Breaking the Efficiency Limit of Deep-Blue Fluorescent OLEDs Based on Anthracene Derivatives.

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%.

Direct Observation of Confinement Effects of Semiconducting Polymers in Polymer Blend Electronic Systems.

The advent of special types of polymeric semiconductors, known as "polymer blends," presents new opportunities for the development of next-generation electronics based on these semiconductors' versatile functionalities in device applications. Although these polymer blends contain semiconducting polymers (SPs) mixed with a considerably high content of insulating polymers, few of these blends unexpectedly yield much higher charge carrier mobilities than those of pure SPs. However, the origin of such an enhancement has remained unclear owing to a lack of cases exhibiting definite improvements in charge carrier mobility, and the limited knowledge concerning the underlying mechanism thereof. In this study, the morphological changes and internal nanostructures of polymer blends based on various SP types with different intermolecular interactions in an insulating polystyrene matrix are investigated. Through this investigation, the physical confinement of donor-acceptor type SP chains in a continuous nanoscale network structure surrounded by polystyrenes is shown to induce structural ordering with more straight edge-on stacked SP chains. Hereby, high-performance and transparent organic field-effect transistors with a hole mobility of ≈5.4 cm2 V-1 s-1 and an average transmittance exceeding 72% in the visible range are achieved.

Design Strategy of Anthracene-Based Fluorophores toward High-Efficiency Deep Blue Organic Light-Emitting Diodes Utilizing Triplet-Triplet Fusion.

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.

Controlling Horizontal Dipole Orientation and Emission Spectrum of Ir Complexes by Chemical Design of Ancillary Ligands for Efficient Deep-Blue Organic Light-Emitting Diodes.

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 by a Fluorescent Emitter Using a Phosphorescent Sensitizer for Blue Organic-Light-Emitting Diodes.

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.

Twisted Linker Effect on Naphthalene Diimide-Based Dimer Electron Acceptors for Non-fullerene Organic Solar Cells.

Naphthalene diimide (NDI) dimers, NDI-Ph-NDI with a phenyl linker and NDI-Xy-NDI with a xylene linker, are designed and synthesized. The influence of the xylene and phenyl linkers on optical properties, electrochemical properties, morphology, and device performance is systematically investigated. Non-fullerene organic solar cells (OSCs) with NDI-Ph-NDI show poor device efficiency due to aggregation of polymer chains and/or NDI dimers caused by the highly planar structure of NDI-Ph-NDI. Although NDI-Xy-NDI is a non-planar structure, uniform surface morphology and weak bimolecular recombination lead to high power conversion efficiencies of 3.11%, which is the highest value in non-fullerene OSCs with NDI small molecules.

Design of New Isoindigo-Based Copolymer for Ambipolar Organic Field-Effect Transistors.

We report the synthesis of a new conjugated polymer composed of isoindigo (IID) and 2,3-bis[thiophenyl-2-yl]thiophene acrylonitrile (CNTVT) subunits for high-performance n-type organic field-effect transistors (OFETs). To realize high electron mobility for the IID-based conjugated polymer, an electron-withdrawing nitrile group is incorporated into the vinylene unit, thereby shifting the energy of the lowest unoccupied molecular orbital for efficient electron injection from Au electrodes without disrupting the backbone planarity. Uniaxially aligned IID24-CNTVT-conjugated polymer films for efficient intramolecular charge transport are achieved by off-center spin-coating from preaggregated solutions. To obtain its stable preaggregation in solution, a binary solvent system (a mixture of good and bad solvents) chosen with the assistance of Hansen solubility parameter simulation is used. Through this process, highly aligned IID24-CNTVT films are obtained by off-center spin coating from a solvent mixture of 9:1 dichlorobenzene/2-methoxyethanol as the good and bad solvents, respectively. The properties of the aligned IID24-CNTVT films are characterized with various analytical techniques, including UV-visible absorption spectroscopy, angle-resolved near-edge X-ray absorption fine structure spectroscopy, and grazing-incidence wide-angle X-ray scattering. Top-gate/bottom-contact OFETs with IID24-CNTVT films aligned in the direction of charge transport exhibit a high-electron field-effect mobility of 0.83 ± 0.13 cm2/V·s.

All-Small-Molecule Solar Cells Incorporating NDI-Based Acceptors: Synthesis and Full Characterization.

A series of naphthalene diimide (NDI)-based small molecules were synthesized as nonfullerene acceptors and incorporated in all-small-molecule solar cells. Three NDI-based small molecules, NDICN-T, NDICN-BT, and NDICN-TVT, were designed with different linkers between two NDI units to induce the different conjugation length and modulate the geometric structures of the NDI dimers. The small NDI-based dimer electron acceptors with slip-stacked structures that facilitate π-π stacking interactions and/or hinder excessive aggregation exhibited different morphological behaviors, such as miscibility or crystallinity in bulk heterojunction blends with 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole) (DTS-F) electron donors. The photovoltaic devices prepared with NDICN-TVT gave the highest power conversion efficiency (PCE) of 3.01%, with an open-circuit voltage (Voc) of 0.75 V, a short-circuit current density (Jsc) of 7.10 mA cm-2, and a fill factor of 56.2%, whereas the DTS-F:NDICN-T and DTS-F:NDICN-BT devices provided PCEs of 1.81 and 0.13%, respectively. Studies of the charge-generation properties, charge-transfer dynamics, and charge-transport properties for understanding the structure-property relations revealed that DTS-F:NDICN-TVT blend films with well-developed domains and well-ordered crystalline structures performed well, whereas an excessive miscibility between DTS-F and NDICN-BT disrupted the crystallinity of the material and yielded a poor device performance.

Effects of alkyl chain length on the optoelectronic properties and performance of pyrrolo-perylene solar cells.

While the impact of alkyl side-chain length on the photovoltaic properties of conjugated polymers and their performance in bulk heterojunction (BHJ) solar cells has been studied extensively, analogous studies on pyrrolo-perylene-based polymers have not received adequate attention. To explore these effects, we synthesized two copolymers based on N-annulated pyrrolo-perylene and consisting of cyano group substituents on thiophene vinylene thiophene units with two different alkyl groups of 2-decyltetradecyl and 7-decylnonadecyl, and we studied them with regard to chemical structure and photovoltaic performance. UV-vis spectroscopy and cyclic voltammetry studies showed that variations in alkyl chain length affect crystallization, light absorption, and the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels. These factors have a pronounced impact on the morphology of BHJ thin films and their charge carrier separation and transportation characteristics, which, in turn, influences photovoltaic properties.