A facile and low-temperature process to prepare planar perovskite solar cells (PSCs) has led to considerable progress in flexible solar cells toward high throughput production based on a roll-to-roll process....

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.

High tolerance regarding photovoltaic performance in terms of donor:acceptor (D:A) composition ratio is reported for all-polymer solar cells (all-PSCs), which is a crucial advantage in producing large-scale devices with high reproducibility. To understand the origin of high D:A ratio tolerance in all-PSCs, we investigate the molecular weight (MW) effects of the P­(NDI2OD-T2) polymer acceptor (P A) on photovoltaic and mechanical robustness of PBDB-T:P­(NDI2OD-T2) all-PSCs. Also, we compare the all-PSCs with other types of PSCs consisting of the same polymer donor but using small molecule acceptors (SMAs) including ITIC and PC71BM. We observe that the D:A ratio tolerances of both the photovoltaic and mechanical properties are highly dependent on the P A MW and the acceptor material types. For example, at a high D:A ratio of 15:1, all-PSCs using high MW P A (number-average molecular weight (M n) = 97 kg mol–1) exhibit 13 times higher normalized power conversion efficiency (PCE) than all-PSCs using low MW P A (M n = 11 kg mol–1), and 20 times higher than ITIC-based PSCs. In addition, the electron mobilities in all-PSCs based on high MW P A are well-maintained even at very high D:A ratio, whereas the electron mobilities in low MW P A all-PSCs and SMA-based PSCs decrease by 3- and 4-orders of magnitude, respectively, when the D:A ratio increases from 1:1 to 15:1. Thus, we suggest that the formation of tie molecules and chain entanglements by long polymer chains bridging adjacent crystalline domains is the main origin of excellent D:A tolerance in both mechanical robustness and photovoltaic performance. This work provides an important material design guideline for the reproducible production of flexible and stretchable all-PSCs.

The development of small-molecule acceptors (SMAs) has significantly enhanced the power conversion efficiency (PCE) of polymer solar cells (PSCs); however, the inferior mechanical properties of SMA-based PSCs often limit their long-term stability and application in wearable power generators. Herein, we demonstrate a simple and effective strategy for enhancing the mechanical robustness and PCE of PSCs by incorporating a high-molecular-weight (MW) polymer acceptor ( P A , P(NDI2OD-T2)). The addition of 10–20 wt % P A leads to a more than 4-fold increase in the mechanical ductility of the SMA-based PSCs in terms of the crack onset strain (COS). At the same time, the incorporation of P A into the active layer improves the charge transport and recombination properties, increasing the PCE of the PSC from 14.6 to 15.4%. The added P A s act as tie molecules, providing mechanical and electrical bridges between adjacent domains of SMAs. Thus, for the first time, we produce highly efficient and mechanically robust PSCs with a 15% PCE and 10% COS at the same time, thereby demonstrating their great potential as stretchable or wearable power generators. To understand the origin of the dual enhancements realized by P A , we investigate the influence of the P A content on electrical, structural, and morphological properties of the PSCs.