Refractive Index Modulation for Metal Electrodeposition-Based Active Smart Window Applications.

One of the remarkable choices for active smart window technology is adopting a metal active layer via reversible metal electrodeposition (RME). As the metal layer efficiently blocks the solar energy gain, even a hundred-nanometer-thick scale, RME-based smart window has great attention. Recent developments are mainly focused on the various cases of electrolyte components and composition meeting technological standards. As metal nanostructures formed through the RME process involve plasmonic phenomena, advanced analysis, including plasmonic optics, which is beyond Beer-Lambert's law, should be considered. However, as there is a lack of debates on the plasmonic optics applied to RME smart window technology, as research is mainly conducted through an exhaustive process. In this paper, in order to provide insight into the RME-based smart window development and alleviate the unclear part of plasmonic optics applied to the field, finite-difference time-domain electromagnetic simulations are conducted. In total, two extremely low-quality (Cr) and high-quality (Mg) plasmonic materials based on a nanoparticle array are considered as a metal medium. In addition, optical effects caused by the metal active layer, electrolyte, and nanoparticle embedment are investigated in detail. Overall simulations suggest that the effective refractive index is a decisive factor in the performance of RME-based smart windows.

Targeted and high-throughput gene knockdown in diverse bacteria using synthetic sRNAs.

Synthetic sRNAs allow knockdown of target genes at translational level, but have been restricted to a limited number of bacteria. Here, we report the development of a broad-host-range synthetic sRNA (BHR-sRNA) platform employing the RoxS scaffold and the Hfq chaperone from Bacillus subtilis. BHR-sRNA is tested in 16 bacterial species including commensal, probiotic, pathogenic, and industrial bacteria, with >50% of target gene knockdown achieved in 12 bacterial species. For medical applications, virulence factors in Staphylococcus epidermidis and Klebsiella pneumoniae are knocked down to mitigate their virulence-associated phenotypes. For metabolic engineering applications, high performance Corynebacterium glutamicum strains capable of producing valerolactam (bulk chemical) and methyl anthranilate (fine chemical) are developed by combinatorial knockdown of target genes. A genome-scale sRNA library covering 2959 C. glutamicum genes is constructed for high-throughput colorimetric screening of indigoidine (natural colorant) overproducers. The BHR-sRNA platform will expedite engineering of diverse bacteria of both industrial and medical interest.

Active modulation of reflective structural colors.

Dynamically controllable reflective structural colors have been garnering growing attention due to increasing commercial interests in smart displays (e.g., colorimetric labels), colored e-readers, etc. To comply with the requirements of future displays, several strategies have been proposed by various research groups to achieve wide color tuning ranges in the visible regime, high on/off contrast ratios, and fast response times. In this review, we first introduce ways to create optical resonances including plasmonic, photonic, and plasmonic-photonic hybrid structures that form the basis of color generation. We then outline strategies that control the refractive index contrast between the system and the surrounding as a means to actively change the reflective structural colors, backed with representative examples from the literature. Finally, we provide a comparison of dynamic structural colors based on various switching mechanisms summarizing performance metrics that are important for future displays, and conclude with an outlook on current challenges.

Designing Microbial Cell Factories for the Production of Chemicals.

The sustainable production of chemicals from renewable, nonedible biomass has emerged as an essential alternative to address pressing environmental issues arising from our heavy dependence on fossil resources. Microbial cell factories are engineered microorganisms harboring biosynthetic pathways streamlined to produce chemicals of interests from renewable carbon sources. The biosynthetic pathways for the production of chemicals can be defined into three categories with reference to the microbial host selected for engineering: native-existing pathways, nonnative-existing pathways, and nonnative-created pathways. Recent trends in leveraging native-existing pathways, discovering nonnative-existing pathways, and designing de novo pathways (as nonnative-created pathways) are discussed in this Perspective. We highlight key approaches and successful case studies that exemplify these concepts. Once these pathways are designed and constructed in the microbial cell factory, systems metabolic engineering strategies can be used to improve the performance of the strain to meet industrial production standards. In the second part of the Perspective, current trends in design tools and strategies for systems metabolic engineering are discussed with an eye toward the future. Finally, we survey current and future challenges that need to be addressed to advance microbial cell factories for the sustainable production of chemicals.

Active electrochemical high-contrast gratings as on/off switchable and color tunable pixels.

To be viable for display applications, active structural colors must be electrically tunable, on/off switchable, and reversible. Independently controlling the first two functions, however, is difficult because of causality that ties the real and imaginary parts of the optical constants or changing overlap of fields during structural variations. Here, we demonstrate an active reflective color pixel that encompasses separate mechanisms to achieve both functions reversibly by electrochemically depositing and dissolving Cu inside the dielectric grating slits on a Pt electrode with ΔV < 3 V. Varying the modal interference via Cu occupancy in the slits changes the CIE space coverage by up to ~72% under cross-polarized imaging. In the same pixel, depolarization and absorption by the dissolving porous Cu switches the color off with a maximum contrast of ~97%. Exploiting these results, we demonstrate an active color-switching display and individually addressable on/off pixel matrix that highlights their potential in reflective display applications.

Crystal Facet Engineering of TiO2 Nanostructures for Enhancing Photoelectrochemical Water Splitting with BiVO4 Nanodots.

Although bismuth vanadate (BiVO4) has been promising as photoanode material for photoelectrochemical water splitting, its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes. As a hole blocking layer of BiVO4, titanium dioxide (TiO2) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity. Herein, a crystal facet engineering of TiO2 nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots. We design two types of TiO2 nanostructures, which are nanorods (NRs) and nanoflowers (NFs) with different (001) and (110) crystal facets, respectively, and fabricate BiVO4/TiO2 heterostructure photoanodes. The BiVO4/TiO2 NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO2 NRs. Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination, which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO2 NFs. This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.

Enhancing photoelectrochemical water splitting with plasmonic Au nanoparticles.

The water-based renewable chemical energy cycle has attracted interest due to its role in replacing existing non-renewable resources and alleviating environmental issues. Utilizing the semi-infinite solar energy source is the most appropriate way to sustain such a water-based energy cycle by producing and feeding hydrogen and oxygen. For production, an efficient photoelectrode is required to effectively perform the photoelectrochemical water splitting reaction. For this purpose, appropriately engineered nanostructures can be introduced into the photoelectrode to enhance light-matter interactions for efficient generation and transport of charges and activation of surface chemical reactions. Plasmon enhanced photoelectrochemical water splitting, whose performance can potentially exceed classical efficiency limits, is of great importance in this respect. Plasmonic gold nanoparticles are widely accepted nanomaterials for such applications because they possess high chemical stability, efficiently absorb visible light unlike many inorganic oxides, and enhance light-matter interactions with localized plasmon relaxation processes. However, our understanding of the physical phenomena behind these particles is still not complete. This review paper focuses on understanding the interfacial phenomena between gold nanoparticles and semiconductors and provides a summary and perspective of recent studies on plasmon enhanced photoelectrochemical water splitting using gold nanoparticles.

Responsive Thin-Film Interference Colors from Polaronic Conjugated Block Copolymers.

Colors responsive to the chemical environment can form the basis for simple and highly accessible diagnostic tools. Herein, the charge modulation of conjugated polymers is demonstrated as a new mechanism for chemically responsive structural colors based on thin-film interference. A liquid-liquid interfacial self-assembly is employed to create a conjugated block copolymer film that is flexible, transferable, and highly homogeneous in thickness over a large area. Gold (Au) complexes are introduced in the self-assembly process for in situ oxidation of conjugated polymers into a hole-polaronic state that renders the polymer film responsive to the chemical environment. When transferred onto a reflective substrate, the film shows thickness-dependent tunable reflective colors due to the optical interference. Furthermore, it experiences drastic changes in its dielectric behavior upon switching of the polaronic state, thereby enabling large modulations to the interferometric colors. Such responsive thin-film colors, in turn, can be used as a simple and intuitive multicolor readout for the recognition of reductive vapors including biological decomposition products.

Water Splitting Exceeding 17% Solar-to-Hydrogen Conversion Efficiency Using Solution-Processed Ni-Based Electrocatalysts and Perovskite/Si Tandem Solar Cell.

Various noble metal-free electrocatalysts have been explored to enhance the overall water splitting efficiency. Ni-based compounds have attracted substantial attention for achieving efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts. Here, we show superior electrocatalysts based on NiFe alloy electroformed by a roll-to-roll process. NiFe (oxy)hydroxide synthesized by an anodization method for the OER catalyst shows an overpotential of 250 mV at 10 mA cm-2, which is dramatically smaller than that of bare NiFe alloy with an overpotential of 380 mV at 10 mA cm-2. Electrodeposited NiMo films for the HER catalyst also exhibit a small overpotential of 100 mV at 10 mA cm-2 compared with that of bare NiFe alloy (550 mV at 10 mA cm-2). A combined spectroscopic and electrochemical analysis reveals a clear relationship between the surface chemistry of NiFe (oxy)hydroxide and the water splitting properties. These outstanding fully solution-processed catalysts facilitate superb overall water splitting properties due to enlarged active surfaces and highly active catalytic properties. We combined a solution-processed monolithic perovskite/Si tandem solar cell with MAPb(I0.85Br0.15)3 for the direct conversion of solar energy into hydrogen energy, leading to the high solar-to-hydrogen efficiency of 17.52%. Based on the cost-effective solution processes, our photovoltaic-electrocatalysis (PV-EC) system has advantages over latest high-performance solar water splitting systems.

Daylight-Induced Metal-Insulator Transition in Ag-Decorated Vanadium Dioxide Nanorod Arrays.

Metal-insulator transition (MIT) in strongly correlated electronic materials has enormous potential with scientific and technological impacts in future oxide nanoelectronic devices. Although photo-induced MIT can provide opportunities to extend the novel functionality of strongly correlated electronic materials, there have rarely been reports on it. Here, we report MIT provoked by visible-near-infrared light in Ag-decorated VO2 nanorod arrays (NRs) because of localized surface plasmon resonance (LSPR) and its application to broadband photodetectors. Our simulation results based on the finite-difference time-domain method show that the electric field resulting from LSPR can be generated at the interface between Ag nanoparticles and VO2 layers under vis NIR illumination. Using high-resolution transmission electronic microscopy and Raman spectroscopy, we observe the MIT and structural phase transition in the Ag-decorated VO2 NRs due to the LSPR effect. The optoelectronic measurements confirm that high, fast, and broad photoresponse of Ag-decorated VO2 NRs is attributed to photo-induced MIT due to LSPR. Our study will open up a new strategy to trigger MIT in strongly correlated electronic materials through functionalization with plasmonic nanoparticles and serve as a valuable proof of concept for next-generation optoelectronic devices with fast response, low power consumption, and high performance.

Lead-Free All-Inorganic Cesium Tin Iodide Perovskite for Filamentary and Interface-Type Resistive Switching toward Environment-Friendly and Temperature-Tolerant Nonvolatile Memories.

Recently, organometallic and all-inorganic halide perovskites (HPs) have become promising materials for resistive switching (RS) nonvolatile memory devices with low power consumption because they show current-voltage hysteresis caused by fast ion migration. However, the toxicity and environmental pollution potential of lead, a common constituent of HPs, has limited the commercial applications of HP-based devices. Here, RS memory devices based on lead-free all-inorganic cesium tin iodide (CsSnI3) perovskites with temperature tolerance are successfully fabricated. The devices exhibit reproducible and reliable bipolar RS characteristics in both Ag and Au top electrodes (TEs) with different switching mechanisms. The Ag TE devices show filamentary RS behavior with ultralow operating voltages (<0.15 V). In contrast, the Au TE devices have interface-type RS behavior with gradual resistance changes. This suggests that the RS characteristics are attributed to either the formation of metal filaments or the ion migration of defects in HPs under applied electric fields. These distinct mechanisms may permit the opportunity to design devices for specific purposes. This work will pave the way for lead-free all-inorganic HP-based nonvolatile memory for commercial application in HP-based devices.

Au decoration of a graphene microchannel for self-activated chemoresistive flexible gas sensors with substantially enhanced response to hydrogen.

Graphene is one of the most promising materials for high-performance gas sensors due to its unique properties such as high sensitivity at room temperature, transparency, and flexibility. However, the low selectivity and irreversible behavior of graphene-based gas sensors are major problems. Here, we present unprecedented room temperature hydrogen detection by Au nanoclusters supported on self-activated graphene. Compared to pristine graphene sensors, the Au-decorated graphene sensors exhibit highly improved gas-sensing properties upon exposure to various gases. In particular, an unexpected substantial enhancement in H2 detection is found, which has never been reported for Au decoration on any type of chemoresistive material. Density functional theory calculations reveal that Au nanoclusters on graphene contribute to the adsorption of H atoms, whereas the surfaces of Au and graphene do not bind with H atoms individually. The discovery of such a new functionality in the existing material platform holds the key to diverse research areas based on metal nanocluster/graphene heterostructures.

Decoration of metal oxide surface with {111} form Au nanoparticles using PEGylation.

The benefit of introducing gold nanoparticles is due to the plasmon relaxation process. The plasmon decay induces various phenomena such as near-field enhancement, hot electron injection, and resonance energy transfer. Shape-controlled octahedral gold nanoparticles can maximize the efficiency of these processes. For practical purposes, a high-coverage decoration method, comparable to physical vapor deposition on a metal oxide semiconductor nanostructure, is indispensable. However, the ligand exchange reaction to attach octahedral gold nanoparticles is limited in aqueous solution due to the inactivity of the gold (111) surface as a result of a densely-packed cetyltrimethylammonium bilayer structure. Herein, we report a controllable high-coverage surface decoration method of octahedral gold nanoparticles on the targeted semiconductor nanostructures via phase transfer by an organic medium with thiolated-polyethylene glycol. Our results deliver an innovative platform for future plasmonic gold nanoparticle applications.

Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape-Controlled Au Nanoparticles.

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape-controlled Au NPs on bismuth vanadate (BiVO4 ) are studied, and a largely enhanced photoactivity of BiVO4 is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO4 achieves 2.4 mA cm-2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO4 . It is the highest value among the previously reported plasmonic Au NPs/BiVO4 . Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape-controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.

Enhanced Endurance Organolead Halide Perovskite Resistive Switching Memories Operable under an Extremely Low Bending Radius.

It was demonstrated that organolead halide perovskites (OHPs) show a resistive switching behavior with an ultralow electric field of a few kilovolts per centimeter. However, a slow switching time and relatively short endurance remain major obstacles for the realization of the next-generation memory. Here, we report a performance-enhanced OHP resistive switching device. To fabricate topologically and electronically improved OHP thin films, we added hydroiodic acid solution (for an additive) in the precursor solution of the OHP. With drastically improved morphology such as small grain size, low peak-to-valley depth, and precise thickness, the OHP thin films showed an excellent performance as insulating layers in Ag/CH3NH3PbI3/Pt cells, with an endurance of over 103 cycles, a high on/off ratio of 106, and an operation speed of 640 µs and without electroforming. We suggest plausible resistive switching and conduction mechanisms with current-voltage characteristics measured at various temperatures and with different top electrodes and device structures. Beyond the extended endurance, highly flexible resistive switching devices with a minimum bending radius of 5 mm create opportunities for use in flexible and wearable electronic devices.

Toward High-Performance Hematite Nanotube Photoanodes: Charge-Transfer Engineering at Heterointerfaces.

Vertically ordered hematite nanotubes are considered to be promising photoactive materials for high-performance water-splitting photoanodes. However, the synthesis of hematite nanotubes directly on conducting substrates such as fluorine-doped tin oxide (FTO)/glass is difficult to be achieved because of the poor adhesion between hematite nanotubes and FTO/glass. Here, we report the synthesis of hematite nanotubes directly on FTO/glass substrate and high-performance photoelectrochemical properties of the nanotubes with NiFe cocatalysts. The hematite nanotubes are synthesized by a simple electrochemical anodization method. The adhesion of the hematite nanotubes to the FTO/glass substrate is drastically improved by dipping them in nonpolar cyclohexane prior to postannealing. Bare hematite nanotubes show a photocurrent density of 1.3 mA/cm(2) at 1.23 V vs a reversible hydrogen electrode, while hematite nanotubes with electrodeposited NiFe cocatalysts exhibit 2.1 mA/cm(2) at 1.23 V which is the highest photocurrent density reported for hematite nanotubes-based photoanodes for solar water splitting. Our work provides an efficient platform to obtain high-performance water-splitting photoanodes utilizing earth-abundant hematite and noble-metal-free cocatalysts.

Organolead Halide Perovskites for Low Operating Voltage Multilevel Resistive Switching.

Organolead halide perovskites are used for low-operating-voltage multilevel resistive switching. Ag/CH3 NH3 PbI3 /Pt cells exhibit electroforming-free resistive switching at an electric field of 3.25 × 10(3) V cm(-1) for four distinguishable ON-state resistance levels. The migration of iodine interstitials and vacancies with low activation energies is responsible for the low-electric-field resistive switching via filament formation and annihilation.

Thermal stability of 2DEG at amorphous LaAlO3/crystalline SrTiO3 heterointerfaces.

At present, the generation of heterostructures with two dimensional electron gas (2DEG) in amorphous LaAlO3 (a-LAO)/SrTiO3 (STO) has been achieved. Herein, we analysed thermal stability of 2DEG at a-LAO/STO interfaces in comparison with 2DEG at crystalline LaAlO3 (c-LAO)/STO interfaces. To create 2DEG at LAO/STO interface, regardless of growing temperature from 25 to 700 °C, we found that environment with oxygen deficient during the deposition of LAO overlayer is essentially required. That indicates that the oxygen-poor condition in the system is more essential than the crystalline nature of LAO layer. 2DEG at a-LAO/STO interface is depleted upon ex situ annealing at 300 °C under 300 Torr of oxygen pressure, while that in c-LAO/STO interface is still maintained. Our result suggests that the LAO overlayer crystallinity critically affects the thermal-annealing-induced depletion of 2DEG at a-LAO/STO interface rather than the generation of 2DEG. We clearly provide that amorphous TiOx can efficiently prevent the thermal degradation of 2DEG at the a-LAO/STO interface, which gives a cornerstone for achieving thermal-stable 2DEG at a-LAO/STO interface.