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.

Direct glass-to-glass bonding obtained via simplified ammonia-based low-temperature procedure resists high shear stress and powerful CW fiber laser irradiation.

Direct glass-to-glass bonding is important for high-technology components in optics, microfluidics, and micro-electromechanical systems applications. We studied direct bonding of 1 mm thick soda-lime float glass substrates. The process is based on the classic RCA-1 cleaning procedure from the semiconductor industry modified with an ammonium hydroxide rinse, followed by a thermal treatment under unidirectional pressure without the need for a dedicated drying step. RCA-1 uses a solution of ammonium hydroxide and hydrogen peroxide to clean contaminants off the surface of silicon and enable subsequent bonding. Bond quality was evaluated using destructive shear testing. Strong bonds (≈7.81 MPa on average) were achieved using unidirectional pressure of approximately 0.88 MPa and bonding temperatures between 160 °C and 300 °C applied for 30 min. Surface roughness and chemistry was characterized before and after cleaning. The optical robustness of the bonds was tested and shown to be capable of surviving high powered continuous wave (CW) fiber laser irradiation of at least 375 W focused for 2 s without delamination. Melting of the substrate was observed at higher powers and longer exposure times.

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.

Photodecomposition of pharmaceuticals and personal care products using P25 modified with Ag nanoparticles in the presence of natural organic matter.

The presence of pharmaceuticals and personal care products (PPCPs) in water remains a concern due to their potential threat to environmental and human health. Advanced oxidation processes (AOPs) have been receiving attention in water treatment studies to remove PPCPs. However, most studies have been focused on pure water containing a limited number of substances. In this study, the photocatalytic efficiency of commercially available titanium dioxide nanoparticles (P25) and P25 modified by silver nanoparticles (Ag-P25) were compared for their ability to degrade 23 target PPCPs (2 µg L-1) in realistic water matrices containing natural organic matter (Suwanee River NOM, 6.12 mg L-1). The experiments were completed under ultraviolet-light emitting diode (UV-LED) illumination at 365 and 405 nm wavelengths, with the latter representing visible light exposure. Under 365 nm UV-LED treatment, 99% of the PPCPs were removed using both P25 and Ag-P25 photocatalysts within 180 min of the treatment duration. The number of PPCPs removed dropped to 57% and 53% for P25 and Ag-P25 respectively under the 405 nm UV-LED irradiation. Dissolved organic carbon (DOC) and UV absorbance at 254 nm (UV254) measured at the end of the experiment indicated that the aromatic fraction of NOM was preferentially removed from the water matrix. Also, Ag-P25 was more effective in DOC removal than P25. The relationships of removal rate constants with physico-chemical properties of the substances were also determined. The molecular weight and charge were strongly associated with removal, with the former and the latter being positively and negatively correlated with the rate constants. The results of this work indicate that Ag-P25 is a promising photocatalyst to degrade persistent substances such as PPCPs and NOM even if they are present in a complex water matrix. The properties of individual substances can also be employed as an indication of their removal using this 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.

Carbon Black-Doped Anatase TiO2 Nanorods for Solar Light-Induced Photocatalytic Degradation of Methylene Blue.

In this work, C-doped TiO2 nanorods were synthesized through doping carbon black into hydrothermally synthesized solid-state TiO2 nanowires (NWs) via calcination. The effects of carbon content on the morphology, phase structure, crystal structure, and photocatalytic property under both UV and solar light by the degradation of methylene blue (MB) were explored. Besides, the photoelectrochemical property of C-TiO2 was systematically studied to illustrate the solar light degradation mechanism. After doping with C, TiO2 NWs were reduced into nanorods and the surface became rough with dispersed particles. Results showed that C has successfully entered the TiO2 lattice, resulting in the lattice distortion, reduction of band gap, and the formation of C-Ti-O, which expands TiO2 to solar light activation. Comparing with P25 and anatase TiO2 NWs, doping with carbon black showed much higher UV light and solar light photocatalytic activity. The photocatalytic activity was characterized via the degradation of MB, showing that K ap was 0.0328 min-1 under solar light, while 0.1634 min-1 under UV irradiation. The main free radicals involved in methylene blue degradation are H+ and OH•-. Doping with carbon black led to the reduction of photocurrent in a long-term operation, while C-doping reduced the electron-hole recombination and enhanced the carrier migration.

A highly sensitive double-layer structured nanodevice for moisture induced power generation.

With the increasing global energy demand, traditional energy sources are gradually failing to meet society's needs while also having a potential of being harmful to the environment. As such, energy generating technologies capable of converting ubiquitous environmental energy into usable forms, such as electricity, have received increasing attention. In this research, a power generating device composed of a graphene (G) and titanium dioxide nanowire (TiO2 NWs) double-layer structure is prepared by an electrophoretic deposition method. Since both materials have special nanochannel structures and non-zero zeta potential, they can convert environmental energy into electricity through the diffusion, ionization, and natural evaporation of water. Furthermore, the efficiency of this novel sensor is much higher than their respective single-layer devices. By application of only 6 µl of water, the open circuit voltage (UOC) generated on the G-TiO2 sensor is as high as 1.067 ± (0.008) V. In comparison, TiO2 NWs single layer can only generate a UOC around 500 mV, and graphene itself can only produce a UOC no more than 250 mV under the same condition. Additionally, the effect of different deposition times of graphene on the surface morphology and thickness of graphene film is explored, and the effects of these changes in microstructure on performance is discussed in depth. Aside from power generation, the high sensitivity of the device to different volumes of water brings its use in the detection of trace amounts of water, and its high efficiency of energy conversion suggests a potential application as a power supply. This research not only provides a satisfactory candidate for inexpensive and efficient evaporative power generation, but also builds a foundation for developing new, intelligent, and self-powered electronic technologies.

Electrochemical Oxidation Induced Multi-Level Memory in Carbon-Based Resistive Switching Devices.

In this work, we report for the first time the electrochemical oxidation as a technique to improve the electrical performances of carbon-based resistive switching devices. The devices obtained through the anodic oxidation of carbon-structures possess superior electrical performances i.e. a 3-level memory behavior and an ON/OFF ratio two order of magnitude higher than the non-oxidized carbon-based devices. It is demonstrated that the chemical composition of the carbon structures (i.e. percentage of oxygen groups, sp2 and sp3 carbon atoms) plays a key role in the improvement of the carbon-based devices. The electrochemical oxidation allows the possibility to control the oxidation degree, and therefore, to tailor the devices electrical performances. We demonstrated that the resistive switching behavior in the electrochemically oxidized devices is originated from the formation of conductive filament paths, which are built from the oxygen vacancies and structural defects of the anodic oxidized carbon materials. The novelty of this work relies on the anodic oxidation as a time- and cost-effective technique that can be employed for the engineering and improvement of the electrical performances of next generation carbon-based resistive switching devices.

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.

Photocatalytic decomposition of selected estrogens and their estrogenic activity by UV-LED irradiated TiO2 immobilized on porous titanium sheets via thermal-chemical oxidation.

The removal of endocrine disrupting compounds (EDCs) remains a big challenge in water treatment. Risks associated with these compounds are not clearly defined and it is important that the water industry has additional options to increase the resiliency of water treatment systems. Titanium dioxide (TiO2) has potential applications for the removal of EDCs from water. TiO2 has been immobilized on supports using a variety of synthesis methods to increase its feasibility for water treatment. In this study, we immobilized TiO2 through the thermal-chemical oxidation of porous titania sheets. The efficiency of the material to degrade target EDCs under UV-LED irradiation was examined under a wide range of pH conditions. A yeast-estrogen screen assay was used to complement chemical analysis in assessing removal efficiency. All compounds but 17ß-estradiol were degraded and followed a pseudo first-order kinetics at all pH conditions tested, with pH 4 and pH 11 showing the most and the least efficient treatments respectively. In addition, the total estrogenic activity was substantially reduced even with the inefficient degradation of 17ß-estradiol. Additional studies will be required to optimize different treatment conditions, UV-LED configurations, and membrane fouling mitigation measures to make this technology a more viable option for water treatment.

Photocatalytic decomposition of organic micropollutants using immobilized TiO2 having different isoelectric points.

Organic micropollutants found in the environment are a diverse group of compounds that includes pharmaceuticals, personal care products, and endocrine disruptors. Their presence in the aquatic environment continues to be a concern as the risk they pose towards both the environment and human health is still inconclusive. Removal of these compounds from water and wastewater is difficult to achieve and often incomplete, but UV-TiO2 is a promising treatment approach. In this study, the efficiency of titanium dioxide (TiO2) immobilized on porous supports were tested for treatment of target pharmaceuticals and their metabolites under UV-LED exposure, a potential low energy and cost effective alternative to conventional UV lamps. Immobilization was completed using two different methods: (1) dip coating of TiO2 onto quartz fiber filters (QFT) or (2) thermal-chemical oxidation of porous titanium sheets (PTT). Comparison against experimental controls (dark QFT, dark PTT, and photolysis using UV-LED only) showed that UV-LED/PTT and UV-LED/QFT treatments have the potential to reduce the concentrations of the target compounds. However, the treatments were found to be selective, such that individual pharmaceuticals were removed well using QFT and PTT but not both. The complementary treatment behavior is likely driven by electrostatic interactions of charged compounds with the membranes. QFT membranes are negatively charged at the experimental pH (4.5-5) while PTT membranes are positively charged. As a result, cationic compounds interact more with QFT while anionic compounds with PTT. Neutral compounds, however, were found to be recalcitrant under any treatment conditions suggesting that ionic interactions were important for reactions to occur. This behavior can be advantageous if specificity is required. The behavior of pharmaceutical metabolites is similar to the parent compounds. However, isomeric metabolites of atorvastatin with functional groups in para and ortho configurations behave differently, suggesting that the positioning of functional groups can have an impact in their interaction with the immobilized TiO2. It was also apparent that PTT can be reused after cleaning by heat treatment. Overall, these newly synthesized membrane materials have potential applications for treatment of trace organic contaminants in water.

Porous silver nanosheets: a novel sensing material for nanoscale and microscale airflow sensors.

Fabrication of nanoscale and microscale machines and devices is one of the goals of nanotechnology. For this purpose, different materials, methods, and devices should be developed. Among them, various types of miniaturized sensors are required to build the nanoscale and microscale systems. In this research, we introduce a new nanoscale sensing material, silver nanosheets, for applications such as nanoscale and microscale gas flow sensors. The silver nanosheets were synthesized through the reduction of silver ions by ascorbic acid in the presence of poly(methacrylic acid) as a capping agent, followed by the growth of silver in the shape of hexagonal and triangular nanoplates, and self-assembly and nanojoining of these structural blocks. At the end of this process, the synthesized nanosheets were floated on the solution. Then, their electrical and thermal stability was demonstrated at 120 °C, and their atmospheric corrosion resistance was clarified at the same temperature range by thermogravimetric analysis. We employed the silver nanosheets in fabricating airflow sensors by scooping out the nanosheets by means of a sensor substrate, drying them at room temperature, and then annealing them at 300 °C for one hour. The fabricated sensors were tested for their ability to measure airflow in the range of 1 to 5 ml min(-1), which resulted in a linear response to the airflow with a response and recovery time around 2 s. Moreover, continuous dynamic testing demonstrated that the response of the sensors was stable and hence the sensors can be used for a long time without detectable drift in their response.

How morphology and surface crystal texture affect thermal stability of a metallic nanoparticle: the case of silver nanobelts and pentagonal silver nanowires.

Thermal instability of metallic nanoparticles is typically attributed to chemical attack by contaminants. However, thermodynamic stability is independent of other affecting parameters. The importance of this will be clarified when the structural change toward a more stable thermodynamic condition may be followed by a chemical reaction with the surroundings, which may cause a wrong diagnosis. In this research, molecular dynamics simulations and experimental observations were performed to investigate the effect of crystallography and surface texture on stability at high temperature using two closely related model nanoparticles: silver nanobelts and pentagonal nanowires. Previously, the instability of silver nanowires was associated with sulfidation of the wire at high temperature. However, we found that the silver nanowires are inherently unstable at high temperature, degrading due to the high-energy nature of the nanowire's predominately (100) crystallographic surface and pentagonal geometry. In contrast, the silver nanobelts resist thermal degradation up to 500 °C because of their predominately low-energy (111) crystallographic surfaces. In this case study, we successfully demonstrate that inherent thermodynamic stability driven by morphology is significant in metallic nanoparticles, and should be investigated when selecting a nanoparticle for high temperature applications. Moreover, we identify a new one-dimensional nanoparticle, the silver nanobelt, with inherent high-temperature stability.

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.

Effect of ultrasonic capillary dynamics on the mechanics of thermosonic ball bonding.

Microelectronic wire bonding is an essential step in today's microchip production. It is used to weld (bond) microwires to metallized pads of integrated circuits using ultrasound with hundreds of thousands of vibration cycles. Thermosonic ball bonding is the most popular variant of the wire bonding process and frequently investigated using finite element (FE) models that simplify the ultrasonic dynamics of the process with static or quasistatic boundary conditions. In this study, the ultrasonic dynamics of the bonding tool (capillary), made from Al(2)O(3), is included in a FE model. For more accuracy of the FE model, the main material parameters are measured. The density of the capillary was measured to be rho(cap) = 3552 +/- 100 kg/m(3). The elastic modulus of the capillary, E(cap) = 389 +/- 11 GPa, is found by comparing an auxiliary FE model of the free vibrating capillary with measured values. A capillary "nodding effect" is identified and found to be essential when describing the ultrasonic vibration shape. A main FE model builds on these results and adds bonded ball, pad, chip, and die attach components. There is excellent agreement between the main model and the ultrasonic force measured at the interface on a test chip with stress microsensors. Bonded ball and underpad stress results are reported. When adjusted to the same ultrasonic force, a simplified model without ultrasonic dynamics and with an infinitely stiff capillary tip is substantially off target by -40% for the maximum underpad stress. The compliance of the capillary causes a substantial inclination effect at the bonding interface between wire and pad. This oscillating inclination effect massively influences the stress fields under the pad and is studied in more detail. For more accurate results, it is therefore recommended to include ultrasonic dynamics of the bonding tool in mechanical FE models of wire bonding.