Self-assembled organic films of imidazole derivatives are vital for metal surface modification, but their effectiveness in the commercialization of high-d. copper interconnects remains limited.To enhance thermal and chem. stability, we synthesized five fluorobenzimidazole monomers by integrating fluorine into the imidazole structure using a solvent-free method.Notably, the 5-chloro-2-(2-chloro-4-fluorobenzyl)-1H-benzo[d]imidazole (5224FIM) demonstrated an impressive inhibition efficiency of 95.00%, forming a robust barrier approx. 4450 Å thick, which effectively withstands damage under high temperature and humidity.XPS anal. revealed that the oxygen content in sample 5442FIM was 9.02%, the lowest among the samples, while the nitrogen content was 8.19%, indicating a substantial presence of imidazole mols.In comparison to non-substituted benzimidazole films, these fluorine-enhanced self-assembled films on copper exhibited superior heat and moisture resistance.Notably, printed circuit boards coated with 5224FIM demonstrated excellent performance in 72-h salt spray and 245°C tin immersion solderability tests, highlighting their enhanced surface protection capabilities.