Thickness‐Dependent Formation Capacity and Mechanism of Planar (β)‐Conformation in Polydiarylfluorenes for Stable Deep‐Blue Polymer Light‐Emitting Diodes

Abstract Conjugated polymers with p‐orbital overlap show intramolecular‐conformation‐dependent photophysical and electrical properties. Compared to the non‐planar segments, the planar conformation segments have a relatively long effective conjugated length and rigid backbone structure, which are beneficial for the enhancement of optoelectronic properties. Herein, the effect of film thickness on the formation capacity of planar ( β ) conformations in polyfluorene (poly[4‐(octyloxy)‐9,9‐diphenylfluorene‐2,7‐diyl]‐co‐[5‐(octyloxy)‐9,9‐diphenylfluorene‐2,7‐diyl], PODPF) for the fabrication of stable deep‐blue polymer light‐emitting diodes (PLEDs) is explored. Thickness‐tunable films with thicknesses ranging from 15 to 270 nm by controlling the concentration of precursor solution are prepared. The main observations are as follows. The PODPF chains in thin films are less likely to adopt the β conformations associated with the loose interchain packing in nano‐aggregates than those in thick films. Red‐shifted and well‐resolved emission spectra are observed for the annealed film with a high thickness, indicating the greater presence of β ‐conformation segments. More interestingly, interchain aggregation is a necessary but not sufficient condition for the formation of β conformations. Finally, PLEDs based on β ‐conformation segments have outstanding brightness, low turn‐on voltage, and stable deep‐blue electroluminescent behavior, confirming the unique advantage of planar conformation for optoelectronic applications.