Emulation of biological synapses that perform memory and learning functions is an essential step toward realization of bioinspired neuromorphic systems. Artificial synaptic devices have been developed based mostly on inorganic materials and conventional semiconductor device fabrication processes. Here, we propose flexible biomemristor devices based on lignin by a simple solution process. Lignin is one of the most abundant organic polymers on Earth and is biocompatible, biodegradable, as well as environmentally benign. This memristor emulates several essential synaptic behaviors, including analog memory switching, short-term plasticity, long-term plasticity, spike-rate-dependent plasticity, and short-term to long-term transition. A flexible lignin-based artificial synapse device can be operated without noticeable degradation under mechanical bending test. These results suggest lignin can be a promising key component for artificial synapses and flexible electronic devices.

Artificial Synapses with Short- and Long-Term Memory for Spiking Neural Networks Based on Renewable Materials.

The single-crystal-to-single-crystal (scsc) synthesis of a 2D polymer based on photochemically triggered [2 + 2]-cycloaddition is reported. Both monomer and polymer single crystals are analyzed by X-ray diffraction, which is the first case of a scsc two-dimensional polymerization based on this cycloaddition and the third ever case for a scsc synthesis of a 2D polymer. The product crystals at quantitative conversion are wet-exfoliated under mild conditions and afford countless features that are single and double layers as judged by their AFM heights of hAFM ≈ 1.2 ± 0.5 and 2.2 ± 0.5 nm, respectively. The X-ray-structure-based molecular weight of the 2D polymers and their degree of polymerization per μm2 are M = 360 MDa and Pn = 464 900, respectively. The sheet size is on the order of 5 × 5 μm2.

A Two-Dimensional Polymer Synthesized through Topochemical [2 + 2]-Cycloaddition on the Multigram Scale

The growing interest in bioinspired and sustainable electronics has induced research on biocompatible and biodegradable materials. However, conventional electronic devices have been restricted due to their nonbiodegradable and sometimes harmful and toxic materials, which can even cause environmental issues. Here, we report a resistive switching random access memory (ReRAM) device based on lignin, which is a biodegradable waste product of the paper industry. The active layer of the device can be easily formed using a simple solution process on a plastic substrate. The memory devices show stable bipolar resistive switching behavior with good endurance and retention. Appropriate control of the maximum reset voltage and compliance current can yield multibit data storage capability with at least four resistance states, which can be exploited to realize a high-density memory device. The resistive switching mechanism may be a result of formation and rupture of carbon-rich filaments. These results suggest that li...

Flexible Multistate Data Storage Devices Fabricated Using Natural Lignin at Room Temperature.

Fundamental mechanisms of energy storage, corrosion, sensing, and multiple biological functionalities are directly coupled to electrical processes and ionic dynamics at solid-liquid interfaces. In many cases, these processes are spatially inhomogeneous taking place at grain boundaries, step edges, point defects, ion channels, etc and possess complex time and voltage dependent dynamics. This necessitates time-resolved and real-space probing of these phenomena. In this review, we discuss the applications of force-sensitive voltage modulated scanning probe microscopy (SPM) for probing electrical phenomena at solid-liquid interfaces. We first describe the working principles behind electrostatic and Kelvin probe force microscopies (EFM & KPFM) at the gas-solid interface, review the state of the art in advanced KPFM methods and developments to (i) overcome limitations of classical KPFM, (ii) expand the information accessible from KPFM, and (iii) extend KPFM operation to liquid environments. We briefly discuss the theoretical framework of electrical double layer (EDL) forces and dynamics, the implications and breakdown of classical EDL models for highly charged interfaces or under high ion concentrations, and describe recent modifications of the classical EDL theory relevant for understanding nanoscale electrical measurements at the solid-liquid interface. We further review the latest achievements in mapping surface charge, dielectric constants, and electrodynamic and electrochemical processes in liquids. Finally, we outline the key challenges and opportunities that exist in the field of nanoscale electrical measurements in liquid as well as providing a roadmap for the future development of liquid KPFM.

Towards nanoscale electrical measurements in liquid by advanced KPFM techniques: a review.

Kelvin probe force microscopy (KPFM) adapts an atomic force microscope to measure electric potential on surfaces at nanometer length scales. Here we demonstrate that Heterodyne-KPFM enables scan rates of several frames per minute in air, and concurrently maintains spatial resolution and voltage sensitivity comparable to frequency-modulation KPFM, the current spatial resolution standard. Two common classes of topography-coupled artifacts are shown to be avoidable with H-KPFM. A second implementation of H-KPFM is also introduced, in which the voltage signal is amplified by the first cantilever resonance for enhanced sensitivity. The enhanced temporal resolution of H-KPFM can enable the imaging of many dynamic processes, such as such as electrochromic switching, phase transitions, and device degredation (battery, solar, etc), which take place over seconds to minutes and involve changes in electric potential at nanometer lengths.

https://iopscience.iop.org/article/10.1088/0957-4484/27/24/245705/pdf

Fast, high-resolution surface potential measurements in air with heterodyne Kelvin probe force microscopy.

Frequency modulated Kelvin probe force microscopy (FM-KFM) is the method of choice for high resolution measurements of local surface potentials, yet on coarse topographic structures most researchers revert to amplitude modulated lift-mode techniques for better stability. This approach inevitably translates into lower lateral resolution and pronounced capacitive averaging of the locally measured contact potential difference. Furthermore, local changes in the strength of the electrostatic interaction between tip and surface easily lead to topography crosstalk seen in the surface potential. To take full advantage of the superior resolution of FM-KFM while maintaining robust topography feedback and minimal crosstalk, we introduce a novel FM-KFM controller based on a Kalman filter and direct demodulation of sidebands. We discuss the origin of sidebands in FM-KFM irrespective of the cantilever quality factor and how direct sideband demodulation enables robust amplitude modulated topography feedback. Finally, we demonstrate our single-scan FM-KFM technique on an active nanoelectronic device consisting of a 70 nm diameter InAs nanowire contacted by a pair of 120 nm thick electrodes.

/pdf/kelvin-probe-force-microscopy-for-local-characterisation-of-440yw9zmd2.pdf

Kelvin probe force microscopy for local characterisation of active nanoelectronic devices

Carbon-based electronic devices are promising candidates for complementing silicon-based electronics in memory device applications. For example, sputtered thin films of amorphous carbon exhibit memristive behavior. The reported devices, however, have a minimal active area of about 50 nm diameter, leading to large set currents in the μA range. Although power efficiency would benefit from reduced drive currents, resistive switching of amorphous carbon confined to a few cubic nanometers has remained largely unexplored. Here, we investigate resistive switching in 30 nm long and 25 nm wide monolayer arrays of 10 nm gold nanoparticles patterned by direct electron-beam exposure followed by a purpose-designed emulsion-based development process. Electron-beam irradiation transforms the alkanethiol ligands of the gold nanoparticles into a solvent-resistant amorphous carbonaceous matrix allowing pattern development and imparting electronic function. We measure changes in conductivity of up to five orders of magnitude for set currents in the nA range.

Resistive switching of alkanethiolated nanoparticle monolayers patterned by electron-beam exposure

This Article shows that water in ethanol colloids of gold nanoparticles enhances the formation of linear clusters and, more important for applications in electronics, determines their assembly on surfaces. We show by dynamic light scattering that ethanol colloids contain mainly monomers and dimers and that wormlike superstructures are mostly absent, despite UV–vis evidence of aggregation. Water added to the colloid as a cosolvent was found to enhance the number of clusters as well as their average size, confirming its role in linear self-assembly, on the scale of a few particles. Water adsorbed from the atmosphere during coating was also found to be a powerful lever to tune self-assembly on surfaces. By varying the relative humidity, a sharp transition from branched to linear superstructures was observed, showing the importance of water as a cosolvent in the formation of cluster superstructures. We show that one-dimensional superstructures may form due to long-range mobility of precursor clusters on wet s...

Water-Mediated Assembly of Gold Nanoparticles into Aligned One-Dimensional Superstructures.

Nanoporous surface morphologies often perform better than their planar or bulk counterparts in phenomena such as catalysis and charge transport. In organic photovoltaics, for example, fullerene films structured on a scale corresponding to the exciton diffusion length, typically a few tens of nanometers, could improve charge separation. Existing methods to form such films, however, typically do not reach features smaller than 100 nm. Here, we propose a simple method based on interfacial nucleation and growth to produce large and flexible 2D percolating assemblies of C60 nanoparticles with diameters below 50 nm that cover up to 60% of the surface. These films can be rendered insoluble by photopolymerization and infiltrated with other functional molecules. We illustrate the benefit of such stabilized nanoporous films on the example of organic solar cells of the architecture ITO/TiO2/C60/P3HT/MoO3/Ag. Structured C60 films with interconnected morphological features perform better than planar C60 films by 50% on average, reaching a power conversion efficiency of 1.3%. Due to the ease of film fabrication and small dimensions of the C60 morphological features, these results may find application beyond organic photovoltaics, in a variety of fields where an enhanced interface with a fullerene surface is needed.

Interfacial Self-Assembly of Nanoporous C60 Thin Films; 8th International Conference on Molecular Electronics (ElecMol)

Carbon materials promise a revolution in optoelectronics, medical applications, and sensing provided that their morphology can be controlled down to the nanometer scale. Nanoporous materials are particularly appealing as they offer a drastically enlarged interfacial area compared to the corresponding planar materials. Entire fields such as organic solar cells, catalysis, or sensing may profit from an enlarged interface and facilitated molecular interaction between a carbon material and the environment. Nanoporous fullerene thin films obtained by the deposition of suspended nanoclusters of fullerene were already reported but suffered from the limitation of the size of these particles to over 100 nm. We study here a complementary method based on interfacial self-assembly forcing C60 clusters to spontaneously form 2D percolating monolayers with most morphological features in the 5–20 nm range. Analysis of these films by means of electron microscopy and scanning probe microscopy proved their morphology to be ...

Patrick A. Reissner

Papers

Kelvin probe force microscopy for local characterisation of active nanoelectronic devices

Resistive switching of alkanethiolated nanoparticle monolayers patterned by electron-beam exposure

Water-Mediated Assembly of Gold Nanoparticles into Aligned One-Dimensional Superstructures.

Interfacial Self-Assembly of Nanoporous C60 Thin Films; 8th International Conference on Molecular Electronics (ElecMol)

Visualizing Local Morphology and Conductivity Switching in Interface-Assembled Nanoporous C60 Thin Films.