Heterosynaptic Plasticity in a Vertical Two-Terminal Synaptic Device.

Vertical two-terminal synaptic devices based on resistive switching have shown great potential for emulating biological signal processing and implementing artificial intelligence learning circuitries. To mimic heterosynaptic behaviors in vertical two-terminal synaptic devices, an additional terminal is required for neuromodulator activity. However, adding an extra terminal, such as a gate of the field-effect transistor, may lead to low scalability. In this study, a vertical two-terminal Pt/bilayer Sr1.8Ag0.2Nb3O10 (SANO) nanosheet/Nb:SrTiO3 (Nb:STO) device emulates heterosynaptic plasticity by controlling the number of trap sites in the SANO nanosheet via modulation of the tunneling current. Similar to biological neuromodulation, we modulated the synaptic plasticity, pulsed pair facilitation, and cutoff frequency of a simple two-terminal device. Therefore, our synaptic device can add high-level learning such as associative learning to a neuromorphic system with a simple cross-bar array structure.

Dynamic mechanical control of local vacancies in NiO thin films.

The manipulation of local ionic behavior via external stimuli in oxide systems is of great interest because it can help in directly tuning material properties. Among external stimuli, mechanical force has attracted intriguing attention as novel stimulus for ionic modulation. Even though effectiveness of mechanical force on local ionic modulation has been validated in terms of static effect, its real-time i.e., dynamic, behavior under an application of the force is barely investigated in spite of its crucial impact on device performance such as force or pressure sensors. In this study, we explore dynamic ionic behavior modulated by mechanical force in NiO thin films using electrochemical strain microscopy (ESM). Ionically mediated ESM hysteresis loops were significantly varied under an application of mechanical force. Based on these results, we were able to investigate relative relationship between the force and voltage effects on ionic motion and, further, control effectively ionic behavior through combination of mechanical and electrical stimuli. Our results can provide comprehensive information on the effect of mechanical forces on ionic dynamics in ionic systems.

Synaptic Plasticity Selectively Activated by Polarization-Dependent Energy-Efficient Ion Migration in an Ultrathin Ferroelectric Tunnel Junction.

Selectively activated inorganic synaptic devices, showing a high on/off ratio, ultrasmall dimensions, low power consumption, and short programming time, are required to emulate the functions of high-capacity and energy-efficient reconfigurable human neural systems combining information storage and processing ( Li et al. Sci. Rep. 2014 , 4 , 4096 ). Here, we demonstrate that such a synaptic device is realized using a Ag/PbZr0.52Ti0.48O3 (PZT)/La0.8Sr0.2MnO3 (LSMO) ferroelectric tunnel junction (FTJ) with ultrathin PZT (thickness of ∼4 nm). Ag ion migration through the very thin FTJ enables a large on/off ratio (107) and low energy consumption (potentiation energy consumption = ∼22 aJ and depression energy consumption = ∼2.5 pJ). In addition, the simple alignment of the downward polarization in PZT selectively activates the synaptic plasticity of the FTJ and the transition from short-term plasticity to long-term potentiation.

Controlled mechnical modification of manganite surface with nanoscale resolution.

We investigated the surfaces of magnetoresistive manganites, La(1-x)Ca(x)MnO3 and La(2-2x)Sr(1+2x)Mn2O7, using a combination of ultrahigh vacuum conductive, electrostatic and magnetic force microscopy methods. Scanning as-grown film with a metal tip, even with zero applied bias, was found to modify the surface electronic properties such that in subsequent scans, the conductivity is reduced below the noise level of conductive probe microscopy. Scanned areas also reveal a reduced contact potential difference relative to the pristine surface by ∼0.3 eV. We propose that contact-pressure of the tip modifies the electrochemical potential of oxygen vacancies via the Vegard effect, causing vacancy motion and concomitant changes of the electronic properties.

Mechanical control of electroresistive switching.

Hysteretic metal-insulator transitions (MIT) mediated by ionic dynamics or ferroic phase transitions underpin emergent applications for nonvolatile memories and logic devices. The vast majority of applications and studies have explored the MIT coupled to the electric field or temperarture. Here, we argue that MIT coupled to ionic dynamics should be controlled by mechanical stimuli, the behavior we refer to as the piezochemical effect. We verify this effect experimentally and demonstrate that it allows both studying materials physics and enabling novel data storage technologies with mechanical writing and current-based readout.

Demonstration of an energy-efficient Ising solver composed of Ovonic threshold switch (OTS)-based nano-oscillators (OTSNOs).

As there is an increasing need for an efficient solver of combinatorial optimization problems, much interest is paid to the Ising machine, which is a novel physics-driven computing system composed of coupled oscillators mimicking the dynamics of the system of coupled electronic spins. In this work, we propose an energy-efficient nano-oscillator, called OTSNO, which is composed of an Ovonic Threshold Switch (OTS) and an electrical resistor. We demonstrate that the OTSNO shows the synchronization behavior, an essential property for the realization of an Ising machine. Furthermore, we have discovered that the capacitive coupling is advantageous over the resistive coupling for the hardware implementation of an Ising solver by providing a larger margin of the variations of components. Finally, we implement an Ising machine composed of capacitively-coupled OTSNOs to demonstrate that the solution to a 14-node MaxCut problem can be obtained in 40 µs while consuming no more than 2.3 µJ of energy. Compared to a previous hardware implementation of the phase-transition nano-oscillator (PTNO)-based Ising machine, the OTSNO-based Ising machine in this work shows the performance of the increased speed by more than one order while consuming less energy by about an order.

Characterization of 12CaO x 7Al2O3 doped indium tin oxide films for transparent cathode in top-emission organic light-emitting diodes.

12CaO x 7Al2O3, insulator (C12A7) doped indium tin oxide (ITO) (ITO:C12A7) films were fabricated using a radio frequency magnetron co-sputtering system with ITO and C12A7 targets. The qualitative and quantitative properties of ITO:C12A7 films, as a function of C12A7 concentration, were examined via X-ray photoemission spectroscopy and synchrotron X-ray scattering as well as by conducting atomic force microscopy. The work function of ITO:C12A7 (1.3%) films of approximately 2.8 eV obtained by high resolution photoemission spectroscopy measurements make them a reasonable cathode for top-emission organic light-emitting diodes.

Ion-selective detection by plasticized poly(vinyl chloride) membrane in glass nanopipette with alternating voltage modulation.

An alternating current (AC) voltage modulation was applied to ion-selective observations with plasticized poly(vinyl chloride) membranes in glass nanopipettes. The liquid confronting the membranes in the nanopipettes, the conditioning process, and AC voltage modulation play important roles in the ion-selective detection. In the AC detection system developed by us, where distilled water was used as the liquid within the nanopipettes, potassium ions were selectively detected in the sample solution of sodium and potassium ions because sodium ions were captured at the membrane containing bis(12-crown-4) ionophores, before the saturation of the ionophores. The membrane lost the selectivity after the saturation. On using sodium chloride as the liquid within the nanopipette, the membrane selectively detected potassium and sodium ions before and after the saturation of ionophores, respectively. The ion-selective detection of our system can be explained by the ion extraction-diffusion-dissolution mechanism through the bis(12-crown-4) ionophores with AC voltage modulation.

Acceleration of poly(L-lactide) degradation by TiO2 nanoparticles in sunlight.

Poly(L-lactide) (PLA) is known to eventually be degraded into water and carbon dioxide by the microorganisms of the natural world. Titanium dioxide (TiO2) has been used in the biomedical and bioengineering fields as a photocatalyst. The purpose of this research project is to evaluate the influence of TiO2 added to PLA films both before and after irradiation of the films with sunlight. The PLA-TiO2 films were prepared by the addition of TiO2 (size: > 100 nm) nanoparticles to PLA. The surface changes of the PLA film were investigated before and after the films were exposed to sunlight. Tiny holes were observed in the PLA film without TiO2 nanoparticles after irradiation with sunlight, whereas large pits formed in the PLA-TiO2 films. It is suggested that PLA was degraded by the ultraviolet rays in sunlight. In addition, the decomposition speed was thought to be enhanced by the addition of TiO2, which acted as a catalyst.

Detection of single nucleotide polymorphisms using a biosensor-containing titanium-well array.

The rapid identification and verification of single nucleotide polymorphisms (SNPs) were demonstrated using a well array sensor containing anti-biofouling titanium (Ti). Probe single-stranded DNA (ssDNA) was immobilized inside a titanium-well array on amine-modified glass surfaces with anti-biofouling behavior via a streptavidin-biotin interaction. Fluorescence intensity changes originating from the hybridization of nucleic acids to protein-bound nucleic acids linked to Alexa Fluor (FL) 647 were observed. The protocol was highly sensitive and reproducible for the detection of DNA hybridization. Significant changes in fluorescence signals were observed when using target DNA with a single base mismatch, indicating that this method is applicable to SNP detection. The microarray technology for the detection of SNPs using anti-biofouling Ti and other methods can be used as a highly sensitive in vitro medical sensor, as highlighted by an increase in genotyping accuracy.

Prominent thermodynamical interaction with surroundings on nanoscale memristive switching of metal oxides.

This study demonstrates the effect of surroundings on a memristive switching at nanoscale by utilizing an open top planar-type device. NiO(x) and CoO(x) planar-type devices have exhibited a memristive behavior under atmospheric pressure, whereas TiO(2-x) planar-type devices did not show a memristive switching even under the same surroundings. A memristive behavior of TiO(2-x) planar-type devices has emerged when reducing an ambient pressure and/or employing a SiO(2) passivation layer. These results reveal that a thermodynamical interaction with surroundings critically determines the occurrence of memristive switching via varying a stability of nonstoichiometry. Since this effect tends to be more significant for smaller devices with larger specific surface area, tailoring the surrounding effect by an appropriate passivation will be essential for high density devices.

Dopamine-Regulated Plasticity in MoO3 Synaptic Transistors.

Field-effect transistor-based biosensors have gained increasing interest due to their reactive surface to external stimuli and the adaptive feedback required for advanced sensing platforms in biohybrid neural interfaces. However, complex probing methods for surface functionalization remain a challenge that limits the industrial implementation of such devices. Herein, a simple, label-free biosensor based on molybdenum oxide (MoO3) with dopamine-regulated plasticity is demonstrated. Dopamine oxidation facilitated locally at the channel surface initiates a charge transfer mechanism between the molecule and the oxide, altering the channel conductance and successfully emulating the tunable synaptic weight by neurotransmitter activity. The oxygen level of the channel is shown to heavily affect the device's electrochemical properties, shifting from a nonreactive metallic characteristic to highly responsive semiconducting behavior. Controllable responsivity is achieved by optimizing the channel's dimension, which allows the devices to operate in wide ranges of dopamine concentration, from 100 nM to sub-mM levels, with excellent selectivity compared with K+, Na+, and Ca2+.

Magnetic Skyrmion Transistor Gated with Voltage-Controlled Magnetic Anisotropy.

The paradigm shift of information carriers from charge to spin has long been awaited in modern electronics. The invention of the spin-information transistor is expected to be an essential building block for the future development of spintronics. Here, a proof-of-concept experiment of a magnetic skyrmion transistor working at room temperature, which has never been demonstrated experimentally, is introduced. With the spatially uniform control of magnetic anisotropy, the shape and topology of a skyrmion when passing the controlled area can be maintained. The findings will open a new route toward the design and realization of skyrmion-based spintronic devices in the near future.

Dual defects of cation and anion in memristive nonvolatile memory of metal oxides.

The electrically driven resistance change of metal oxides, called bipolar memristive switching, is a fascinating phenomenon in the development of next-generation nonvolatile memory alternatives to flash technology. However, our understanding of the nature of bipolar memristive switching is unfortunately far from comprehensive, especially the relationship between the electrical transport and the local nonstoichiometry. Here we demonstrate that the coexistence of anion and cation defects is critical to the transport properties of NiO, one of the most promising memristive oxides, by utilizing first-principles calculations. We find that, in the presence of both nickel and oxygen defects, which must exist in any real experimental systems, carrier concentrations of holes generated by nickel defects can be modulated by the presence or absence of oxygen defects around the nickel defect. Such alternation of local nonstoichiometry can be understood in terms of an oxygen ion drift induced by an external electric field. This implication provides a foundation for understanding universally the nature of bipolar memristive switching in various p-type metal oxides.

The role of zinc vacancies in bipolar resistance switching of Ag/ZnO/Pt memory structures.

We have presented a study of the bipolar resistance switching characteristics in the Ag/ZnO/Pt cell. This switching is accompanied by a change in intensity of the photoluminescence emission at 3.33 eV which is attributed to zinc vacancy related transitions in ZnO film. Besides voltage-driven resistance switching phenomena, a transition from a high-resistance state to a lower one is observed under laser illumination at low temperature. These results demonstrate that the bipolar resistance switching can originate due to an electron trapping/de-trapping process at zinc-vacancy defects localized in the interface layer. The Mott metal-insulator transition is proposed as a possible mechanism of the memory effect.

Intrinsic mechanisms of memristive switching.

Resistive switching (RS) memory effect in metal-oxide-metal junctions is a fascinating phenomenon toward next-generation universal nonvolatile memories. However the lack of understanding the electrical nature of RS has held back the applications. Here we demonstrate the electrical nature of bipolar RS in cobalt oxides, such as the conduction mechanism and the switching location, by utilizing a planar single oxide nanowire device. Experiments utilizing field effect devices and multiprobe measurements have shown that the nanoscale RS in cobalt oxides originates from redox events near the cathode with p-type conduction paths, which is in contrast with the prevailing oxygen vacancy based model.

Ion-Movement-Based Synaptic Device for Brain-Inspired Computing.

As the amount of data has grown exponentially with the advent of artificial intelligence and the Internet of Things, computing systems with high energy efficiency, high scalability, and high processing speed are urgently required. Unlike traditional digital computing, which suffers from the von Neumann bottleneck, brain-inspired computing can provide efficient, parallel, and low-power computation based on analog changes in synaptic connections between neurons. Synapse nodes in brain-inspired computing have been typically implemented with dozens of silicon transistors, which is an energy-intensive and non-scalable approach. Ion-movement-based synaptic devices for brain-inspired computing have attracted increasing attention for mimicking the performance of the biological synapse in the human brain due to their low area and low energy costs. This paper discusses the recent development of ion-movement-based synaptic devices for hardware implementation of brain-inspired computing and their principles of operation. From the perspective of the device-level requirements for brain-inspired computing, we address the advantages, challenges, and future prospects associated with different types of ion-movement-based synaptic devices.

Charge Transport in UV-Oxidized Graphene and Its Dependence on the Extent of Oxidation.

Graphene oxides with different degrees of oxidation are prepared by controlling UV irradiation on graphene, and the charge transport and the evolution of the transport gap are investigated according to the extent of oxidation. With increasing oxygenous defect density nD, a transition from ballistic to diffusive conduction occurs at nD≃1012 cm-2 and the transport gap grows in proportion to nD. Considering the potential fluctuation related to the e-h puddle, the bandgap of graphene oxide is deduced to be Eg≃30nD(1012cm-2) meV. The temperature dependence of conductivity showed metal-insulator transitions at nD≃0.3×1012 cm-2, consistent with Ioffe-Regel criterion. For graphene oxides at nD≥4.9×1012 cm-2, analysis indicated charge transport occurred via 2D variable range hopping conduction between localized sp2 domain. Our work elucidates the transport mechanism at different extents of oxidation and supports the possibility of adjusting the bandgap with oxygen content.

Progressive and Stable Synaptic Plasticity with Femtojoule Energy Consumption by the Interface Engineering of a Metal/Ferroelectric/Semiconductor.

In the era of "big data," the cognitive system of the human brain is being mimicked through hardware implementation of highly accurate neuromorphic computing by progressive weight update in synaptic electronics. Low-energy synaptic operation requires both low reading current and short operation time to be applicable to large-scale neuromorphic computing systems. In this study, an energy-efficient synaptic device is implemented comprising a Ni/Pb(Zr0.52 Ti0.48 )O3 (PZT)/0.5 wt.% Nb-doped SrTiO3 (Nb:STO) heterojunction with a low reading current of 10 nA and short operation time of 20-100 ns. Ultralow femtojoule operation below 9 fJ at a synaptic event, which is comparable to the energy required for synaptic events in the human brain (10 fJ), is achieved by adjusting the Schottky barrier between the top electrode and ferroelectric film. Moreover, progressive domain switching in ferroelectric PZT successfully induces both low nonlinearity/asymmetry and good stability of the weight update. The synaptic device developed here can facilitate the development of large-scale neuromorphic arrays for artificial neural networks with low energy consumption and high accuracy.

Spatial nonuniformity in resistive-switching memory effects of NiO.

Electrically driven resistance change phenomenon in metal/NiO/metal junctions, so-called resistive switching (RS), is a candidate for next-generation universal nonvolatile memories. However, the knowledge as to RS mechanisms is unfortunately far from comprehensive, especially the spatial switching location, which is crucial information to design reliable devices. In this communication, we demonstrate the identification of the spatial switching location of bipolar RS by introducing asymmetrically passivated planar NiO nanowire junctions. We have successfully identified that the bipolar RS in NiO occurs near the cathode rather than the anode. This trend can be interpreted in terms of an electrochemical redox model based on ion migration and p-type conduction.