Deep‐blue emitting Iridium (Ir) complexes with horizontally oriented emitting dipoles are newly designed and synthesized through engineering of the ancillary ligand, where 2′,6′‐difluoro‐4‐(trimethylsilyl)‐2,3′‐bipyridine (dfpysipy) is used as the main ligand. Introduction of a trimethylsilyl group at the pyridine and a nitrogen at the difluoropyrido group increases the bandgap of the emitter, resulting in deep‐blue emission. Addition of a methyl group (mpic) to a picolinate (pic) ancillary ligand or replacement of an acetate structure of pic with a perfluoromethyl‐triazole structure (fptz) increases the horizontal component of the emitting dipoles in sequence of mpic (86%) > fptz (77%) > pic (74%). The organic light‐emitting diode (OLED) using the Ir complex with the mpic ancillary ligand shows the highest external quantum efficiency (31.9%) among the reported blue OLEDs with a y‐coordinate value lower than 0.2 in the 1931 Commission Internationale de L'Eclairage (CIE) chromaticity diagram.

Triplet harvesting is important for the realization of high‐efficiency fluorescent organic light‐emitting diodes (OLEDs). Triplet–triplet annihilation (TTA) is one triplet‐harvesting strategy. However, for blue‐emitting anthracene derivatives, the theoretical maximum radiative singlet‐exciton ratio generated from the TTA process is known to be 15% in addition to the initially generated singlets of 25%, which is insufficient for high‐efficiency fluorescent devices. In this study, nearly 25% of the radiative singlet‐exciton ratio is realized by TTA using an anthracene derivative, breaking the theoretical limit. As a result, efficient deep‐blue TTA fluorescent devices are developed, exhibiting external quantum efficiencies of 10.2% and 8.6% with Commission Internationale de l'Eclairage color coordinates of (0.134, 0.131) and (0.137, 0.076), respectively. The theoretical model provided herein explains the experimental results considering both the TTA and reverse intersystem crossing to a singlet state from higher triplet states formed by the TTA, clearly demonstrating that the radiative singlet ratio generated from TTA can reach 37.5% (total radiative singlet‐exciton ratio: 62.5%), well above 15% (total 40%), despite the molecule having S1, T2 < 2T1 < Q1 energy levels, which will lead to the development of high‐efficiency fluorescent OLEDs with external quantum efficiencies exceeding 28% if the outcoupling efficiency is 45%.

The development of highly efficient blue organic light-emitting diodes (OLEDs) with good stability is currently the most important issue in OLED displays and lighting. This paper reports an efficient blue fluorescent OLED based on a deep-blue-emitting phosphorescent sensitizer [(dfpysipy)2Ir­(mpic)] and a conventional fluorescent emitter (TBPe). Efficient triplet harvesting by the fluorescent emitter occurs in the OLED because of sensitization even though the difference in the emission energy between the phosphorescent and fluorescent emissions was only 0.05 eV. These results clearly demonstrate the potential for realizing highly efficient blue fluorescent OLEDs using phosphorescent sensitizers without requiring ultraviolet-emitting phosphorescent dye.

In contrast to the red and green regions, conventional fluorescent emitters continue to serve as blue emitters in commercialized organic light-emitting diodes. Many researchers have studied anthracene moieties as blue emitters, given their appropriate energy levels and good emission properties. We herein report two new deep blue-emitting anthracene derivatives that include p-xylene as moieties connecting the anthracene cores to side groups. We enhanced the efficiency by maximizing triplet− triplet fusion (TTF) without sacrificing emission color. The large steric hindrance imposed by the methyl groups of p-xylene creates a perpendicular geometry between p-xylene and the neighboring aromatic rings. Any extension of π-conjugation is thus disrupted, and the isolated core anthracene moiety emits a deep blue color with a high photoluminescence quantum yield. Moreover, the extensive steric hindrance suppresses vibration and rotation because the molecules are rigid. The high horizontal dipole ratio attributable to the large aspect ratio increases the outcoupling efficiency of the emitted light. Furthermore, the charge mobility and triplet harvesting ability are enhanced by decreasing the bulkiness of the side groups. Molecular dynamics simulation revealed that the bulkiness of the side group significantly impacted molecular density, which in turn affected the charge transport and TTF. We used two molecules, 2PPIAn (containing a phenyl side group) and 4PPIAn (containing a terphenyl side group), to form nondoped emission layers that exhibited maximum external quantum efficiencies of 8.9 and 7.1% with Commission Internationale de L'Eclairage coordinates of (0.150, 0.060) and (0.152, 0.085), respectively.

The organic solar cell (OSC) performance of a series of new donor–acceptor copolymers containing indolo­[3,2-b]­indole as a key donor block and benzothiadiazole (BT) units with various degrees of fluorination as acceptors is reported. Compared with the simple carbazole unit, the strategically developed indolo­[3,2-b]­indole unit is found to significantly extend π-conjugation and thus increase the intermolecular interactions of the resulting copolymer, as probed by density functional theory calculations, photophysical studies, and structural/morphological analyses. In addition, fluorination of BT can facilitate nanostructuring of the copolymers, mainly due to further planarization of the backbone, which leads to apparently higher hole/electron charge carrier mobilities. The OSC properties of this series of new copolymers blended with fullerene show a strong dependence on the fine and continuous fibrous nanostructure of the blend film. The indolo­[3,2-b]­indole-based copolymer with singly fluorinated BT units possesses optimal intermolecular interactions and achieves the highest power conversion efficiency of 8.84% under AM 1.5G illumination. This result shows the potential of π-extended carbazole moieties for achieving high-performance OSCs with many of the favorable properties induced by large heteroacene blocks.