Low-Loss Organic Hyperbolic Materials in the Visible Spectral Range: A Joint Experimental and First-Principles Study

Hyperbolic media strengthen numerous attractive applications in optics such as super-resolution imaging, enhanced spontaneous emission, and nanoscale waveguiding. Natural hyperbolic materials exist at visible frequencies; however, implementations of these materials suffer substantial compromises resulting from the high loss in the currently available candidates. Here, the first experimental and theoretical investigation of regioregular poly(3-alkylthiophenes) (rr-P3ATs), a naturally low-loss organic hyperbolic material (OHM) in the visible frequency range, is shown. These hyperbolic properties arise from a highly ordered structure of layered electron-rich conjugated thiophene ring backbones separated by insulating alkyl side chains. The optical and electronic properties of the rr-P3AT can be tuned by controlling the degree of crystallinity and alkyl side chain length. First-principles calculations support the experimental observations, which result from the rr-P3AT's structural and optical anisotropy. Conveniently, rr-P3AT-based OHMs are facile to fabricate, flexible, and biocompatible, which may lead to tremendous new opportunities in a wide range of applications.     

UV‐Curable Silver Electrode for Screen‐Printed Thermoelectric Generator

Fabricating thermoelectric generators (TEGs) using the screen‐printing process has advantages, including mass production, device scalability, and system applicability. However, the thick film formed through the process typically has low film density, and reduced performance, because of the presence of pores in the film created by the vaporization of the resin during high‐temperature annealing. During the soldering process used for thermoelectric module fabrication, the printed solder infiltrates into the screen‐printed electrodes through the micropores in the electrodes, causing cracks of the electrode film and an increase in resistivity. In this paper, an ultraviolet radiation (UV)‐curable process for screen‐printed electrodes is reported. The paste for the electrodes is synthesized by mixing Ag flakes that can be cured at low temperature with a UV resin. Scanning electron microscope images show that the UV‐curing process significantly reduces pores and thereby results in a smooth‐surfaced electrode layer. The film density after crystallization is also enhanced. TEGs composed of 72 couples with UV‐curable Ag electrodes generate a high power density of ≈6.69 mW cm^?2 at a temperature difference of 25 °C; the device resistance is ≈0.75 Ω, and the figure of merit of the device is recorded to be 0.57, which is the highest among the printed TEGs.     

Modus Operandi of Simultaneous Covering Synthesis from Precursor Heterogeneity for Shelled Nanorods for Multipotent Cancer Theranostics

The synthesis of nanostructures using homogeneous precursors in the solution phase is widely used to achieve uniformity and well‐defined morphological control. However, drawbacks such as the lack of diversity due to the limited reaction rate modulation exist. One‐step, core–shell nanorod formation using simultaneous covering synthesis using solid and ionic heterogeneous precursors is proposed in this study. A Te‐Bi₂Te₃/TeO₂ core–shell structure is successfully synthesized by precisely controlling various influencing factors, including concentration, temperature, and pH, and its physicochemical and photochemical properties are thoroughly investigated. The proposed nanostructure overcomes the oxidation susceptibility of Te and can be applied to multipotent cancer theranostics in vitro and in vivo in combination with computed tomography imaging.     

Enhanced Controllability of Fries Rearrangements Using High‐Resolution 3D‐Printed Metal Microreactor with Circular Channel

High‐resolution 3D‐printed stainless steel metal microreactors (3D‐PMRs) with different cross‐sectional geometry are fabricated to control ultrafast intramolecular rearrangement reactions in a comparative manner. The 3D‐PMR with circular channel demonstrates the improved controllability in rapid Fries‐type rearrangement reactions, because of the superior mixing efficiency to rectangular cross‐section channels (250 µm × 125 µm) which is confirmed based on the computational flow dynamics simulation. Even in case of very rapid intramolecular rearrangement of sterically small acetyl group occurring in 333 µs of reaction time, the desired intermolecular reaction can outpace to the undesired intramolecular rearrangement using 3D‐PMR to result in high conversion and yield.     

Dual Catalytic and Self-Assembled Growth of Two-Dimensional Transition Metal Dichalcogenides Through Simultaneous Predeposition Process

The recent introduction of alkali metal halide catalysts for chemical vapor deposition (CVD) of transition metal dichalcogenides (TMDs) has enabled remarkable two-dimensional (2D) growth. However, the process development and growth mechanism require further exploration to enhance the effects of salts and understand the principles. Herein, simultaneous predeposition of a metal source (MoO₃) and salt (NaCl) by thermal evaporation is adopted. As a result, remarkable growth behaviors such as promoted 2D growth, easy patterning, and potential diversity of target materials can be achieved. Step-by-step spectroscopy combined with morphological analyses reveals a reaction path for MoS₂ growth in which NaCl reacts separately with S and MoO₃ to form Na₂SO₄ and Na₂Mo₂O₇ intermediates, respectively. These intermediates provide a favorable environment for 2D growth, including an enhanced source supply and liquid medium. Consequently, large grains of monolayer MoS₂ are formed by self-assembly, indicating the merging of small equilateral triangular grains on the liquid intermediates. This study is expected to serve as an ideal reference for understanding the principles of salt catalysis and evolution of CVD in the preparation of 2D TMDs.     

Overcoming the Trade-Off between Optical Transmittance and Areal Capacitance of Transparent Supercapacitors for Practical Application

It is substantially challenging for transition metal oxide nanoparticle (NP)-based electrodes for supercapacitors to achieve high transparency and large capacity simultaneously due to the inherent trade-off between optical transmittance (T) and areal capacitance (C_A). This study demonstrates how this trade-off limitation can be overcome by replacing some electrode NPs with transparent tin oxide (SnO₂) NPs. Although SnO₂ NPs are non-capacitive, they provide effective paths for charge transport, which simultaneously increase the C_A and T_550nm of the manganese oxide (Mn₃O₄) NP electrode from 11.7 to 13.4 mF cm⁻² and 82.1% to 87.4%, respectively, when 25 wt% of Mn₃O₄ are replaced by SnO₂. The obtained C_A values at a given T are higher than those of the transparent electrodes previously reported. An energy storage window fabricated using the mixed-NP electrodes exhibits the highest energy density among transparent supercapacitors previously reported. The improved energy density enables the window to operate various electronic devices for a considerable amount of time, demonstrating its applicability in constructing a reliable and space-efficient building-integrated power supply system.     

Mesoporous Metal Fluoride Nanocomposite Films with Tunable Optical Properties Derived from Precursor Instability

The precisely tailored refractive index of optical materials is the key to utilizing and manipulating light during its propagation through the matrix, thereby improving their application performances. In this paper, mesoporous metal fluoride films with engineered composition (MgF₂:LaF₃) are demonstrated to achieve finely tunable refractive indices. These films are prepared using a precursor-derived one-step assembly approach via the simple mixing of precursor solutions (Mg(CF₃OO)₂ and La(CF₃OO)₃); then pores are formed simultaneously during solidification owing to the inherent instability of La(CF₃OO)₃. The mesoporous structures are realized through Mg(CF₃OO)₂ and La(CF₃OO)₃ ions, which interacted with each other based on their electrostatic forces, providing a wide range of refractive indices (from 1.37 to 1.16 at 633 nm). Furthermore, it is systematically several MgF_2(1-x)-LaF_3(x) layers with different compositions (x = 0.0, 0.3, and 0.5) to form the graded refractive index coating that is optically consecutive between the substrate and the air for broadband and omnidirectional antireflection. An average transmittance of ≈98.03% (400–1100 nm) is achieved with a peak transmittance of ≈99.04% (at 571 nm), and the average antireflectivity is maintained at ≈15.75% even at an incidence of light of 65° (400–850 nm).     

Effective Polysulfide Rejection by Dipole‐Aligned BaTiO3 Coated Separator in Lithium–Sulfur Batteries

Although the exceptional theoretical specific capacity (1672 mAh g^?1) of elemental sulfur makes lithium–sulfur (Li–S) batteries attractive for upcoming rechargeable battery applications (e.g., electrical vehicles, drones, unmanned aerial vehicles, etc.), insufficient cycle lives of Li–S cells leave a substantial gap before their wide penetration into commercial markets. Among the key features that affect the cyclability, the shuttling process involving polysulfides (PS) dissolution is most fatal. In an effort to suppress this chronic PS shuttling, herein, a separator coated with poled BaTiO₃ or BTO particles is introduced. Permanent dipoles that are formed in the BTO particles upon the application of an electric field can effectively reject PS from passing through the separator via electrostatic repulsion, resulting in significantly improved cyclability, even when a simple mixture of elemental sulfur and conductive carbon is used as a sulfur cathode. The coating of BTO particles also considerably suppresses thermal shrinkage of the poly(ethylene) separator at high temperatures and thus enhances the safety of the cell adopting the given separator. The incorporation of poled particles can be universally applied to a wide range of rechargeable batteries (i.e., metal‐air batteries) that suffer from cross‐contamination of charged species between both electrodes.     

Delocalized Electron Accumulation at Nanorod Tips: Origin of Efficient H2 Generation

Photocatalytic hydrogen (H₂) evolution requires efficient electron transfer to catalytically active sites in competition with charge recombination. Thus, controlling charge‐carrier dynamics in the photocatalytic H₂ evolution process is essential for optimized photocatalyst nanostructures. Here, the efficient delocalization of electrons is demonstrated in a heterostructure consisting of optimized MoS₂ tips and CdS nanorods (M‐t‐CdS Nrs) synthesized by amine‐assisted oriented attachment. The heterostructure achieves photocatalytic H₂ activity of 8.44 mmol h^?1 g^?1 with excellent long‐term durability (>23 h) without additional passivation under simulated solar light (AM 1.5, 100 mW cm^?2). This activity is nearly two orders of magnitude higher than that of pure CdS Nrs. The impressive photocatalytic H₂ activity of M‐t‐CdS Nrs reflects favorable charge‐carrier dynamics, as determined by steady‐state PL and time‐correlated single photon counting correlation analysis at low temperature. The MoS₂ cocatalysts precisely located at the end of the CdS Nrs exhibit ultrafast charge transfer and slow charge recombination via spatially localized deeper energy states, resulting in a highly efficient H₂ evolution reaction in lactic acid containing an electrolyte.     

Surface‐Shielding Nanostructures Derived from Self‐Assembled Block Copolymers Enable Reliable Plasma Doping for Few‐Layer Transition Metal Dichalcogenides

Precise modulation of electrical and optical properties of 2D transition metal dichalcogenides (TMDs) is required for their application to high‐performance devices. Although conventional plasma‐based doping methods have provided excellent controllability and reproducibility for bulk or relatively thick TMDs, the application of plasma doping for ultrathin few‐layer TMDs has been hindered by serious degradation of their properties. Herein, a reliable and universal doping route is reported for few‐layer TMDs by employing surface‐shielding nanostructures during a plasma‐doping process. It is shown that the surface‐protection oxidized polydimethylsiloxane nanostructures obtained from the sub‐20 nm self‐assembly of Si‐containing block copolymers can preserve the integrity of 2D TMDs and maintain high mobility while affording extensive control over the doping level. For example, the self‐assembled nanostructures form periodically arranged plasma‐blocking and plasma‐accepting nanoscale regions for realizing modulated plasma doping on few‐layer MoS₂, controlling the n‐doping level of few‐layer MoS₂ from 1.9 × 10¹¹ cm^?2 to 8.1 × 10¹¹ cm^?2 via the local generation of extra sulfur vacancies without compromising the carrier mobility.