1：Experimental Design and Method Selection:

The study utilized a series of readily accessible and scalable benzo[1,2-b:4,5-b0]dithiophene (BDT)-2,5-dithienyl-thieno[3,4-c]pyrrole-4,6-dione (TPD-T2)-based donor polymers blended with the non-fullerene acceptor IT-4F. The photoactive blend films were processed in ambient from a chlorine-free solvent to fabricate cells with power conversion efficiencies (PCEs) >12%–14%.

2：4F. The photoactive blend films were processed in ambient from a chlorine-free solvent to fabricate cells with power conversion efficiencies (PCEs) >12%–14%. Sample Selection and Data Sources:

2. Sample Selection and Data Sources: The polymers and acceptor were synthesized and characterized for their physical properties, including UV-vis absorption, PL, fsTA, AFM, TEM, GIWAXS, and SCLC measurements.

3：List of Experimental Equipment and Materials:

Instruments used include a Bruker Avance 500 MHz spectrometer for NMR, Hitachi U-3900 and F-7000 spectrometers for UV-vis absorption and PL spectra, CH Instruments electrochemical analyzer for CV, Mettler Toledo DSC822e for DSC, TA-600 for TGA, and a Polymer Laboratories PL-GPC 220 instrument for molecular mass determination.

4：Experimental Procedures and Operational Workflow:

OPV cells with inverted structures were fabricated using o-xylene as the solvent, with the blend spin-coated in an N2-filled glove box and annealed under N2. Modules were fabricated with an active area of 20.4 cm2 and characterized under AM 1.5 G solar irradiation.

5：Modules were fabricated with an active area of 4 cm2 and characterized under AM 5 G solar irradiation. Data Analysis Methods:

5. Data Analysis Methods: The performance metrics of the OPV cells and modules were recorded using a Keithley 2400 source measurement unit under a simulated AM 1.5 G spectrum. EQE spectra were taken using an Enlitech QE-R spectrometer.