Effects of Mg Doping to a LiCoO2 Channel on the Synaptic Plasticity of Li Ion-Gated Transistors.

Artificial synapses with ideal functionalities are essential in hardware neural networks to allow for energy-efficient analog computing. However, the realization of linear and symmetric weight updates in real synaptic devices has proven challenging and ultimately limits the online training capabilities of neural network systems. Herein, we investigate the effect of Mg doping on a LiCoO2 (LCO) channel in a Li ion-gated synaptic transistor, so as to improve long-term and short-term plasticity. Two transistor structures, based on a lithium phosphorus oxynitride electrolyte, were examined by using undoped LCO and Mg-doped LCO as the channel material between the source and drain electrodes. It was found that Mg doping increased the initial channel conductance by 3 orders of magnitude, which is probably due to the substitution of Co3+ by Mg2+ and the compensation of hole creation. It was further found that the doped channel transistor showed good retention characteristics and better linearity of long-term potentiation and depression when voltage pulses were applied to the gate electrode. The improved retention and linearity are attributed to an extended range of the insulator-to-conductor transition by Mg doping and Li-ion extraction/insertion cooperated in the LCO channel. Using the obtained synaptic weight update, artificial neural network simulations demonstrated that the doped channel transistor shows an image recognition accuracy of ∼80% for handwritten digits, which is higher than ∼65% exhibited by the undoped channel transistor. Mg doping also improved short-term plasticity such as paired-pulse facilitation/depression and Hebbian spike timing-dependent plasticity. These results indicate that elemental doping to the channel of Li ion-gated synaptic transistors could be a useful procedure for realizing robust neuromorphic systems based on analog computing.

Proton-Gated Synaptic Transistors, Based on an Electron-Beam Patterned Nafion Electrolyte.

Neuromorphic processors using artificial neural networks are the center of attention for energy-efficient analog computing. Artificial synapses act as building blocks in such neural networks for parallel information processing and data storage. Herein we describe the fabrication of a proton-gated synaptic transistor using a Nafion electrolyte thin film, which is patterned by electron-beam lithography (EBL). The device has an active channel of indium-zinc-oxide (IZO) between the source and drain electrodes, which shows Ohmic behavior with a conductance level on the order of 100 µS. Under voltage applications to the gate electrode, the channel conductance is changed due to the injection and extraction of protons between the IZO channel and the Nafion electrolyte, emulating various synaptic functions with short-term and long-term plasticity. When positive (negative) gate voltage pulses are consecutively applied, the device exhibits long-term potentiation (depression) at the same number of steps as the number of input pulses. Based on these characteristics, an artificial neural network using this transistor shows ∼84% image recognition accuracy for handwritten digits. The subject transistor also successfully mimics paired-pulse facilitation and depression, Hebbian spike-timing-dependent plasticity, and Pavlovian associative learning followed by extinction activities. Finally, dynamical pattern image memorization is demonstrated in a 5 × 5 array of these synaptic transistors. The results indicate that EBL patternable Nafion electrolytes have great potential for use in the fabrication and circuit-level integration of synaptic devices for neuromorphic computing applications.

Nitrogen Plasma Enhanced Low Temperature Atomic Layer Deposition of Magnesium Phosphorus Oxynitride (MgPON) Solid-State Electrolytes.

Solid-state batteries (SSBs) that use solid electrolytes instead of flammable liquid electrolytes have the potential to generate higher specific capacity and offer better safety. Magnesium (Mg) based SSBs with Mg metal anodes are considered to be one of the most promising energy storage candidates, because it gives high theoretical volumetric capacities of 3830 mAh cm-3 . Here, we demonstrate an atomic layer deposition (ALD) process with a double nitrogen plasma process that successfully produces nitrogen-incorporated magnesium phosphorus oxynitride (MgPON) solid-state electrolyte (SSE) thin films at a low deposition temperature of 125 °C. The ALD MgPON SSEs exhibit an ionic conductivity of 0.36 and 1.2 µS cm-1 at 450 and 500 °C, respectively. The proposed ALD strategy shows the ability of conformal deposition nitrogen-doped SSEs on pattered substrates and is attractive for using nitride ion-conducing films as protective or wetting interlayers in solid-state Mg and Li batteries.

Neuromorphic System for Edge Information Encoding: Emulating Retinal Center-Surround Antagonism by Li-Ion-Mediated Highly Interactive Devices.

Center-surround antagonism, a key mechanism in the retina, contributes to the encoding of edge contrast rather than of the overall information on a visual image. Here, a neuromorphic system consisting of multiple ionic devices is built, where each device has a lithium cobalt oxide channel arranged on a common lithium phosphorus oxynitride electrolyte. Because of the migration of Li ions between the channels through the electrolyte, the devices are highly interactive, as is seen with retinal neurons. On the basis of the excitation of single devices and device-to-device inhibition, the system successfully emulates the antagonistic center-surround receptive field and the Mach band effect in which perceived contrast is enhanced at the edges between dark and bright regions. Furthermore, a two-dimensional array system is simulated to implement edge detection for real images. This scheme enables computer vision tasks with simple and effective operations, owing to the intrinsic properties of the materials employed.

Resistivity control by the electrochemical removal of dopant atoms from a nanodot.

Doping impurity atoms into semiconductor materials changes the resistance of the material. Selecting the atomic species of a dopant and the precise control of the number of dopant atoms in a unit volume can control the resistance to a desired value. The number of dopant atoms is usually controlled when the materials are synthesized. It can also be controlled after synthesizing by injecting dopant atoms using an ion implantation technique. This physical method has now enabled atom by atom implantation at the desired position. Here, we propose an additional technique, based on the electrochemical potential of dopant atoms in a material. The technique enables the dynamic control of the number of dopant atoms through the application of bias to the material. We demonstrate the controlled removal of dopant atoms using Ag2+δS and Ag-doped Ta2O5 as model materials. The change in resistance accompanying the removal of dopant atoms is also observed.

Ionic decision-maker created as novel, solid-state devices.

Decision-making is being performed frequently in areas of computation to obtain better performance in a wide variety of current intelligent activities. In practical terms, this decision-making must adapt to dynamic changes in environmental conditions. However, because of limited computational resources, adaptive decision-making is generally difficult to achieve using conventional computers. The ionic decision-maker reported here, which uses electrochemical phenomena, has excellent dynamic adaptabilities, as demonstrated by its ability to solve multiarmed bandit problems (MBPs) in which a gambler given a choice of slot machines must select the appropriate machines to play so as to maximize the total reward in a series of trials. Furthermore, our ionic decision-maker successfully solves dynamic competitive MBPs, which cause serious loss due to the collision of selfish users in communication networks. The technique used in our devices offers a shift toward decision-making using the motion of ions, an approach that could find myriad applications in computer science and technology, including artificial intelligence.

Nanoarchitectonics for Controlling the Number of Dopant Atoms in Solid Electrolyte Nanodots.

Controlling movements of electrons and holes is the key task in developing today's highly sophisticated information society. As transistors reach their physical limits, the semiconductor industry is seeking the next alternative to sustain its economy and to unfold a new era of human civilization. In this context, a completely new information token, i.e., ions instead of electrons, is promising. The current trend in solid-state nanoionics for applications in energy storage, sensing, and brain-type information processing, requires the ability to control the properties of matter at the ultimate atomic scale. Here, a conceptually novel nanoarchitectonic strategy is proposed for controlling the number of dopant atoms in a solid electrolyte to obtain discrete electrical properties. Using α-Ag2+δ S nanodots with a finite number of nonstoichiometry excess dopants as a model system, a theory matched with experiments is presented that reveals the role of physical parameters, namely, the separation between electrochemical energy levels and the cohesive energy, underlying atomic-scale manipulation of dopants in nanodots. This strategy can be applied to different nanoscale materials as their properties strongly depend on the number of doping atoms/ions, and has the potential to create a new paradigm based on controlled single atom/ion transfer.

Laser Patterning of Optically Reconfigurable Transistor Channels in a Photochromic Diarylethene Layer.

Optical switching organic field-effect transistors (OFETs) provide a new direction for optoelectronics based on photochromic molecules. However, the patterning of OFETs is difficult because conventional fabrication processes, including lithography and ion etching, inevitably cause severe damage to organic molecules. Here, we demonstrate laser patterning of one-dimensional (1D) channels on an OFET with a photochromic diarylethene (DAE) layer. The main findings are (i) a number of 1D channels can be repeatedly written and erased in the DAE layer by scanning focused ultraviolet and visible light laser beams alternately between the source and drain electrodes, (ii) the conductivity (or resistivity) of the 1D channel can be controlled by the illumination conditions, such as the laser power density and the scan speed, and (iii) it is possible to draw an analogue adder circuit by optically writing 1D channels so that a portion of the channels overlaps and to perform optical summing operations by local laser illumination of the respective channels. These findings will open new possibilities for realizing various optically reconfigurable, low-dimensional organic transistor circuits, which are not possible with conventional thin film OFETs.

Surfactant-Triggered Nanoarchitectonics of Fullerene C60 Crystals at a Liquid-Liquid Interface.

Here, we report the structural and morphological modulation of fullerene C60 crystals induced by nonionic surfactants diglycerol monolaurate (C12G2) and monomyristate (C14G2). C60 crystals synthesized at a liquid-liquid interface comprising isopropyl alcohol (IPA) and a saturated solution of C60 in ethylbenzene (EB) exhibited a one-dimensional (1D) morphology with well-defined faceted structure. Average length and diameter of the faceted rods were ca. 4.8 µm and 747 nm, respectively. Powder X-ray diffraction pattern (pXRD) confirmed a hexagonal-close packed (hcp) structure with cell dimensions ca. a = 2.394 nm and c = 1.388 nm. The 1D rod morphology of C60 crystals was transformed into "Konpeito candy-like" crystals (average diameter ca. 1.2 µm) when the C60 crystals were grown in the presence of C12G2 or C14G2 surfactant (1%) in EB. The pXRD spectra of "Konpeito-like" crystals could be assigned to the face-centered cubic (fcc) phase with cell dimensions ca. a = 1.4309 nm (for C12G2) and a = 1.4318 nm (for C14G2). However, clusters or aggregates of C60 lacking a uniform morphology were observed at lower surfactant concentrations (0.1%), although these crystals exhibited an fcc crystal structure. The self-assembled 1D faceted C60 crystals and "Konpeito-like" C60 crystals exhibited intense photoluminescence (PL) (∼35 times greater than pC60) and a blue-shifted PL intensity maximum (∼15 nm) compared to those of pC60, demonstrating the potential use of this method for the control of the optoelectronic properties of fullerene nanostructures. The "Konpeito-like" crystals were transformed into high surface area nanoporous carbon with a graphitic microstructure upon heat-treatment at 2000 °C. The heat-treated samples showed enhanced electrochemical supercapacitance performance (specific capacitance is ca. 175 F g-1, which is about 20 times greater than pC60) with long cyclic stability demonstrating the potential of the materials in supercapacitor device fabrication.

Functional double-shelled silicon nanocrystals for two-photon fluorescence cell imaging: spectral evolution and tuning.

Functional near-IR (NIR) emitting nanoparticles (NPs) adapted for two-photon excitation fluorescence cell imaging were obtained starting from octadecyl-terminated silicon nanocrystals (ncSi-OD) of narrow photoluminescence (PL) spectra having no long emission tails, continuously tunable over the 700-1000 nm window, PL quantum yields exceeding 30%, and PL lifetimes of 300 µs or longer. These NPs, consisting of a Pluronic F127 shell and a core made up of assembled ncSi-OD kept apart by an octadecyl (OD) layer, were readily internalized into the cytosol, but not the nucleus, of NIH3T3 cells and were non-toxic. Asymmetrical field-flow fractionation (AF4) analysis was carried out to determine the size of the NPs in water. HiLyte Fluor 750 amine was linked via an amide link to NPs prepared with Pluronic-F127-COOH, as a first demonstration of functional NIR-emitting water dispersible ncSi-based nanoparticles.

Kinetic factors determining conducting filament formation in solid polymer electrolyte based planar devices.

Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices.

Mechanism for Conducting Filament Growth in Self-Assembled Polymer Thin Films for Redox-Based Atomic Switches.

The switching mechanisms of atomic switches based on poly(ethylene oxide) (PEO) are systematically investigated. By using self-assembled PEO and Ag-PEO thin films, stack-structured devices exhibit stable bipolar switching behavior over 10(3) cycles. Direct observation of filament growth behavior in planar-structured devices reveals the effects of the polymer thin-film morphology, and the presence of electrochemically active electrodes, on the switching characteristics.

Ultra-low voltage and ultra-low power consumption nonvolatile operation of a three-terminal atomic switch.

Nonvolatile three-terminal operation, with a very small range of bias sweeping (-80 to 250 mV), a high on/off ratio of up to six orders of magnitude, and a very small gate leakage current (<1 pA), is demonstrated using an Ag (gate)/Ta2 O5 (ionic transfer layer)/Pt (source), Pt (drain) three-terminal atomic switch structure.

Position detection and observation of a conducting filament hidden under a top electrode in a Ta2O5-based atomic switch.

Resistive random access memories (ReRAMs) are promising next-generation memory devices. Observation of the conductive filaments formed in ReRAMs is essential in understanding their operating mechanisms and their expected ultimate performance. Finding the position of the conductive filament is the key process in the preparation of samples for cross-sectional transmission electron microscopy (TEM) imaging. Here, we propose a method for locating the position of conductive filaments hidden under top electrodes. Atomic force microscopy imaging with a conductive tip detects the current flowing through a conductive filament from the bottom electrode, which reaches its maximum at a position that is above the conductive filament. This is achieved by properly biasing a top electrode, a bottom electrode and the conductive tip. This technique was applied to Cu/Ta2O5/Pt atomic switches, revealing the formation of a single Cu filament in a device, although the device had a large area of 5 × 5 µm(2). Change in filament size was clearly observed depending on the compliance current used in the set process. It was also found from the TEM observation that the cross-sectional shape of the formed filament varies considerably, which is attributable to different Cu nuclei growth mechanisms.

In situ and nonvolatile photoluminescence tuning and nanodomain writing demonstrated by all-solid-state devices based on graphene oxide.

In situ and nonvolatile tuning of photoluminescence (PL) has been achieved based on graphene oxide (GO), the PL of which is receiving much attention because of various potential applications of the oxide (e.g., display, lighting, and nano-biosensor). The technique is based on in situ and nonvolatile tuning of the sp(2) domain fraction to the sp(3) domain fraction (sp(2)/sp(3) fraction) in GO through an electrochemical redox reaction achieved by solid electrolyte thin films. The all-solid-state variable PL device was fabricated by GO and proton-conducting mesoporous SiO2 thin films, which showed an extremely low PL background. The device successfully tuned the PL peak wavelength in a very wide range from 393 to 712 nm, covering that for chemically tuned GO, by adjusting the applied DC voltage within several hundred seconds. We also demonstrate the sp(2)/sp(3) fraction tuning using a conductive atomic force microscope. The device achieved not only writing, but also erasing of the sp(2)/sp(3)-fraction-tuned nanodomain (both directions operation). The combination of these techniques is applicable to a wide range of nano-optoelectronic devices including nonvolatile PL memory devices and on-demand rewritable biosensors that can be integrated into nano- and microtips which are transparent, ultrathin, flexible, and inexpensive.

Aligned 1-D nanorods of a π-gelator exhibit molecular orientation and excitation energy transport different from entangled fiber networks.

Linear π-gelators self-assemble into entangled fibers in which the molecules are arranged perpendicular to the fiber long axis. However, orientation of gelator molecules in a direction parallel to the long axes of the one-dimensional (1-D) structures remains challenging. Herein we demonstrate that, at the air-water interface, an oligo(p-phenylenevinylene)-derived π-gelator forms aligned nanorods of 340 ± 120 nm length and 34 ± 5 nm width, in which the gelator molecules are reoriented parallel to the long axis of the rods. The orientation change of the molecules results in distinct excited-state properties upon local photoexcitation, as evidenced by near-field scanning optical microscopy. A detailed understanding of the mechanism by which excitation energy migrates through these 1-D molecular assemblies might help in the design of supramolecular structures with improved charge-transport properties.

Synaptic plasticity and memory functions achieved in a WO3-x-based nanoionics device by using the principle of atomic switch operation.

A compact neuromorphic nanodevice with inherent learning and memory properties emulating those of biological synapses is the key to developing artificial neural networks rivaling their biological counterparts. Experimental results showed that memorization with a wide time scale from volatile to permanent can be achieved in a WO3-x-based nanoionics device and can be precisely and cumulatively controlled by adjusting the device's resistance state and input pulse parameters such as the amplitude, interval, and number. This control is analogous to biological synaptic plasticity including short-term plasticity, long-term potentiation, transition from short-term memory to long-term memory, forgetting processes for short- and long-term memory, learning speed, and learning history. A compact WO3-x-based nanoionics device with a simple stacked layer structure should thus be a promising candidate for use as an inorganic synapse in artificial neural networks due to its striking resemblance to the biological synapse.

Generic relevance of counter charges for cation-based nanoscale resistive switching memories.

Resistive switching memories (ReRAMs) are the major candidates for replacing the state-of-the-art memory technology in future nanoelectronics. These nonvolatile memory cells are based on nanoionic redox processes and offer prospects for high scalability, ultrafast write and read access, and low power consumption. The interfacial electrochemical reactions of oxidation and reduction of ions necessarily needed for resistive switching result inevitably in nonequilibrium states, which play a fundamental role in the processes involved during device operation. We report on nonequilibrium states in SiO2-based ReRAMs being induced during the resistance transition. It is demonstrated that the formation of metallic cations proceeds in parallel to reduction of moisture, supplied by the ambient. The latter results in the formation of an electromotive force in the range of up to 600 mV. The outcome of the study highlights the hitherto overlooked necessity of a counter charge/reaction to keep the charge electroneutrality in cation-transporting thin films, making it hard to analyze and compare experimental results under different ambient conditions such as water partial pressure. Together with the dependence of the electromotive force on the ambient, these results contribute to the microscopic understanding of the resistive switching phenomena in cation-based ReRAMs.

Surfactant-assisted assembly of fullerene (C60) nanorods and nanotubes formed at a liquid-liquid interface.

Herein we report the surfactant-triggered assembly of fullerene (C60) into 3D flowerlike microcrystals at the liquid-liquid interface. C60 crystals were grown using a liquid-liquid interfacial precipitation (LLIP) method by layering surfactant solution in butanol with a saturated solution of C60 in benzene. In the LLIP method, it is suggested that the crystal formation mechanism is driven by supersaturation related to the low C60 solubility in alcohol. We found that the dimensions of the synthesized C60 flowers depend on the concentration and surfactant type. In the absence of surfactant (i.e., in the butanol/benzene system), 1D C60 nanowhiskers (nanorods) and C60 nanotubes (diameter 400 nm-2 µm and length 5-20 µm) are obtained. However, when surfactants are incorporated into the system flowerlike microcrystals consisting of C60 nanotubes are observed. For instance, crystals grown at the interface of a 0.01% diglycerol monolaurate (C12G2) nonionic surfactant in butanol with benzene lead to the formation of flower-shaped microcrystals of average sizes in the range of 10-35 µm. To the best of our knowledge, this is the first example of the surfactant-assisted assembly of C60 crystals. X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements have shown that fullerene flowers have a hexagonal structure with cell dimensions of a = 2.539 nm and c = 1.021 nm, which differ from that of pristine C60. Mixtures of flower-shaped C60 crystals and free-standing C60 nanotubes are found in the 0.1% C12G2/butanol system. However, clusters or giant aggregates of nanowhiskers lacking any specific shape are observed in the 1% C12G2/butanol system although these crystals exhibit hexagonal close-packed structures. Flower-shaped C60 microcrystals are also observed with anionic surfactants cetyltrimethylammonium bromide (CTAB) and cetyltrimethylammonium chloride (CTAC). C60 flowers obtained from 0.01% CTAB and 0.01% CTAC also exhibit hexagonal structures with cell dimensions of a = 2.329 nm and c = 1.273 nm, a = 2.459 nm and c = 0.938 nm, respectively. Our C60 flowers exhibit intense photoluminescence (PL) and a blue-shifted PL intensity maximum compared to the same parameters for pristine C60, demonstrating the potential to control the optoelectronic properties of fullerene-based nanostructures.

Conductance quantization and synaptic behavior in a Ta2O5-based atomic switch.

Quantized conductance was observed in a cation-migration-based resistive switching memory cell with a simple metal-insulator-metal (MIM) structure using a thin Ta(2)O(5) layer. The observed conductance changes are attributed to the formation and dissolution of a metal filament with an atomic point contact of different integer multiples in the Ta(2)O(5) layer. The results demonstrate that atomic point contacts can be realized in an oxide-based MIM structure that functions as a nanogap-based atomic switch (Terabe et al 2005 Nature 433 47). By applying consecutive voltage pulses at periodic intervals of different times, we also observed an effect analogous to the long-term potentiation of biological synapses, which shows that the oxide-based atomic switch has potential for use as an essential building block of neural computing systems.