Electrochemical Analysis of Ion Effects on Electrolyte-Gated Synaptic Transistor Characteristics.

Electrolyte-gated transistors (EGTs) are promising candidates as artificial synapses owing to their precise conductance controllability, quick response times, and especially their low operating voltages resulting from ion-assisted signal transmission. However, it is still vague how ion-related physiochemical elements and working mechanisms impact synaptic performance. Here, to address the unclear correlations, we suggest a methodical approach based on electrochemical analysis using poly(ethylene oxide) EGTs with three alkali ions: Li+, Na+, and K+. Cyclic voltammetry is employed to identify the kind of electrochemical reactions taking place at the channel/electrolyte interface, which determines the nonvolatile memory functionality of the EGTs. Additionally, using electrochemical impedance spectroscopy and qualitative analysis of electrolytes, we confirm that the intrinsic properties of electrolytes (such as crystallinity, solubility, and ion conductivity) and ion dynamics ultimately define the linearity/symmetricity of conductance modulation. Through simple but systematic electrochemical analysis, these results offer useful insights for the selection of components for high-performing artificial synapses.

Oxide Semiconductor Heterojunction Transistor with Negative Differential Transconductance for Multivalued Logic Circuits.

Multivalued logic (MVL) technology is a promising solution for improving data density and reducing power consumption in comparison to complementary metal-oxide-semiconductor (CMOS) technology. Currently, heterojunction transistors (TRs) with negative differential transconductance (NDT) characteristics, which play an important role in the function of MVL circuits, adopt organic or 2D semiconductors as active layers, but it is still difficult to apply conventional CMOS processes. Herein, we demonstrate an oxide semiconductor (OS) heterojunction TR with NDT characteristics composed of p-type copper(I) oxide (Cu2O) and n-type indium gallium zinc oxide (IGZO) using the conventional CMOS manufacturing processes. The electrical characteristics of the fabricated device exhibit a high Ion/Ioff ratio (∼3 × 103), wide NDT ranges (∼29 V), and high peak-to-valley current ratios (PVCR ≈ 25). The electrical properties of 15 devices were measured, confirming uniform performance in the PVCR, NDT range, and Ion/Ioff ratio. We analyze the device operation by varying the source/drain (S/D) position and changing the device geometry and the thickness of the Cu2O layer. Additionally, we demonstrate heterojunction ambipolar TR to elucidate the transport mechanism of NDT devices at a high gate voltage (VGS). To confirm the feasibility of the MVL circuit, we present a ternary inverter with three clearly expressed logic states that have a long intermediate state and greater margin of error induced by wide NDT regions and high PVCR.

Machine Learning Driven Channel Thickness Optimization in Dual-Layer Oxide Thin-Film Transistors for Advanced Electrical Performance.

Machine learning (ML) provides temporal advantage and performance improvement in practical electronic device design by adaptive learning. Herein, Bayesian optimization (BO) is successfully applied to the design of optimal dual-layer oxide semiconductor thin film transistors (OS TFTs). This approach effectively manages the complex correlation and interdependency between two oxide semiconductor layers, resulting in the efficient design of experiment (DoE) and reducing the trial-and-error. Considering field effect mobility (𝜇) and threshold voltage (Vth ) simultaneously, the dual-layer structure designed by the BO model allows to produce OS TFTs with remarkable electrical performance while significantly saving an amount of experimental trial (only 15 data sets are required). The optimized dual-layer OS TFTs achieve the enhanced field effect mobility of 36.1 cm2  V-1  s-1 and show good stability under bias stress with negligible difference in its threshold voltage compared to conventional IGZO TFTs. Moreover, the BO algorithm is successfully customized to the individual preferences by applying the weight factors assigned to both field effect mobility (𝜇) and threshold voltage (Vth ).

Solvent-assisted sulfur vacancy engineering method in MoS2 for a neuromorphic synaptic memristor.

Recently, two-dimensional transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) have attracted great attention due to their unique properties. To modulate the electronic properties and structure of TMDs, it is crucial to precisely control chalcogenide vacancies and several methods have already been suggested. However, they have several limitations such as plasma damage by ion bombardment. Herein, we introduced a novel solvent-assisted vacancy engineering (SAVE) method to modulate sulfur vacancies in MoS2. Considering polarity and the Hansen solubility parameter (HSP), three solvents were selected. Sulfur vacancies can be modulated by immersing MoS2 in each solvent, supported by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses. The SAVE method can further expand its application in memory devices representing memristive performance and synaptic behaviors. We represented the charge transport mechanism of sulfur vacancy migration in MoS2. The non-destructive, scalable, and novel SAVE method controlling sulfur vacancies is expected to be a guideline for constructing a vacancy engineering system of TMDs.

Sustainable Low-Temperature Hydrogen Production from Lignocellulosic Biomass Passing through Formic Acid: Combination of Biomass Hydrolysis/Oxidation and Formic Acid Dehydrogenation.

Hydrogen production from renewable resources, such as lignocellulosic biomass, is highly desired, under the most sustainable and mildest reaction conditions. In this study, a new sustainable three-step process for the production of hydrogen has been proposed. In the first step, a crude formic acid (CF) solution, which included typical reaction byproducts, in particular, acetic acid, levulinic acid, saccharides, 5-hydroxymethylfurfural, furfural, and lignin, was obtained through the combined hydrolysis/oxidation of the biomass, in the presence of diluted sulfuric acid/hydrogen peroxide, as homogeneous catalysts. In the second one, the distilled formic acid (DF) solution was obtained by distillation of the CF solution, for example, by isolating liquid byproducts, or the lignin-free CF (LCF) solution was recovered by CF filtration for the elimination of only solid lignin particles. In the final step, hydrogen was produced from the DF or LCF solutions through formic acid dehydrogenation over Pd supported on amine-functionalized mesoporous silica catalysts, in the presence of sodium formate, as an additive. The clean hydrogen, which is produced from biomass passing through formic acid, could be applied as an energy source of fuel cells. This new hydrogen production process is smart, allowing the hydrogen production with mild reaction conditions, eventually starting from different lignocellulosic feedstocks, and it could be integrated within the existing hydrothermal technology for levulinic acid production, which has been already recognized as efficient and sustainable. In addition to the production of hydrogen as an energy source of fuel cells, formic acid derived from biomass could be utilized as a platform chemical for chemical, agricultural, textile, leather, pharmaceutical, and rubber industries.

Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition.

For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h-1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance.

Reducing-Agent-Free Instant Synthesis of Carbon-Supported Pd Catalysts in a Green Leidenfrost Droplet Reactor and Catalytic Activity in Formic Acid Dehydrogenation.

The development of green synthesis methods for supported noble metal catalysts remains important challenges to improve their sustainability. Here we first synthesized carbon-supported Pd catalysts in a green Leidenfrost droplet reactor without reducing agents, high-temperature calcination and reduction procedures. When the aqueous solution containing Pd nitrate precursor, carbon support, and water is dripped on a hot plate, vapor layer is formed between a solution droplet and hot surface, which allow the solution droplet to be levitated on the hot surface (Leidenfrost phenomena). Subsequently, Pd nanoparticles can be prepared without reducing agents in a weakly basic droplet reactor created by the Leidenfrost phenomena, and then the as-prepared Pd nanoparticles are loaded on carbon supports during boiling down the droplet on hot surface. Compared to conventional incipient wetness and chemical synthetic methods, the Leidenfrost droplet reactor does not need energy-consuming, time-consuming, and environmentally unfriendly procedures, which leads to much shorter synthesis time, lower carbon dioxide emission, and more ecofriendly process in comparison with conventional synthesis methods. Moreover, the catalysts synthesized in the Leidenfrost droplet reactor provided much better catalytic activity for room-temperature formic acid decomposition than those prepared by the incipient wetness method.

Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid.

The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h(-1)) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol.

Facile synthesis of mesoporous silica and titania supraparticles by a meniscus templating route on a superhydrophobic surface and their application to adsorbents.

Mesoporous silica and titania supraparticles with controllable pore size, particle size, and macroscopic morphology were readily synthesized by a novel synthetic pathway using meniscus templating on a superhydrophobic surface, which is much simpler than well-known emulsion systems. Moreover, we first report that despite the very large radius of droplet curvature on a millimeter scale, supraparticles kept the round cap morphology due to addition of sucrose as a shape preserver as well as a pore-forming agent. In addition, mesoporous silica and titania supraparticles provided good adsorption performance for Acid Blue 25 and Cr(VI), and were easily separated from the solution by using a scoop net after adsorption tests.