Improved red dopants for organic electroluminescent devices

A t-butyl substituted red fluorescent dye, 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB), has been found to be an excellent dopant in AIQ₃ which produces a highly efficient organic EL device with improved red chromaticity. Unlike 4-(dicyanomethylene)-2-methyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJT), DCJTB can be synthesized in a pure form directly from the unsymmetrical 4-(dicyanomethylene)-2-(t-butyl)-6-methyl-4H-pyran without the contamination of the non-fluorescent bis-condensation byproduct which is prevalent in the DCJT preparation. Both photoluminescence and electroluminescence in the solid films of DCJTB in AlQ₃ are modestly enhanced by the extra t-butyl substitution as a result of a reduction in the effect of concentration quenching. The operation stability of the DCJTB doped EL device is superior, having a half-life of over 5,000 h driven at an initial brightness > 400 cd/m².     

Dispirofluorene-indenofluorene derivatives as new building blocks for blue organic electroluminescent devices and electroactive polymers

A series of new dispiro[fluorene-9',6,9',12-indeno[1,2b]fluorenes] (DSF-IFs) has been synthesised. These new building blocks for blue-light-emitting devices and electroactive polymers combine indenofluorene (IF) and spirobifluorene (SBF) properties. We report here our synthetic investigations towards these new structures and their thermal, structural, photophysical and electrochemical properties. These properties have been compared to those of IF and SBF. We also report the anodic oxidation of DSF-IFs that leads to the formation of non-soluble transparent three-dimensional polymers. The structural and electrochemical behaviour of these polymers has been studied. The first application of these building blocks as new blue-light-emitting materials in organic light-emitting diodes (OLED) is also reported.     

Plasma-polymerized carbon disulfide films as a hole transport layer in organic electroluminescent devices

Electroluminescent devices were fabricated using plasma-polymerized carbon disulfide films, poly(CS₂), and tris(8-quinolinolato)aluminum(III) complex, Alq, as the hole transport layer and the emitting layer, respectively. A cell structure of glass substrate/indium–tin–oxide/poly(CS₂/Alq/Mg/Ag) was employed. Smooth hole injection from the electrode through the poly(CS₂) layer and concomitant electroluminescence from the Alq layer were observed. Green emission with a luminance of 250 cd/m² was achieved at a drive voltage of 14 V.     

Synthesis and properties of novel hole transport materials for electroluminescent devices

We synthesized low molecular weight triphenyldiamines (TPDs), novel 1,3,5-tris(diarylamino)benzenes (TDABs), polymeric triphenyldiamines and insoluble triphenylamine networks based on tris(4-ethynylphenyl)amine as hole transport materials for electroluminescent displays. The HOMO energy values as determined from cyclic voltammetry measurements for TPDs and TDABs are between −4.97 and −5.16 eV. By using a polymeric TPD as hole transport layer and tris(8-quinolinolato) aluminium as emitter, LEDs with an onset voltage of 3V and a luminance up to 900 cd/m² were obtained under ambient conditions.     

Organic electroluminescent devices using organosilicon polymers containing phenylene or diethynylanthracene units

Double‐layer electroluminescent (EL) devices composed of an alternating polymer with mono‐, di‐, or tri‐silanylene and phenylene units, [(Si R) _m (C₆H₄)] _n (R = alkyl, m = 1–3) as a hole‐transporting layer, and tris(8‐quinolinolato)­aluminium(III) complex (Alq) as an electron‐transporting–emitting layer were fabricated. The longer silanylene chain lengths in the polymer, on going from m = 1 to m = 2 and 3, result in better electrical properties for the EL devices, implying that the σ–π conjugation in the polymers plays an important role in the hole‐transporting properties, including the hole‐injection efficiency from an anode. This is in marked contrast to the improved hole‐transporting properties that occur in response to reducing the silanylene chain length of silanylene‐diethynylanthracene polymers previously reported. The UV absorption maxima of silanylene‐phenylene polymers shift to longer wavelengths with increasing m, and their oxidation peak potentials in cyclic voltammograms shift to lower potential with increasing m, in accordance with the improved electrical properties of the device that are observed with the polymers containing the longer silanylene chain. A triple‐layer EL device with a hole‐transporting layer of monosilanylene‐diethynylanthracene polymer, an electron‐transporting–emitting layer of Alq, and an electron‐blocking layer of N,N′‐diphenyl‐N,N′‐bis(3‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine (TPD) exhibited a maximum efficiency of 1.0 lm W⁻¹ and a maximum luminance of 14750 cd m⁻², both of which are much higher than the values obtained from a conventional EL device with TPD/Alq. Copyright © 1999 John Wiley & Sons, Ltd.     

Charge transport and structure in semimetallic polymers

Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low‐cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi‐metallic conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm²/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X‐ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer‐based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 97–104     

Organic electroluminescent devices with molecularly doped polymers and anode interface phthalocyanine layer

We studied the properties of organic electroluminescent devices using molecularly doped polymers as a hole transport layer and having a metal-free phthalocyanine (H₂Pc) layer between anode and hole transport layer. A vacuum-deposited H₂Pc metastable layer was converted to a more stable microcrystalline layer by dichloromethane solvent treatment. The devices exhibited good current–voltage and luminance properties. Because the activation energy of carrier transport for the devices with H₂Pc was almost the same as that for the devices without it, it is considered that the H₂Pc layer in this device is electrically inert. This means that improved contact efficiency may be obtained at the anode interface due to the introduction of the H₂Pc layer. © 1997 John Wiley & Sons, Ltd.     

Ab initio study of phosphorescent emitters based on rare-earth complexes with organic ligands for organic electroluminescent devices

An ab initio approach is developed for calculation of low-lying excited states in Ln(3+) complexes with organic ligands. The energies of the ground and excited states are calculated using the XMCQDPT2/CASSCF approximation; the 4f electrons of the Ln(3+) ion are included in the core, and the effects of the core electrons are described by scalar quasirelativistic 4f-in-core pseudopotentials. The geometries of the complexes in the ground and triplet excited states are fully optimized at the CASSCF level, and the resulting excited states have been found to be localized on one of the ligands. The efficiency of ligand-to-lanthanide energy transfer is assessed based on the relative energies of the triplet excited states localized on the organic ligands with respect to the receiving and emitting levels of the Ln(3+) ion. It is shown that ligand relaxation in the excited state should be properly taken into account in order to adequately describe energy transfer in the complexes. It is demonstrated that the efficiency of antenna ligands for lanthanide complexes used as phosphorescent emitters in organic light-emitting devices can be reasonably predicted using the procedure suggested in this work. Hence, the best antenna ligands can be selected in silico based on theoretical calculations of ligand-localized excited energy levels.     

Conjugated and electroluminescent polymers

Several advances were reported in the field of conjugated polymer semiconductors over the last year. Major breakthroughs relate to the achievement of high electroluminescence efficiency via exploitation of phosphorescence, of high efficiency photovoltaic cells, and of a better understanding of the properties of charged and neutral excitations in this class of unconventional semiconductors.     

分子尺度电致发光器件

近年来,有机单分子电致发光研究在材料和器件方面取得了突破,是分子电子学新兴的研究方向之一。本文综述了扫描隧道显微镜法、纳米间隙电极法等测量单分子尺度电致发光的研究进展。根据电致发光谱图,可以确定分子器件的发光类型,并得到单个分子的指纹信息。     

Thermal stability of organic electroluminescent devices fabricated using novel charge transporting materials

Novel hole and electron transporting materials have been synthesized to improve the thermal stability of organic electroluminescent (EL) devices. Molecular structures of such hole and electron transporting materials were designed based on triphenylamine (TPA) and oxadiazole (OXD) moieties, respectively. It has been found that the resulting materials have high glass transition temperatures (Tg) over 100°C and the vacuum-deposited thin films are significantly thermally stable. For the two-layer EL devices using the novel hole transporting materials and the typical emitting material, tris(8-quinolinolato) aluminum, the thermal stability has been clearly seen to depend on the Tg of the hole transporting material; excellent thermal stability was achieved. For the three-layer EL device using the novel electron transporting material, good emission efficiency and good stability were achieved. The electron transporting materials have been also applied to the polymeric system with polyvinylcarbazole matrix.     

Carbazole dendronised triphenylamines as solution processed high Tg amorphous hole-transporting materials for organic electroluminescent devices

Carbazole dendrimers up to 4th generation were synthesized. They showed significantly high T(g), amorphous and stable electrochemical properties, and great potential as solution processed hole-transporting materials for OLEDs. Alq3-based green devices exhibited high luminance efficiency and CIE coordinates of 4.45 cd A(-1) and (0.29, 0.53), respectively.     

An organic electroluminescent device with a molecularly doped polymer hole transport layer

Electroluminescent(EL) devices have been fabricated using four different polymers with different glass transition temperatures (T_g) dispersed with N,N′-bis-(3-methylphenyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (TPD) as a hole transport layer and tris(8-hydroxyquinoline) aluminum (Alq₃) as an emitting layer. It was found that the higher the T_g of the polymer, the longer the lifetime of the device. From observations of TPD-doped polymer films with optical microscope and atomic force microscope, dispersing TPD in the polymers was found to suppress the crystallization that causes the roughness of the film surface. It was also observed that the higher the T_g of the host polymers, the more difficult TPD crystallization was. The property of the EL device with polyethersulfone (PES) dispersed with TPD was also investigated. The lifetime of EL device with the TPD doped PES film was improved more than five times at a current density below 10 mA/cm² compared with the device with a conventional TPD hole transport layer. © 1997 John Wiley & Sons, Ltd.     

Charge recombination in organic photovoltaic devices with high open-circuit voltages

A detailed charge recombination mechanism is presented for organic photovoltaic devices with a high open-circuit voltage. In a binary blend comprised of polyfluorene copolymers, the performance-limiting process is found to be the efficient recombination of tightly bound charge pairs into neutral triplet excitons. We arrive at this conclusion using optical transient absorption (TA) spectroscopy with visible and IR probes and over seven decades of time resolution. By resolving the polarization of the TA signal, we track the movement of polaronic states generated at the heterojunction not only in time but also in space. It is found that the photogenerated charge pairs are remarkably immobile at the heterojunction during their lifetime. The charge pairs are shown to be subject to efficient intersystem crossing and terminally recombine into F8BT triplet excitons within approximately 40 ns. Long-range charge separation competes rather unfavorably with intersystem crossing--75% of all charge pairs decay into triplet excitons. Triplet exciton states are thermodynamically accessible in polymer solar cells with high open circuit voltage, and we therefore suggest this loss mechanism to be general. We discuss guidelines for the design of the next generation of organic photovoltaic materials where separating the metastable interfacial charge pairs within approximately 40 ns is paramount.     

Thieno[3,2-b]thiophene-diketopyrrolopyrrole-containing polymers for high-performance organic field-effect transistors and organic photovoltaic devices

We report the synthesis and polymerization of a novel thieno[3,2-b]thiophene-diketopyrrolopyrrole-based monomer. Copolymerization with thiophene afforded a polymer with a maximum hole mobility of 1.95 cm(2) V(-1) s(-1), which is the highest mobility from a polymer-based OFET reported to date. Bulk-heterojunction solar cells comprising this polymer and PC(71)BM gave a power conversion efficiency of 5.4%.     

Infrared spectroscopy of electroluminescent conjugated polymers

The infrared spectra of the light-emitting diodes and the metal-insulator-semiconductor devices based on a poly(p-phenylenevinylene) derivative MEH-PPV have been measured in situ with a reflection configuration. The voltage-induced infrared spectra of these devices have been measured by the FT-IR difference-spectrum method. The observed bands have been attributed to the carriers injected into the polymer layers. The observation of positive carriers in the polymer light-emitting diode is probably related to the predominance of injected positive carriers, which is one of the factors in the low efficiency of the polymer light-emitting diode. In situ infrared reflective absorption measurements provide the information about injected carriers, which play a central role in the properties and the functions of polymer electronic devices.     

Photonic materials for electroluminescent,laser and photovoltaic devices

This article presents an overview of the work that has been done recently in our laboratory concerning the development and application of new conjugated materials with tunable properties. We have designed polymers containing oligo(phenylenevinylene)-type conjugated segments of well defined size and structure isolated either in their main-chain or in the side-chains. Model oligomers corresponding to the conjugated parts of the polymers have also been studied. We show how these materials perform in light-emission applications (light-emitting diodes, lasers) or photovoltaic cells.     

Charge transport in luminescent polymers studied by in situ fluorescence spectroscopy

Modulation of the photoluminescence of poly-[2,7-(fluorene)-1,4-(phenylene)] can be attained by reversible electrochemical modification of the conjugated chain (p- or n-doping). Controlled injection of charge quenches the fluorescent emission of the conjugated polymer. The injection of holes completely eliminates the emission, while the electrons only quench up to one-third of the initial fluorescence of the polymer. Analogous quenching effects have been previously reported for solid-state organoelectronic devices. Electrochemical Stern-Volmer plots permit the estimation of the relative mobility of charge carriers in the polymer layer. The mobility of holes is 1 order of magnitude higher that the mobility of electrons, as determined by this method.     

Tuning of metal work function with organic carboxylates and its application in top-emitting electroluminescent devices

By fine-tuning of work functions and thus the hole-injection properties of Ag and Al anodes, an electroluminescent device was achieved by using various self-assembled monolayers of organic carboxylate on the electrode surfaces. The IR spectra evidenced different binding behaviors of the carboxylates on Ag and Al. A correlation between the change in work function with the effective dipole moment along the surface normal and the currents in the hole-only devices was observed. These self-assembled-monolayer-modified metals were used as anodes in the fabrication of top-emitting organic light-emitting diodes (TOLEDs). The TOLED with the Ag anode modified by the perfluoroalkanoate exhibited a luminous efficiency as high as 18 cdA(-1), superior to that of the Ag2O-based device. With Al as the anode, the highest luminous efficiency was merely 6 cdA(-1) and decayed rapidly. The poorer EL property and performance of Al-based TOLEDs could be attributed to the weaker ionic bindings of carboxylates on Al and the weaker microcavity effect resulting from the inferior reflectivity of Al as compared to Ag.