摘要： The synthesis and characterization of new semiconducting materials is essential for developing high-efficiency organic solar cells. Here, the synthesis, physiochemical properties, thin film morphology, and photovoltaic response of ITN-F4 and ITzN-F4, the first indacenodithienothiophene nonfullerene acceptors that combine π-extension and fluorination, are reported. The neat acceptors and bulk-heterojunction blend films with fluorinated donor polymer poly{[4,8-bis[5-(2-ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b′]-dithiophene-2,6-diyl]-alt-[2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c′]dithiophene-1,3-diyl]]} (PBDB-TF, also known as PM6) are investigated using a battery of techniques, including single crystal X-ray diffraction, fs transient absorption spectroscopy (fsTA), photovoltaic response, space-charge-limited current transport, impedance spectroscopy, grazing incidence wide angle X-ray scattering, and density functional theory level computation. ITN-F4 and ITzN-F4 are found to provide power conversion efficiencies greater and internal reorganization energies less than their non-π-extended and non-fluorinated counterparts when paired with PBDB-TF. Additionally, ITN-F4 and ITzN-F4 exhibit favorable bulk-heterojunction relevant single crystal packing architectures. fsTA reveals that both ITN-F4 and ITzN-F4 undergo ultrafast hole transfer (<300 fs) in films with PBDB-TF, despite excimer state formation in both the neat and blend films. Taken together and in comparison to related structures, these results demonstrate that combined fluorination and π-extension synergistically promote crystallographic π-face-to-face packing, increase crystallinity, reduce internal reorganization energies, increase interplanar π–π electronic coupling, and increase power conversion efficiency.