Photo-Assisted Ferroelectric Domain Control for α-In2Se3 Artificial Synapses Inspired by Spontaneous Internal Electric Fields.

α-In2Se3 semiconductor crystals realize artificial synapses by tuning in-plane and out-of-plane ferroelectricity with diverse avenues of electrical and optical pulses. While the electrically induced ferroelectricity of α-In2Se3 shows synaptic memory operation, the optically assisted synaptic plasticity in α-In2Se3 has also been preferred for polarization flipping enhancement. Here, the synaptic memory behavior of α-In2Se3 is demonstrated by applying electrical gate voltages under white light. As a result, the induced internal electric field is identified at a polarization flipped conductance channel in α-In2Se3/hexagonal boron nitride (hBN) heterostructure ferroelectric field effect transistors (FeFETs) under white light and discuss the contribution of this built-in electric field on synapse characterization. The biased dipoles in α-In2Se3 toward potentiation polarization direction by an enhanced internal built-in electric field under illumination of white light lead to improvement of linearity for long-term depression curves with proper electric spikes. Consequently, upon applying appropriate electric spikes to α-In2Se3/hBN FeFETs with illuminating white light, the recognition accuracy values significantly through the artificial learning simulation is elevated for discriminating hand-written digit number images.

Sacrificial Catalyst of Carbothermal-Shock-Synthesized 1T-MoS2 Layers for Ultralong-Lifespan Seawater Battery.

A Pt-nanoparticle-decorated 1T-MoS2 layer is designed as a sacrificial electrocatalyst by carbothermal shock (CTS) treatment to improve the energy efficiency and lifespan of seawater batteries. The phase transition of MoS2 crystals from 2H to metallic 1T─induced by the simple but potent CTS treatment─improves the oxygen-reduction-reaction (ORR) activity in seawater catholyte. In particular, the MoS2-based sacrificial catalyst effectively decreases the overpotential during charging via edge oxidation of MoS2, enhancing the cycling stability of the seawater battery. Furthermore, Pt nanoparticles are deposited onto CTS-MoS2 via an additional CTS treatment. The resulting specimen exhibits a significantly low charge/discharge potential gap of Δ0.39 V, high power density of 6.56 mW cm-2, and remarkable cycling stability up to ∼200 cycles (∼800 h). Thus, the novel strategy reported herein for the preparation of Pt-decorated 1T-MoS2 by CTS treatment could facilitate the development of efficient bifunctional electrocatalysts for fabricating seawater batteries with long service life.

Gradient Lithium Metal Infusion in Ag-Decorated Carbon Fibers for High-Capacity Lithium Metal Battery Anodes.

Lithium (Li) metal is a promising anode material for high-energy-density Li batteries due to its high specific capacity. However, the uneven deposition of Li metal causes significant volume expansion and safety concerns. Here, we investigate the impact of a gradient-infused Li-metal anode using silver (Ag)-decorated carbonized cellulose fibers (Ag@CC) as a three-dimensional (3D) current collector. The loading level of the gradient-infused Li-metal anode is controlled by the thermal infusion time of molten Li. In particular, a 5 s infusion time in the Ag@CC current collector creates an appropriate space with a lithiophilic surface, resulting in improved cycling stability and a reduced volume expansion rate. Moreover, integrating a 5 s Ag@CC anode with a high-capacity cathode demonstrates superior electrochemical performance with minimal volume expansion. This suggests that a gradient-infused Li-metal anode using Ag@CC as a 3D current collector represents a novel design strategy for Li-metal-based high-capacity Li-ion batteries.

Coupling structural evolution and oxygen-redox electrochemistry in layered transition metal oxides.

Lattice oxygen redox offers an unexplored way to access superior electrochemical properties of transition metal oxides (TMOs) for rechargeable batteries. However, the reaction is often accompanied by unfavourable structural transformations and persistent electrochemical degradation, thereby precluding the practical application of this strategy. Here we explore the close interplay between the local structural change and oxygen electrochemistry during short- and long-term battery operation for layered TMOs. The substantially distinct evolution of the oxygen-redox activity and reversibility are demonstrated to stem from the different cation-migration mechanisms during the dynamic de/intercalation process. We show that the π stabilization on the oxygen oxidation initially aids in the reversibility of the oxygen redox and is predominant in the absence of cation migrations; however, the π-interacting oxygen is gradually replaced by σ-interacting oxygen that triggers the formation of O-O dimers and structural destabilization as cycling progresses. More importantly, it is revealed that the distinct cation-migration paths available in the layered TMOs govern the conversion kinetics from π to σ interactions. These findings constitute a step forward in unravelling the correlation between the local structural evolution and the reversibility of oxygen electrochemistry and provide guidance for further development of oxygen-redox layered electrode materials.

Tailored Poly(vinylidene fluoride-co-trifluoroethylene) Crystal Orientation for a Triboelectric Nanogenerator through Epitaxial Growth on a Chitin Nanofiber Film.

Tailoring the crystal orientation of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) has attracted widespread interest because of its effects on the ferroelectric properties required for various electronic devices. In this study, we investigated the epitaxial growth of PVDF-TrFE on a chitin film for developing triboelectric nanogenerators (TENGs). The crystallographic match between the chitin and PVDF-TrFE enables the development of the intended crystal orientation, with the PVDF-TrFE polarization axis aligned perpendicular to the substrate. In addition, the epitaxially grown PVDF-TrFE on chitin not only enhances the performance of the TENG but also increases the stability of the hygroscopic chitin film against water. The corresponding TENG exhibits a significantly higher output current compared to that of a nonepitaxial PVDF-TrFE/chitin film. Furthermore, the triboelectric sensors based on epitaxial PVDF-TrFE/chitin films allow the monitoring of subtle pressures, suggesting that tailoring the crystal orientation of PVDF-TrFE is a promising approach for developing high-performance TENGs.

Ordered Mesoporous Carbons with Graphitic Tubular Frameworks by Dual Templating for Efficient Electrocatalysis and Energy Storage.

Ordered mesoporous carbons (OMCs) have attracted considerable interest owing to their broad utility. OMCs reported to date comprise amorphous rod-like or tubular or graphitic rod-like frameworks, which exhibit tradeoffs between conductivity and surface area. Here we report ordered mesoporous carbons constructed with graphitic tubular frameworks (OMGCs) with tunable pore sizes and mesostructures via dual templating, using mesoporous silica and molybdenum carbide as exo- and endo-templates, respectively. OMGCs simultaneously realize high electrical conductivity and large surface area and pore volume. Benefitting from these features, Ru nanoparticles (NPs) supported on OMGC exhibit superior catalytic activity for alkaline hydrogen evolution reaction and single-cell performance for anion exchange membrane water electrolysis compared to Ru NPs on other OMCs and commercial catalysts. Further, the OMGC-based full-carbon symmetric cell demonstrates excellent performances for Li-ion capacitors.

Unveiling 79-Year-Old Ixene and Its BN-Doped Derivative.

Polycyclic aromatic hydrocarbons (PAHs) are key components of organic electronics. The electronic properties of these carbon-rich materials can be controlled through doping with heteroatoms such as B and N, however, few convenient syntheses of BN-doped PAHs have been reported. Described herein is the rationally designed, two-step syntheses of previously unknown ixene and BN-doped ixene (B2 N2 -ixene), and their characterizations. Compared to ixene, B2 N2 -ixene absorbs longer-wavelength light and has a smaller electrochemical energy gap. In addition to its single-crystal structure, scanning tunneling microscopy revealed that B2 N2 -ixene adopts a nonplanar geometry on a Au(111) surface. The experimentally obtained electronic structure of B2 N2 -ixene and the effect of BN-doping were confirmed by DFT calculations. This synthesis enables the efficient and convenient construction of BN-doped systems with extended π-conjugation that can be used in versatile organic electronics applications.

Epitaxially Grown Ferroelectric PVDF-TrFE Film on Shape-Tailored Semiconducting Rubrene Single Crystal.

Epitaxial crystallization of thin poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) films is important for the full utilization of their ferroelectric properties. Epitaxy can offer a route for maximizing the degree of crystallinity with the effective orientation of the crystals with respect to the electric field. Despite various approaches for the epitaxial control of the crystalline structure of PVDF-TrFE, its epitaxy on a semiconductor is yet to be accomplished. Herein, the epitaxial growth of PVDF-TrFE crystals on a single-crystalline organic semiconductor rubrene grown via physical vapor deposition is presented. The epitaxy results in polymer crystals globally ordered with specific crystal orientations dictated by the epitaxial relation between the polymer and rubrene crystal. The lattice matching between the c-axis of PVDF-TrFE crystals and the (210) plane of orthorhombic rubrene crystals develops two degenerate crystal orientations of the PVDF-TrFE crystalline lamellae aligned nearly perpendicular to each other. Thin PVDF-TrFE films with epitaxially grown crystals are incorporated into metal/ferroelectric polymer/metal and metal/ferroelectric polymer/semiconductor/metal capacitors, which exhibit excellent nonvolatile polarization and capacitance behavior, respectively. Furthermore, combined with a printing technique for micropatterning rubrene single crystals, the epitaxy of a PVDF-TrFE film is formed selectively on the patterned rubrene with characteristic epitaxial crystal orientation over a large area.

Epitaxial Growth of Thin Ferroelectric Polymer Films on Graphene Layer for Fully Transparent and Flexible Nonvolatile Memory.

Enhancing the device performance of organic memory devices while providing high optical transparency and mechanical flexibility requires an optimized combination of functional materials and smart device architecture design. However, it remains a great challenge to realize fully functional transparent and mechanically durable nonvolatile memory because of the limitations of conventional rigid, opaque metal electrodes. Here, we demonstrate ferroelectric nonvolatile memory devices that use graphene electrodes as the epitaxial growth substrate for crystalline poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) polymer. The strong crystallographic interaction between PVDF-TrFE and graphene results in the orientation of the crystals with distinct symmetry, which is favorable for polarization switching upon the electric field. The epitaxial growth of PVDF-TrFE on a graphene layer thus provides excellent ferroelectric performance with high remnant polarization in metal/ferroelectric polymer/metal devices. Furthermore, a fully transparent and flexible array of ferroelectric field effect transistors was successfully realized by adopting transparent poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] semiconducting polymer.

First-Principles Study of the Role of O2 and H2O in the Decoupling of Graphene on Cu(111).

The structural and electronic properties of graphene coated on a Cu(111) surface can be strongly influenced by the arrangement of adsorbates at the graphene edges. Oxygen and water intercalation at the graphene edges could lead to oxidation and hydrolysis at the graphene/Cu(111) interface, eventually causing decoupling of graphene from the Cu substrate. However, the reaction pathways for oxygen or water (or both) intercalation at the graphene edges are not well understood at the molecular level. Using ab initio density functional theory calculations, we observed a strong hybridization of π orbitals at a zigzag edge of a graphene nanoribbon (GNR) on a bare Cu(111) surface, whereas such hybridization was absent for the corresponding armchair edge under otherwise identical conditions. These results indicate that the edge type influences the oxidation chemistry beneath the GNR. Moreover, we demonstrate that the presence of oxygen species, as well as GNR, facilitates the propagation of H2O. The following decoupling mechanisms are discussed: (i) GNRs with armchair edge configurations on Cu(111) can be decoupled via a sequential reaction that involves O2 dissociation followed by H2O intercalation, whereas (ii) GNRs with zigzag edge configurations on Cu(111) can be decoupled by oxygen intercalation.

A thienoisoindigo-naphthalene polymer with ultrahigh mobility of 14.4 cm(2)/V·s that substantially exceeds benchmark values for amorphous silicon semiconductors.

By considering the qualitative benefits associated with solution rheology and mechanical properties of polymer semiconductors, it is expected that polymer-based electronic devices will soon enter our daily lives as indispensable elements in a myriad of flexible and ultra low-cost flat panel displays. Despite more than a decade of research focused on designing and synthesizing state-of-the-art polymer semiconductors for improving charge transport characteristics, the current mobility values are still not sufficient for many practical applications. The confident mobility in excess of ∼10 cm(2)/V·s is the most important requirement for enabling the realization of the aforementioned near-future products. We report on an easily attainable donor-acceptor (D-A) polymer semiconductor: poly(thienoisoindigo-alt-naphthalene) (PTIIG-Np). An unprecedented mobility of 14.4 cm(2)/V·s, by using PTIIG-Np with a high-k gate dielectric poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)), is achieved from a simple coating processing, which is of a magnitude that is very difficult to obtain with conventional TFTs by means of molecular engineering. This work, therefore, represents a major step toward truly viable plastic electronics.

Activating reversible carbonate reactions in Nasicon solid electrolyte-based Na-air battery via in-situ formed catholyte.

Out of practicality, ambient air rather than oxygen is preferred as a fuel in electrochemical systems, but CO2 and H2O present in air cause severe irreversible reactions, such as the formation of carbonates and hydroxides, which typically degrades performance. Herein, we report on a Na-air battery enabled by a reversible carbonate reaction (Na2CO3·xH2O, x = 0 or 1) in Nasicon solid electrolyte (Na3Zr2Si2PO12) that delivers a much higher discharge potential of 3.4 V than other metal-air batteries resulting in high energy density and achieves > 86 % energy efficiency at 0.1 mA cm-2 over 100 cycles. This cell design takes advantage of moisture in ambient air to form an in-situ catholyte via the deliquescent property of NaOH. As a result, not only reversible electrochemical reaction of Na2CO3·xH2O is activated but also its kinetics is facilitated. Our results demonstrate the reversible use of free ambient air as a fuel, enabled by the reversible electrochemical reaction of carbonates with a solid electrolyte.

Using self-organization to control morphology in molecular photovoltaics.

This work explores the formation of well-defined molecular p-n junctions in solution-processed self-assembled heterojunction solar cells using dodecyloxy-substituted contorted hexabenzocoronene (12-c-HBC) as a donor material and phenyl-C(70)-butyric acid methyl ester (PC(70)BM) as an acceptor. We find that the contorted 12-c-HBC molecules effectively assemble in solution to form a nested structure with the ball-shaped PC(70)BM. The result is a self-assembled molecular-scale p-n junction. When this well-defined p-n junction is embedded in active films, we can make efficient self-assembled solar cells with minimal amounts of donor material relative to the acceptor. The power conversion efficiency is drastically enhanced by the mode of donor and acceptor assembly within the film.

Controlled doping in thin-film transistors of large contorted aromatic compounds.

Bigger and better: The new thin-film organic material octabenzcircumbiphenyl (OBCB; see scheme) forms an active layer in a field effect transistor, which can be switched simultaneously with two different inputs, that is, electrical bias and protonation.

Acid- and Gas-Scavenging Electrolyte Additive Improving the Electrochemical Reversibility of Ni-Rich Cathodes in Li-Ion Batteries.

In view of their high theoretical capacities, nickel-rich layered oxides are promising cathode materials for high-energy Li-ion batteries. However, the practical applications of these oxides are hindered by transition metal dissolution, microcracking, and gas/reactive compound formation due to the undesired reactions of residual lithium species. Herein, we show that the interfacial degradation of the LiNi0.9CoxMnyAlzO2 (NCMA, x + y + z = 0.1) cathode and the graphite (Gr) anode of a representative Li-ion battery by HF can be hindered by supplementing the electrolyte with tert-butyldimethylsilyl glycidyl ether (tBS-GE). The silyl ether moiety of tBS-GE scavenges HF and PF5, thus stabilizing the interfacial layers on both electrodes, while the epoxide moiety reacts with CO2 released by the parasitic reaction between HF and Li2CO3 on the NCMA surface to afford cyclic carbonates and thus suppresses battery swelling. NCMA/Gr full cells fabricated by supplementing the baseline electrolyte with 0.1 wt % tBS-GE feature an increased capacity retention of 85.5% and deliver a high discharge capacity of 162.9 mAh/g after 500 cycles at 1 C and 25 °C. Thus, our results reveal that the molecular aspect-based design of electrolyte additives can be efficiently used to eliminate reactive species and gas components from Li-ion batteries and increase their performance.

Reversible Na Plating/Stripping with High Areal Capacity Using an Electroconductive Liquid Electrolyte System.

Anode-free sodium-metal batteries (AFSMBs) are promising candidates for maximizing energy density and minimizing cost and safety hazards in the absence of metallic sodium during cell assembly. The practical implementation of AFSMBs is hindered by the low cycling stability of Na-metal plating and stripping, particularly under high areal capacities, due to unstable solid electrolyte interphase (SEI) layer formation with electrolyte decomposition and inactive dead Na formation. Here, we proposed an electroconductive electrolyte system consisting of liquid electrolytes that accept electrons at a certain energy level and form electronically conductive and solid electrolytes that prevent internal short circuit through low electronic conductivity. The electron acceptability and high electronic conductivity of the liquid electrolyte can suppress the irreversible electron transfer with electrolyte decomposition and reutilize the inactive dead metal, respectively. The functions of the system were demonstrated using a sodium biphenyl liquid electrolyte-NASICON solid electrolyte in a seawater battery (SWB) system, which features an infinite sodium source. The anode-free SWB cells achieved a high Coulombic efficiency of ≥99.9% for over 60 cycles at a high areal capacity of ∼24 mAh/cm2. This study provides insight into the Na plating/stripping properties in anode-free systems and proposes a significant strategy for improving the reversibility of metal anodes for various battery systems with solid electrolytes.

Nanocomposite Engineering of a High-Capacity Partially Ordered Cathode for Li-Ion Batteries.

Understanding the local cation order in the crystal structure and its correlation with electrochemical performances has advanced the development of high-energy Mn-rich cathode materials for Li-ion batteries, notably Li- and Mn-rich layered cathodes (LMR, e.g., Li1.2 Ni0.13 Mn0.54 Co0.13 O2 ) that are considered as nanocomposite layered materials with C2/m Li2 MnO3 -type medium-range order (MRO). Moreover, the Li-transport rate in high-capacity Mn-based disordered rock-salt (DRX) cathodes (e.g., Li1.2 Mn0.4 Ti0.4 O2 ) is found to be influenced by the short-range order of cations, underlining the importance of engineering the local cation order in designing high-energy materials. Herein, the nanocomposite is revealed, with a heterogeneous nature (like MRO found in LMR) of ultrahigh-capacity partially ordered cathodes (e.g., Li1.68 Mn1.6 O3.7 F0.3 ) made of distinct domains of spinel-, DRX- and layered-like phases, contrary to conventional single-phase DRX cathodes. This multi-scale understanding of ordering informs engineering the nanocomposite material via Ti doping, altering the intra-particle characteristics to increase the content of the rock-salt phase and heterogeneity within a particle. This strategy markedly improves the reversibility of both Mn- and O-redox processes to enhance the cycling stability of the partially ordered DRX cathodes (nearly ≈30% improvement of capacity retention). This work sheds light on the importance of nanocomposite engineering to develop ultrahigh-performance, low-cost Li-ion cathode materials.

6,12-Diarylindeno[1,2-b]fluorenes: syntheses, photophysics, and ambipolar OFETs.

Herein we report the synthesis and characterization of a series of 6,12-diarylindeno[1,2-b]fluorenes (IFs). Functionalization with electron donor and acceptor groups influences the ability of the IF scaffold to undergo two-electron oxidation and reduction to yield the corresponding 18- and 22-π-electron species, respectively. A single crystal of the pentafluorophenyl-substituted IF can serve as an active layer in an organic field-effect transistor (OFET). The important finding is that the single-crystal OFET yields an ambipolar device that is able to transport holes and electrons.

AC field-induced polymer electroluminescence with single wall carbon nanotubes.

We developed a high-performance field-induced polymer electroluminescence (FPEL) device consisting of four stacked layers: a top metal electrode/thin solution-processed nanocomposite film of single wall carbon nanotubes (SWNTs) and a fluorescent polymer/insulator/transparent bottom electrode working under an alternating current (AC) electric field. A small amount of SWNTs that were highly dispersed in the fluorescent polymer matrix by a conjugate block copolymer dispersant significantly enhanced EL, and we were able to realize an SWNT-FPEL device with a light emission of approximately 350 cd/m(2) at an applied voltage of ±25 V and an AC frequency of 300 kHz. The brightness of the SWNT-FPEL device is much greater than those of other AC-based organic or even inorganic ELs that generally require at least a few hundred volts. Light is emitted from our SWNT-FPEL device because of the sequential injection of field-induced holes and then electron carriers through ambipolar carbon nanotubes under an AC field, followed by exciton formation in the conjugated organic layer. Field-induced bipolar charge injection provides great material design freedom for our devices; the energy level does not have to be aligned between the electrode and the emission layer, and the balance of the carrier injected and transported can be altered in contrast to that in conventional organic light-emitting diodes, leading to an extremely cost-effective and unified device architecture that is applicable to all red-green-blue fluorescent polymers.

Nonvolatile polymer memory with nanoconfinement of ferroelectric crystals.

We demonstrate significantly improved performance of a nonvolatile polymeric ferroelectric field effect transistor (FeFET) memory using nanoscopic confinement of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) within self-assembled organosilicate (OS) lamellae. Periodic OS lamellae with 30 nm in width and 50 nm in periodicity were templated using block copolymer self-assembly. Confined crystallization of PVDF-TrFE not only significantly reduces gate leakage current but also facilitates ferroelectric polarization switching. These benefits are due to the elimination of structural defects and the development of an effective PVDF-TrFE crystal orientation through nanoconfinement. A bottom gate FeFET fabricated using a single-crystalline triisopropylsilylethynyl pentacene channel and PVDF-TrFE/OS hybrid gate insulator shows characteristic source-drain current hysteresis that is fully saturated at a programming voltage of ±8 V with an ON/OFF current ratio and a data retention time of approximately 10(2) and 2 h, respectively.