Tethered Trimeric Small-molecular Acceptors through Aromatic-core engineering for Highly Efficient and Thermally Stable Polymer Solar Cells

Abstract

Polymer solar cells (PSCs) rely on a blend of small molecular acceptors (SMAs) with polymer donors, where thermodynamic relaxation of SMAs poses critical concerns on operational stability. To tackle this issue, tethered SMAs, wherein multiple SMA-subunits are connected to the aromatic-core via flexible chains, are proposed. This design aims to an elevated glass transition temperature (Tg) for a dynamical control. However, attaining an elevated Tg value with additional SMA subunits introduces complexity to the molecular packing, posing a significant challenge in realizing both high stability and power conversion efficiency (PCE). In this study, we initiate isomer engineering on the benzene-carboxylate core and find that meta-positioned dimeric BDY-beta exhibits more favorable molecular packing compared to its para-positioned counterpart, BDY-alpha. With this encouraging result, we expand our approach by introducing an additional SMA unit onto the aromatic core of BDY-beta, maintaining a meta-position relative to each SMA unit location in the tethered acceptor. This systematic aromatic-core engineering results in a star-shaped C3h-positioned molecular geometry. The supramolecular interactions of SMA units in the trimer contribute to enhancements in Tg value, crystallinity, and a red-shifted absorption compared to dimers. These characteristics result in a noteworthy increase in PCE to 18.24 %, coupled with a remarkable short-circuit current density of 27.06 mA cm-2. More significantly, the trimer-based devices delivered an excellent thermal stability with over 95 % of their initial efficiency after 1200 h thermal degradation. Our findings underscore the promise and feasibility of tethered trimeric structures in achieving highly ordered aggregation behavior and increased Tg value in PSCs, simultaneously improving in device efficiency and thermal stability. In this study, meta-isomerization was conducted on the benzene-carboxylate core to precisely regulate the geometry of tethered dimeric acceptors, revealing a more advantageous molecular packing for the meta-positioned dimers. This finding led to the design of a star-shaped C3h-positioned trimer, demonstrating enhanced device stability and performance.+ image