An Artificial Olfactory System Based on a Chemi-Memristive Device.

Technologies based on the fusion of gas sensors and neuromorphic computing to mimic the olfactory system have immense potential. However, the implementation of neuromorphic olfactory systems remains in a state of infancy because conventional gas sensors lack the necessary functions. Therefore, this study proposes a hysteretic "chemi-memristive gas sensor" based on oxygen vacancy chemi-memristive dynamics that differ from that of conventional gas sensors. After the memristive switching operation, the redox reaction with the external gas molecules is enhanced, resulting in the generation and elimination of oxygen vacancies that induce rapid current changes. In addition, the pre-generated oxygen vacancies enhance the post-sensing properties. Therefore, fast responses, short recovery times, and hysteretic gas response are achieved by the proposed sensor at room temperature. Based on the advantageous functionality of the sensor, device-level olfactory systems that can monitor the history of input gas stimuli are experimentally demonstrated as a potential application. Moreover, analog conductance modulation induced by oxidizing and reducing gases enables the conversion of external gas stimuli into synaptic weights and hence the realization of typical synaptic functionalities without an additional device or circuit. The proposed chemi-memristive device represents an advance in the bioinspired technology adopted in creating artificial intelligence systems.

Breathable MOFs Layer on Atomically Grown 2D SnS2 for Stable and Selective Surface Activation.

2D transition metal dichalcogenides (TMDs) have significant research interests in various novel applications due to their intriguing physicochemical properties. Notably, one of the 2D TMDs, SnS2 , has superior chemiresistive sensing properties, including a planar crystal structure, a large surface-to-volume ratio, and a low electronic noise. However, the long-term stability of SnS2 in humid conditions remains a critical shortcoming towards a significant degradation of sensitivity. Herein, it is demonstrated that the subsequent self-assembly of zeolite imidazolate framework (ZIF-8) can be achieved in situ growing on SnS2 nanoflakes as the homogeneous porous materials. ZIF-8 layer on SnS2 allows the selective diffusion of target gas species, while effectively preventing the SnS2 from severe oxidative degradation. Molecular modeling such as molecular dynamic simulation and DFT calculation, further supports the mechanism of sensing stability and selectivity. From the results, the in situ grown ZIF-8 porous membrane on 2D materials corroborates the generalizable strategy for durable and reliable high-performance electronic applications of 2D materials.

Highly Reliable Threshold Switching Characteristics of Surface-Modulated Diffusive Memristors Immune to Atmospheric Changes.

Active cation-based diffusive memristors featuring essentially volatile threshold switching have been proposed for novel applications, such as a selector in a one-selector-and-one-resistor structure and signal generators in neuromorphic computing. However, the high variability of the switching behavior, which results from the high electroforming voltage, external environmental conditions, and transition to the non-volatile switching mode in a high-current range, is considered a major impediment to such applications. Herein, for the first time, we developed a highly reliable threshold switching device immune to atmospheric changes based on an ultraviolet-ozone (UVO)-treated diffusive memristor consisting of Ag and SiO2 nanorods (NRs). UVO treatment forms a stable water reservoir on the surface of SiO2 NRs, facilitating the redox reaction and ion migration of Ag. Consequently, diffusive memristors possess reliable switching characteristics, including electroforming-free, repeatable, and consistent switching with resistance to changes in ambient conditions and compliance levels during operation. We demonstrated that our approach is suitable for various metal oxides and can be used in numerous applications.

Autonomous Resonance-Tuning Mechanism for Environmental Adaptive Energy Harvesting.

An innovative autonomous resonance-tuning (ART) energy harvester is reported that utilizes adaptive clamping systems driven by intrinsic mechanical mechanisms without outsourcing additional energy. The adaptive clamping system modulates the natural frequency of the harvester's main beam (MB) by adjusting the clamping position of the MB. The pulling force induced by the resonance vibration of the tuning beam (TB) provides the driving force for operating the adaptive clamp. The ART mechanism is possible by matching the natural frequencies of the TB and clamped MB. Detailed evaluations are conducted on the optimization of the adaptive clamp tolerance and TB design to increase the pulling force. The energy harvester exhibits an ultrawide resonance bandwidth of over 30 Hz in the commonly accessible low vibration frequency range (<100 Hz) owing to the ART function. The practical feasibility is demonstrated by evaluating the ART performance under both frequency and acceleration-variant conditions and powering a location tracking sensor.

Surface-Dominated HfO2 Nanorod-Based Memristor Exhibiting Highly Linear and Symmetrical Conductance Modulation for High-Precision Neuromorphic Computing.

The switching characteristics and performance of oxide-based memristors are predominately determined by oxygen- or oxygen-vacancy-mediated redox reactions and the consequent formation of conducting filaments (CFs). Devices using oxide thin films as the switching layer usually require an electroforming process for subsequent switching operations, which induces large device-to-device variations. In addition, the hard-to-control redox reaction during repeated switching causes random fluctuations or degradation of each resistance state, hindering reliable switching operations. In this study, an HfO2 nanorod (NR)-based memristor is proposed for simultaneously achieving highly uniform, electroforming-free, fast, and reliable analogue switching properties. The well-controlled redox reaction due to the easy gas exchange with the environment at the surface of the NRs enhances the generation of oxygen or oxygen vacancies during the switching operation, resulting in electroforming-free and reliable switching behavior. In addition, the one-dimensional surface growth of CFs facilitates highly linear conductance modulation with smaller conductance changes compared with the two-dimensional volume growth in thin-film-based memristors, resulting in a high accuracy of >92% in the Modified National Institute of Standards and Technology pattern-recognition test and desirable spike-timing-dependent plasticity.

Identification of Chemical Vapor Mixture Assisted by Artificially Extended Database for Environmental Monitoring.

A fully integrated sensor array assisted by pattern recognition algorithm has been a primary candidate for the assessment of complex vapor mixtures based on their chemical fingerprints. Diverse prototypes of electronic nose systems consisting of a multisensory device and a post processing engine have been developed. However, their precision and validity in recognizing chemical vapors are often limited by the collected database and applied classifiers. Here, we present a novel way of preparing the database and distinguishing chemical vapor mixtures with small data acquisition for chemical vapors and their mixtures of interest. The database for individual vapor analytes is expanded and the one for their mixtures is prepared in the first-order approximation. Recognition of individual target vapors of NO2, HCHO, and NH3 and their mixtures was evaluated by applying the support vector machine (SVM) classifier in different conditions of temperature and humidity. The suggested method demonstrated the recognition accuracy of 95.24%. The suggested method can pave a way to analyze gas mixtures in a variety of industrial and safety applications.

Controllable SiOx Nanorod Memristive Neuron for Probabilistic Bayesian Inference.

Modern artificial neural network technology using a deterministic computing framework is faced with a critical challenge in dealing with massive data that are largely unstructured and ambiguous. This challenge demands the advances of an elementary physical device for tackling these uncertainties. Here, we designed and fabricated a SiOx nanorod memristive device by employing the glancing angle deposition (GLAD) technique, suggesting a controllable stochastic artificial neuron that can mimic the fundamental integrate-and-fire signaling and stochastic dynamics of a biological neuron. The nanorod structure provides the random distribution of multiple nanopores all across the active area, capable of forming a multitude of Si filaments at many SiOx nanorod edges after the electromigration process, leading to a stochastic switching event with very high dynamic range (≈5.15 × 1010 ) and low energy (≈4.06 pJ). Different probabilistic activation (ProbAct) functions in a sigmoid form are implemented, showing its controllability with low variation by manufacturing and electrical programming schemes. Furthermore, as an application prospect, based on the suggested memristive neuron, we demonstrated the self-resting neural operation with the local circuit configuration and revealed probabilistic Bayesian inferences for genetic regulatory networks with low normalized mean squared errors (≈2.41 × 10-2 ) and its robustness to the ProbAct variation.

Artificial Adaptive and Maladaptive Sensory Receptors Based on a Surface-Dominated Diffusive Memristor.

A biological receptor serves as sensory transduction from an external stimulus to an electrical signal. It allows humans to better match the environment by filtering out repetitive innocuous information and recognize potentially damaging stimuli through key features, including adaptive and maladaptive behaviors. Herein, for the first time, the authors develop substantial artificial receptors involving both adaptive and maladaptive behaviors using diffusive memristor. Metal-oxide nanorods (NR) as a switching matrix enable the electromigration of an active metal along the surface of the NRs under electrical stimulation, resulting in unique surface-dominated switching dynamics with the advantage of fast Ag migration and fine controllability of the conductive filament. To experimentally demonstrate its potential application, a thermoreceptor system is constructed using memristive artificial receptors. The proposed surface-dominated diffusive memristor allows the direct emulation of the biological receptors, which represents an advance in the bioinspired technology adopted in creating artificial intelligence systems.

Metal Oxide Nanorods-Based Sensor Array for Selective Detection of Biomarker Gases.

The breath gas analysis through gas phase chemical analysis draws attention in terms of non-invasive and real time monitoring. The array-type sensors are one of the diagnostic methods with high sensitivity and selectivity towards the target gases. Herein, we presented a 2 × 4 sensor array with a micro-heater and ceramic chip. The device is designed in a small size for portability, including the internal eight-channel sensor array. In2O3 NRs and WO3 NRs manufactured through the E-beam evaporator's glancing angle method were used as sensing materials. Pt, Pd, and Au metal catalysts were decorated for each channel to enhance functionality. The sensor array was measured for the exhaled gas biomarkers CH3COCH3, NO2, and H2S to confirm the respiratory diagnostic performance. Through this operation, the theoretical detection limit was calculated as 1.48 ppb for CH3COCH3, 1.9 ppt for NO2, and 2.47 ppb for H2S. This excellent detection performance indicates that our sensor array detected the CH3COCH3, NO2, and H2S as biomarkers, applying to the breath gas analysis. Our results showed the high potential of the gas sensor array as a non-invasive diagnostic tool that enables real-time monitoring.

Polarization- and Electrode-Optimized Polyvinylidene Fluoride Films for Harsh Environmental Piezoelectric Nanogenerator Applications.

While piezoelectric nanogenerators have demonstrated the effective conversion of tiny mechanical vibrations to electricity, their performances are rarely examined under harsh environmental conditions. Here, a multilayered polyvinylidene fluoride (PVDF) film-based piezoelectric nanogenerator (ML-PENG) is demonstrated to generate considerable and stable power outputs even at extremely low temperatures and pressures, and under strong UV. Up-/down-polarized PVDF films are alternately stacked, and Ag electrodes are intercalated between the two adjacent films. At -266 °C and 10-5  Torr, the ML-PENG generates an open-circuit voltage of 1.1 V, a short-circuit current density of 8 nA cm-2 , and a power density of 4.4 nW cm-2 . The piezoelectric outputs are quite stable against prolonged illumination of UV, large temperature- and pressure-variations, and excessive mechanical vibrations. The piezoelectric power density is greatly enhanced above the freezing and glass transition temperatures of PVDF and recorded to be 10, 105, and 282 nW cm-2 at -73, 0, and 77 °C, respectively. The ML-PENG generates sufficient power to operate five light-emitting diodes by harvesting biomechanical energy under simulated Martian conditions. This work suggests that polarization- and electrode-optimized ML-PENG can serve as a reliable and economic power source in harsh and inaccessible environments like polar areas of Earth and extraterrestrial Mars.

On-Chip Chemiresistive Sensor Array for On-Road NO x Monitoring with Quantification.

The adverse effects of air pollution on respiratory health make air quality monitoring with high spatial and temporal resolutions essential especially in cities. Despite considerable interest and efforts, the application of various types of sensors is considered immature owing to insufficient sensitivity and cross-interference under ambient conditions. Here, a fully integrated chemiresistive sensor array (CSA) with parts-per-trillion sensitivity is demonstrated with its application for on-road NO x monitoring. An analytical model is suggested to describe the kinetics of the sensor responses and quantify molecular binding affinities. Finally, the full characterization of the system is connected to implement on-road measurements on NO x vapor with quantification as its ultimate field application. The obtained results suggest that the CSA shows potential as an essential unit to realize an air-quality monitoring network with high spatial and temporal resolutions.

Piezoelectric Energy Harvesting Design Principles for Materials and Structures: Material Figure-of-Merit and Self-Resonance Tuning.

Piezoelectric energy harvesters (PEHs) aim to generate sufficient power to operate targeting device from the limited ambient energy. PEH includes mechanical-to-mechanical, mechanical-to-electrical, and electrical-to-electrical energy conversions, which are related to PEH structures, materials, and circuits, respectively; these should be efficient for increasing the total power. This critical review focuses on PEH structures and materials associated with the two major energy conversions to improve PEH performance. First, the resonance tuning mechanisms for PEH structures maintaining continuous resonance, regardless of a change in the vibration frequency, are presented. Based on the manual tuning technique, the electrically- and mechanically-driven self-resonance tuning (SRT) techniques are introduced in detail. The representative SRT harvesters are summarized in terms of tunability, power consumption, and net power. Second, the figure-of-merits of the piezoelectric materials for output power are summarized based on the operating conditions, and optimal piezoelectric materials are suggested. Piezoelectric materials with large kij , dij , and gij values are suitable for most PEHs, whereas those with large kij and Qm values should be used for on-resonance conditions, wherein the mechanical energy is directly supplied to the piezoelectric material. This comprehensive review provides insights for designing efficient structures and selection of proper piezoelectric materials for PEHs.

Cellular Auxetic Structures for Mechanical Metamaterials: A Review.

Recent advances in lithography technology and the spread of 3D printers allow us a facile fabrication of special materials with complicated microstructures. The materials are called "designed materials" or "architectured materials" and provide new opportunities for material development. These materials, which owing to their rationally designed architectures exhibit unusual properties at the micro- and nano-scales, are being widely exploited in the development of modern materials with customized and improved performance. Meta-materials are found to possess superior and unusual properties as regards static modulus (axial stress divided by axial strain), density, energy absorption, smart functionality, and negative Poisson's ratio (NPR). However, in spite of recent developments, it has only been feasible to fabricate a few such meta-materials and to implement them in practical applications. Against such a backdrop, a broad review of the wide range of cellular auxetic structures for mechanical metamaterials available at our disposal and their potential application areas is important. Classified according to their geometrical configuration, this paper provides a review of cellular auxetic structures. The structures are presented with a view to tap into their potential abilities and leverage multidimensional fabrication advances to facilitate their application in industry. In this review, there is a special emphasis on state-of-the-art applications of these structures in important domains such as sensors and actuators, the medical industry, and defense while touching upon ways to accelerate the material development process.

Wafer-Scale, Conformal, and Low-Temperature Synthesis of Layered Tin Disulfides for Emerging Nonplanar and Flexible Electronics.

Two-dimensional (2D) metal dichalcogenides have drawn considerable interest because they offer possibilities for the implementation of emerging electronics. The emerging electronics are moving toward two major directions: vertical expansion of device space and flexibility. However, the development of a synthesis method for 2D metal dichalcogenides that meets all the requirements remains a significant challenge. Here, we propose a promising method for wafer-scale, conformal, and low-temperature (≤240 °C) synthesis of single-phase SnS2 via the atomic layer deposition technique. There is a trade-off relationship between the crystallinity and orientation preference of SnS2, which is efficiently eliminated by the two-step growth occurring at different temperatures. Consequently, the van der Waals layers of the highly crystalline SnS2 are parallel to the substrate. Thin-film transistors (TFTs) comprising the SnS2 layer show reasonable electrical performances (field-effect mobility: ∼0.8 cm2 V-1 s-1 and on/off ratio: ∼106), which are comparable to that of a single-crystal SnS2 flake. Moreover, we demonstrate nonplanar and flexible TFTs to identify the feasibility of the implementation of future electronics. Both the diagonal-structured TFT and flexible TFT fabricated without a transfer process show electrical performances comparable to those of rigid and planar TFTs. Particularly, the flexible TFT does not exhibit substantial degradation even after 2000 bending cycles. Our work would provide decisive opportunities for the implementation of future electronic devices utilizing 2D metal chalcogenides.

Strong stress-composition coupling in lithium alloy nanoparticles.

The stress inevitably imposed during electrochemical reactions is expected to fundamentally affect the electrochemistry, phase behavior and morphology of electrodes in service. Here, we show a strong stress-composition coupling in lithium binary alloys during the lithiation of tin-tin oxide core-shell nanoparticles. Using in situ graphene liquid cell electron microscopy imaging, we visualise the generation of a non-uniform composition field in the nanoparticles during lithiation. Stress models based on density functional theory calculations show that the composition gradient is proportional to the applied stress. Based on this coupling, we demonstrate that we can directionally control the lithium distribution by applying different stresses to lithium alloy materials. Our results provide insights into stress-lithium electrochemistry coupling at the nanoscale and suggest potential applications of lithium alloy nanoparticles.

Ionic-Activated Chemiresistive Gas Sensors for Room-Temperature Operation.

The development of high performance gas sensors that operate at room temperature has attracted considerable attention. Unfortunately, the conventional mechanism of chemiresistive sensors is restricted at room temperature by insufficient reaction energy with target molecules. Herein, novel strategy for room temperature gas sensors is reported using an ionic-activated sensing mechanism. The investigation reveals that a hydroxide layer is developed by the applied voltages on the SnO2 surface in the presence of humidity, leading to increased electrical conductivity. Surprisingly, the experimental results indicate ideal sensing behavior at room temperature for NO2 detection with sub-parts-per-trillion (132.3 ppt) detection and fast recovery (25.7 s) to 5 ppm NO2 under humid conditions. The ionic-activated sensing mechanism is proposed as a cascade process involving the formation of ionic conduction, reaction with a target gas, and demonstrates the novelty of the approach. It is believed that the results presented will open new pathways as a promising method for room temperature gas sensors.

SnS2 Nanograins on Porous SiO2 Nanorods Template for Highly Sensitive NO2 Sensor at Room Temperature with Excellent Recovery.

In order to develop high performance chemoresistive gas sensors for Internet of Everything applications, low power consumption should be achieved due to the limited battery capacity of portable devices. One of the most efficient ways to reduce power consumption is to lower the operating temperature to room temperature. Herein, we report superior gas sensing properties of SnS2 nanograins on SiO2 nanorods toward NO2 at room temperature. The gas response is as high as 701% for 10 ppm of NO2 with excellent recovery characteristics and the theoretical detection limit is evaluated to be 408.9 ppb at room temperature, which has not been reported for SnS2-based gas sensors to the best of our knowledge. The SnS2 nanograins on the template used in this study have excessive sulfur component (Sn:S = 1:2.33) and exhibit p-type conduction behavior. These results will provide a new perspective of nanostructured two-dimensional materials for gas sensor applications on demand.

Morphological Evolution Induced through a Heterojunction of W-Decorated NiO Nanoigloos: Synergistic Effect on High-Performance Gas Sensors.

Morphological evolution accompanying a surface roughening and preferred orientation is an effective way to realize a high-performance gas sensor because of its significant potential as a chemical catalyst through chemical potentials and atomic energy states. In this work, we investigated a heterojunction of double-side-W-decorated NiO nanoigloos fabricated through radio frequency sputtering and a soft-template method. Interestingly, a morphological evolution characterized by a pyramidal rough surface and the preferred orientation of the (111) plane was observed upon decorating the bare NiO nanoigloos with W. The underlying mechanism of the morphological evolution was precisely demonstrated based on the van der Drift competitive growth model originating from the oxygen transport and chemical strain in the lattice. The gas sensing properties of W-decorated NiO show an excellent NO2 response and selectivity when compared to other gases. In addition, high response stability was evaluated under interference gas and humidity conditions. The synergistic effects on the sensing performance were interpreted on the basis of the morphological evolution of W-decorated NiO nanoigloos.

Self-Powered Chemical Sensing Driven by Graphene-Based Photovoltaic Heterojunctions with Chemically Tunable Built-In Potentials.

Ultralow power chemical sensing is essential toward realizing the Internet of Things. However, electrically driven sensors must consume power to generate an electrical readout. Here, a different class of self-powered chemical sensing platform based on unconventional photovoltaic heterojunctions consisting of a top graphene (Gr) layer in contact with underlying photoactive semiconductors including bulk silicon and layered transition metal dichalcogenides is proposed. Owing to the chemically tunable electrochemical potential of Gr, the built-in potential at the junction is effectively modulated by absorbed gas molecules in a predictable manner depending on their redox characteristics. Such ability distinctive from bulk photovoltaic counterparts enables photovoltaic-driven chemical sensing without electric power consumption. Furthermore, it is demonstrated that the hydrogen (H2 ) sensing properties are independent of the light intensity, but sensitive to the gas concentration down to the 1 ppm level at room temperature. These results present an innovative strategy to realize extremely energy-efficient sensors, providing an important advancement for future ubiquitous sensing.

Mechanical Fatigue Resistance of Piezoelectric PVDF Polymers.

The fatigue resistance of piezoelectric PVDF has been under question in recent years. While some report that a significant degradation occurs after 106 cycles of repeated voltage input, others report that the reported degradation originates from the degraded metal electrodes instead of the piezoelectric PVDF itself. Here, we report the piezoelectric response and remnant polarization of PVDF during 107 cycles of repeated compression and tension, with silver paste-based electrodes to eliminate any electrode effect. After applying repeated tension and compression of 1.8% for 107 times, we do not observe any notable decrease in the output voltage generated by PVDF layers. The results from tension experiments show stable remnant polarization of 5.5 µC/cm², however, the remnant polarization measured after repeated compression exhibits a 7% decrease as opposed to the tensed PVDF. These results suggest a possible anisotropic response to stress direction. The phase analyses by Raman spectroscopy reveals no significant change in the phase content, demonstrating the fatigue resistance of PVDF.