Simple Self-Powered Sensor for the Detection of D2O and Other Isotopologues of Liquid Water.

Distinguishing between heavy water and regular water has been a continuing challenge since these isotopologues of water have very similar physical and chemical properties. We report the development and evaluation of a simple, inexpensive sensor capable of detecting liquid D2O and other isotopologues of liquid water through the measurement of electrical signals generated from a nanoporous alumina film. This electrical output, consisting of a sharp voltage pulse followed by a separate broad voltage pulse, is present during the application of microliter volumes of liquid. The amplitude and temporal characteristics of these pulses have been combined to enable four diagnostic parameters for sensing D2O and H218O. The sensing mechanism is based on different modification effects on the alumina surface by H2O and D2O, spatially localized variations in the surface potential of alumina induced by isotopically substituted water molecules, combined with the effect of isotopic composition on charge transfer. As a proof-of-concept demonstration, a sensing system has been developed that provides real-time detection of liquid D2O in a stand-alone system.

Engineering the defect distribution in ZnO nanorods through laser irradiation.

In recent years, defect engineering has shown great potential to improve the properties of metal oxide nanomaterials for various applications thus received extensive investigations. While traditional techniques mostly focus on controlling the defects during the synthesis of the material, laser irradiation has emerged as a promising post-deposition technique to further modulate the properties of defects yet there is still limited information. In this article, defects such as oxygen vacancies are tailored in ZnO nanorods through nanosecond (ns) laser irradiation. The relation between laser parameters and the temperature rise in the ZnO due to laser heating was established based on the observation in the SEM and the simulation. Raman spectra indicated that the concentration of the oxygen vacancies in the ZnO is temperature-dependent and can be controlled by changing the laser fluence and exposure time. This is also supported by the absorption spectra and the photoluminescence spectra of ZnO NRs irradiated under these conditions. On the other hand, the distribution of the oxygen vacancies was studied by XPS depth profiling, and it was confirmed that the surface-to-bulk ratio of the oxygen vacancies can be modulated by varying the laser fluence and exposure time. Based on these results, four distinctive regimes containing different ratios of surface-to-bulk oxygen vacancies have been identified. Laser-processed ZnO nanorods were also used as the catalyst for the photocatalytic degradation of rhodamine B (RhB) dye to demonstrate the efficacy of this laser engineering technique.

Laser modification of Au-CuO-Au structures for improved electrical and electro-optical properties.

CuO nanomaterials are one of the metal-oxides that received extensive investigations in recent years due to their versatility for applications in high-performance nano-devices. Tailoring the device performance through the engineering of properties in the CuO nanomaterials thus attracted lots of effort. In this paper, we show that nanosecond (ns) laser irradiation is effective in improving the electrical and optoelectrical properties in the copper oxide nanowires (CuO NWs). We find that ns laser irradiation can achieve joining between CuO NWs and interdigital gold electrodes. Meanwhile, the concentration and type of point defects in CuO can be controlled by ns laser irradiation as well. An increase in the concentration of defect centers, together with a reduction in the potential energy barrier at the Au/CuO interfaces due to laser irradiation increases electrical conductivity and enhances photo-conductivity. We demonstrate that the enhanced electrical and photo-conductivity achieved through ns laser irradiation can be beneficial for applications such as resistive switching and photo-detection.

Multifunctional Self-Powered Electronics Based on a Reusable Low-Cost Polypropylene Fabric Triboelectric Nanogenerator.

We report the development of low-cost triboelectric nanogenerators (TENGs) based on polypropylene (PP) fabrics formulated via an inexpensive melt-blowing process with an output voltage as high as 50 V. By disinfection methods such as exposure to steam, ethanol, and dry heat at 75 °C, the commercial medical masks and N95 filtering facepiece respirators (FFRs) can be reused to fabricate PP fiber based TENGs, which provide a novel regime for energy-harvesting devices based on reusable materials. As a power source, the output of one TENG can drive 15 serially connected light-emitting diodes (LEDs) or a commercial electric calculator. PP fabric TENGs can also work as self-powered sensors for the high-sensitivity detection of mechanical impact. We provide examples where the TENG is used to detect biomechanical motion such as that associated with the extension of an elbow, the touch of a finger, the impact of footsteps, and the bending of a knee without an external power supply. Most importantly, these PP fabrics for TENGs can be obtained from decontaminated medical masks that are generated as tremendous wastes every day, which provide a great potential as sustainable energy. These properties suggest that PP fabric based TENGs are promising for harvesting energy from biological systems and that they may facilitate the large-scale production of a new range of inexpensive self-powered multifunctional wearable sensors for applications in healthcare, security, and information networks.

A Simple High Power, Fast Response Streaming Potential/Current-Based Electric Nanogenerator Using a Layer of Al2O3 Nanoparticles.

Harvesting energy from ambient moisture and natural water sources is currently of great interest due to the need for standalone self-powered nano/micro-systems. In this work, we report on the development of a cost-effective nanogenerator based on a carbon paper-Al2O3 nanoparticle layer-carbon paper (CAC) sandwich structure, where the 3D Al2O3 layer is deposited via vacuum filtration. This type of device can produce an open-circuit voltage (UOC) of up to 4 V and a short-circuit current (ISC) of ∼18 µA with only an 8 µL water droplet applied. To our knowledge, this is the highest voltage yet reported from a single moisture/water-induced electricity nanogenerator using solid oxides and carbon-based materials. A remarkable output power of 14.8 µW can be reached with an optimized resistive load. An LED with a working voltage of 3-3.2 V can operate for a short time with the power from a single CAC device exposed to one 8 µL water droplet. Furthermore, a CAC generator adsorbing as little as 2 µL water droplets every 3 min can also give a UOC of 3.63 V. We show that CAC devices provide a robust electrical output over more than 200 wet-dry cycles without any deterioration in performance. These units demonstrate much promise as cost-effective electricity generators for harvesting energy from natural sources like rainwater, tap water, snow runoff, and dew. The response time of CAC devices can be as fast as 10-100 ms, making them ideal for applications as self-powered water detectors. The generation of power in this device arises from the streaming current. To assist in the optimization of these devices, we have analyzed how their response is related to such factors as layer thickness, time interval between application of water droplets, and the volume of each water droplet.

Moisture-Enabled Electricity Generation: From Physics and Materials to Self-Powered Applications.

The exploration of the utilization of sustainable, green energy represents one way in which it is possible to ameliorate the growing threat of the global environmental issues and the crisis in energy. Moisture, which is ubiquitous on Earth, contains a vast reservoir of low-grade energy in the form of gaseous water molecules and water droplets. It has now been found that a number of functionalized materials can generate electricity directly from their interaction with moisture. This suggests that electrical energy can be harvested from atmospheric moisture and enables the creation of a new range of self-powered devices. Herein, the basic mechanisms of moisture-induced electricity generation are discussed, the recent advances in materials (including carbon nanoparticles, graphene materials, metal oxide nanomaterials, biofibers, and polymers) for harvesting electrical energy from moisture are summarized, and some strategies for improving energy conversion efficiency and output power in these devices are provided. The potential applications of moisture electrical generators in self-powered electronics, healthcare, security, information storage, artificial intelligence, and Internet-of-things are also discussed. Some remaining challenges are also considered, together with a number of suggestions for potential new developments of this emerging technology.

High-Performance Magnesium-Carbon Nanofiber Hygroelectric Generator Based on Interface-Mediation-Enhanced Capacitive Discharging Effect.

This study reports the concept of a water/moisture-induced hygroelectric generator based on the direct contact between magnesium (Mg) alloy and oxidized carbon nanofibers (CNFs). This device generates an open-circuit voltage up to 2.65 V within only 10 ms when the unit is placed in contact with liquid water, which is higher than the reduction potential of magnesium. The average peak short-circuit current density is ∼6 mA/cm2, which is among the highest values yet reported for water-induced electricity generators. Our results indicate that galvanic corrosion occurs at the interface between the CNF and Mg electrode, but the device can still generate electricity because of the high contact resistance caused by the work function difference between Mg and CNF and the surface oxidation. The oxidized CNF is shown to absorb water/moisture and get reduced, leading to a capacitive discharging effect to provide enhanced signal amplitude and sensitivity. These devices are found to be highly sensitive to small quantities of water, and their high output voltage and current make them useful for the detection of water vapor in the human breath as well as changes in ambient humidity. The Mg/CNF systems thus provide a new technology for use in the fabrication of self-powered water/moisture sensors and the development of portable electric power generators.

Self-powered, flexible and remote-controlled breath monitor based on TiO2 nanowire networks.

Smart breath monitor devices with high stretchability, fast response/recovery times and self-powered characteristic are essential in the wearable medical and life science applications. In this work, we report on the development of a versatile high-performance humidity sensor based on TiO2 nanowire networks for self-powered sensing application of human breath monitoring. These sensors, with typical response times of ∼3.6 s and recovery times of ∼14 s, exhibit high sensitivity to water vapor and can yield an output voltage that is directly proportional to the humidity level of ambient environment. The structure of nanowire networks is highly flexible and maintains the output voltage even after 10 000 times bending. By combining this type of sensor with a commercial signal transmission and processing system, it shows the good basis for real-time/remote-controlled monitoring and analysis of human breath under a variety of respiratory conditions. Our results suggest a new class of humidity sensing for self-powered biomedical devices and open to new technologies in energy, electronics, and sensor applications.

Self-Powered, Rapid-Response, and Highly Flexible Humidity Sensors Based on Moisture-Dependent Voltage Generation.

Most advanced humidity sensors are powered by batteries that need regular charging and replacement, causing environmental problems and complicated management issues. This paradigm has been overcome through the development of new technology based on the concept of simple, self-powered, rapid-response, flexible humidity sensors enabled by the properties of densely packed titanium dioxide (TiO2) nanowire networks. These sensors eliminate the need for an external power source and produce an output voltage that can be readily related to ambient humidity level over a wide range of ambient conditions. They are characterized by rapid response and relaxation times (typically 4.5 and 2.8 s, respectively). These units are mechanically flexible and maintain a constant voltage output after 10 000 bending cycles. This new type of humidity sensor is easily attached to a human finger for use in the monitoring of ambient humidity level in the environment around human skin, near wet objects, or in the presence of moist materials. The unique properties of this new self-powered wearable humidity sensor technology open up a variety of new applications, including the development of electronic skin, personal healthcare products, and smart tracking in the future Internet-of-things.

A Self-Powered Nanogenerator for the Electrical Protection of Integrated Circuits from Trace Amounts of Liquid.

With the increase in the use of electronic devices in many different environments, a need has arisen for an easily implemented method for the rapid, sensitive detection of liquids in the vicinity of electronic components. In this work, a high-performance power generator that combines carbon nanoparticles and TiO2 nanowires has been fabricated by sequential electrophoretic deposition (EPD). The open-circuit voltage and short-circuit current of a single generator are found to exceed 0.7 V and 100 µA when 6 µL of water was applied. The generator is also found to have a stable and reproducible response to other liquids. An output voltage of 0.3 V was obtained after 244, 876, 931, and 184 µs, on exposure of the generator to 6 µL of water, ethanol, acetone, and methanol, respectively. The fast response time and high sensitivity to liquids show that the device has great potential for the detection of small quantities of liquid. In addition, the simple easily implemented sequential EPD method ensures the high mechanical strength of the device. This compact, reliable device provides a new method for the sensitive, rapid detection of extraneous liquids before they can impact the performance of electronic circuits, particularly those on printed circuit board.

Investigation of impact and spreading of molten nanosized gold droplets on solid surfaces.

Understanding the impact dynamics and spreading of molten nanosized droplets on a solid surface is a crucial step towards the design and control of nano-fabrication in many novel applications of nanotechnology. In this context, molecular dynamic (MD) simulations have been conducted to compute temperature and dynamic contact angles of nano-droplets during impact. The evolution of the morphology of a molten metallic nano-droplet impacting on a substrate has been studied using a combination of experimental and simulation techniques. Femtosecond lasers have been used to transfer nanosized gold droplets. Droplet morphology calculated in MD simulations is found to be in good agreement with that seen in scanning electron microscopy (SEM) images. It is found that the spreading of nanoscale molten gold droplets upon impact is enhanced by increasing the droplet impact energy. As observed in experimental data, MD simulation results show that a high droplet-substrate heat transfer rate together with increased wettability of the substrate facilitates spreading and results in a thinner metal deposit after solidification.

Oxygen vacancy migration/diffusion induced synaptic plasticity in a single titanate nanobelt.

Neuromorphic computational systems that emulate biological synapses in the human brain are fundamental in the development of artificial intelligence protocols beyond the standard von Neumann architecture. Such systems require new types of building blocks, such as memristors that access a quasi-continuous and wide range of conductive states, which is still an obstacle for the realization of high-efficiency and large-capacity learning in neuromorphoric simulation. Here, we introduce hydrogen and sodium titanate nanobelts, the intermediate products of hydrothermal synthesis of TiO2 nanobelts, to emulate the synaptic behavior. Devices incorporating a single titanate nanobelt demonstrate robust and reliable synaptic functions, including excitatory postsynaptic current, paired pulse facilitation, short term plasticity, potentiation and depression, as well as learning-forgetting behavior. In particular, the gradual modulation of conductive states in the single nanobelt device can be achieved by a large number of identical pulses. The mechanism for synaptic functionality of the titanate nanobelt device is attributed to the competition between an electric field driven migration of oxygen vacancies and a thermally induced spontaneous diffusion. These results provide insight into the potential use of titanate nanobelts in synaptic applications requiring continuously addressable states coupled with high processing efficiency.

Self-Powered Wearable Electronics Based on Moisture Enabled Electricity Generation.

Most state-of-the-art electronic wearable sensors are powered by batteries that require regular charging and eventual replacement, which would cause environmental issues and complex management problems. Here, a device concept is reported that can break this paradigm in ambient moisture monitoring-a new class of simple sensors themselves can generate moisture-dependent voltage that can be used to determine the ambient humidity level directly. It is demonstrated that a moisture-driven electrical generator, based on the diffusive flow of water in titanium dioxide (TiO2 ) nanowire networks, can yield an output power density of up to 4 µW cm-2 when exposed to a highly moist environment. This performance is two orders of magnitude better than that reported for carbon-black generators. The output voltage is strongly dependent on humidity of ambient environment. As a big breakthrough, this new type of device is successfully used as self-powered wearable human-breathing monitors and touch pads, which is not achievable by any existing moisture-induced-electricity technology. The availability of high-output self-powered electrical generators will facilitate the design and application of a wide range of new innovative flexible electronic devices.

Scalable High-Performance Ultraminiature Graphene Micro-Supercapacitors by a Hybrid Technique Combining Direct Writing and Controllable Microdroplet Transfer.

Miniaturization of energy storage devices can significantly decrease the overall size of electronic systems. However, this miniaturization is limited by the reduction of electrode dimensions and the reproducible transfer of small electrolyte drops. This paper reports first a simple scalable direct writing method for the production of ultraminiature microsupercapacitor (MSC) electrodes, based on femtosecond laser reduced graphene oxide (fsrGO) interlaced pads. These pads, separated by 2 µm spacing, are 100 µm long and 8 µm wide. A second stage involves the accurate transfer of an electrolyte microdroplet on top of each individual electrode, which can avoid any interference of the electrolyte with other electronic components. Abundant in-plane mesopores in fsrGO induced by a fs laser together with ultrashort interelectrode spacing enables MSCs to exhibit a high specific capacitance (6.3 mF cm-2 and 105 F cm-3) and ∼100% retention after 1000 cycles. An all graphene resistor-capacitor (RC) filter is also constructed by combining the MSC and a fsrGO resistor, which is confirmed to exhibit highly enhanced performance characteristics. This new hybrid technique combining fs laser direct writing and precise microdroplet transfer easily enables scalable production of ultraminiature MSCs, which is believed to be significant for practical application of micro-supercapacitor microelectronic systems.

Improving the electrical contact at a Pt/TiO2 nanowire interface by selective application of focused femtosecond laser irradiation.

In this paper, we show that tightly focused femtosecond laser irradiation is effective in improving nanojoining of an oxide nanowire (NW) (TiO2) to a metal electrode (Pt), and how this process can be used to modify contact states. Enhanced chemical bondings are created due to localized plasmonically enhanced optical absorption at the Pt/TiO2 interface as confirmed by finite element simulations of the localized field distribution during irradiation. Nano Auger electron spectroscopy shows that the resulting heterojunction is depleted in oxygen, suggesting that a TiO2-x layer is formed between the Pt electrode and the TiO2 NW. The presence of this redox layer at the metal/oxide interface plays an important role in decreasing the Schottky barrier height and in facilitating chemical bonding. After laser irradiation at the cathode for 10 s at a fluence of 5.02 mJ cm-2, the Pt/TiO2 NW/Pt structure displays different electrical properties under forward and reverse bias voltage, respectively. The creation of this asymmetric electrical characteristic shows the way in which modification of the electronic interface by laser engineering can replace the electroforming process in resistive switching devices and how it can be used to control contact states in a metal/oxide interface.

Reliable and Low-Power Multilevel Resistive Switching in TiO2 Nanorod Arrays Structured with a TiOx Seed Layer.

The electrical performance of TiO2 nanorod array (NRA)-based resistive switching memory devices is examined in this paper. The formation of a seed layer on the fluorine-doped tin oxide (FTO) glass substrate after treatment in TiCl4 solution, before the growth of TiO2 NRAs on the FTO substrate via a hydrothermal process, is shown to significantly improve the resistive switching performance of the resulting TiO2 NRA-based device. As fabricated, the Al/TiO2 NRA/TiOx layer/FTO device displayed electroforming-free bipolar resistive switching behavior while maintaining a stable ON/OFF ratio for more than 500 direct sweeping cycles over a retention period of 3 × 104 s. Meanwhile, the programming current as low as ∼10-8 A and 10-10 A for low resistance state and high resistance state respectively makes the fabricated devices suitable for low-power memristor applications. The TiOx precursor seed layer not only promotes the uniform and preferred growth of TiO2 nanorods on the FTO substrate but also functions as an additional source layer of trap centers due to its oxygen-deficient composition. Our data suggest that the primary conduction mechanism in these devices arises from trap-mediated space-charge-limited current (SCLC). Multilevel memory performance in this new device is achieved by varying the SET voltage. The origin of this effect is also discussed.

Resistive Switching Memory of TiO2 Nanowire Networks Grown on Ti Foil by a Single Hydrothermal Method.

The resistive switching characteristics of TiO2 nanowire networks directly grown on Ti foil by a single-step hydrothermal technique are discussed in this paper. The Ti foil serves as the supply of Ti atoms for growth of the TiO2 nanowires, making the preparation straightforward. It also acts as a bottom electrode for the device. A top Al electrode was fabricated by e-beam evaporation process. The Al/TiO2 nanowire networks/Ti device fabricated in this way displayed a highly repeatable and electroforming-free bipolar resistive behavior with retention for more than 104 s and an OFF/ON ratio of approximately 70. The switching mechanism of this Al/TiO2 nanowire networks/Ti device is suggested to arise from the migration of oxygen vacancies under applied electric field. This provides a facile way to obtain metal oxide nanowire-based ReRAM device in the future.

Investigation of splashing phenomena during the impact of molten sub-micron gold droplets on solid surfaces.

The dynamics of splashing accompanying the impact of molten 800 nm diameter gold droplets on silicon, gold coated silicon, gold coated glass and polished solid gold surfaces has been studied. A novel method based on laser induced forward transfer has been developed to generate single submicron molten gold droplets. Splashing morphology has been characterized using Scanning Electron Microscopy (SEM) and Focused Ion Beam (FIB) techniques. It is found that the splashing of submicron gold droplets upon impact is enhanced by high droplet impact energy achieved by reducing the droplet flight distance and that an air layer resulting in a bubble becomes trapped under the impacting droplets even when the size of the droplet is less than one micron. Our results show that, under these conditions, heat transfer between the submicron droplet and the solid substrate is more important than surface roughness and surface tension in the evolution of splashing. A theoretical model has been developed to simulate the splashing characteristics of submicron gold droplets during impact. Both the experimental data and the analytical model show that splashing is enhanced by high heat transfer rates to the surface.

Femtosecond laser ablation of highly oriented pyrolytic graphite: a green route for large-scale production of porous graphene and graphene quantum dots.

Porous graphene (PG) and graphene quantum dots (GQDs) are attracting attention due to their potential applications in photovoltaics, catalysis, and bio-related fields. We present a novel way for mass production of these promising materials. The femtosecond laser ablation of highly oriented pyrolytic graphite (HOPG) is employed for their synthesis. Porous graphene (PG) layers were found to float at the water-air interface, while graphene quantum dots (GQDs) were dispersed in the solution. The sheets consist of one to six stacked layers of spongy graphene, which form an irregular 3D porous structure that displays pores with an average size of 15-20 nm. Several characterization techniques have confirmed the porous nature of the collected layers. The analyses of the aqueous solution confirmed the presence of GQDs with dimensions of about 2-5 nm. It is found that the formation of both PG and GQDs depends on the fs-laser ablation energy. At laser fluences less than 12 J cm(-2), no evidence of either PG or GQDs is detected. However, polyynes with six and eight carbon atoms per chain are found in the solution. For laser energies in the 20-30 J cm(-2) range, these polyynes disappeared, while PG and GQDs were found at the water-air interface and in the solution, respectively. The origin of these materials can be explained based on the mechanisms for water breakdown and coal gasification. The absence of PG and GQDs, after the laser ablation of HOPG in liquid nitrogen, confirms the proposed mechanisms.

Nonlinear optical and chemical effects in the irradiation of liquid benzene with femtosecond pulses.

We show that a spectral resonance between the π→π* absorption band in liquid benzene and the third harmonic (TH) of a propagating 800 nm femtosecond laser beam causes large positive changes in the real refractive index at the TH wavelength. This produces an increase in the third-order optical susceptibility and leads to the enhancement of nonlinear optical effects including TH generation and self-focusing. Enhanced filamentation is observed in liquid benzene, but this effect is not seen in perdeuterated liquid benzene under similar irradiation conditions. Filamentation is associated with the decomposition of benzene molecules, plasma emission from the focal region, and the appearance of carbon nanoparticles. This indicates that a complex chemistry accompanies the onset of filamentation. Chemical products formed under these conditions have been characterized using combined gas chromatography mass spectroscopy techniques. We also find that the presence of a TH filament is indicated by the appearance of a photocurrent and increased electrical conductivity in the solution. This photocurrent is found to be 50-60 times smaller in C6D6 where the π→π* resonance with the TH is much weaker. The intensity dependence of this photocurrent confirms the role played by TH generation in the overall interaction.