Layer‐by‐Layer Spin Self‐Assembled Hole Injection Layers Containing a Perfluorinated Ionomer for Efficient Polymer Light‐Emitting Diodes

Deposition of hole injection layers including a perfluorinated ionomer has been demonstrated using layer‐by‐layer spin self‐assembly for enhanced device efficiency and lifetime in PLEDs. We show that the LBL spin self‐assembled thin films enable to control work functions of indium‐tin oxide anodes by changing the PFI concentration and that a resulting green‐emitting device has an enhanced luminescence efficiency and 18 times longer half lifetime than a device using a conventional HIL. We also fabricate a gradient of energy levels by the LBL self‐assembly of the PFI that results in a work function of 5.74 eV, which can be used to improve carrier injection even for an emitting layer whose ionization potential is over 5.7 eV.

     

Highly Conductive PEDOT:PSS Films with 1,3‐Dimethyl‐2‐Imidazolidinone as Transparent Electrodes for Organic Light‐Emitting Diodes

Highly conductive poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films as transparent electrodes for organic light‐emitting diodes (OLEDs) are doped with a new solvent 1,3‐dimethyl‐2‐imidazolidinone (DMI) and are optimized using solvent post‐treatment. The DMI doped PEDOT:PSS films show significantly enhanced conductivities up to 812.1 S cm⁻¹. The sheet resistance of the PEDOT:PSS films doped with DMI is further reduced by various solvent post‐treatment. The effect of solvent post‐treatment on DMI doped PEDOT:PSS films is investigated and is shown to reduce insulating PSS in the conductive films. The solvent posttreated PEDOT:PSS films are successfully employed as transparent electrodes in white OLEDs. It is shown that the efficiency of OLEDs with the optimized DMI doped PEDOT:PSS films is higher than that of reference OLEDs doped with a conventional solvent (ethylene glycol). The results present that the optimized PEDOT:PSS films with the new solvent of DMI can be a promising transparent electrode for low‐cost, efficient ITO‐free white OLEDs.

     

Thermally Cross‐Linkable Hole Transport Polymers for Solution‐Based Organic Light‐Emitting Diodes

Two thermally cross‐linkable hole transport polymers that contain phenoxazine and triphenylamine moieties, X‐P1 and X‐P2, are developed for use in solution‐processed multi‐stack organic light‐emitting diodes (OLEDs). Both X‐P1 and X‐P2 exhibit satisfactory cross‐linking and optoelectronic properties. The highest occupied molecular orbital (HOMO) levels of X‐P1 and X‐P2 are −5.24 and −5.16 eV, respectively. Solution‐processed super yellow polymer devices (ITO/X‐P1 or X‐P2/PDY‐132/LiF/Al) with X‐P1 or X‐P2 hole transport layers of various thicknesses are fabricated with the aim of optimizing the device characteristics. The fabricated multi‐stack yellow devices containing the newly synthesized hole transport polymers exhibit satisfactory currents and power efficiencies. The optimized X‐P2 device exhibits a device efficiency that is dramatically improved by more than 66% over that of a reference device without an HTL.

     

Poly(3,4‐ethylenedioxythiophene) Derived from Poly(ionic liquid) for the Use as Hole‐Injecting Material in Organic Light‐Emitting Diodes

We report that poly(3,4‐ethylenedioxythiophene) derived from poly(ionic liquid) (PEDOT:PIL) constitutes a unique polymeric hole‐injecting material capable of improving device lifetime in organic light‐emitting diodes (OLEDs). Imidazolium‐based poly(ionic liquid)s were engineered to impart non‐acidic and non‐aqueous properties to PEDOT without compromising any other properties of PEDOT. A fluorescent OLED was fabricated using PEDOT:PIL as a hole‐injection layer and subjected to a performance evaluation test. In comparison with a control device using a conventional PEDOT‐based material, the device with PEDOT:PIL was found to achieve a significant improvement in terms of device lifetime. This improvement was attributed to a lower indium content in the PEDOT:PIL layer, which can be also interpreted as the effective protection characteristics of PEDOT:PIL for indium extraction from the electrodes.

     

Photoprogrammable Organic Light‐Emitting Diodes

Enlightening the memory : The integration of a crosslinkable photochromic dithienylperfluorocyclopentene (DTE) into organic light‐emitting diodes (OLED) allows for the individualization of the emissive area of the OLED device, for example, for signage applications. The operation principle is based on switching the injection barrier for holes (positive charge carriers). Very large ON/OFF ratios of up to 3000 for current as well as electroluminescence have been achieved.

     

Hyperbranched copolyfluorene from a 2,4,7‐trifunctional fluorene monomer

A new hyperbranched ( P1 ) and linear copolyfluorene ( P2 ) were prepared from 2,4,7‐trifunctional (branching) and 2,7‐bifunctional fluorene monomer, respectively, by the Wittig reaction, followed with end‐capping by aromatic oxadiazole groups, to study the effect of hyperbranch structure. The weight‐average molecular weights (M_w) of P1 and P2 , determined by gel permeation chromatography using polystyrene as standard, were 33,000 and 25,700, respectively. The polymers were readily soluble in common organic solvents and exhibited good thermal stability (T_d > 400 °C). Optical properties, both in solution and film state, were investigated using absorption and photoluminescence (PL) spectra. In film state, the absorption and PL spectra peaked at 401–425 nm and 480–495 nm, respectively. The P1 showed energy funnel effect and enhanced fluorescence efficiency owing to hyperbranched structure and terminal oxadiazole groups. The HOMO and LUMO levels of P1 ( P2) , estimated from cyclic voltammograms, are ?5.34 (?5.25) eV and ?2.94 (?2.94) eV, respectively. Two‐layer polymer light‐emitting diodes devices (ITO/PEDOT/ P1 /Ca/Al) exhibited maximal luminance and luminous efficiency of 3630 cd/m² and 0.78 cd/A, respectively, which are superior to its linear counterpart P2 (598 cd/m², 0.11 cd/A). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5541–5551, 2007     

Bipolar Host Materials for Organic Light‐Emitting Diodes

It is important to balance holes and electrons in the emitting layer of organic light‐emitting diodes to maximize recombination efficiency and the accompanying external quantum efficiency. Therefore, the host materials of the emitting layer should transport both holes and electrons for the charge balance. From this perspective, bipolar hosts have been popular as the host materials of thermally activated delayed fluorescent devices and phosphorescent organic light‐emitting diodes. In this review, we have summarized recent developments of bipolar hosts and suggested perspectives of host materials for organic light‐emitting diodes.     

Supramolecular Sky‐Blue Phosphorescent Polymer Iridium Complexes for Single‐Emissive‐Layer Organic Light‐Emitting Diodes

Novel supramolecular phosphorescent polymers (SPPs) are synthesized as a new class of solution‐processable electroluminescent emitters. The formation of these SPPs takes advantage of the efficient non‐bonding assembly between bis(dibenzo‐24‐crown‐8)‐functionalized iridium complex monomer and bis(dibenzylammonium)‐tethered co‐monomer, which is monitored by ¹H NMR spectroscopy and viscosity measurements. These SPPs show good film morphology and an intrinsic glass transition with a T_g of 94–116 °C. Noticeably, they are highly photoluminescent in solid state with quantum efficiency up to ca. 78%. The photophysical and electroluminescent properties are strongly dependent on the molecular structures of the iridium complex monomers.

     

Novel Red Phosphorescent Polymers Bearing Both Ambipolar and Functionalized IrIII Phosphorescent Moieties for Highly Efficient Organic Light‐Emitting Diodes

A series of novel red phosphorescent polymers is successfully developed through Suzuki cross‐coupling among ambipolar units, functionalized Ir^III phosphorescent blocks, and fluorene‐based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy‐transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light‐emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency (η _L) of 8.31 cd A⁻¹, external quantum efficiency (η _ext) of 16.07%, and power efficiency (η _P) of 2.95 lm W⁻¹, representing the state‐of‐the‐art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers.

     

Novel Hole‐Transport Material for Efficient Polymer Light‐Emitting Diodes by Photoreaction

Summary: The photo‐crosslinking of carbazole dendrimers was analyzed by UV and IR spectroscopic methods. Photoirradiation results in the formation of a film that is insoluble in toluene and benzene. Time‐of‐flight mass spectrometry studies revealed that the photoirradiation lead to an oligomerization of the dendrimer through crosslinking. The resulting insoluble dendrimer film could be applied as a hole‐transport layer in efficient polymer electroluminescence devices (PLEDs).

Luminance‐voltage characteristics for PLEDs wherein PEDOT:PSS and CbzG3 complex with SnCl₂ were employed as the hole transport layer (ITO/HTL/EML/Ca/Ag).     

White Polymer Light‐Emitting Diodes Based on Star‐Shaped Polymers with an Orange Dendritic Phosphorescent Core

A series of new star‐shaped polymers with a triphenylamine‐based iridium(III) dendritic complex as the orange‐emitting core and poly(9,9‐dihexylfluorene) (PFH) chains as the blue‐emitting arms is developed towards white polymer light‐emitting diodes (WPLEDs). By fine‐tuning the content of the orange phosphor, partial energy transfer and charge trapping from the blue backbone to the orange core is realized to achieve white light emission. Single‐layer WPLEDs with the configuration of ITO (indium‐tin oxide)/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer/CsF/Al exhibit a maximum current efficiency of 1.69 cd A⁻¹ and CIE coordinates of (0.35, 0.33), which is very close to the pure white‐light point of (0.33, 0.33). To the best of our knowledge, this is the first report on star‐shaped white‐emitting single polymers that simultaneously consist of fluorescent and phosphorescent species.

     

Organic Light Emitting Diodes with Lithium Contained Alq3 as Electron Injection Layer

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｏｒｇａｎｉｃｌｉｇｈｔｅｍｉｔｔｉｎｇｄｉｏｄｅ(ＯＬＥＤ) ,ｓｏｍｅｍｅｔａｌｓｗｉｔｈｌｏｗｗｏｒｋｆｕｎｃｔｉｏｎ ,ｓｕｃｈａｓａｌｌｏｙｏｆｍａｇ ｎｅｓｉｕｍａｎｄｓｉｌｖｅｒ(Ｍｇ∶Ａｇ) [1] ａｎｄａｌｕｍｉｎｉｕｍ[2 ] ,ａｒｅｕｓｅｄａｓｔｈｅｅｌｅｃｔｒｏｎｉｎｊｅｃｔｉｏｎｃａｔｈｏｄｅｓ .ＩｎＭｇ∶Ａｇａｌ ｌｏｙｓｉｌｖｅｒｉｓｕｓｅｄｔｏｐｒｏｔｅｃｔｍａｇｎｅｓｉｕｍｆｒｏｍｔｈｅｒｅａｃ ｔｉｏｎｏｆｍａｇｎｅｓｉｕｍｗｉｔｈｏｘｙｇｅｎａｎｄ…     

An Ionic Molecular Glass as Electron Injection Layer for Efficient Polymer Light‐Emitting Diode

An ionic molecular glass based on a dendronized monoammonium salt has been facilely synthesized and utilized as an interfacial electron‐injection layer in a light‐emitting diode (LED). The characterization of a yellow‐green LED that involves an Al cathode and a thin layer of the new compound spin cast from a methanol solution has shown device performances comparable to those obtained with a Ba/Al cathode. Photovoltaic measurements under white light irradiation reveal that a thin layer of the new compound can significantly increase the built‐in potential and thus facilitate electron injection from an Al cathode. Furthermore, it is interesting to observe that the new ionic salt could undergo reorganization on the emissive conjugated polymer layer, which leads to the formation of nearly uniform nanoaggregates.

     

A Facile Method for Controlling the Molecular Weight of Hyperbranched Light‐Emitting Polymers

Summary: Two series of hyperbranched conjugated polymers were synthesized via an A₃ + B₂ type Wittig reaction. The molecular weights of the polymers were successfully tuned by simply changing the feed ratio of the monomers. Polymers with higher molecular weights presented more efficient photoluminescence, higher thermal stability and higher performance of LEDs.

     

Triarylboron‐Based Fluorescent Organic Light‐Emitting Diodes with External Quantum Efficiencies Exceeding 20 %

Triarylboron compounds have attracted much attention, and found wide use as functional materials because of their electron‐accepting properties arising from the vacant p orbitals on the boron atoms. In this study, we design and synthesize new donor–acceptor triarylboron emitters that show thermally activated delayed fluorescence. These emitters display sky‐blue to green emission and high photoluminescence quantum yields of 87–100 % in host matrices. Organic light‐emitting diodes using these emitting molecules as dopants exhibit high external quantum efficiencies of 14.0–22.8 %, which originate from efficient up‐conversion from triplet to singlet states and subsequent efficient radiative decay from singlet to ground states.     

Organic Light‐Emitting Diodes Using a Neutral π Radical as Emitter: The Emission from a Doublet

Triplet harvesting is a main challenge in organic light‐emitting devices (OLEDs), because the radiative decay of the triplet is spin‐forbidden. Here, we propose a new kind of OLED, in which an organic open‐shell molecule, (4‐N‐carbazolyl‐2,6‐dichlorophenyl)bis(2,4,6‐trichlorophenyl)methyl (TTM‐1Cz) radical, is used as an emitter, to circumvent the transition problem of triplet. For TTM‐1Cz, there is only one unpaired electron in the highest singly occupied molecular orbital (SOMO). When this electron is excited to the lowest singly unoccupied molecular orbital (SUMO), the SOMO is empty. Thus, transition back of the excited electron to the SOMO is totally spin‐allowed. Spectral analysis showed that electroluminescence of the OLED originated from the electron transition between SUMO and SOMO. The magneto‐electroluminescence measurements revealed that the spin configuration of the excited state of TTM‐1Cz is a doublet. Our results pave a new way to obtain 100 % internal quantum efficiency of OLEDs.     

2,5‐Difluorenyl‐Substituted Siloles for the Fabrication of High‐Performance Yellow Organic Light‐Emitting Diodes

2,3,4,5‐Tetraarylsiloles are a class of important luminogenic materials with efficient solid‐state emission and excellent electron‐transport capacity. However, those exhibiting outstanding electroluminescence properties are still rare. In this work, bulky 9,9‐dimethylfluorenyl, 9,9‐diphenylfluorenyl, and 9,9′‐spirobifluorenyl substituents were introduced into the 2,5‐positions of silole rings. The resulting 2,5‐difluorenyl‐substituted siloles are thermally stable and have low‐lying LUMO energy levels. Crystallographic analysis revealed that intramolecular π–π interactions are prone to form between 9,9′‐spirobifluorene units and phenyl rings at the 3,4‐positions of the silole ring. In the solution state, these new siloles show weak blue and green emission bands, arising from the fluorenyl groups and silole rings with a certain extension of π conjugation, respectively. With increasing substituent volume, intramolecular rotation is decreased, and thus the emissions of the present siloles gradually improved and they showed higher fluorescence quantum yields (Φ_F=2.5–5.4 %) than 2,3,4,5‐tetraphenylsiloles. They are highly emissive in solid films, with dominant green to yellow emissions and good solid‐state Φ_F values (75–88 %). Efficient organic light‐emitting diodes were fabricated by adopting them as host emitters and gave high luminance, current efficiency, and power efficiency of up to 44 100 cd m^?2, 18.3 cd A^?1, and 15.7 lm W^?1, respectively. Notably, a maximum external quantum efficiency of 5.5 % was achieved in an optimized device.