Electrostatic steering of thermal emission with active metasurface control of delocalized modes.

We theoretically describe and experimentally demonstrate a graphene-integrated metasurface structure that enables electrically-tunable directional control of thermal emission. This device consists of a dielectric spacer that acts as a Fabry-Perot resonator supporting long-range delocalized modes bounded on one side by an electrostatically tunable metal-graphene metasurface. By varying the Fermi level of the graphene, the accumulated phase of the Fabry-Perot mode is shifted, which changes the direction of absorption and emission at a fixed frequency. We directly measure the frequency- and angle-dependent emissivity of the thermal emission from a fabricated device heated to 250 °C. Our results show that electrostatic control allows the thermal emission at 6.61 µm to be continuously steered over 16°, with a peak emissivity maintained above 0.9. We analyze the dynamic behavior of the thermal emission steerer theoretically using a Fano interference model, and use the model to design optimized thermal steerer structures.

Design parameters of free-form color splitters for subwavelength pixelated image sensors.

Metasurface-based color splitters are emerging as next-generation optical components for image sensors, replacing classical color filters and microlens arrays. In this work, we report how the design parameters such as the device dimensions and refractive indices of the dielectrics affect the optical efficiency of the color splitters. Also, we report how the design grid resolution parameters affect the optical efficiency and discover that the fabrication of a color splitter is possible even in legacy fabrication facilities with low structure resolutions.

Wearable Surface-Lighting Micro-Light-Emitting Diode Patch for Melanogenesis Inhibition.

Wearable light-emitting diode (LED)-based phototherapeutic devices have recently attracted attention as skin care tools for wrinkles, acne, and hyperpigmentation. However, the therapeutic effectiveness and safety of LED stimulators are still controversial due to their inefficient light transfer, high heat generation, and non-uniform spot irradiation. Here, a wearable surface-lighting micro-LED (SµLED) photostimulator is reported for skin care and cosmetic applications. The SµLEDs, consisting of a light diffusion layer (LDL), 900 thin film µLEDs, and polydimethylsiloxane (PDMS), achieve uniform surface-lighting in 2 × 2 cm2 -sized area with 100% emission yields. The SµLEDs maximize photostimulation effectiveness on the skin surface by uniform irradiation, high flexibility, and thermal stability. The SµLED's effect on melanogenesis inhibition is evaluated via in vitro and in vivo experiments to human skin equivalents (HSEs) and mouse dorsal skin, respectively. The anti-melanogenic effect of SµLEDs is confirmed by significantly reduced levels of melanin contents, melan-A, tyrosinase, and microphthalmia-associated transcription factor (MITF), compared to a conventional LED (CLED) stimulator.

Full 2π tunable phase modulation using avoided crossing of resonances.

Active metasurfaces have been proposed as one attractive means of achieving high-resolution spatiotemporal control of optical wavefronts, having applications such as LIDAR and dynamic holography. However, achieving full, dynamic phase control has been elusive in metasurfaces. In this paper, we unveil an electrically tunable metasurface design strategy that operates near the avoided crossing of two resonances, one a spectrally narrow, over-coupled resonance and the other with a high resonance frequency tunability. This strategy displays an unprecedented upper limit of 4π range of dynamic phase modulation with no significant variations in optical amplitude, by enhancing the phase tunability through utilizing two coupled resonances. A proof-of-concept metasurface is justified analytically and verified numerically in an experimentally accessible platform using quasi-bound states in the continuum and graphene plasmon resonances, with results showing a 3π phase modulation capacity with a uniform reflection amplitude of ~0.65.

Impacts of KF Post-Deposition Treatment on the Band Alignment of Epitaxial Cu(In,Ga)Se2 Heterojunctions.

In this study, we investigated band alignments at CdS/epitaxial CuInxGa1-xSe2 (epi-CIGSe) and epi-CIGSe/GaAs heterointerfaces for solar cell applications using ultraviolet, inverse, and X-ray photoemission spectroscopy (UPS, IPES, and XPS) techniques. We clarified the impacts of KF postdeposition treatment (KF-PDT) at the CdS/epi-CIGSe front heterointerfaces. We found that KF-PDT changed the conduction band alignment at the CdS/epi-CIGSe heterointerface from a cliff to flat configuration, attributed to an increase in the electron affinity (EA) and ionization potential (IP) of the epi-CIGSe surface because of a decrease in Cu and Ga contents. Herein, we discuss the correlation between the impacts of KF-PDT and the solar cell performance. Furthermore, we also investigated the band alignment at the epi-CIGSe/GaAs rear heterointerface. Electron barriers were formed at the epi-CIGSe/GaAs interface, suppressing carrier recombination as the back surface field. Contrarily, a hole accumulation layer is formed by the valence band bending, which is like Ohmic contact.

Cobalt-Iron-Phosphate Hydrogen Evolution Reaction Electrocatalyst for Solar-Driven Alkaline Seawater Electrolyzer.

Seawater splitting represents an inexpensive and attractive route for producing hydrogen, which does not require a desalination process. Highly active and durable electrocatalysts are required to sustain seawater splitting. Herein we report the phosphidation-based synthesis of a cobalt-iron-phosphate ((Co,Fe)PO4) electrocatalyst for hydrogen evolution reaction (HER) toward alkaline seawater splitting. (Co,Fe)PO4 demonstrates high HER activity and durability in alkaline natural seawater (1 M KOH + seawater), delivering a current density of 10 mA/cm2 at an overpotential of 137 mV. Furthermore, the measured potential of the electrocatalyst ((Co,Fe)PO4) at a constant current density of -100 mA/cm2 remains very stable without noticeable degradation for 72 h during the continuous operation in alkaline natural seawater, demonstrating its suitability for seawater applications. Furthermore, an alkaline seawater electrolyzer employing the non-precious-metal catalysts demonstrates better performance (1.625 V at 10 mA/cm2) than one employing precious metal ones (1.653 V at 10 mA/cm2). The non-precious-metal-based alkaline seawater electrolyzer exhibits a high solar-to-hydrogen (STH) efficiency (12.8%) in a commercial silicon solar cell.

Microcellular sensing media with ternary transparency states for fast and intuitive identification of unknown liquids.

Rapid, accurate, and intuitive detection of unknown liquids is greatly important for various fields such as food and drink safety, management of chemical hazards, manufacturing process monitoring, and so on. Here, we demonstrate a highly responsive and selective transparency-switching medium for on-site, visual identification of various liquids. The light scattering­based sensing medium, which is designed to be composed of polymeric interphase voids and hollow nanoparticles, provides an extremely large transmittance window (>95%) with outstanding selectivity and versatility. This sensing medium features ternary transparency states (transparent, semitransparent, and opaque) when immersed in liquids depending on liquid-polymer interactions and diffusion kinetics. Several different types of these transparency-changing media can be configured into an arrayed platform to discriminate a wide variety of liquids and also quantify their mixing ratios. The outstanding versatility and user friendliness of the sensing platform allow the development of a practical tool for discrimination of diverse organic liquids.

Ultracompact electro-optic waveguide modulator based on a graphene-covered λ/1000 plasmonic nanogap.

The extreme field confinement and electro-optic tunability of plasmons in graphene make it an ideal platform for compact waveguide modulators, with device footprints aggressively scaling orders of magnitude below the diffraction limit. The miniaturization of modulators based on graphene plasmon resonances is however inherently constrained by the plasmon wavelength, while their performance is bounded by material loss in graphene. In this report, we propose to overcome these limitations using a graphene-covered λ/1000 plasmonic nanogap waveguide that concentrates light on length scales more than an order of magnitude smaller than the graphene plasmon wavelength. The modulation mechanism relies on interference between the non-resonant background transmission and the transmission mediated by the gate-tunable nanogap mode, enabling modulation depths over 20 dB. Since the operation of the device does not rely on graphene plasmons, the switching behavior is robust against low graphene carrier mobility even under 1000 cm2/Vs, which is desirable for practical applications.

Plasma-Enhanced Atomic Layer Deposition of TiN Thin Films as an Effective Se Diffusion Barrier for CIGS Solar Cells.

Plasma-enhanced atomic layer deposition (PEALD) of TiN thin films were investigated as an effective Se diffusion barrier layer for Cu (In, Ga) Se2 (CIGS) solar cells. Before the deposition of TiN thin film on CIGS solar cells, a saturated growth rate of 0.67 Å/cycle was confirmed using tetrakis(dimethylamido)titanium (TDMAT) and N2 plasma at 200 °C. Then, a Mo (≈30 nm)/PEALD-TiN (≈5 nm)/Mo (≈600 nm) back contact stack was fabricated to investigate the effects of PEALD-TiN thin films on the Se diffusion. After the selenization process, it was revealed that ≈5 nm-thick TiN thin films can effectively block Se diffusion and that only the top Mo layer prepared on the TiN thin films reacted with Se to form a MoSe2 layer. Without the TiN diffusion barrier layer, however, Se continuously diffused along the grain boundaries of the entire Mo back contact electrode. Finally, the adoption of a TiN diffusion barrier layer improved the photovoltaic efficiency of the CIGS solar cell by approximately 10%.

Promoting electrocatalytic overall water splitting by sulfur incorporation into CoFe-(oxy)hydroxide.

The design and fabrication of highly cost-effective electrocatalysts with high activity, and stability to enhance the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has been considered to be one of the most promising approaches toward overall water splitting. In this study, sulfur-incorporated cobalt-iron (oxy)hydroxide (S-(Co,Fe)OOH) nanosheets were directly grown on commercial iron foam via galvanic corrosion and hydrothermal methods. The incorporation of sulfur into (Co,Fe)OOH results in superior catalytic performance and high stability in both the HER and OER conducted in 1 M KOH. The incorporation of sulfur enhanced the electrocatalytic activity by modifying the electronic structure and chemical states of (Co,Fe)OOH. An alkaline water electrolyzer for overall water splitting was fabricated using a two-electrode configuration utilizing the S-(Co,Fe)OOH bifunctional electrocatalyst in both the HER and OER. The fabricated electrolyzer outperformed a precious metal-based electrolyzer using Pt/C as the HER electrocatalyst and IrO2 as the OER electrocatalyst, which are the benchmark catalysts. This electrolyzer provides a lower potential of 1.641 V at 10 mA cm-2 and maintains 98.4% of its performance after 50 h of durability testing. In addition, the S-(Co,Fe)OOH-based electrolyzer successfully generated hydrogen under natural illumination upon its combination with a commercial silicon solar cell and exhibited a solar to hydrogen (STH) efficiency of up to 13.0%. This study shows that S-(Co,Fe)OOH is a promising candidate for application in the future renewable energy industry due to its high cost-effectiveness, activity, and stability during overall water splitting. In addition, the combination of a commercial silicon solar cell with an alkaline water electrolyzer has great potential for the production of hydrogen.

Simulation and Fabrication of Nanoscale Spirals Based on Dual-Scale Self-Assemblies.

Archimedean spirals in nanometer scale have shown remarkable plasmonic responses derived from their linear and rotational asymmetry. Despite the unique optical properties of nanoscale spirals, their applications have been limited due to the difficulty in fabricating large-scale arrays with uniform and systematic control of the morphology. Here, we report simulation results of spiral morphologies, which are used to design a scalable fabrication process for nanoscale spirals and predict their plasmonic responses. First, self-consistent field theory (SCFT) simulations were performed to design optimal templates to guide self-assembly into spiral morphologies. Using the SCFT results, we developed a scalable fabrication process, which is based on the micron-scale assembly of microspheres combined with glancing angle deposition and nanoscale assembly of block copolymers, to induce the formation of uniform nanospirals with diverse size, handedness, orientation, and winding number. Finally, finite-difference time-domain simulation results show linear dichroism and electric field intensity enhancement effects of these nanospirals, which are highly dependent on the winding number of the spirals, indicating the importance of precise control of the structural parameters.

Unique and overlapping effects of triiodothyronine (T3) and thyroxine (T4) on sensory innervation of the chick cornea.

Multiple aspects of cornea development, including the innervation of the cornea by trigeminal axons, are sensitive to embryonic levels of thyroid hormone (TH). Although previous work showed that increased TH levels could enhance the rate of axonal extension within the cornea in a thyroxine (T4)-dependent manner, details underlying the stimulatory effect of TH on cornea innervation are unclear. Here, by examining the effects throughout all stages of cornea innervation of the two main THs, triiodothyronine (T3) and T4, we provide a more complete characterization of the stimulatory effects of TH on corneal nerves and begin to unravel the underlying molecular mechanisms. During development, trigeminal axons are initially repelled at the corneal periphery and encircle the cornea in a pericorneal nerve ring prior to advancing into the corneal stroma radially from all along the nerve ring. Overall, exogenous T3 led to pleiotropic effects throughout all stages of cornea innervation, whereas the effects of exogenous T4 was confined to timepoints following completion of the nerve ring. Specifically, exogenous T3 accelerated the formation of the pericorneal nerve ring. By utilizing in vitro neuronal explants studies we demonstrated that T3 acts as a trophic factor to directly stimulate trigeminal nerve growth. Further, exogenous T3 caused disorganized and precocious innervation of the cornea, accompanied by the downregulation of inhibitory Robo receptors that normally act to regulate the timing of nerve advancement into the Slit-expressing corneal tissues. Following nerve ring completion, the growth rate and branching behavior of nerves as they advanced into and through the cornea were found to be stimulated equally by T3 or T4. These stimulatory influences of T3/T4 over nerves likely arose as secondary consequences brought on by TH-mediated modulations to the corneal extracellular matrix. Specifically, we found that the levels of nerve-inhibitory keratan- and chondroitin-sulfate containing proteoglycans and associated sulfation enzymes were dramatically altered in the presence of exogenous T3 or T4. Altogether, these findings uncover new roles for TH on corneal development and shed insight into the mechanistic basis of both T3 and T4 on cornea innervation.

Complete Complex Amplitude Modulation with Electronically Tunable Graphene Plasmonic Metamolecules.

Dynamic high-resolution wavefront modulation of light is a long-standing quest in photonics. Metasurfaces have shown potential for realizing light manipulation with subwavelength resolution through nanoscale optical elements, or metaatoms, to overcome the limitations of conventional spatial light modulators. State-of-the-art active metasurfaces operate via phase modulation of the metaatoms, and their inability to also independently control the scattered amplitude leads to an inferior reconstruction of the desired wavefronts. This fundamental problem posed severe performance limitations particularly for applications relying on subwavelength spatiotemporal complex field modulation, which includes dynamic holography, high-resolution imaging, optical tweezing, and optical information processing. Here, we present the "metamolecule" strategy, which incorporates two independent subwavelength scatterers composed of noble metal antennas coupled to gate-tunable graphene plasmonic nanoresonators. The two-parametric control of the metamolecule secures the complete control of both amplitude and phase of light, enabling 2π phase shift as well as large amplitude modulation including perfect absorption. We further develop a generalized graphical model to examine the underlying requirements for complete complex amplitude modulation, offering intuitive design guidelines to maximize the tunability in metasurfaces. To illustrate the reconfigurable capability of our designs, we demonstrate dynamic beam steering and holographic wavefront reconstruction in periodically arranged metamolecules.

Order-of-Magnitude, Broadband-Enhanced Light Emission from Quantum Dots Assembled in Multiscale Phase-Separated Block Copolymers.

Achieving high emission efficiency in solid-state quantum dots (QDs) is an essential requirement for high-performance QD optoelectronics. However, most QD films suffer from insufficient excitation and light extraction efficiencies, along with nonradiative energy transfer between closely adjacent QDs. Herein, we suggest a highly effective strategy to enhance the photoluminescence (PL) of QD composite films through an assembly of QDs and poly(styrene-b-4-vinylpyridine)) (PS-b-P4VP) block copolymer (BCP). A BCP matrix casted under controlled humidity provides multiscale phase-separation features based on (1) submicrometer-scale spinodal decomposition between polymer-rich and water-rich phases and (2) sub-10 nm-scale microphase separation between polymer blocks. The BCP-QD composite containing bicontinuous random pores achieves significant enhancement of both light absorption and extraction efficiencies via effective random light scattering. Moreover, the microphase-separated morphology substantially reduces the Förster resonance energy transfer efficiency from 53% (pure QD film) to 22% (BCP-QD composite), collectively achieving an unprecedented 21-fold enhanced PL over a broad spectral range.

Improving the Open Circuit Voltage through Surface Oxygen Plasma Treatment and 11.7% Efficient Cu2ZnSnSe4 Solar Cell.

The photovoltaic performance of Cu2ZnSnSe4 (CZTSe) solar cells subjected to surface oxygen plasma treatments is investigated. The observed improvements are related to an enhancement of the open circuit voltage VOC, that is, the suppression of the VOC deficit. The VOC monotonically increases with treatment time up to 0.460 V. The origin of this improvement is discussed, and it is concluded that the effectiveness of the surface treatment is not due to oxygen-related alloying but instead to the homogeneous oxidation and removal of the oxidized CZTSe surface layer. The surface oxygen content increases with surface treatment time, although surface oxides are fully removed after ammonia treatment, which is conducted in a similar manner to CdS buffer deposition. The reduction of surface recombination is confirmed by time-resolved photoluminescence measurements, and the minority carrier lifetime deduced using the fast decay component increases with increasing treatment time. The relationship between photovoltaic properties and lifetime is clearly demonstrated. The best-performing CZTSe solar cell obtained using surface oxygen treatment demonstrates a conversion efficiency of 11.7%, which is higher than those of previous reports on CZTSe cells.

Observation of Wavelength-Dependent Quantum Plasmon Tunneling with Varying the Thickness of Graphene Spacer.

Plasmonic coupling provides a highly localized electromagnetic field in the gap of noble metals when illuminated by a light. The plasmonic field enhancement is generally known to be inversely proportional to the gap distance. Given such a relation, reducing the gap distance appears to be necessary to achieve the highest possible field enhancement. At the sub-nanometer scale, however, quantum mechanical effects have to be considered in relation to plasmonic coupling. Here, we use graphene as a spacer to observe plasmonic field enhancement in sub-nanometer gap. The gap distance is precisely controlled by the number of stacked graphene layers. We propose that the sudden drop of field enhancement for the single layer spacer is originated from the plasmon tunneling through the thin spacer. Numerical simulation which incorporates quantum tunneling is also performed to support the experimental results. From the fact that field enhancement with respect to the number of graphene layers exhibits different behavior in two wavelengths corresponding to on- and off-resonance conditions, tunneling phenomenon is thought to destroy the resonance conditions of plasmonic coupling.

Band Alignment of the CdS/Cu2Zn(Sn1- xGe x)Se4 Heterointerface and Electronic Properties at the Cu2Zn(Sn1- xGe x)Se4 Surface: x = 0, 0.2, and 0.4.

The surface electronic properties of the light absorber and band alignment at the p/n heterointerface are key issues for high-performance heterojunction solar cells. We investigated the band alignment of the heterointerface between cadmium sulfide (CdS) and Ge-incorporated Cu2ZnSnSe4 (CZTGSe), with Ge/(Ge + Sn) ratios ( x) between 0 and 0.4, by X-ray photoelectron, ultraviolet, and inversed photoemission spectroscopies (XPS, UPS, and IPES, respectively). In particular, we used interface-induced band bending in order to determine the conduction band offset (CBO) and valence-band offset (VBO), which were calculated from the core-level shifts of each element in both the CdS overlayer and the CZTGSe bottom layer. Moreover, the surface electronic properties of CZTGSe were also investigated by laser-irradiated XPS. The CBO at the CdS/CZTGSe heterointerface decreased linearly, from +0.36 to +0.20 eV, as x was increased from 0 to 0.4; in contrast, the VBO at the CdS/CZTGSe heterointerface was independent of Ge content. Both UPS and IPES revealed that the Fermi level at the CZTGSe surface is located near the center of the band gap. The hole concentration at the CZTGSe surface was on the order of 1011 cm-3, which is much smaller than that of the bulk (∼1016 cm-3). We discuss the differences in hole deficiencies near the surface and in the bulk on the basis of laser-irradiated XPS and conclude that hole deficiencies are due to defects distributed near the surface with densities that are lower than in the bulk, and the Fermi level is not pinned at the CZTGSe surface.

Synthesis and Consolidation of Nanostructured Nb2C-Al2O3 Composite.

Although an extremely hard ceramic material, niobium carbide has low fracture toughness to use wide applications. To fabricate nanostructured composite is common method to improve fracture toughness. Nanopowder mixture of Nb2C and Al2O3 were synthesized according to the reaction (Al4C3+6Nb+3O2 → 3Nb2C+2Al2O3) from Al4C3 and Nb powders by high-energy ball milling. The synthesized mixture of Nb2C and Al2O3 powders was consolidated by pulsed current activated sintering method within two min under the 80 MPa pressure. Nb2C and Al2O3 in the composite were nano-sized phases. The fracture toughness of a nanostructured Nb2C-Al2O3 composite of this study is better than that of previous study.

All-Solid-State Lithium Battery Working without an Additional Separator in a Polymeric Electrolyte.

Considering the safety issues of Li ion batteries, an all-solid-state polymer electrolyte has been one of the promising solutions. Achieving a Li ion conductivity of a solid-state electrolyte comparable to that of a liquid electrolyte (>1 mS/cm) is particularly challenging. Even with characteristic ion conductivity, employment of a polyethylene oxide (PEO) solid electrolyte has not been sufficient due to high crystallinity. In this study, hybrid solid electrolyte (HSE) systems have been designed with Li1.3Al0.3Ti0.7(PO4)3 (LATP), PEO and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). A hybrid solid cathode (HSC) is also designed using LATP, PEO and lithium cobalt oxide (LiCoO2, LCO)-lithium manganese oxide (LiMn2O4, LMO). The designed HSE system has 2.0 × 10-4 S/cm (23 °C) and 1.6 × 10-3 S/cm (55 °C) with a 6.0 V electrochemical stability without an additional separator membrane introduction. In these systems, succinonitrile (SN) has been incorporated as a plasticizer to reduce crystallinity of PEO for practical all-solid Li battery system development. The designed HSC/HSE/Li metal cell in this study operates without any leakage and short-circuits even under the broken cell condition. The designed HSC/HSE/Li metal cell in this study displays an initial charge capacity of 82/62 mAh/g (23 °C) and 123.4/102.7 mAh/g (55 °C). The developed system overcomes typical disadvantages of internal resistance induced by Ti ion reduction. This study contributes to a new technology development of all-solid-state Li battery for commercial product design.

Flash-Induced Self-Limited Plasmonic Welding of Silver Nanowire Network for Transparent Flexible Energy Harvester.

The outstanding performance (sheet resistance of 5 Ω sq-1 at transmittance of 90%) and strongly adhesive (30.7 J m-2 ) silver nanowires (AgNWs) are fabricated using flash-induced plasmonic welding (FPW) based on theoretical research of photothermal interactions. The FPW-processed AgNWs are utilized as electrodes of a transparent flexible energy harvester, and this device exhibits excellent transmittance and high electric output performance. The FPW methodology provides a high-tech solution for transparent flexible electronics.