The Role of the Internal Capacitance in Organic Memristive Device for Neuromorphic and Sensing Applications

Organic electronics has recently emerged as a promising candidate for the emulation of brain-like functionalities, especially at the device level. Among the proposed technologies, memristive devices have gained an increasing attention due to their non-volatile behavior which makes them suitable for the implementation of artificial neuronal networks. However, most of them have an energy-costly switching mechanism which limits the approach of brain like energy efficiency. Different from them, organic memristive devices (OMDs) have a narrow switching window and implement neuromorphic characteristics at voltages <= 1 V. Despite OMDs potentialities in bioinspired electronics, guidelines for the design of devices and materials are still missing. Here it is shown that the device capacitance represents a significant degree of freedom for targeting devices applications. It is also shown that a single OMD emulates activity dependent synaptic functions and neuronal temporal and spatial summation, taking advantage of its three-terminals configuration. Interestingly, despite the neuromorphic applications, OMDs can also sense and amplify incoming signals on the basis of their capacitive and/or resistive values. This spectrum of applications, ranging from volatile to non-volatile characteristics and from neuromorphic computing to bio signals sensing, sets the stage for the realization of integrated circuits for adaptive sensing

On the Interpretation of Hysteresis Loop for Electronic and Ionic Currents in Organic Memristive Devices

Being promising elements for neuromorphic computation, memristive devices have been often described as crucial elements for mimicking important synapse properties, such as memory and learning. Among them, organic memristive devices (OMDs) can claim low-cost fabrication processes and the easy tunability of their electrical properties. Up to now, the major bottleneck for their larger uses in neuromorphic computation is low rate of the resistance switching and stability. Herein, a new approach is reported, based on the use of a liquid electrolyte, leading to the manufacturing of OMD with higher stability and faster resistive switching

Electrical conductivity modulation of crosslinked composite nanofibers based on PEO and PEDOT:PSS

The aim of this work is to investigate the development of nanofiber mats, based on intrinsically conductive polymers (ICPs), which show simultaneously a high electrical conductivity and mandatory insoluble water properties. In particular, the nanofibers, thanks to their properties such as high surface area, porosity, and their ability to offer a preferential pathway for electron flow, play a crucial role to improve the essential characteristics ensured by ICPs. The nanofiber mats are obtained by electrospinning process, starting from a polymeric solution made of polyethylene oxide (PEO) and poly(styrene sulfonate) (PEDOT:PSS). PEO is selected not only as a dopant to increase the electrical/ionic conductivity, as deeply reported in the literature, but also to ensure the proper stability of the polymeric jet, to collect a dried nanofiber mat. Moreover, in the present work, two different treatments are proposed in order to induce crosslinking between PEO chains and PEDOT:PSS, made insoluble into water which is the final sample. The first process is based on a heating treatment, conducted at 130°C under nitrogen atmosphere for 6 h, named the annealing treatment. The second treatment is provided by UV irradiation that is effective to induce a final crosslinking, when a photoinitiator, such as benzophenone, is added. Furthermore, we demonstrate that both crosslinking treatments can be used to verify the preservation of nanostructures and their good electrical conductivity after water treatment (i.e., water resistance). In particular, we confirm that the crosslinking method with UV irradiation results to being more effective than the standard annealing treatment. Indeed, we demonstrate that the processing time, required to obtain the final crosslinked nanofiber mats with a high electrical conductance, results to being smaller than the one needed during the heating treatment

PEDOT:PSS Morphostructure and ion-to-electron transduction and amplification mechanisms in organic electrochemical transistors

Organic electrochemical transistors (OECTs) represent a powerful and versatile type of organic-based device, widely used in biosensing and bioelectronics due to potential advantages in terms of cost, sensitivity, and system integration. The benchmark organic semiconductor they are based on is poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), the electrical properties of which are reported to be strongly dependent on film morphology and structure. In particular, the literature demonstrates that film processing induces morphostructural changes in terms of conformational rearrangements in the PEDOT:PSS in-plane phase segregation and out-of-plane vertical separation between adjacent PEDOT-rich domains. Here, taking into account these indications, we show the thickness-dependent operation of OECTs, contextualizing it in terms of the role played by PEDOT:PSS film thickness in promoting film microstructure tuning upon controlled-atmosphere long-lasting thermal annealing (LTA). To do this, we compared the LTA-OECT response to that of OECTs with comparable channel thicknesses that were exposed to a rapid thermal annealing (RTA). We show that the LTA process on thicker films provided OECTs with an enhanced amplification capability. Conversely, on lower thicknesses, the LTA process induced a higher charge carrier modulation when the device was operated in sensing mode. The provided experimental characterization also shows how to optimize the OECT response by combining the control of the microstructure via solution processing and the effect of postdeposition processing

Flexible and reusable parylene C mask technology for applications in cascade impactor air quality monitoring systems

The development of traceable new methodologies to quantify elemental air pollutants in particulate matter (PM) supports modernization of methods used in air quality monitoring networks in Europe. In the framework of the EURAMET EMPIR AEROMET II project, the combination of cascade impactor aerosol sampling and total reflection X-ray fluorescence elemental spectroscopy (TXRF) was investigated. This technique requires a traceable calibration based on reference samples. This paper describes a new, simple and effective method to produce such reference samples using flexible, reusable, and low-cost parylene C shadow masks, fabricated by photolithographic steps. These shadow masks can be used to produce reference samples that mimic the Dekati cascade impactor's deposition patterns by applying as-prepared micro stencils to 30 mm acrylic substrates and evaporating a reference material (Ti) in arrangements of thin circular dots. The highly flexible direct patterning of acrylic discs with reference material, otherwise impossible with conventional photolithography, allows multiple reusing of the same micro stencils. The aspect ratios of the dots could be repeated with an error less than 4%. A first set of standard reference samples for the 13 stages of the Dekati cascade impactor was produced and preliminary TXRF measurements of the deposited Ti masses were performed. The centricity of the deposition patterns turned out to be an important parameter for the quality of the TXRF results. The parylene mask technology for the production of reference samples turns out to be a promising new approach for the traceable calibration of TXRF spectrometers for the quantification of element concentrations in environmental aerosol samples but, due to its great versatility, it could be used for several other micropatterning applications on conventional and unconventional substrates

Electrospun nanofibers: From food to energy by engineered electrodes in microbial fuel cells

Microbial fuel cells (MFCs) are bio-electrochemical devices able to directly transduce chemical energy, entrapped in an organic mass named fuel, into electrical energy through the metabolic activity of specific bacteria. During the last years, the employment of bio-electrochemical devices to study the wastewater derived from the food industry has attracted great interest from the scientific community. In the present work, we demonstrate the capability of exoelectrogenic bacteria used in MFCs to catalyze the oxidation reaction of honey, employed as a fuel. With the main aim to increase the proliferation of microorganisms onto the anode, engineered electrodes are proposed. Polymeric nanofibers, based on polyethylene oxide (PEO-NFs), were directly electrospun onto carbon-based material (carbon paper, CP) to obtain an optimized composite anode. The crucial role played by the CP/PEO-NFs anodes was confirmed by the increased proliferation of microorganisms compared to that reached on bare CP anodes, used as a reference material. A parameter named recovered energy (Erec) was introduced to determine the capability of bacteria to oxidize honey and was compared with the Erec obtained when sodium acetate was used as a fuel. CP/PEO-NFs anodes allowed achieving an Erec three times higher than the one reached with a bare carbon-based anode

Nanomolar detection of the antitumor drug tamoxifen by flexible organic electrochemical devices

Organic Electrochemical Transistors (OECTs) represent a versatile tool successfully exploited in the field of Bioelectronics. In particular, OECTs have been used for the detection of a wide set of bioanalytes, often showing superior performance compared to that of commonly used sensors. In this study, we propose a flexible, disposable OECT, based on poly (3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) channels and few layers graphene (FLG) sheets gate electrodes, for the detection of Tamoxifen (TAM), an important antitumor drug widely used in breast cancer therapy. The optimal device operation conditions in terms of sensitivity and limit of detection (LOD) have been investigated too

Design, Fabrication, and Experimental Validation of Microfluidic Devices for the Investigation of Pore-Scale Phenomena in Underground Gas Storage Systems

The understanding of multiphase flow phenomena occurring in porous media at the pore scale is fundamental in a significant number of fields, from life science to geo and environmental engineering. However, because of the optical opacity and the geometrical complexity of natural porous media, detailed visual characterization is not possible or is limited and requires powerful and expensive imaging techniques. As a consequence, the understanding of micro-scale behavior is based on the interpretation of macro-scale parameters and indirect measurements. Microfluidic devices are transparent and synthetic tools that reproduce the porous network on a 2D plane, enabling the direct visualization of the fluid dynamics. Moreover, microfluidic patterns (also called micromodels) can be specifically designed according to research interests by tuning their geometrical features and surface properties. In this work we design, fabricate and test two different micromodels for the visualization and analysis of the gas-brine fluid flow, occurring during gas injection and withdrawal in underground storage systems. In particular, we compare two different designs: a regular grid and a real rock-like pattern reconstructed from a thin section of a sample of Hostun rock. We characterize the two media in terms of porosity, tortuosity and pore size distribution using the A* algorithm and CFD simulation. We fabricate PDMS-glass devices via soft lithography, and we perform preliminary air-water displacement tests at different capillary numbers to observe the impact of the design on the fluid dynamics. This preliminary work serves as a validation of design and fabrication procedures and opens the way to further investigations

Single-Step 3D Printing of Silver-Patterned Polymeric Devices for Bacteria Proliferation Control

This work describes the fabrication of silver-patterned polymeric devices via light-based 3D printing methods from a tailored resin. An acrylate resin containing silver nitrate (AgNO3) as a silver precursor is employed to generate silver nanoparticles (AgNPs) through the in situ reduction of the metallic salt. The silver-based resin is processed through a customized stereolithography SL-3D printing to fabricate structures with silver-patterned surfaces. This customized SL-printer (emitting at 405&nbsp;nm) offers the possibility of adjusting the machine settings during the printing process allowing for AgNPs to be selectively generated by modifying the laser settings during the 3D printing step. Thus, the resin photopolymerization and the photoinduced formation of AgNPs-based strands can be sequentially achieved during the same printing process with the same light source and using the same printable resin. The fabricated silver-patterned devices exhibit different surface features that might be exploited in systems working in a marine environment to control biofilm proliferation. As a proof-of-concept, the antimicrobial behavior of the silver-based 3D printed device is tested against environmental bacterial mixed communities via UV–vis spectroscopy and evaluating the absorbance change. Further tests, however, would be needed to reinforce the evidence of the bacteria behavior on the silver-patterned 3D printed devices

Aerosol Jet Printed Organic Memristive Microdevices Based on a Chitosan:PANI Composite Conductive Channel

In this study we show a chitosan:polyaniline (CPA)-based ink, responding to eco-biofriendly criteria, specifically developed for the manufacturing of the first organic memristive device (OMD) with an aerosol jet printed conductive channel. Our contribution is in the context of bioelectronics, where there is an increasing interest in emulating neuro-morphic functions. In this framework, memristive devices and systems have been shown to be well suited. In particular organic-based devices are envisaged as very promising in some applications, such as brain-machine interfacing, owing to specific properties of organics (e.g., biocompatibility, mixed ionic-electronic conduction). On the other hand, the research activities on flexible organic (bio)electronic devices and direct writing (DW) noncontact techniques increasingly overlap in the effort of achieving reliable applications benefiting from the rapid prototyping to accomplish a fast device optimization. In this context, ink-based techniques, such as aerosol jet printing (AJP), although particularly well suited to implement 3D-printed electronics due to advantages it offers in terms of a wide set of allowed printable materials, still require research efforts aimed at conferring printability to the desired precursors. The developed CPA composite was characterized by FTIR, DLS, and MALDI-TOF techniques, while the related aerosol jet printed films were studied by SEM and profilometry. Taking advantage of the intrinsic and stable electrical conductivity of CPA films, which do not necessarily require any acidic treatment to promote a sustained charge carrier conduction, 10 mu m short-channel OMDs were hence manufactured by interfacing the printed CPA layers with a solid polyelectrolyte (SPE). We accordingly demonstrated prototypes of stable and best performing OMD devices with downscaled features, showing well-defined counterclockwise hysteresis/rectification and an enhanced durability. These properties pave the way to further improving performance, as well as to realizing a direct integration of the devices into hardware neural networks by in-line fabrication routes