Single-molecule detection with enhanced Raman scattering of tungsten oxide nanostructure.

We have found that tungsten oxide nanorods have a very large enhancement effect on Raman scattering. The nanorods with adsorbed 12CO and 13CO at the ratio of 1 : 1 were dispersed on a Si substrate and Raman mapping was performed. The Raman images of 12CO and 13CO were completely different, indicating that a very small number of molecules at the single-molecule level were observed. We also confirmed the characteristic blinking phenomenon when single-molecule detection was performed. The very large enhancement effect of Raman scattering can be attributed to the {001}CS structure of the tungsten oxide nanorods. It was confirmed from the DFT calculation results that the {001}CS structure exhibits two-dimensional electrical conduction properties.

Quantum Conductance in Memristive Devices: Fundamentals, Developments, and Applications.

Quantum effects in novel functional materials and new device concepts represent a potential breakthrough for the development of new information processing technologies based on quantum phenomena. Among the emerging technologies, memristive elements that exhibit resistive switching, which relies on the electrochemical formation/rupture of conductive nanofilaments, exhibit quantum conductance effects at room temperature. Despite the underlying resistive switching mechanism having been exploited for the realization of next-generation memories and neuromorphic computing architectures, the potentialities of quantum effects in memristive devices are still rather unexplored. Here, a comprehensive review on memristive quantum devices, where quantum conductance effects can be observed by coupling ionics with electronics, is presented. Fundamental electrochemical and physicochemical phenomena underlying device functionalities are introduced, together with fundamentals of electronic ballistic conduction transport in nanofilaments. Quantum conductance effects including quantum mode splitting, stability, and random telegraph noise are analyzed, reporting experimental techniques and challenges of nanoscale metrology for the characterization of memristive phenomena. Finally, potential applications and future perspectives are envisioned, discussing how memristive devices with controllable atomic-sized conductive filaments can represent not only suitable platforms for the investigation of quantum phenomena but also promising building blocks for the realization of integrated quantum systems working in air at room temperature.

Tunable Magnetism of Organometallic Nanoclusters by Graphene Oxide On-Surface Chemistry.

Assembly of interacting molecular spins is an attractive candidate for spintronic and quantum computing devices. Here, we report on-surface chemical assembly of aminoferrocene molecules on a graphene oxide (GO) sheet and their magnetic properties. On the GO surface, organometallic molecules having individual spins through charge transfer between the molecule and the sheet are arranged in nanoclusters having diameters of about 2 nm. The synthetic fine tuning of the reaction time enables to change the interspacing between the nanoclusters, keeping their size intact. Their magnetism changes from paramagnetic behavior to collective one gradually as the interspacing decreases. The creation of collective nature among weakly interacting molecular spins through their nanoscale arrangement on the GO surface opens a new avenue to molecular magnetism.

Dark-Field Scattering and Local SERS Mapping from Plasmonic Aluminum Bowtie Antenna Array.

On the search for the practical plasmonic materials beyond noble metals, aluminum has been emerging as a favorable candidate as it is abundant and offers the possibility of tailoring the plasmonic resonance spanning from ultra-violet to the infrared range. In this letter, in combination with the numerical electromagnetic simulations, we experimentally study the dark-field scattering spectral mapping of plasmonic resonance from the free-standing Al bowtie antenna arrays and correlate their strong nearfield enhancement with the sensing capability by means of surface-enhanced Raman spectroscopy. The spatial matching of plasmonic and Raman mapping puts another step to realize a very promising application of free-standing Al bowtie antennas for plasmonic sensing.

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.

Self-Sensitization and Photo-Polymerization of Diacetylene Molecules Self-Assembled on a Hexagonal-Boron Nitride Nanosheet.

Long poly-diacetylene chains are excellent candidates for planar, on-surface synthesized molecular electronic wires. Since hexagonal-Boron Nitride (h-BN) was identified as the best available atomically flat insulator for the deposition of poly-diacetylene precursors, we demonstrate the polymerization patterns and rate on it under UV-light irradiation, with subsequent polymer identification by atomic force microscopy. The results on h-BN indicate self-sensitization which yields blocks comprised of several polymers, unlike on the well-studied graphite/diacetylene system, where the polymers are always isolated. In addition, the photo-polymerization proceeds at least 170 times faster on h-BN, where it also results in longer polymers. Both effects are explained by the h-BN bandgap, which is larger than the diacetylene electronic excitation energy, thus allowing the transfer of excess energy absorbed by polymerized wires to adjacent monomers, triggering their polymerization. This work sets the stage for conductance measurements of single molecular poly-diacetylene wires on h-BN.

Quantum transport localization through graphene.

Localization of atomic defect-induced electronic transport through a single graphene layer is calculated using a full-valence electronic structure description as a function of the defect density and taking into account the atomic-scale deformations of the layer. The elementary electronic destructive interferences leading to Anderson localization are analyzed. The low-voltage current intensity decreases with increasing length and defect density, with a calculated localization length ζ = 3.5 nm for a defect density of 5%. The difference from the experimental defect density of 0.5% required for an oxide surface-supported graphene to obtain the same ζ is discussed, pointing out how interactions of the graphene supporting surface and surface chemical modifications also control electronic transport localization.

Self-assembling diacetylene molecules on atomically flat insulators.

Single crystal sapphire and diamond surfaces are used as planar, atomically flat insulating surfaces, for the deposition of the diacetylene compound 10,12-nonacosadiynoic acid. The surface assembly is compared with results on hexagonal boron nitride (h-BN), highly oriented pyrolytic graphite (HOPG) and MoS2 surfaces. A perfectly flat-lying monolayer of 10,12-nonacosadiynoic acid self-assembles on h-BN like on HOPG and MoS2. On sapphire and oxidized diamond surfaces, we observed assemblies of standing-up molecular layers. Surface assembly is driven by surface electrostatic dipoles. Surface polarity is partially controlled using a hydrogenated diamond surface or totally screened by the deposition of a graphene layer on the sapphire surface. This results in a perfectly flat and organized SAM on graphene, which is ready for on-surface polymerization of long and isolated molecular wires under ambient conditions.

Self-assembled diacetylene molecular wire polymerization on an insulating hexagonal boron nitride (0001) surface.

The electrical characterization of single-polymer chains on a surface is an important step towards novel molecular device development. The main challenge is the lack of appropriate atomically flat insulating substrates for fabricating single-polymer chains. Here, using atomic force microscopy, we demonstrate that the (0001) surface of an insulating hexagonal boron nitride (h-BN) substrate leads to a flat-lying self-assembled monolayer of diacetylene compounds. The subsequent heating or ultraviolet irradiation can initiate an on-surface polymerization process leading to the formation of long polydiacetylene chains. The frequency of photo-polymerization occurrence on h-BN(0001) is two orders of magnitude higher than that on graphite(0001). This is explained by the enhanced lifetime of the molecular excited state, because relaxation via the h-BN is suppressed due to a large band gap. We also demonstrate that on-surface polymerization on h-BN(0001) is possible even after the lithography process, which opens up the possibility of further electrical investigations.

Nanoionic devices enabling a multitude of new features.

In recent years, interesting nanoscale phenomena caused by physical or chemical effects due to local ion transfers near heterointerfaces using ionic conductors have been discovered, and the so-called "nanoionic devices" (which apply new functionalities gained by exploiting those phenomena) are being proposed. Up until now, nanoionic devices with unique functions that have been unattainable with conventional semiconductor devices have been developed. These devices include brain-type devices, completely solid-state electric-double-layer transistors, multi-functional on-demand-type devices, superconducting elements capable of modulating transition temperature, and so on. As for research and development on nanodevices for next-generation information and communication technologies, expected developments of these devices in the field of solid-state ionics are introduced based on the results of our research.

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.

In Situ Tuning of Magnetization and Magnetoresistance in Fe3O4 Thin Film Achieved with All-Solid-State Redox Device.

An all-solid-state redox device composed of Fe3O4 thin film and Li(+) ion conducting solid electrolyte was fabricated for use in tuning magnetization and magnetoresistance (MR), which are key factors in the creation of high-density magnetic storage devices. Electrical conductivity, magnetization, and MR were reversibly tuned by Li(+) insertion and removal. Tuning of the various Fe3O4 thin film properties was achieved by donation of an electron to the Fe(3+) ions. This technique should lead to the development of spintronics devices based on the reversible switching of magnetization and spin polarization (P). It should also improve the performance of conventional magnetic random access memory (MRAM) devices in which the ON/OFF ratio has been limited to a small value due to a decrease in P near the tunnel barrier.

Controlled Fabrication of Silk Protein Sericin Mediated Hierarchical Hybrid Flowers and Their Excellent Adsorption Capability of Heavy Metal Ions of Pb(II), Cd(II) and Hg(II).

Fabrication of protein-inorganic hybrid materials of innumerable hierarchical patterns plays a major role in the development of multifunctional advanced materials with their improved features in synergistic way. However, effective fabrication and applications of the hybrid structures is limited due to the difficulty in control and production cost. Here, we report the controlled fabrication of complex hybrid flowers with hierarchical porosity through a green and facile coprecipitation method by using industrial waste natural silk protein sericin. The large surface areas and porosity of the microsize hybrid flowers enable water purification through adsorption of different heavy metal ions. The high adsorption capacity depends on their morphology, which is changed largely by sericin concentration in their fabrication. Superior adsorption and greater selectivity of the Pb(II) ions have been confirmed by the characteristic growth of needle-shaped nanowires on the hierarchical surface of the hybrid flowers. These hybrid flowers show excellent thermal stability even after complete evaporation of the protein molecules, significantly increasing the porosity of the flower petals. A simple, cost-effective and environmental friendly fabrication method of the porous flowers will lead to a new solution to water pollution required in the modern industrial society.

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.

The Way to Nanoarchitectonics and the Way of Nanoarchitectonics.

The critical differences between microtechnology and nanotechnology are discussed, and the necessity of a new paradigm, nanoarchitectonics, is proposed for the future development of nanotechnology. An important task in material fabrication is to harmonize various factors and effects, and to combine them into functional nanomaterials and nanosystems. It is the way of architectonics rather than that of an individual technology. Therefore, a novel terminology, nanoarchitectonics (nano + architecto +nics) has been proposed as a new paradigm of materials science and technology on the nanoscale. The statement by Feynman that "there's plenty of room at the bottom" is really true. With nanoarchitectonics in our hands, we can re-open the door to Feynman's huge room.

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.

Moiré Nanosphere Lithography.

We have developed moiré nanosphere lithography (M-NSL), which incorporates in-plane rotation between neighboring monolayers, to extend the patterning capability of conventional nanosphere lithography (NSL). NSL, which uses self-assembled layers of monodisperse micro/nanospheres as masks, is a low-cost, scalable nanofabrication technique and has been widely employed to fabricate various nanoparticle arrays. Combination with dry etching and/or angled deposition has greatly enriched the family of nanoparticles NSL can yield. In this work, we introduce a variant of this technique, which uses sequential stacking of polystyrene nanosphere monolayers to form a bilayer crystal instead of conventional spontaneous self-assembly. Sequential stacking leads to the formation of moiré patterns other than the usually observed thermodynamically stable configurations. Subsequent O2 plasma etching results in a variety of complex nanostructures. Using the etched moiré patterns as masks, we have fabricated complementary gold nanostructures and studied their optical properties. We believe this facile technique provides a strategy to fabricate complex nanostructures or metasurfaces.

Effect of Ionic Conductivity on Response Speed of SrTiO3-Based All-Solid-State Electric-Double-Layer Transistor.

An all-solid-state electric-double-layer transistor (EDLT) with a Y-stabilized ZrO2 (YSZ) proton conductor/SrTiO3 (STO) single crystal has been fabricated to investigate ionic conductivity effect on the response speed, which should be a key parameter for development of next-generation EDLTs. The drain current exhibited a 4-order-of-magnitude increment by electrostatic carrier doping at the YSZ/STO interface due to ion migration, and the behavior strongly depended on the operation temperature. An Arrhenius-type plot of the ionic conductivity (σ(i)) in the YSZ and t(c)⁻¹, which is a current-rise time needed for charge accumulation at the YSZ/STO interface, shows a synchronized variation, indicating a proportional relationship between the two parameters. Analysis of the σ(i)-t(c) diagram shows that, in contrast to conventional EDLTs, the response speed should reach picosecond order at room temperature by using extreme miniaturization and superionic conductors. Furthermore, the diagram indicates that plenty of solid electrolytes, which have not been used due to the lack of criteria for evaluation, can be a candidate for all-solid-state EDLTs exceeding the carrier density of conventional EDLTs, even though the response speed becomes comparably lower than those of FETs.

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.