Suppression of the plasmon-quenching effect on light amplification in 20-µm-diameter plasmonic whispering gallery mode resonators fabricated from bowl-shaped organic/metal thin films.

Bowl-shaped plasmonic whispering gallery mode (WGM) resonators were fabricated from a 10-nm-thick metal (Al, Ag, or Au) plasmonic layer that was covered with a 100-nm-thick 4,4'-bis(N-carbazolyl)-1,1'-biphenyl spacer layer and a 250-nm-thick 2,7-bis[9,9-di(4-methylphenyl)-fluoren-2-yl]-9,9-di(4-methylphenyl)fluorene light-emitting layer; the layer structure was grown on a 20-µm-diameter silica microsphere. When compared with a reference structure without the plasmonic layer, the resonators, which included either Al or Ag, showed almost the same threshold excitation intensities for generation of amplified spontaneous emission (ASE). This result indicates that the ease of light amplification in the plasmonic resonators was comparable to that in the reference structure. Excitons that exist in the vicinity of metal thin films are generally easy to quench because propagating surface plasmon polaritons (SPPs) absorb the exciton energy. Therefore, the observed comparability demonstrates that the plasmonic WGM resonators overcome this quenching effect on ASE via localization of the SPPs in the vicinity of the excitons.

Device parameter to evaluate exciton energy transfer in organic whispering-gallery-mode microresonators and its dependence on the amplified spontaneous emission threshold.

Exciton energy transfer in organic whispering-gallery-mode (WGM) resonators and its effect on the amplified spontaneous emission (ASE) threshold have been investigated using the stilbene-based energy donor 4,4'-bis[(N-carbazole)styryl]biphenyl (BSB-Cz) and the coumarin-based energy acceptor 2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinolizino[9,9a,1gh]coumarin (C545T). Using the stacked-layer structure of BSB-Cz/C545T/BSB-Cz, we fabricated bowl-shaped microresonators on silica microspheres with a total thickness of 250 nm fixing the thickness of the C545T layer to 1 nm. The ASE threshold depended on the thicknesses of the top and bottom BSB-Cz layers, which affect the magnitude of the energy transfer. To assess the relationship between the ASE threshold and energy transfer, we developed a device parameter to evaluate the magnitude of the energy transfer by formulating the rate equations. We found that ASE easily occurs under the condition that the C545T molecules become unable to accept energy from the BSB-Cz excitons owing to the high exciton density of C545T, and that the ASE threshold decreases with decreasing device parameter. The device parameter is useful for optimizing microresonator structures in multi-component organic WGM resonators that utilize energy transfer.

Surface Segregation of a Star-Shaped Polyhedral Oligomeric Silsesquioxane in a Polymer Matrix.

A simple way to control only the surface properties of polymer materials, without changing the bulk properties, has long been desired. The segregation behavior when a component with a tiny amount fed into the matrix is thermodynamically enriched at the surface is one of the candidate methods. This capability was examined herein by focusing on a star-shaped polyhedral oligomeric silsesquioxane (s-POSS), where the central POSS unit is tethered to eight isobutyl-substituted POSS cages as a surface modifier. X-ray photoelectron spectroscopy revealed that the surface of a film of poly(methyl methacrylate) (PMMA) was almost completely covered with POSS units by adding just 5 wt % s-POSS to it. The segregated POSS dramatically altered the physical properties such as molecular motion and the mechanical and dielectric responses at the surface of the PMMA film. These findings make it clear that s-POSS is an excellent surface modifier for glassy polymers.

High performance from extraordinarily thick organic light-emitting diodes.

Organic light-emitting diode (OLED) technology is promising for applications in next-generation displays and lighting. However, it is difficult-especially in large-area mass production-to cover a large substrate uniformly with organic layers, and variations in thickness cause the formation of shunting paths between electrodes1,2, thereby lowering device production yield. To overcome this issue, thicker organic transport layers are desirable because they can cover particles and residue on substrates, but increasing their thickness increases the driving voltage because of the intrinsically low charge-carrier mobilities of organics. Chemical doping of organic layers increases their electrical conductivity and enables fabrication of thicker OLEDs3,4, but additional absorption bands originating from charge transfer appear5, reducing electroluminescence efficiency because of light absorption. Thick OLEDs made with organic single crystals have been demonstrated6, but are not practical for mass production. Therefore, an alternative method of fabricating thicker OLEDs is needed. Here we show that extraordinarily thick OLEDs can be fabricated by using the organic-inorganic perovskite methylammonium lead chloride, CH3NH3PbCl3 (MAPbCl3), instead of organics as the transport layers. Because MAPbCl3 films have high carrier mobilities and are transparent to visible light, we were able to increase the total thickness of MAPbCl3 transport layers to 2,000 nanometres-more than ten times the thickness of standard OLEDs-without requiring high voltage or reducing either internal electroluminescence quantum efficiency or operational durability. These findings will contribute towards a higher production yield of high-quality OLEDs, which may be used for other organic devices, such as lasers, solar cells, memory devices and sensors.

Simple Molecular-Engineering Approach for Enhancing Orientation and Outcoupling Efficiency of Thermally Activated Delayed Fluorescent Emitters without Red-Shifting Emission.

The inclusion of a tetraphenylbenzene (4Ph) unit in thermally activated delayed fluorescence emitters is demonstrated as a novel strategy for greatly enhancing the horizontally oriented alignment of the emitters without shifting the emission spectrum to longer wavelengths. Doping of blue-emitting 4PhOXDDMAC or greenish-blue-emitting 4PhOXDPXZ into o-DiCbzBz host layers yielded much higher degrees of horizontally oriented alignment for the emitter (up to 92%) compared to those when the 4Ph unit was excluded (69 and 75%, respectively). The enhanced alignment results in high outcoupling efficiencies of 24 and 35% in organic light-emitting diodes based on 4PhOXDDMAC and 4PhOXDPXZ, respectively, and boosts the external quantum efficiencies to values (8.8 and 29.2%, respectively) that are higher than what would be expected for randomly oriented emitters (outcoupling efficiency of 20%). These enhancements are achieved while avoiding the redshift that often occurs using the common strategy of increasing molecular length and, thereby, conjugation, to increase orientation.

Enhanced Electroluminescence from Organic Light-Emitting Diodes with an Organic-Inorganic Perovskite Host Layer.

The development of host materials with high performance is essential for fabrication of efficient and stable organic light-emitting diodes (OLEDs). Although host materials used in OLEDs are typically organics, in this study, it is shown that the organic-inorganic perovskite CH3 NH3 PbCl3 (MAPbCl3 ) can be used as a host layer for OLEDs. Vacuum-evaporated MAPbCl3 films have a wide band gap of about 3 eV and very high and relatively balanced hole and electron mobilities, which are suitable for the host material. Photoluminescence and electroluminescence take place through energy transfer from MAPbCl3 to an organic emitter in films. Incorporation of an MAPbCl3 host layer into OLEDs leads to a reduction of driving voltage and enhancement of external quantum efficiency as compared to devices with a conventional organic host layer. Additionally, OLEDs with an MAPbCl3 host layer demonstrate very good operational stability under continuous current operation. These results can be extensively applied to organic- and perovskite-based optoelectronics.

Enhanced Electrical Properties and Air Stability of Amorphous Organic Thin Films by Engineering Film Density.

The influences of film density and molecular orientation on the carrier conduction and air stability of vacuum-deposited amorphous organic films of N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (α-NPD) were investigated. The substrate temperature (Tsub) during vacuum deposition had different effects on the film density and molecular orientation of α-NPD. Film density was a concave function of Tsub; maximum density was attained at Tsub = 270-300 K. α-NPD molecules were randomly oriented at Tsub = 342 K, and their horizontal orientation on the substrate became dominant as Tsub decreased. Hole current and air stability were clearly raised by increasing the film density by 1 to 2%; these effects were, respectively, attributed to enhanced carrier hopping between neighboring α-NPD molecules and suppressed penetration of oxygen and water. These results imply that increasing film density is more effective to enhance the electrical performance of organic thin-film devices with α-NPD films than control of molecular orientation.

Highly Efficient Thermally Activated Delayed Fluorescence from an Excited-State Intramolecular Proton Transfer System.

Thermally activated delayed fluorescence (TADF) materials have shown great potential for highly efficient organic light-emitting diodes (OLEDs). While the current molecular design of TADF materials primarily focuses on combining donor and acceptor units, we present a novel system based on the use of excited-state intramolecular proton transfer (ESIPT) to achieve efficient TADF without relying on the well-established donor-acceptor scheme. In an appropriately designed acridone-based compound with intramolecular hydrogen bonding, ESIPT leads to separation of the highest occupied and lowest unoccupied molecular orbitals, resulting in TADF emission with a photoluminescence quantum yield of nearly 60%. High external electroluminescence quantum efficiencies of up to 14% in OLEDs using this emitter prove that efficient triplet harvesting is possible with ESIPT-based TADF materials. This work will expand and accelerate the development of a wide variety of TADF materials for high performance OLEDs.

In-Plane Anisotropic Molecular Orientation of Pentafluorene and Its Application to Linearly Polarized Electroluminescence.

By preparing parallelly aligned 1.9-µm-high SiO2 microfluidic channels on an indium tin oxide substrate surface, the solution flow direction during spin-coating was controlled to be parallel to the grating. Using this technique, a pentafluorene-4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) binary solution in chloroform was spin-coated to embed a 40-50 nm-thick 10 wt %-pentafluorene:CBP thin film in the channels. In-plane polarized photoluminescence measurements revealed that the pentafluorene molecules tended to orient along the grating, demonstrating that one-dimensional fluid flow can control the in-plane molecular orientation. Furthermore, the dependences of the photoluminescence anisotropy on the spin speed and substrate material suggest that the velocity of the solution flow and/or its gradient in the vertical direction greatly affects the resulting orientation. This indicates that the mechanism behind the molecular orientation is related to stress such as the shear force. The effect of the solution flow on the molecular orientation was demonstrated even in organic light-emitting diodes (OLEDs). Linearly polarized electroluminescence was obtained by applying the in-plane orientation to OLEDs, and it was found that the dichroic ratio of the electroluminescence orthogonal (x) and parallel (y) to the grating is x/y = 0.75.

Dipole orientation analysis without optical simulation: application to thermally activated delayed fluorescence emitters doped in host matrix.

The dipole orientation of guest emitters doped into host matrices is usually investigated by angular dependent photoluminescence (PL) measurements, which acquire an out-of-plane PL radiation pattern of the guest-host thin films. The PL radiation patterns generated by these methods are typically analysed by optical simulations, which require expertise to perform and interpret in the simulation. In this paper, we developed a method to calculate an orientational order parameter S without the use of full optical simulations. The PL radiation pattern showed a peak intensity (I sp) in the emission direction tilted by 40°-60° from the normal of the thin film surface plane, indicating an inherent dipole orientation of the emitter. Thus, we directly correlated I sp with S. The S - I sp relation was found to depend on the film thickness (d) and refractive indices of the substrate (n sub) and the organic thin film (n org). Hence, S can be simply calculated with information of I sp, d, n sub, and n org. We applied our method to thermally activated delayed fluorescence materials, which are known to be highly efficient electroluminescence emitters. We evaluated S and found that the error of this method, compared with an optical simulation, was less than 0.05.

Blue organic light-emitting diodes realizing external quantum efficiency over 25% using thermally activated delayed fluorescence emitters.

Improving the performance of blue organic light-emitting diodes (OLEDs) is needed for full-colour flat-panel displays and solid-state lighting sources. The use of thermally activated delayed fluorescence (TADF) is a promising approach to efficient blue electroluminescence. However, the difficulty of developing efficient blue TADF emitters lies in finding a molecular structure that simultaneously incorporates (i) a small energy difference between the lowest excited singlet state (S1) and the lowest triplet state (T1), ΔE ST, (ii) a large oscillator strength, f, between S1 and the ground state (S0), and (iii) S1 energy sufficiently high for blue emission. In this study, we develop TADF emitters named CCX-I and CCX-II satisfying the above requirements. They show blue photoluminescence and high triplet-to-singlet up-conversion yield. In addition, their transition dipole moments are horizontally oriented, resulting in further increase of their electroluminescence efficiency. Using CCX-II as an emitting dopant, we achieve a blue OLED showing a high external quantum efficiency of 25.9%, which is one of the highest EQEs in blue OLEDs reported previously.

Purely organic electroluminescent material realizing 100% conversion from electricity to light.

Efficient organic light-emitting diodes have been developed using emitters containing rare metals, such as platinum and iridium complexes. However, there is an urgent need to develop emitters composed of more abundant materials. Here we show a thermally activated delayed fluorescence material for organic light-emitting diodes, which realizes both approximately 100% photoluminescence quantum yield and approximately 100% up-conversion of the triplet to singlet excited state. The material contains electron-donating diphenylaminocarbazole and electron-accepting triphenyltriazine moieties. The typical trade-off between effective emission and triplet-to-singlet up-conversion is overcome by fine-tuning the highest occupied molecular orbital and lowest unoccupied molecular orbital distributions. The nearly zero singlet-triplet energy gap, smaller than the thermal energy at room temperature, results in an organic light-emitting diode with external quantum efficiency of 29.6%. An external quantum efficiency of 41.5% is obtained when using an out-coupling sheet. The external quantum efficiency is 30.7% even at a high luminance of 3,000 cd m(-2).

Influence of deposition substrate temperature on the morphology and molecular orientation of chloroaluminum phthalocyanine films as well the performance of organic photovoltaic cells.

The dependence of the morphology of neat chloroaluminum phthalocyanine (ClAlPc) films on substrate temperature (Tsub) during deposition is investigated by variable angle spectroscopic ellipsometry (VASE), x-ray diffraction (XRD), and atomic force microscopy (AFM) to obtain detailed information about the molecular orientation, phase separation, and crystallinity. AFM images indicate that both grain size and root mean square (RMS) roughness noticeably increase with Tsub both in neat and blend films. Increasing Tsub from room temperature to 420 K increases the horizontal orientation of the ClAlPc molecules with an increase of the mean molecular tilt angle from 60.13° (300 K) to 65.86° (420 K). The UV-vis absorption band of the corresponding films increases and the peak wavelength slightly red shifts with the Tsub increase. XRD patterns show a clear diffraction peak at Tsub over 390 K, implying the π-stacking of interconnected ClAlPc molecules at high Tsub. Planar and bulk heterojunction (BHJ) photovoltaic cells containing pristine ClAlPc films and ClAlPc:C60 blend films fabricated at Tsub of 390 K show increases in the power conversion efficiency (ηPCE) of 28% (ηPCE = 3.12%) and 36% (ηPCE = 3.58%), respectively, relative to devices as-deposited at room temperature. The maximum short circuit current in BHJs is obtained at 390 K in the Tsub range from 300 K to 450 K.

Droplet manipulation by an external electric field for crystalline film growth.

Combining droplet manipulation by the application of an electric field with inkjet printing is proposed as a unique technique to control the surface wettability of substrates for solution-processed organic field-effect transistors (FETs). With the use of this technique, uniform thin films of 2,7-dioctyl[1]benzothieno[2,3,-b][1]benzothiopene (C8-BTBT) could be fabricated on the channels of FET substrates without self-assembled monolayer treatment. High-speed camera observation revealed that the crystals formed at the solid/liquid interface. The coverage of the crystals on the channels depended on the ac frequency of the external electric field applied during film formation, leading to a wide variation in the carrier transport of the films. The highest hole mobility of 0.03 cm(2) V(-1) s(-1) was obtained when the coverage was maximized with an ac frequency of 1 kHz.