Enhancing Carrier Behavior via Controlled Molecular Film Formation Engineering Leads to Significant Improvement in Electroluminescence.

The quality of organic thin films critically influences carrier dynamics in organic semiconductors. In neat/doped films, even tiny voids can be penetrated by water or oxygen molecules to create charge-trap states called water/oxygen-induced traps that significantly hinder carrier mobility. While the water/oxygen-induced traps in non-doped films and crystalline states have been investigated comprehensively, there is a lack of thorough examination regarding their properties in the doped state. Therefore, there is a high demand for a molecular design strategy that effectively modulates the molecular stacking behavior in doped films and practical devices and enhances the quality of these films. Herein, we proposed a versatile molecular design principle that enables the formation of "nano-cluster" structures on both the surface and interior of doped films in target molecule 10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-1'-(4-fluorophenyl)-10H-spiro[acridine-9,9'-xanthene] (DspiroO-F-TRZ), which is modified with a fluorophenyl group. These "nano-cluster" structures exhibit more uniform shapes within doped films and effectively reduce defective state densities while enhancing carrier injection and transport properties, ultimately improving device performance. Notably, TADF-OLED based on DspiroO-F-TRZ demonstrates nearly twice as much efficiency as its control counterpart due to contributions from 'nano-cluster' structure enhancements toward improved electroluminescence performance.