LiF-Rich Solid Electrolyte Interphase Formation by Establishing Sacrificial Layer on the Separator.

The formation of a stable solid electrolyte interphase (SEI) layer is crucial for enhancing the safety and lifespan of Li metal batteries. Fundamentally, a homogeneous Li+ behavior by controlling the chemical reaction at the anode/electrolyte interface is the key to establishing a stable SEI layer. However, due to the highly reactive nature of Li metal anodes (LMAs), controlling the movement of Li+ at the anode/electrolyte interface remains challenging. Here, an advanced approach is proposed for coating a sacrificial layer called fluorinated self-assembled monolayer (FSL) on a boehmite-coated polyethylene (BPE) separator to form a stable SEI layer. By leveraging the strong affinity between the fluorine functional group and Li+, the rapid formation of a LiF-rich SEI layer in the cell production and early cycling stage is facilitated. This initial stable SEI formation promotes the subsequent homogeneous Li+ flux, thereby improving the LMA stability and yielding an enhanced battery lifespan. Further, the mechanism behind the stable SEI layer generation by controlling the Li+ dynamics through the FSL-treated BPE separator is comprehensively verified. Overall, this research offers significant contributions to the energy storage field by addressing challenges associated with LMAs, thus highlighting the importance of interfacial control in achieving a stable SEI layer.

Surface Oxygen Vacancy Inducing Li-Ion-Conducting Percolation Network in Composite Solid Electrolytes for All-Solid-State Lithium-Metal Batteries.

Composite solid electrolytes (CSEs) are newly emerging components for all-solid-state Li-metal batteries owing to their excellent processability and compatibility with the electrodes. Moreover, the ionic conductivity of the CSEs is one order of magnitude higher than the solid polymer electrolytes (SPEs) by incorporation of inorganic fillers into SPEs. However, their advancement has come to a standstill owing to unclear Li-ion conduction mechanism and pathway. Herein, the dominating effect of the oxygen vacancy (Ovac ) in the inorganic filler on the ionic conductivity of CSEs is demonstrated via Li-ion-conducting percolation network model. Based on density functional theory, indium tin oxide nanoparticles (ITO NPs) are selected as inorganic filler to determine the effect of Ovac on the ionic conductivity of the CSEs. Owing to the fast Li-ion conduction through the Ovac inducing percolation network on ITO NP-polymer interface, LiFePO4 /CSE/Li cells using CSEs exhibit a remarkable capacity in long-term cycling (154 mAh g-1 at 0.5C after 700 cycles). Moreover, by modifying the Ovac concentration of ITO NPs via UV-ozone oxygen-vacancy modification, the ionic conductivity dependence of the CSEs on the surface Ovac from the inorganic filler is directly verified.

Verification of Carrier Concentration-Dependent Behavior in Water-Infiltration-Induced Electricity Generation by Ionovoltaic Effect.

Water-infiltration-induced power generation has the renewable characteristic of generating electrical energy from ambient water. Importantly, it is found that the carrier concentration in semiconductor constituting the energy generator seriously affect the electricity generation. Nevertheless, few studies are conducted on the influence of semiconductor carrier concentration, a crucial factor on electricity generation. Due to this, understanding of the energy harvesting mechanism is still insufficient. Herein, the semiconductor carrier concentration-dependent behavior in water-infiltration-induced electricity generation and the energy harvesting mechanism by ionovoltaic effect are comprehensively verified. A clue to enhance the electric power generation efficiency is also proposed. When 20 µL of water (NaCl, 0.1 m) infiltrates into a porous CuO nanowires film (PCNF), electric power of ≈0.5 V and ≈1 µA are produced for 25 min. Moreover, the PCNF shows good practicability by generating electricity using various ambient water, turning on LEDs, and being fabricated as a curved one.

The effect of surface energy characterized functional groups of self-assembled monolayers for enhancing the electrical stability of oxide semiconductor thin film transistors.

The exact direction of the surface energy characterized functional groups of self-assembled monolayers (SAMs) is proposed for achieving enhanced electrical stability of indium gallium zinc oxide (IGZO) semiconductor thin film transistors (TFTs). The SAM treatment, particularly with the SAM functional group having lower surface energy, makes it difficult to adsorb oxygen molecules difficult onto IGZO. Such an effect greatly improves the positive bias stability (PBS) and clockwise hysteresis stability. For NH2 and CF3 functional groups, SAMs with surface energies of 49.4 mJ m-2 and 23.5 mJ m-2, respectively, improved the IGZO TFT PBS from 2.47 V to 0.32 V after the SAM treatment and the IGZO TFT clockwise hysteresis was also enhanced from 0.23 V to 0.11 V without any deterioration of TFT characteristics. Employing lower surface energy functional groups to the SAM, of the same head and body groups, passivates and protects the IGZO backchannel region from oxygen molecules in the atmosphere. Consequently, the enhanced electrical stability of IGZO TFTs can be achieved by the simple and economic SAM treatment.

The effect of Surface energy characterized functional group of self-assembled monolayer for enhancing electrical stability of oxide semiconductor thin film transistor.

The exact direction, of the surface energy characterized functional group of self-assembled monolayer (SAM), is proposed for achieving the enhanced electrical stability of indium gallium zinc oxide (IGZO) semiconductor thin film transistor (TFT). The SAM treatment, particularly at the SAM functional group having lower surface energy, makes oxygen molecules difficult to be adsorbed onto IGZO. And such an effect much improves positive bias stability (PBS) and clockwise hysteresis stability to the same tendency. For NH2 and CF3 functional group SAMs with surface energies of 49.4 mJ/m2 and 23.5 mJ/m2, respectively, the IGZO TFT PBS was improved from 2.47 V to 0.32 V after the SAM treatment and the IGZO TFT clockwise hysteresis was also enhanced from 0.23 V to 0.11 V without any deterioration of TFT characteristics. Employing lower surface energy functional group to the SAM, of same head group and body group, does passivate and protect the IGZO backchannel region from oxygen molecules in the atmosphere. Consequently, the enhanced electrical stability of IGZO TFT can be achieved by the simple and economic SAM treatment.

Atmospheric-pressure plasma treatment toward high-quality solution-processed aluminum oxide gate dielectric films in thin-film transistors.

We present an atmospheric-pressure plasma (APP) treatment technique to improve the electrical performance of solution-processed dielectric films. This technique can successfully reduce leakage current and frequency dependence of solution-processed dielectric films. The APP treatment contributes to the conversion of metal hydroxide to metal oxide, and in the case of a solution-treated AlO x dielectric thin film, it effectively ascribes to the formation of high-quality AlO x dielectric thin films. The capacitance of the untreated AlO x dielectric thin film varies up to 9.9% with frequency change, but the capacitance of the APP treated AlO x dielectric thin film varies within 1.5%. When the solution-processed InO x thin-film transistors (TFTs) were fabricated using these dielectric films, the field-effect mobility of TFTs with the APP-treated AlO x dielectric film was increased significantly from 9.77 to 26.79 cm2 V-1 s-1 in comparison to that of TFTs with the untreated AlO x dielectric film. We also have confirmed that these results are similar to the properties of the sample prepared at high annealing temperature including electrical performance, conduction mechanism and chemical structure. The APP treatment technique provides a new opportunity to effectively improve the electrical performance of solution-processed dielectrics in the atmosphere at low temperature.

Lattice Transparency of Graphene.

Here, we demonstrated the transparency of graphene to the atomic arrangement of a substrate surface, i.e., the "lattice transparency" of graphene, by using hydrothermally grown ZnO nanorods as a model system. The growth behaviors of ZnO nanocrystals on graphene-coated and uncoated substrates with various crystal structures were investigated. The atomic arrangements of the nucleating ZnO nanocrystals exhibited a close match with those of the respective substrates despite the substrates being bound to the other side of the graphene. By using first-principles calculations based on density functional theory, we confirmed the energetic favorability of the nucleating phase following the atomic arrangement of the substrate even with the graphene layer present in between. In addition to transmitting information about the atomic lattice of the substrate, graphene also protected its surface. This dual role enabled the hydrothermal growth of ZnO nanorods on a Cu substrate, which otherwise dissolved in the reaction conditions when graphene was absent.

Ion Specificity on Electric Energy Generated by Flowing Water Droplets.

The development of energy-conversion devices using water movement has actively progressed. Ionovoltaic devices, which are driven by ion dynamics, show ion specificity by which different ions with identical charges show different output performance. However, the ion specificity remains poorly understood because the influence of the ion species on generated electric signals is not elucidated. The ion specificity in electric signals induced by flowing water droplet was investigated in terms of its relationship with the potential profile across the solid-liquid interface.

Identification of Droplet-Flow-Induced Electric Energy on Electrolyte-Insulator-Semiconductor Structure.

Recently, various energy transducers driven by the relative motion of solids and liquids have been demonstrated. However, in relation to the energy transducer, a proper understanding of the dynamic behavior of ions remains unclear. Moreover, the energy density is low for practical usage mainly due to structural limitations, a lack of material development stemming from the currently poor understanding of the mechanisms, and the intermittently generated electricity given the characteristics of the water motion (pulsed signals). Here, we verify a hypothesis pertaining to the ion dynamics which govern the operation mechanism of the transducer. In addition, we demonstrate enhanced energy transducer to convert the mechanical energy of flowing water droplets into continuous electrical energy using an electrolyte-insulator-semiconductor structure as a device structure. The output power per droplet mass and the ratio of generated electric energy to the kinetic energy of water drops are 0.149v2 mW·g-1·m-2·s2 and 29.8%, respectively, where v is the speed of the water droplet.

Synthesis of Copper Oxide/Graphite Composite for High-Performance Rechargeable Battery Anode.

A novel copper oxide/graphite composite (GCuO) anode with high capacity and long cycle stability is proposed. A simple, one-step synthesis method is used to prepare the GCuO, through heat treatment of the Cu ion complex and pristine graphite. The gases generated during thermal decomposition of the Cu ion complex (H2 and CO2 ) induce interlayer expansion of the graphite planes, which assists effective ion intercalation. Copper oxide is formed simultaneously as a high-capacity anode material through thermal reduction of the Cu ion complex. Material analyses reveal the formation of Cu oxide nanoparticles and the expansion of the gaps between the graphite layers from 0.34 to 0.40 nm, which is enough to alleviate layer stress for reversible ion intercalation for Li or Na batteries. The GCuO cell exhibits excellent Li-ion battery half-cell performance, with a capacity of 532 mAh g-1 at 0.2 C (C-rate) and capacity retention of 83 % after 250 cycles. Moreover, the LiFePO4 /GCuO full cell is fabricated to verify the high performance of GCuO in practical applications. This cell has a capacity of 70 mAh g-1 and a coulombic efficiency of 99 %. The GCuO composite is therefore a promising candidate for use as an anode material in advanced Li- or Na-ion batteries.

Graphene as a thin-film catalyst booster: graphene-catalyst interface plays a critical role.

Due to its extreme thinness, graphene can transmit some surface properties of its underlying substrate, a phenomenon referred to as graphene transparency. Here we demonstrate the application of the transparency of graphene as a protector of thin-film catalysts and a booster of their catalytic efficiency. The photocatalytic degradation of dye molecules by ZnO thin films was chosen as a model system. A ZnO thin film coated with monolayer graphene showed greater catalytic efficiency and long-term stability than did bare ZnO. Interestingly, we found the catalytic efficiency of the graphene-coated ZnO thin film to depend critically on the nature of the bottom ZnO layer; graphene transferred to a relatively rough, sputter-coated ZnO thin film showed rather poor catalytic degradation of the dye molecules while a smooth sol-gel-synthesized ZnO covered with monolayer graphene showed enhanced catalytic degradation. Based on a systematic investigation of the interface between graphene and ZnO thin films, we concluded the transparency of graphene to be critically dependent on its interface with a supporting substrate. Graphene supported on an atomically flat substrate was found to efficiently transmit the properties of the substrate, but graphene suspended on a substrate with a rough nanoscale topography was completely opaque to the substrate properties. Our experimental observations revealed the morphology of the substrate to be a key factor affecting the transparency of graphene, and should be taken into account in order to optimally apply graphene as a protector of catalytic thin films and a booster of their catalysis.

Novel Synthesis, Coating, and Networking of Curved Copper Nanowires for Flexible Transparent Conductive Electrodes.

In this work, a whole manufacturing process of the curved copper nanowires (CCNs) based flexible transparent conductive electrode (FTCE) is reported with all solution processes, including synthesis, coating, and networking. The CCNs with high purity and good quality are designed and synthesized by a binary polyol coreduction method. In this reaction, volume ratio and reaction time are the significant factors for the successful synthesis. These nanowires have an average 50 nm in width and 25-40 µm range in length with curved structure and high softness. Furthermore, a meniscus-dragging deposition (MDD) method is used to uniformly coat the well-dispersed CCNs on the glass or polyethylene terephthalate substrate with a simple process. The optoelectrical property of the CCNs thin films is precisely controlled by applying the MDD method. The FTCE is fabricated by networking of CCNs using solvent-dipped annealing method with vacuum-free, transfer-free, and low-temperature conditions. To remove the natural oxide layer, the CCNs thin films are reduced by glycerol or NaBH4 solution at low temperature. As a highly robust FTCE, the CCNs thin film exhibits excellent optoelectrical performance (T = 86.62%, R(s) = 99.14 Ω â—»(-1)), flexibility, and durability (R/R(0) < 1.05 at 2000 bending, 5 mm of bending radius).

Synthesis of Cu3Sn alloy nanocrystals through sequential reduction induced by gradual increase of the reaction temperature.

Cu3Sn alloy nanocrystals are synthesized by sequential reduction of Cu and Sn precursors through a gradual increase of the reaction temperature. By transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), UV/Vis spectroscopy, and X-ray diffraction (XRD) analyses, the alloy formation mechanism of Cu3Sn nanocrystals has been studied. The incremental increase of the reaction temperature sequentially induces the reduction of Sn, the diffusion of Sn into the preformed Cu nanocrystals, resulting in the intermediate phase of Cu-Sn alloy nanocrystals, and then the formation of Cu3Sn alloy nanocrystals. We anticipate that the synthesis of Cu3Sn alloy nanocrystals encourages studies toward the synthesis of various alloy nanomaterials.

Facile synthesis of oxidation-resistant copper nanowires toward solution-processable, flexible, foldable, and free-standing electrodes.

Oxidation-resistant copper nanowires (Cu NWs) are synthesized by a polyol reduction method. These Cu NWs show excellent oxidation resistance, good dispersibility, and have a low sintering temperature. A Cu NW-based flexible, foldable, and free-standing electrode is fabricated by filtration and a sintering process. The electrode also exhibits high electrical conductivity even bending, folding, and free-standing.

Efficient Ionovoltaic Energy Harvesting via Water-Induced p-n Junction in Reduced Graphene Oxide.

Water motion-induced energy harvesting has emerged as a prominent means of facilitating renewable electricity from the interaction between nanostructured materials and water over the past decade. Despite the growing interest, comprehension of the intricate solid-liquid interfacial phenomena related to solid state physics remains elusive and serves as a hindrance to enhancing energy harvesting efficiency up to the practical level. Herein, the study introduces the energy harvester by utilizing inversion on the majority charge carrier in graphene materials upon interaction with water molecules. Specifically, various metal electrode configurations are employed on reduced graphene oxide (rGO) to unravel its distinctive charge carriers that experience the inversion in semiconductor type upon water contact, and exploit this characteristic to leverage the efficacy of generated electricity. Through the strategic arrangement of the metal electrodes on rGO membrane, the open-circuit voltage (Voc) and short-circuit current (Isc) have exhibited a remarkable augmentation, reaching 1.05 V and 31.6 µA, respectively. The demonstration of effectively tailoring carrier dynamics via electrode configuration expands the practicality by achieving high power density and elucidating how the water-induced carrier density modulation occurs in 2D nanomaterials.

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.

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.

Unveiling the Role of Side Chain for Improving Nonvolatile Characteristics of Conjugated Polymers-Based Artificial Synapse.

Interest has grown in services that consume a significant amount of energy, such as large language models (LLMs), and research is being conducted worldwide on synaptic devices for neuromorphic hardware. However, various complex processes are problematic for the implementation of synaptic properties. Here, synaptic characteristics are implemented through a novel method, namely side chain control of conjugated polymers. The developed devices exhibit the characteristics of the biological brain, especially spike-timing-dependent plasticity (STDP), high-pass filtering, and long-term potentiation/depression (LTP/D). Moreover, the fabricated synaptic devices show enhanced nonvolatile characteristics, such as long retention time (≈102 s), high ratio of Gmax/Gmin, high linearity, and reliable cyclic endurance (≈103 pulses). This study presents a new pathway for next-generation neuromorphic computing by modulating conjugated polymers with side chain control, thereby achieving high-performance synaptic properties.

Organic nonvolatile resistive switching memory based on molecularly entrapped fullerene derivative within a diblock copolymer nanostructure.

Organic nonvolatile resistive switching memory is developed via selective incorporation of fullerene derivatives, [6,6]-phenyl-C61 butyric acid methyl ester (PCBM), into the nanostructure of self-assembled poly(styrene-b-methyl methacrylate) (PS10 -b-PMMA130) diblock copolymer. PS10 -b-PMMA130 diblock copolymer provides a spatially ordered nanotemplate with a 10-nm PS nanosphere domain surrounded by a PMMA matrix. Spin casting of the blend solution of PS10 -b-PMMA130 and PCBM spontaneously forms smooth films without PCBM aggregation in which PCBM molecules are incorporated within a PS nanosphere domain of PS10 -b-PMMA130 nanostructure by preferential intermixing propensity of PCBM and PS. Based on the well-defined PS10-b-PMMA 130/PCBM nanostructure, resistive random access memory (ReRAM) exhibits significantly improved bipolar-switching behavior with stable and reproducible properties at low operating voltages (RESET at 1.3 V and SET at -1.5 V) under ambient conditions. Finally, flexible memory devices are achieved using a nanostructured PS10 -b-PMMA130 /PCBM composite in which no significant degradation of electrical properties is observed before and after bending.

Probing impact of interface mixing on the charge carrier dynamics of a solution-processed organic light emitting diode via impedance spectroscopy.

Recently, several studies have revealed that the thermal annealing process induces intermixing at the interfaces of multilayered solution-processed organic light emitting diodes (OLEDs) and enhances their device performance. Depth profiling measurements, such as neutron reflectometry, have meticulously shown that significant intermixing occurs when the annealing temperature exceeds the glass transition temperature (Tg) of OLED materials. However, electrical characterization to unveil the physical origins of the correlation between interfacial characteristics and device performance is still lacking. Here, we introduce impedance spectroscopy (IS) analysis to examine the thermally induced modifications of charge carrier dynamics in a solution-processed bilayer OLED, consisting of an emission layer and an electron transporting layer (ETL). The characteristic relaxation frequency and capacitance extracted from the capacitance-frequency spectra of the OLEDs thermally annealed at varying temperatures were utilized to separately assess the conductance of the ETL and interfacial carrier accumulation, respectively. The results show that the improved charge transport of the ETL upon thermal annealing is mainly responsible for the performance enhancement since annealing the OLEDs at a temperature above the Tg of the ETL, at which significant intermixing occurs, promotes non-radiative trap-assisted recombination and thereby deteriorates the current efficiency. The proposed IS analysis exhibits that IS can separately probe the charge transport, interfacial charge accumulation and recombination process which are crucial for accurate analysis of charge carrier dynamics in solution-processed OLEDs and can thus be utilized to identify the key factors limiting the device performance.