Manipulating the Alkyl Chains of Naphthodithiophene Imide-Based Polymers to Concurrently Boost the Efficiency and Stability of Organic Solar Cells

Morphology instability holds the major responsibility for efficiency degradation of organic solar cells (OSCs). However, how to develop polymer donors simultaneously with high efficiency and excellent morphology stability remains challenging. Herein, we reported naphtho[2,1-b:3,4-b′]dithiophene-5,6-imide (NDTI)-based new polymers PNDT1 and PNDT2. The alkyl chain engineering leads to high crystallinity, high hole mobility (>10–3 cm2 V–1 S–1), and nanofibrous film morphology, which enable PNDT2 to exhibit an efficiency of 18.13% and a remarkable FF value of 0.80. Moreover, the NDTIs have short π–π stacking and abundant short interactions, and their polymers exhibit superior morphological stability. Therefore, the PNDT2-based OSCs exhibit much better device stability than that of PNDT1, PAB-α, and benchmark polymers PM6 and D18. This work suggests the great importance of the large conjugated backbone of the monomer and alkyl chain engineering to develop high-performance and morphology-stable polymers for OSCs.