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.

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.

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.

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.

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.

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.

Ionic Diffusion-Driven Ionovoltaic Transducer for Probing Ion-Molecular Interactions at Solid-Liquid Interface.

Ion-solid surface interactions are one of the fundamental principles in liquid-interfacing devices ranging from various electrochemical systems to electrolyte-driven energy conversion devices. The interplays between these two phases, especially containing charge carriers in the solid layer, work as a pivotal role in the operation of these devices, but corresponding details of those effects remain as unrevealed issues in academic fields. Herein, an ion-charge carrier interaction at an electrolyte-semiconductor interface is interrogated with an ion-dynamics-induced (ionovoltaic) energy transducer, controlled by interfacial self-assembled molecules. An electricity generating mechanism from interfacial ionic diffusion is elucidated in terms of the ion-charge carrier interaction, originated from a dipole potential effect of the self-assembled molecular layer (SAM). In addition, this effect is found to be modulated via chemical functionalization of the interfacial molecular layer and transition metal ion complexation therein. With the aiding of surface analytic techniques and a liquid-interfacing Hall measurement, electrical behaviors of the device depending on the magnitude of the ion-ligand complexation are interrogated, thereby demonstrating the ion-charge carrier interplays spanning at electrolyte-SAM-semiconductor interface. Hence, this system can be applied to study molecular interactions, including chemical and physical influences, occurring at the solid-liquid interfacial region.

Probing an Interfacial Ionic Pairing-Induced Molecular Dipole Effect in Ionovoltaic System.

A surficial molecular dipole effect depending on ion-molecular interactions has been crucial issues regarding to an interfacial potential, which can modulate solid electronic and electrochemical systems. Their properties near the interfacial region can be dictated by specific interactions between surface and adsorbates, but understandings of the corresponding details remain at interesting issues. Here, intuitive observations of an ionic pair formation-induced interfacial potential shifts are presented with an ionovoltaic system, and corresponding output signal variations are analyzed in terms of the surficial dipole changes on self-assembled monolayer. With aiding of photoelectron spectroscopies and density function theory simulation, the ionic pair formation-induced potential shifts are revealed to strongly rely on a paired molecular structure and a binding affinity of the paired ionic moieties. Chemical contributions to the binding event are interrogated in terms of polarizability in each ionic group and consistent with chaotropic/kosmotropic character of the ionic groups. Based on these findings, the ionovoltaic output changes are theoretically correlated with an adsorption isotherm reflecting the molecular dipole effect, thereby demonstrating as an efficient interfacial molecular probing method under electrolyte interfacing conditions.

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.

Analysis of Interface Phenomena for High-Performance Dual-Stacked Oxide Thin-Film Transistors via Equivalent Circuit Modeling.

Oxide thin-film transistors (TFTs) have attracted much attention because they can be applied to flexible and large-scaled switching devices. Especially, oxide semiconductors (OSs) have been developed as active layers of TFTs. Among them, indium-gallium-zinc oxide (IGZO) is actively used in the organic light-emitting diode display field. However, despite their superior off-state properties, IGZO TFTs are limited by low field-effect mobility, which critically affects display resolution and power consumption. Herein, we determine new working mechanisms in dual-stacked OS, and based on this, we develop a dual-stacked OS-based TFT with improved performance: high field-effect mobility (∼80 cm2/V·s), ideal threshold voltage near 0 V, high on-off current ratio (>109), and good stability at bias stress. Induced areas are formed at the interface by the band offset: band offset-induced area (BOIA) and BOIA-induced area (BIA). They connect the gate bias-induced area (GBIA) and electrode bias-induced area (EBIA), resulting in high current flow. Equivalent circuit modeling and the transmission line method are also introduced for more precise verification. By verifying current change with gate voltage in the single OS layer, the current flowing direction in the dual-stacked OS is calculated and estimated. This is powerful evidence to understand the conduction mechanism in a dual-stacked OS-based TFT, and it will provide new design rules for high-performance OS-based TFTs.

Conductive Polymer-Assisted Metal Oxide Hybrid Semiconductors for High-Performance Thin-Film Transistors.

Metal oxide semiconductors doped with additional inorganic cations have insufficient electron mobility for next-generation electronic devices so strategies to realize the semiconductors exhibiting stability and high performance are required. To overcome the limitations of conventional inorganic cation doping to improve the electrical characteristics and stability of metal oxide semiconductors, we propose solution-processed high-performance metal oxide thin-film transistors (TFTs) by incorporating polyaniline (PANI), a conductive polymer, in a metal oxide matrix. The chemical interaction between the metal oxide and PANI demonstrated that the defect sites and crystallinity of the semiconductor layer are controllable. In addition, the change in oxygen-related chemical bonding of PANI-doped indium oxide (InOx) TFTs induces superior electrical characteristics compared to pristine InOx TFTs, even though trace amounts of PANI are doped in the semiconductor. In particular, the average field-effect mobility remarkably enhanced from 15.02 to 26.58 cm2 V-1 s-1, the on/off current ratio improved from 108 to 109, and the threshold voltage became close to 0 V actually from -7.9 to -1.4 V.

Electron Density-Change in Semiconductor by Ion-Adsorption at Solid-Liquid Interface.

The change in electrical properties of electrodes by adsorption or desorption at interfaces is a well-known phenomenon required for signal production in electrically transduced sensing technologies. Furthermore, in terms of electrolyte-insulator-semiconductor (EIS) structure, several studies of energy conversion techniques focused on ion-adsorption at the solid-liquid interface have suggested that the electric signal is generated by ionovoltaic phenomena. However, finding substantial clues for the ion-adsorption phenomena in the EIS structure is still a difficult task because direct evidence for carrier accumulation in semiconductors by Coulomb interactions is insufficient. Here, a sophisticated Hall measurement system is demonstrated to quantitatively analyze accumulated electron density-change inside the semiconductor depending on the ion-adsorption at the solid-liquid interface. Also, an enhanced EIS-structured device is designed in an aqueous-soaked system that works with the ionovoltaic principle to monitor the ion-dynamics in liquid electrolyte media, interestingly confirming ion-concentration dependence and ion-specificity by generated peak voltages. This newly introduced peculiar method contributes to an in-depth understanding of the ionovoltaic phenomena in terms of carrier actions in the semiconductors and ionic behaviors in the aqueous-bulk phases, providing informative analysis about interfacial adsorptions that can expand the scope of ion-sensing platforms.

Precise Turn-On Voltage Control of MIOSM Thin-Film Diodes with Amorphous Indium-Gallium-Zinc Oxide.

Recently, metal-insulator-oxide semiconductor-metal (MIOSM) thin-film diodes (TFDs) have received attention as next-generation diodes due to their high rectification ratio and broad option on the operating voltage range. Nevertheless, precise turn-on voltage control of the MIOSM TFDs has been required for circuit design convenience. Here, we present a simple and accurate method of controlling the turn-on voltage of MIOSM TFDs. Studies on current-voltage characteristics reveal that controlling carrier injection into trap states in an insulator by oxygen vacancy variation of the oxide semiconductor plays a key role in the turn-on voltage shift of MIOSM TFDs. Moreover, by controlling the trap states in the insulator, the finely tuned turn-on voltages of the MIOSM TFDs are demonstrated for both low-voltage- and high-voltage-driving diodes. MIOSM TFDs with adjustable turn-on voltage, which can be built more efficiently and accurately, are expected to make oxide-based circuit designs more precise and straightforward.

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.

Highly transparent phototransistor based on quantum-dots and ZnO bilayers for optical logic gate operation in visible-light.

Highly transparent optical logic circuits operated with visible light signals are fabricated using phototransistors with a heterostructure comprised of an oxide semiconductor (ZnO) with a wide bandgap and quantum dots (CdSe/ZnS QDs) with a small bandgap. ZnO serves as a highly transparent active channel, while the QDs absorb visible light and generate photoexcited charge carriers. The induced charge carriers can then be injected into the ZnO conduction band from the QD conduction band, which enables current to flow to activate the phototransistor. The photoexcited charge transfer mechanism is investigated using time-resolved photoluminescence spectroscopy, scanning Kelvin probe microscopy, and ultraviolet photoelectron spectroscopy. Measurements show that carriers in the QD conduction band can transfer to the ZnO conduction band under visible light illumination due to a change in the Fermi energy level. Moreover, the barrier for electron injection into the ZnO conduction band from the QD conduction band is low enough to allow photocurrent generation in the QDs/ZnO phototransistor. Highly transparent NOT, NOR, and NAND optical logic circuits are fabricated using the QDs/ZnO heterostructure and transparent indium tin oxide electrodes. This work provides a means of developing highly transparent optical logic circuits that can operate under illumination with low-energy photons such as those found in visible light.

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.