Fluidic self-assembly for MicroLED displays by controlled viscosity.

Displays in which arrays of microscopic 'particles', or chiplets, of inorganic light-emitting diodes (LEDs) constitute the pixels, termed MicroLED displays, have received considerable attention1,2 because they can potentially outperform commercially available displays based on organic LEDs3,4 in terms of power consumption, colour saturation, brightness and stability and without image burn-in issues1,2,5-7. To manufacture these displays, LED chiplets must be epitaxially grown on separate wafers for maximum device performance and then transferred onto the display substrate. Given that the number of LEDs needed for transfer is tremendous-for example, more than 24 million chiplets smaller than 100 µm are required for a 50-inch, ultra-high-definition display-a technique capable of assembling tens of millions of individual LEDs at low cost and high throughput is needed to commercialize MicroLED displays. Here we demonstrate a MicroLED lighting panel consisting of more than 19,000 disk-shaped GaN chiplets, 45 µm in diameter and 5 µm in thickness, assembled in 60 s by a simple agitation-based, surface-tension-driven fluidic self-assembly (FSA) technique with a yield of 99.88%. The creation of this level of large-scale, high-yield FSA of sub-100-µm chiplets was considered a significant challenge because of the low inertia of the chiplets. Our key finding in overcoming this difficulty is that the addition of a small amount of poloxamer to the assembly solution increases its viscosity which, in turn, increases liquid-to-chiplet momentum transfer. Our results represent significant progress towards the ultimate goal of low-cost, high-throughput manufacture of full-colour MicroLED displays by FSA.

Chiroptical Performances in Self-Assembled Hierarchical Nanosegregated Chiral Intermediate Phases Composed of Two Different Achiral Bent-Core Molecules.

In this paper, chiral intermediate phases composed of two achiral molecules are fabricated by utilizing nanophase separation and molecular hierarchical self-organization. An achiral bent-core guest molecule, exhibiting a calamitic nematic and a dark conglomerate phase according to the temperature, is mixed with another achiral bent-core host molecule possessing a helical nanofilament to separate the phases between them. Two nanosegregated phases are identified, and considerable chiroptical changes, such as circular dichroism and circularly polarized luminescence, are detected at the transition temperatures between the different nanophase-separated states. The nanosegregated chiral phase-wherein the helical nanofilament and dark conglomerate phases are phase-separated-exhibits the highest chiroptical intensities. The luminescence dissymmetry factor, |glum|, in this phase is amplified by an order of magnitude compared with that of another nanosegregated phase, wherein the helical nanofilament and nematic phases are phase-separated.

Twist to Boost: Circumventing Quantum Yield and Dissymmetry Factor Trade-Off in Circularly Polarized Luminescence.

Circularly polarized luminescence (CPL) enables promising applications in asymmetric photonics. However, the performances of CPL molecules do not yet meet the requirements of these applications. The shortcoming originates from the trade-off in CPL between the photoluminescence quantum yield (PLQY) and the photoluminescence dissymmetry factor (gPL). In this study, we developed a molecular strategy to circumvent this trade-off. Our approach takes advantage of the strong propensity of [Pt(N^C^N)Cl], where the N^C^N ligand is 1-(2-oxazoline)-3-(2-pyridyl)phenylate, to form face-to-face stacks. We introduced chiral substituents, including (S)-methyl, (R)- and (S)-isopropyl, and (S)-indanyl groups, into the ligand framework. This asymmetric control induces torsional displacements that give homohelical stacks of the Pt(II) complexes. X-ray single-crystal structure analyses for the (S)-isopropyl Pt(II) complex reveal the formation of a homohelical dimer with a Pt···Pt distance of 3.48 Å, which is less than the sum of the van der Waals radii of Pt. This helical stack elicits the metal-metal-to-ligand charge-transfer (MMLCT) transition that exhibits strong chiroptical activity due to the electric transition moment making an acute angle to the magnetic transition moment. The PLQY and gPL values of the MMLCT phosphorescence emission of the (S)-isopropyl Pt(II) complex are 0.49 and 8.4 × 10-4, which are improved by factors of ca. 6 and 4, respectively, relative to the values of the unimolecular emission (PLQY, 0.078; gPL, 2.4 × 10-4). Our photophysical measurements for the systematically controlled Pt(II) complexes reveal that the CPL amplifications depend on the chiral substituent. Our investigations also indicate that excimers are not responsible for the enhanced chiroptical activity. To demonstrate the effectiveness of our approach, organic electroluminescence devices were fabricated. The MMLCT emission devices were found to exhibit simultaneous enhancements in the external quantum efficiency (EQE, 9.7%) and the electroluminescence dissymmetry factor (gEL, 1.2 × 10-4) over the unimolecular emission devices (EQE, 5.8%; gEL, 0.3 × 10-4). These results demonstrate the usefulness of using the chiroptically active MMLCT emission for achieving an amplified CPL.

High-performance circular-polarization-sensitive organic photodetectors based on a chiral plasmonic nanocavity.

Chiral photodetectors, optoelectronic devices that can detect circularly polarized light (CPL), have attracted much attention as building blocks of next-generation information technology. However, their performance has been severely limited by the tradeoff between the external quantum efficiency (ηE) and the dissymmetry factor of photocurrent, the latter typically being limited by the small dissymmetry factor of absorption (gA). This work numerically demonstrates that a circular polarization-sensitive organic photodetector (CP-OPD) based on a chiral plasmonic nanocavity can achieve both high ηE and gA. The design of the chiral nanocavity, featuring a circular dichroic plasmonic mode with a high photonic density of states in the subwavelength thick photoactive layer, is decoupled with that of the photoactive layer, which enables the independent control of the circular dichroic and photon-to-charge conversion properties. By investigating the interaction between CPL and the molecules constituting the photoactive layer, a design principle of the plasmonic CP-OPD is established, resulting in superior performance with ηE = 23.8 % and gA = 1.6.

Carbon-Nanosheet Based Large-Area Electrochemical Capacitor that is Flexible, Foldable, Twistable, and Stretchable.

With the growing demand for wearable electronics, developing new compatible energy systems is a prominent topic of research. Energy systems mounted on wearable electronics should exhibit high cost efficiency, mechanical robustness, and high electrochemical activity. Herein, all-carbon-based large-area nanocomposites for freely deformable electrochemical capacitors are suggested to address these requirements. The three-dimensionally integrated, self-supported nanocomposites consist of activated carbons (ACs) distributed in direct spinning-derived carbon nanotube (DS-CNT) sheets without any additives, including conducting agents or binders. Owing to synergetic effects of the highly porous AC particles, high electron transport kinetics of CNTs, and facile ion accessibility resulting from acid treatment, the nanocomposites show a greatly improved specific capacitance of 128 F g-1 , compared to that of pristine ACs (62 F g-1 ), based on the total mass of the electrodes. The exceptional mechanical stability of the nanocomposites, which are attached on prestretched elastomer substrates, is confirmed; only a ≈15% increase in the electrical resistance is observed under a tensile strain of 100%, and the initial resistance is fully recovered after releasing. Finally, the outstanding durability and electrochemical performance of the deformable all-carbon-based symmetric capacitors under various mechanical deformations of bending, folding, twisting, and stretching are successfully demonstrated.

Scattering of surface plasmon polaritons at a planar interface by an embedded dielectric nanocube.

We investigate scattering of surface plasmon polaritons (SPPs) at a planar metal-dielectric interface by a dielectric nanocube embedded in the metal layer using finite element method-based simulations. The scattering characteristics of the embedded nanocube, such as the scattering and absorption cross sections, far-field scattering patterns, reflectance, and transmittance, are calculated as functions of the wavelength of the incident SPP waves in the visible range. The main features of the characteristics are explained in connection with the excitation of plasmonic eigenmodes of the embedded nanocube. The most efficient scattering into waves propagating away from the metal surface, i.e., the radiating modes, occurs when a dipolar-like plasmonic mode is excited, whose eigenfrequency can be tuned by changing the edge length of the nanocube.

Design and numerical analysis of surface plasmon-enhanced fin Ge-Si light-emitting diode.

Heavily-doped strained germanium (Ge) can emit light efficiently thanks to its pseudo direct band gap characteristic. This makes Ge a good candidate for on-chip monolithic light sources in silicon (Si) photonics systems. We propose fin-shaped Ge-Si heterojunction light-emitting diode (LED) with metal gates, which can enhance light emission by coupling with surface plasmon resonant modes and modulate light emission from the LED. We verify these two aspects through numerical analysis and device simulations. We develop the method to find the optimal device structure and specific device dimensions to maximize the spontaneous emission rate enhancement. Also we find that the LED can be modulated by a gate voltage bias.

Analysis and optimization of surface plasmon-enhanced organic solar cells with a metallic crossed grating electrode.

We perform a systematic analysis of enhanced short-circuit current density (J(sc) in organic solar cells (OSCs) where one metallic electrode is optically thick and the other consists of a two-dimensional metallic crossed grating. By examining a model device representative of such surface plasmon (SP)-enhanced OSCs by the Fourier modal and finite-element methods for electromagnetic and exciton diffusion calculations, respectively, we provide general guidelines to maximize J(sc) of the SP-enhanced OSCs. Based on this study, we optimize the performance of a small-molecule OSC employing a copper phthalocyanine-fullerene donor-acceptor pair, demonstrating that the optimized SP-enhanced device has J(sc) that is 75 % larger than that of the optimized device with an ITO-based conventional structure.

Large-Scale, Lightweight, and Robust Nanocomposites Based on Ruthenium-Decorated Carbon Nanosheets for Deformable Electrochemical Capacitors.

Despite the increase in demand for deformable electrochemical capacitors as a power source for wearable electronics, significant obstacles remain in developing these capacitors, including their manufacturing complexity and insufficient deformability. With recognition of these challenges, a facile strategy is proposed to fabricate large-scale, lightweight, and mechanically robust composite electrodes composed of ruthenium nanoparticles embedded in freestanding carbon nanotube (CNT)-based nanosheets (Ru@a-CNTs). Surface-modified CNT sheets with hierarchical porous structures can behave as an ideal platform to accommodate a large number of uniformly distributed Ru nanoparticles (Ru/CNT weight ratio of 5:1) while improving compatibility with aqueous electrolytes. Accordingly, Ru@a-CNTs offer a large electrochemically active area, showing a high specific capacitance (∼253.3 F g-1) and stability for over 2000 cycles. More importantly, the exceptional performance and mechanical durability of quasi-solid-state capacitors assembled with Ru@a-CNTs and a PVA-H3PO4 hydrogel electrolyte are successfully demonstrated in that 94% of the initial capacitance is retained after 100 000 cycles of bending deformation and a commercial smartwatch is charged by multiple cells. The feasible large-scale production and potential applicability shown in this study provide a simple and highly effective design strategy for a wide range of energy storage applications from small- to large-scale wearable electronics.

Chiral polymer hosts for circularly polarized electroluminescence devices.

Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. The fabrication of a CP PLED requires a polymer host that provides the appropriate chiral environment around the emitting dopant. However, chemical strategies for the design of chiral polymer hosts remain underdeveloped. We have developed new polymer hosts for CP PLED applications. These polymers were prepared through a free-radical polymerization of 3-vinylcarbazole with a chiral N-alkyl unit. This chiral unit forces the carbazole repeat units to form mutually helical half-sandwich conformers with preferred (P)-helical sense along the polymer main chain. Electronic circular dichroism measurements demonstrate the occurrence of chirality transfer from chiral monomers to achiral monomers during chain growth. The (P)-helical-sense-enriched polymer interacts diastereoselectively with an enantiomeric pair of new phosphorescent (R)- and (S)-dopants. The magnitude of the Kuhn dissymmetry factor (g abs) for the (P)-helically-enriched polymer film doped with the (R)-dopant was found to be one order of magnitude higher than that of the film doped with the (S)-dopant. Photoluminescence dissymmetry factors (g PL) of the order of 10-3 were recorded for the doped films, but the magnitude of diastereomeric enhancement decreased to that of g abs. The chiral polymer host permits faster energy transfer to the phosphorescent dopants than the achiral polymer host. Our photophysical and morphological investigations indicate that the acceleration in the chiral polymer host is due to its longer Förster radius and improved compatibility with the dopants. Finally, multilayer CP PLEDs were fabricated and evaluated. Devices based on the chiral polymer host with the (R)- and (S)-dopants exhibit electroluminescence dissymmetry factors (g EL) of 1.09 × 10-4 and -1.02 × 10-4 at a wavelength of 540 nm, respectively. Although challenges remain in the development of polymer hosts for CP PLEDs, our research demonstrates that chiroptical performances can be amplified by using chiral polymer hosts.

Europium-Diethylenetriaminepentaacetic Acid Loaded Radioluminescence Liposome Nanoplatform for Effective Radioisotope-Mediated Photodynamic Therapy.

Photodynamic therapy (PDT) is an effective anticancer strategy with a higher selectivity and fewer adverse effects than conventional therapies; however, shallow tissue penetration depth of light has hampered the clinical utility of PDT. Recently, reports have indicated that Cerenkov luminescence-induced PDT may overcome the tissue penetration limitation of conventional PDT. However, the effectiveness of this method is controversial because of its low luminescence intensity. Herein, we developed a radiolabeled diethylenetriaminepentaacetic acid chelated Eu3+ (Eu-DTPA)/photosensitizer (PS) loaded liposome (Eu/PS-lipo) that utilizes ionizing radiation from radioisotopes for effective in vivo imaging and radioluminescence-induced PDT. We utilized Victoria blue-BO (VBBO) as a PS and observed an efficient luminescence resonance energy transfer between Eu-DTPA and VBBO. Furthermore, 64Cu-labeled Eu lipo demonstrated a strong radioluminescence with a 2-fold higher intensity than Cerenkov luminescence from free 64Cu. In our radioluminescence liposome, radioluminescence energy transfer showed a 6-fold higher energy transfer efficiency to VBBO than Cerenkov luminescence energy transfer (CLET). 64Cu-labeled Eu/VBBO lipo (64Cu-Eu/VBBO lipo) showed a substantial tumor uptake of up to 19.3%ID/g by enhanced permeability and retention effects, as revealed by in vivo positron emission tomography. Finally, the PDT using 64Cu-Eu/VBBO lipo demonstrated significantly higher in vitro and in vivo therapeutic effects than Cerenkov luminescence-induced PDT using 64Cu-VBBO lipo. This study envisions a great opportunity for clinical PDT application by establishing the radioluminescence liposome which has high tumor targeting and efficient energy transfer capability from radioisotopes.

Computational wrapping: A universal method to wrap 3D-curved surfaces with nonstretchable materials for conformal devices.

This study starts from the counterintuitive question of how we can render conventional stiff, nonstretchable, and even brittle materials sufficiently conformable to fully wrap curved surfaces, such as spheres, without failure. Here, we extend the geometrical design method of computational origami to wrapping. Our computational wrapping approach provides a robust and reliable method for fabricating conformal devices for arbitrary curved surfaces with a computationally designed nonpolyhedral developable net. This computer-aided design transforms two-dimensional (2D)-based materials, such as Si wafers and steel sheets, into various targeted conformal structures that can fully wrap desired 3D structures without fracture or severe plastic deformation. We further demonstrate that our computational wrapping approach enables a design platform that can transform conventional nonstretchable 2D-based devices, such as electroluminescent lighting and flexible batteries, into conformal 3D curved devices.

Multiplexed broadband beam steering system utilizing high speed MEMS mirrors.

We present a beam steering system based on micro-electromechanical systems technology that features high speed steering of multiple laser beams over a broad wavelength range. By utilizing high speed micromirrors with a broadband metallic coating, our system has the flexibility to simultaneously incorporate a wide range of wavelengths and multiple beams. We demonstrate reconfiguration of two independent beams at different wavelengths (780 and 635 nm) across a common 5x5 array with 4 micros settling time. Full simulation of the optical system provides insights on the scalability of the system. Such a system can provide a versatile tool for applications where fast laser multiplexing is necessary.

Optically multiplexed imaging with superposition space tracking.

We describe a novel method to track targets in a large field of view. This method simultaneously images multiple, encoded sub-fields of view onto a common focal plane. Sub-field encoding enables target tracking by creating a unique connection between target characteristics in superposition space and the target's true position in real space. This is accomplished without reconstructing a conventional image of the large field of view. Potential encoding schemes include spatial shift, rotation, and magnification. We discuss each of these encoding schemes, but the main emphasis of the paper and all examples are based on one-dimensional spatial shift encoding. System performance is evaluated in terms of two criteria: average decoding time and probability of decoding error. We study these performance criteria as a function of resolution in the encoding scheme and signal-to-noise ratio. Finally, we include simulation and experimental results demonstrating our novel tracking method.

Controlled Enhancement in Hole Injection at Gold-Nanoparticle-on-Organic Electrical Contacts Fabricated by Spark-Discharge Aerosol Technique.

We demonstrate that hole injection from a top electrode composed of Au nanoparticles (AuNPs) capped with a thick Au layer into an underlying organic semiconductor, N, N'-diphenyl- N, N'-bis-[4-(phenyl- m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine (DNTPD), is significantly enhanced compared to that in a control device whose top electrode is composed entirely of a thick Au layer. The fabrication of this organic hole-only device with the AuNP electrode is made possible by dry, room-temperature distribution of AuNPs onto DNTPD using a spark-discharge aerosol technique capable of varying the average diameter ( D̅) of the AuNPs. The enhancement in hole injection is found to increase with decreasing D̅, with the current density of a device with D̅ = 1.1 nm being more than 3 orders of magnitude larger than that of the control device. Intensity-modulated photocurrent measurements show that the built-in potentials of the devices with the AuNP electrode are smaller than that of the control device by as much as 0.68 V, indicating that the enhanced hole injection originates from the increased work functions of these devices, which in turn decreases the hole injection barrier heights. X-ray photoelectron spectroscopy reveals that the increased work functions of the AuNP electrodes are due to surface oxidation of the AuNPs resulting in AuN and Au3N. The degree of oxidation of the AuNPs increases with decreasing D̅, consistent with the D̅-dependencies of the hole injection enhancement and the built-in potential reduction.

Amplified circularly polarized phosphorescence from co-assemblies of platinum(ii) complexes.

Molecules capable of producing zero-field circularly polarized phosphorescence (CPP) are highly valuable for chiroptoelectronic applications that rely on triplet exciton. However, the paucity of tractable molecular design rules for obtaining CPP emission has inhibited full utilization. We report amplification of CPP by the formation of helical co-assemblies consisting of achiral square planar cycloplatinated complexes and small fractions of homochiral cycloplatinated complexes. The latter has a unique Pfeiffer effect during the formation of superhelical co-assemblies, enabling versatile chiroptical control. Large dissymmetry factors in electronic absorption (g abs, 0.020) and phosphorescence emission (g lum, 0.064) are observed from the co-assemblies. These values are two orders of magnitude improved relative to those of individual molecules. In addition, photoluminescence quantum yields (PLQY) also increase by a factor of ten. Our structural, photophysical, and quantum chemical investigations reveal that the chiroptical amplification is attributable to utilization of both the magnetically allowed electronic transition and asymmetric coupling of excitons. The strategy overcomes the trade-off between g lum and PLQY which has frequently been found for previous molecular emitters of circularly polarized luminescence. It is anticipated that our study will provide new insight into the future research for the exploitation of the full potential of CPP.

Selective crack suppression during deformation in metal films on polymer substrates using electron beam irradiation.

While cracks are usually considered detrimental, crack generation can be harnessed for various applications, for example in ceramic materials, via directing crack propagation and crack opening. Here, we find that electron beam irradiation prompts a crack suppression phenomenon in a copper (Cu) thin film on a polyimide substrate, allowing for the control of crack formation in terms of both location and shape. Under tensile strain, cracks form on the unirradiated region of the Cu film whereas cracks are prevented on the irradiated region. We attribute this to the enhancement of the adhesion at the Cu-polyimide interface by electrons transmitted through the Cu film. Finally, we selectively form conductive regions in a Cu film on a polyimide substrate under tension and fabricate a strain-responsive organic light-emitting device.

Organic photovoltaic cell in lateral-tandem configuration employing continuously-tuned microcavity sub-cells.

We propose a lateral-tandem organic photovoltaic system consisting of a dispersive-focusing element and continuously-tuned, series-connected sub-cells. The proposed system overcomes the efficiency limitation of organic photovoltaic devices by spectral re-distribution of incoming solar photons and their delivery to the wavelength-matched, resonant sub-cells. By numerical simulations, we demonstrate that optical resonance in a microcavity sub-cell with a metal/organic multilayer/metal structure can be tuned over a broad spectrum by varying the thickness of the organic multilayer. We show that the power-conversion efficiency exceeding 18% can be obtained in a lateral-tandem system employing an ideal dispersive-focusing element and the microcavity sub-cells.

Superimposed video disambiguation for increased field of view.

Many infrared optical systems in wide-ranging applications such as surveillance and security frequently require large fields of view (FOVs). Often this necessitates a focal plane array (FPA) with a large number of pixels, which, in general, is very expensive. In a previous paper, we proposed a method for increasing the FOV without increasing the pixel resolution of the FPA by superimposing multiple sub-images within a static scene and disambiguating the observed data to reconstruct the original scene. This technique, in effect, allows each sub-image of the scene to share a single FPA, thereby increasing the FOV without compromising resolution. In this paper, we demonstrate the increase of FOVs in a realistic setting by physically generating a superimposed video from a single scene using an optical system employing a beamsplitter and a movable mirror. Without prior knowledge of the contents of the scene, we are able to disambiguate the two sub-images, successfully capturing both large-scale features and fine details in each sub-image. We improve upon our previous reconstruction approach by allowing each sub-image to have slowly changing components, carefully exploiting correlations between sequential video frames to achieve small mean errors and to reduce run times. We show the effectiveness of this improved approach by reconstructing the constituent images of a surveillance camera video.

Poly(dimethylsiloxane) Stamp Coated with a Low-Surface-Energy, Diffusion-Blocking, Covalently Bonded Perfluoropolyether Layer and Its Application to the Fabrication of Organic Electronic Devices by Layer Transfer.

It is demonstrated that a stamp composed of a poly(dimethylsiloxane) (PDMS) bulk and perfluoropolyether (PFPE) coating fabricated by a simple dip-coating method has the following properties that are ideal for the transfer patterning of various materials. Deposited by a condensation reaction between PDMS and PFPE molecules as well as the adjacent PFPE molecules, the PFPE coating has a strong adhesion to the PDMS surface and strong internal cohesion, while providing a low energy surface. Furthermore, it is found to function as a bidirectional diffusion barrier: it effectively prevents organic small molecules deposited on the stamp from being absorbed into free volumes of PDMS; it also prevents PDMS oligomers from migrating onto the layer to be transferred, thereby avoiding the contamination of that layer. Morphological and elemental characterization of the surfaces of the transferred organic semiconductor and graphene layers confirms a successful transfer with a high degree of surface cleanliness. The quality of interfaces mechanically bonded using the PFPE-coated stamps and the cleanliness of the transferred layers are remarkably high that the electronic functions of a transfer-bonded organic heterojunction are comparable to those of the same interface formed by vacuum deposition, and that the charge transport across the transfer-bonded graphene-graphene and graphene-MoO3 interfaces is efficient. Our results demonstrate that the PFPE-coated stamp enables patterned depositions of materials with high quality interfaces while avoiding a high temperature or wet process.