<i>In-situ</i> understanding on the formation of fibrillar morphology in green solvent processed all-polymer solar cells

Solid additive engineering has been intensively explored on morphology tuning for highly efficient all-polymer solar cells (all-PSCs), a promising photovoltaic technology towards multi-scenario application. Although the nano-fibrillar network of the active layer induced by additive treatment is confirmed as the key factor for power conversion efficiency (PCE) of all-PSCs, its formation mechanism is not clearly revealed, for lack of precise and convincing real-time observation of crystallization and phase separation during the liquid-to-solid transition process of spin-coating. Herein we report an <i>in-situ</i> grazing incidence wide-angle/small-angle X-ray scattering (GIWAXS/GISAXS) screening that reveals the fact that naphthalene derived solid additives can suppress the aggregation of the polymer acceptor (PY-IT) at the beginning stage of spin coating, which provides sufficient time and space for the polymer donor (PM6) to form the fibril structure. Moreover, guided by this knowledge, a ternary all-polymer system is proposed, which achieves cutting-edge level PCEs for both small-area (0.04 cm²) (also decent operational stability) and large-area (1 cm²) devices.