Anthracene derivatives with strong spin-orbit coupling and efficient high-lying reverse intersystem crossing beyond the El-Sayed rule.

The attention to materials with hot exciton channel and triplet-triplet fusion (TTF) mediated high-lying reverse intersystem crossing (hRISC) has been raised for their ability to convert non-emissive 'dark' triplets into radiative singlet excitons. This spin conversion process results in high exciton utilization efficiency (EUE) that exceeds the theoretical limits. Notably, it is known that such spin conversion processes from the high-lying excited triplet to the singlet state are facilitated by the orthogonal orbital transition effect governed by the El-Sayed's rule. In this study, an anthracene derivative with indenoquinoline substituent 7,7-dimethyl-9-(10-(4-(naphthalen-1-yl)phenyl)anthracen-9-yl)-7H-indeno[1,2-f]quinoline (2MIQ-NPA) was synthesized and analyzed to investigate whether the hRISC process occurs in these molecules, even when the El-Sayed's rule is not followed. The hRISC channels of the emitter were fully unraveled through DFT calculations and experiments, which were quantitatively subdivided using transient electroluminescence measurements. The results showed that 2MIQ-NPA, which does not follow the El-Sayed's rule and has a relatively strong spin-orbit coupling matrix element of 0.116 cm-1 between the high-lying triplet state of T4 and the lowest singlet state of S1, effectively converted triplet excitons into singlet excitons with an EUE of 64.3%, contributed by a direct hot exciton channel of 19.2% and a TTF-mediated hot exciton channel of 15.1%. Despite the low outcoupling efficiency, the non-doped device with 2MIQ-NPA achieved an excellent device performance with an external quantum efficiency of 7.0%.

Oxygen Plasma Treatment of Rear Multilayered Graphene: A Potential Top Electrode for Transparent Organic Light-Emitting Diodes.

One of the core technologies of transparent organic light-emitting diodes (TOLEDs) is to develop an optically transparent and high electrical conductivity electrode so that light generated inside the device can efficiently escape into the air through the electrodes. We recently reported in TOLED research that two flipping processes are required to dry-transfer the front multilayered graphene (MLG) to the top electrode, while the rear MLG requires one dry transfer process. As the transfer process increases, the electrical properties of graphene deteriorate due to physical damage and contamination by impurities. At the charge-injecting layer/MLG interface constituting the TOLED, the rear MLG electrode has significantly lower charge injection characteristics than the front MLG electrode, so it is very important to improve the electrical characteristics of the rear MLG. In this paper, we report that the light-emitting properties of the TOLED are improved when an oxygen plasma-treated rear MLG is used as the top electrode, as compared with untreated rear MLG. In addition, the fabricated device exhibits a transmittance of 74-75% at the maximum electroluminescence wavelength, and the uniformity of transmittance and reflectance is more constant at a wavelength of 400-700 nm than in a device with a metal electrode. Finally, near-edge X-ray absorption fine structure spectroscopic analysis proves that the MLG crystallinity is improved with the removal of impurities on the surface after oxygen plasma treatment.

Enhanced Electron Heat Conduction in TaS3 1D Metal Wire.

The 1D wire TaS3 exhibits metallic behavior at room temperature but changes into a semiconductor below the Peierls transition temperature (Tp), near 210 K. Using the 3ω method, we measured the thermal conductivity κ of TaS3 as a function of temperature. Electrons dominate the heat conduction of a metal. The Wiedemann-Franz law states that the thermal conductivity κ of a metal is proportional to the electrical conductivity σ with a proportional coefficient of L0, known as the Lorenz number-that is, κ=σLoT. Our characterization of the thermal conductivity of metallic TaS3 reveals that, at a given temperature T, the thermal conductivity κ is much higher than the value estimated in the Wiedemann-Franz (W-F) law. The thermal conductivity of metallic TaS3 was approximately 12 times larger than predicted by W-F law, implying L=12L0. This result implies the possibility of an existing heat conduction path that the Sommerfeld theory cannot account for.

Unraveled Face-Dependent Effects of Multilayered Graphene Embedded in Transparent Organic Light-Emitting Diodes.

With increasing demand for transparent conducting electrodes, graphene has attracted considerable attention, owing to its high electrical conductivity, high transmittance, low reflectance, flexibility, and tunable work function. Two faces of single-layer graphene are indistinguishable in its nature, and this idea has not been doubted even in multilayered graphene (MLG) because it is difficult to separately characterize the front (first-born) and the rear face (last-born) of MLG by using conventional analysis tools, such as Raman and ultraviolet spectroscopy, scanning probe microscopy, and sheet resistance. In this paper, we report the striking difference of the emission pattern and performance of transparent organic light-emitting diodes (OLEDs) depending on the adopted face of MLG and show the resolved chemical and physical states of both faces by using depth-selected absorption spectroscopy. Our results strongly support that the interface property between two different materials rules over the bulk property in the driving performance of OLEDs.

Crystallization-assisted nano-lens array fabrication for highly efficient and color stable organic light emitting diodes.

To date, all deposition equipment has been developed to produce planar films. Thus lens arrays with a lens diameter of <1 mm have been manufactured by combining deposition with other technologies, such as masks, surface treatment, molding etc. Furthermore, a nano-lens array (NLA) with a sufficiently small lens diameter (<1 µm) is necessary to avoid image quality degradation in high resolution displays. In this study, an organic NLA made using a conventional deposition technique - without combining with other techniques - is reported. Very interestingly, grazing-incidence small-angle X-ray scattering (GI-SAXS) experiments indicate that the NLA is formed by the crystallization of organic molecules and the resulting increase in surface tension. The lens diameter can be tuned for use with any kind of light by controlling the process parameters. As an example of their potential applications, we use NLAs as a light extraction film for organic light emitting diodes (OLEDs). The NLA is integrated by directly depositing it on the top electrode of a collection of OLEDs. This is a dry process, meaning that it is fully compatible with the current OLED production process. Devices with NLAs exhibited a light extraction efficiency 1.5 times higher than devices without, which corresponds well with simulation results. The simulations show that this high efficiency is due to the reduction of the guided modes by scattering at the NLA. The NLAs also reduce image blurring, indicating that they increase color stability.

A Light Scattering Layer for Internal Light Extraction of Organic Light-Emitting Diodes Based on Silver Nanowires.

We propose and fabricate a random light scattering layer for light extraction in organic light-emitting diodes (OLEDs) with silver nanodots, which were obtained by melting silver nanowires. The OLED with the light scattering layer as an internal light extraction structure was enhanced by 49.1% for the integrated external quantum efficiency (EQE). When a wrinkle structure is simultaneously used for an external light extraction structure, the total enhancement of the integrated EQE was 65.3%. The EQE is maximized to 65.3% at a current level of 2.0 mA/cm(2). By applying an internal light scattering layer and wrinkle structure to an OLED, the variance in the emission spectra was negligible over a broad viewing angle. Power mode analyses with finite difference time domain (FDTD) simulations revealed that the use of a scattering layer effectively reduced the waveguiding mode while introducing non-negligible absorption. Our method offers an effective yet simple approach to achieve both efficiency enhancement and spectral stability for a wide range of OLED applications.

Simultaneously enhanced device efficiency, stabilized chromaticity of organic light emitting diodes with lambertian emission characteristic by random convex lenses.

An optical functional film applicable to various lighting devices is demonstrated in this study. The phase separation of two immiscible polymers in a common solvent was used to fabricate the film. In this paper, a self-organized lens-like structure is realized in this manner with optical OLED functional film. For an OLED, there are a few optical drawbacks, including light confinement or viewing angle distortion. By applying the optical film to an OLED, the angular spectra distortion resulting from the designed organic stack which produced the highest efficiency was successfully stabilized, simultaneously enhancing the efficiency of the OLED. We prove the effect of the film on the efficiency of OLEDs through an optical simulation. With the capability to overcome the main drawbacks of OLEDs, we contend that the proposed film can be applied to various lighting devices.

Fluorination of aluminum oxide gate dielectrics using fluorine neutral/ion beams.

The effect of the fluorination of aluminum oxide (Al2O3) in an oxide-nitride-aluminum oxide (SiO2-Si3N4-Al2O3, ONA) layer through fluorine (F) ion and neutral-beam treatments on the characteristics of the ONA layer was investigated to study the effect of charge-related damage during F ion beam treatment. The treatment with an F beam at approximately 10 eV energy produced an about-5-nm-thick fluorinated alumina layer by replacing the aluminum-oxygn (Al-O) bonding with Al-F bonding for both the F neutral-beam and F ion beam treatments. Moreover, no significant differences in the physical and chemical properties of the ONA layers treated with the two beams were observed. When the electrical characteristics of the metal-oxide-semiconductor (MOS) devices were compared, however, the lowest leakage current and highest memory window characteristics were observed in the MOS device fabricated with an F neutral beam, due to the Al-F layer formed on the Al2O3 surface. In the case of the MOS device fabricated with the F-ion-beam-treated ONA layer, however, lower electrical characteristics were observed compared to the MOS device fabricated with the F-neutral-beam-treated ONA layer, possibly due to the charge-related damage that occurred during the F ion beam treatment, even though the memory characteristics were improved compared to the reference due to the Al-F layer formed on the Al2O3 surface.

Chemical and electronic properties of Ba/bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) interfaces for organic light-emitting diodes.

The chemistry, electronic structure, and electron-injecting characteristics at the interfaces that were formed between bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (BAlq) and barium (Ba) were investigated using ultraviolet photoemission spectroscopy, near-edge X-ray absorption fine structure spectroscopy, X-ray photoemission spectroscopy, and current-voltage-luminance measurements. The device performance of organic light-emitting diodes (OLEDs), which have a glass/ITO/MoO3/2-TNATA/NPB/BAlq/Ba/Au structure, was significantly improved by inserting a Ba coverage (thetaBa) of 0.2 nm between BAlq and the cathode. For thetaBa'S that were thicker than 0.2 nm, however, even though the electron-injecting barrier heights at the Ba-on-BAlq interfaces were all 0.1 eV, the device performance of the OLEDs with Ba at the interface was degraded with increasing thetaBa. This result indicates that the device performance is largely dependent on the interfacial chemical degradation of the BAlq molecule itself, rather than the electron-injecting barrier height that is determined by the width and chemical structure of the interface, and the formation of barium-induced new gap states at the Ba-on-BAlq interface.

Device characteristics of organic light-emitting diodes based on electronic structure of the Ba-doped Alq3 layer.

Organic light-emitting diodes (OLEDs) with a Ba-doped tris(8-quinolinolato)aluminum(III) (Alq3) layer were fabricated to reduce the barrier height for electron injection and to improve the electron conductivity. In the OLED consisting of glass/ITO/4,4',4"-tris[2-naphthylphenyl-1-phenylamino]triphenylamine (2-TNATA, 30 nm)/4,4'-bis[N-(1-napthyl)-N-phenyl-amino]-biphenyl (NPB, 18 nm)/Alq3 (42 nm)/Ba-doped Alq3 (20 nm, x%: x = 0, 10, 25, and 50)/Al (100 nm), the device with the Alq3 layer doped with 10% Ba showed the highest light out-coupling characteristic. However, as the Ba dopant concentration was increased from 25% to 50%, this device characteristic was largely reduced. The characteristics of these devices were interpreted on the basis of the chemical reaction between Ba and Alq3 and the electron injection property by analyzing the electronic structure of the Ba-doped Alq3 layer. At a low Ba doping of 10%, mainly the Alq3 radical anion species was formed. In addition, the barrier height for electron injection in this layer was decreased to 0.6 eV, when compared to the pristine Alq3 layer. At a high Ba doping of 50%, the Alq3 molecules were severely decomposed. When the Ba dopant concentration was changed, the light-emitting characteristics of the devices were well coincided with the formation mechanism of Alq3 radical anion and Alq3 decomposition species.

Complete mitochondrial genome of a troglobite millipede Antrokoreana gracilipes (Diplopoda, Juliformia, Julida), and juliformian phylogeny.

The complete mitochondrial genome of a troglobite millipede Antrokoreana gracilipes (Verhoeff, 1938) (Dipolopoda, Juliformia, Julida) was sequenced and characterized. The genome (14,747 bp) contains 37 genes (2 ribosomal RNA genes, 22 transfer RNA genes and 13 protein-encoding genes) and two large non-coding regions (225 bp and 31 bp), as previously reported for two diplopods, Narceus annularus (order Spirobolida) and Thyropygus sp. (order Spirostreptida). The A + T content of the genome is 62.1% and four tRNAs (tRNA(Ser(AGN)), tRNA(Cys), tRNA(Ile) and tRNA(Met)) have unusual and unstable secondary structures. Whereas Narceus and Thyropygus have identical gene arrangements, the tRNA(Thr) and tRNA(Trp) of Antrokoreana differ from them in their orientations and/or positions. This suggests that the Spirobolida and Spirostreptida are more closely related to each other than to the Dipolopoda. Three scenarios are proposed to account for the unique gene arrangement of Antrokoreana. The data also imply that the Duplication and Nonrandom Loss (DNL) model is applicable to the order Julida. Bayesian inference (BI) and maximum likelihood (ML) analyses using amino acid sequences deduced from the 12 mitochondrial protein-encoding genes (excluding ATP8) support the view that the three juliformian members are monophyletic (BI 100%; ML 100%), that Thyropygus (Spirostreptida) and Narceus (Spirobolida) are clustered together (BI 100%; ML 83%), and that Antrokoreana (Julida) is a sister of the two. However, due to conflict with previous reports using cladistic approaches based on morphological characteristics, further studies are needed to confirm the close relationship between Spirostreptida and Spirobolida.

The complete mitochondrial genome of Pollicipes mitella (Crustacea, Maxillopoda, Cirripedia): non-monophylies of maxillopoda and crustacea.

The whole mitochondrial genome (14,915 nt) of Pollicipes mitella (Crustacea, Maxillopoda, Cirripedia, Thoracica) was sequenced and characterized. It is the shortest of the 31 completely sequenced crustacean mitochondrial genomes, with the exception of a copepod Tigriopus japonicus (14,628 nt). It consists of the usual 13 protein-coding genes, 22 tRNA genes, 2 rRNA genes, and 1 relatively short non-coding region (294 nt). The thoracican cirripeds apart from Megabalanus volcano have the same arrangement of protein-coding genes as Limulus polypemus, but there are frequent tRNA gene translocations (at least 8). Some interesting translocation features that may be specific to the thoracican cirriped lineage are as follows: 1) trnK-trnQ lies between the control region and trnI, 2) trnA-trnE lies between trnN and trnS1, 3) trnP lies between ND4L and trnT, and 4) trnY-trnC lies between trnS2 and ND1. In P. mitella there are two trnL genes (L1 and L2) in the typical crustacean positions (ND1-L1-LrRNA and CO1-L2-CO2). The present result is compared and discussed with the other three cirriped mitochondrial genomes from one pedunculate (Pollicipes polymerus) and two sessiles (Tetraclita japonica and M. volcano) published so far. Mitochondrial protein phylogenies reconstructed by the BI and ML algorithms show that the thoracican Cirripedia is monophyletic (BPP 100/BP 100) and associated with Remipedia (BPP 98/BP 35). In addition, Oligostraca, including Ostracoda, Branchiura, and Pentastomida, is a monophyletic group (BPP 99/BP 68), and is basal to all the other examined arthropods. Remipedia + Cirripedia appears as an independent lineage within Arthropoda, apart from Thoracopoda (Malacostraca, Branchiopda, and Cephalocarida). The Thoracopoda is paraphyletic to Hexapoda. The present result suggests that the monophylies of Crustacea and Maxillopoda should be reconsidered.