Benzotriazole‐Based D–π–A‐Type Photovoltaic Polymers Break Through 17% Efficiency

Abstract Benzo[d][1,2,3]triazole (BTA) unit is one of the most classic electron‐accepting units (A) to construct donor (D)‐π‐A‐type photovoltaic polymers. However, the highest power conversion efficiency (PCE) of organic photovoltaics (OPVs) based on BTA‐containing polymers is restricted to 15–16%, lagging other promising polymers. Thus, investigating the structure‐performance relationship and breaking the efficiency bottleneck of BTA‐based polymers is challenging but critical. Herein, the effects of fusing two thiophene rings at D ( PE52 ), π ( PE4 ), and A ( PE39 ) units of a classic D–π–A‐type BTA‐containing polymer J52‐Cl, respectively, on the backbone conformation, crystallinity, molecular stacking, and photovoltaic performance are systematically investigated. When blended with a BTA‐containing non‐fullerene acceptor (NFA), Y18 , all three polymers with extending conjugated backbones can decrease the energy loss of photovoltaic devices. Notably, PE4 , with a linear backbone conformation, realizes the champion PCE of 17.08%, with a short‐circuit current density ( J SC ) of 26.83 mA cm −2 , a large breakthrough for BTA‐based photovoltaic polymers. What's more, the photovoltaic device based on PE4:Y18 combination fabricated by a non‐halogenated solvent of o ‐xylene also displays an excellent PCE of 16.87%. The results indicate that fusing thiophene rings to BTA‐polymers, especially at π‐bridge, is a simple and effective method to improve the photovoltaic performance via modulating the molecular conformation and crystallinity.