐halogenated solvent. In addition, the OEG‐FS in the PDs enhances PD‐SMA interfacial interactions and improves blend morphology, resulting in efficient charge generation and mechanical stress dissipation. The resulting PSCs demonstrate a superior PCE (17.74%) and high crack‐onset strain (COS = 10.50%), outperforming the PSCs without OEG (PCE = 15.64% and COS = 2.99%). Importantly, intrinsically stretchable (IS) PSCs containing the PD featuring OEG‐FS exhibit a high PCE (12.05%) and stretchability (maintaining 80% of the initial PCE after 22% strain), demonstrating their viability for wearable applications.

The design of terpolymers is a compelling strategy to improve the polymer solar cell (PSC) performance. However, the terpolymer composition at which the power conversion efficiency (PCE) of associated PSCs is typically optimized generally falls within a very narrow range, complicating the reproducible fabrication of optimal PSCs. In this study, a series of D–A1–D–A2 type random terpolymers (DTTz-X, where X = 10–60) is designed with structurally similar A1 and A2 accepting units. The sulfur atom of the benzothiadiazole subunit in the A1 (DTBT) unit is replaced by a nitrogen atom in the A2 (DTTz) unit, enabling the introduction of an alkyl solubilizing group while maintaining the overall structural properties of the terpolymer system. Consequently, the DTTz-X P Ds maintain good optoelectronic properties at various A1/A2 ratios, while their processability in nonhalogenated solvents is significantly enhanced. Accordingly, the PSC performance of the terpolymer system shows good composition tolerance; i.e., the terpolymer system affords PSCs with PCEs exceeding 15% (up to 16.4%) over a broad range of DTTz compositions (10–40 mol %). This study establishes a useful design strategy for the development of efficient terpolymer donors for reproducible and eco-friendly fabrication of high-performance PSCs.

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.