Fluorescence detection of nitrogen dioxide with perylene/PMMA thin films

Thin films of polymethylmethacrylate (PMMA) doped with perylene provide selective, robust and easily prepared optical sensor films for NO₂ gas with suitable response times for materials aging applications. The materials are readily formed as 200 nm thin spin cast films on glass from chlorobenzene solution. The fluorescence emission of the films (λ_max=442 nm) is quenched upon exposure to NO₂ gas through an irreversible reaction forming non-fluorescent nitroperylene. Infrared, UV–VIS and fluorescence spectroscopies confirmed the presence of the nitro adduct in the films. In other atmospheres examined, such as air and 1000 ppm concentrations of SO₂, CO, Cl₂ and NH₃, the films exhibited no loss of fluorescence intensity over a period of days to weeks. Response curves were obtained for 1000, 100 and 10 ppm NO₂ at room temperature with equilibration times varying from hours to weeks. The response curves were fit using a numerical solution to the coupled diffusion and a nonlinear chemical reaction problem assuming that the situation is reaction limiting. The forward reaction constant fitted to experimental data was k_f∼0.06 (ppm min)⁻¹.     

Electrical properties of nickel oxide thin films for flow sensor application

In this work, Ni oxide thin films, with thermal sensitivity superior to Pt and Ni thin films, were formed through annealing of Ni films deposited by a r.f. magnetron sputtering. The annealing was carried out in the temperature range of 300–500 °C under atmospheric conditions. Resistivity of the resulting Ni oxide films were in the range of 10.5 μΩ cm/°C to 2.84 × 10⁴ μΩ cm/°C, depending on the extent of Ni oxidation. The temperature coefficient of resistance (TCR) of the Ni oxide films also depended on the extent of Ni oxidation; the average TCR of Ni oxide resistors, measured between 0 and 150 °C, were 5630 ppm/°C for the 300 °C and 2188 ppm/°C for 500 °C films. Because of their high resistivity and very linear TCR, Ni oxide thin films are superior to pure Ni and Pt thin films for flow and temperature sensor applications.     

Fabrication and characterization of polyaniline-based gas sensor by ultra-thin film technology

Pure polyaniline (PAN) film, polyaniline and acetic acid (AA) mixed film, as well as PAN and polystyrenesulfonic acid (PSSA) composite film with various number of layers were prepared by Langmuir–Blodgett (LB) and self-assembly (SA) techniques. These ultra-thin films were characterized by ultraviolet–visible (UV–VIS) spectroscopy and ellipsometry. It is found that the thickness of PAN-based ultra-thin films increases linearly with the increase of the number of film layers. The gas-sensitivity of these ultra-thin films with various layers to NO₂ was studied. It is found that pure polyaniline films prepared by LB technique had good sensitivity to NO₂, while SA films exhibited faster recovery property. The response time to NO₂ and the relative change of resistance of ultra-thin films increased with the increase of the number of film layers. The response time of three-layer PAN film prepared by LB technique to 20 ppm NO₂ was about 10 s, two-layer SA film was about 8 s. The mechanism of sensitivity to NO₂ of PAN-based ultra-thin films was also discussed.     

All-optical hydrogen sensor based on a high alloy content palladium thin film

Optical reflectance measurements were performed to determine the hydrogen response characteristics of 20 nm thick Pd_0.6Au_0.4 films. The response time and signal change characteristics were determined as a function of hydrogen concentrations ranging from 0.05% to 4% in a balance of dry CO₂ free air. The detection limit was determined to be 0.05%, with a corresponding response time of 130 s, while at 4% hydrogen concentrations the response time was 5 s at ambient temperatures. A linear decrease of both the signal change and response time was measured within an operating temperature range between 25 °C and 100 °C for a 1% hydrogen in air gas mixture. The sensor response dependence of the Pd_0.6Au_0.4 film with a change in humidity was determined between ambient levels and 95% relative humidity (RH). While the signal change was independent of humidity the response time increased due to water adsorption on the Pd alloy sensing layer. A similar increase in response time was shown for 100 ppm of background CO mixed with 1% hydrogen in nitrogen at room temperature. At an elevated operating temperature of 80 °C, 100 ppm of CO did not affect the sensor response towards 1% hydrogen in a balance of nitrogen. Reliability tests have been performed over a 1-year time period and the sensing specifications have not drifted beyond 2% and 13% of the calibrated signal change and response time, respectively. A response time on the order of seconds and the proven stability of the high alloy content Pd thin film demonstrate the promising attributes of this material for use in an all-optical hydrogen sensor.     

Fabrication and characterization of Pb-free transparent dielectric layer for plasma display panel

Glasses within the Bi₂O₃–B₂O₃–BaO–ZnO system were examined as potential replacements for PbO-based glass frits with low firing temperatures. These frits are used in the transparent dielectric layer of plasma display panels (PDP). The glass transition temperature (T_g) of the prepared glasses varied between 450 and 460 °C. These glasses display dynamic dielectric properties, high transparency and thermal expansion as well as matching well with substrate glass. The thermal coefficient of expansion (TCE) was with the desired range of 81–86×10⁻⁷/K. Moreover, when the screen printed film was heat-treated at 570 °C for 30 min, optical transmittance (83%), root-mean square (rms) roughness (177.6 Å), dielectric constant (10.25) and withstand voltage (4.15 kV) satisfied the requirements necessary for transparent dielectric layers to be used in PDP applications.     

Thin film temperature sensor for real-time measurement of electrolyte temperature in a polymer electrolyte fuel cell

This paper describes a technique for the measurement of the electrolyte temperature in an operating polymer electrolyte fuel cell (PEFC). A patterned thin film gold thermistor embedded in a 16 μm thick parylene film was laminated in the Nafion^® electrolyte layer for in situ temperature measurements. Experimental results show that the sensor has a linear response of (3.03 ± 0.09) × 10⁻³ °C⁻¹ in the 20–100 °C temperature range and is robust enough to withstand the electrolyte expansion forces that occur during water uptake. An electrolyte temperature increase of 1.5 °C was observed in real-time when operating the fuel cell at 0.2 V and a current density of 0.19 A/cm². The temperature sensitivity of the present sensor is in an order of magnitude better than the conventional micro-thermocouples that have been reported. Additionally, use of micro-fabrication techniques allows for an accurate placement of the temperature sensor within the fuel cell. Simulation results show that the sensor has no significant effect on the local temperature distribution.     

A microtranslation table with scratch-drive actuators fabricated from silicon-on-insulator wafer

From a silicon-on-insulator (SOI) wafer, a microtranslation table with scratch-drive actuator (SDA) has been fabricated. The device Si layer of SOI wafer is etched to form the plate of SDA, which is partially connected to the handle Si substrate by the SiO₂ layer. Dicing the handle Si substrate, a microtranslation table with the SDA array has been fabricated. Placing the microtranslation table upside down on the other Si substrate on which a thin conductive film is patterned for the electrical connection, the microtranslation table is moved by the SDA without carrying a metal wire. The moving velocity of 45.5 μm/s has been obtained by applying the voltage of 120 V at the operating frequency of 500 Hz.     

Orientation and thickness dependence of electrical and gas sensing properties in heteroepitaxial indium tin oxide films

Heteroepitaxial indium tin oxide (ITO) films were grown on three differently oriented yttria-stabilized zirconia (YSZ) substrates ((1 0 0), (1 1 0), (1 1 1)) by rf magnetron sputtering, and their structural characteristics and electrical and gas sensing properties were investigated. The initially formed ITO exhibited an island structure on the very thin layer and became a continuous film after the prolonged deposition. The heteroepitaxial relationships between ITO films and YSZ substrates were confirmed by X-ray diffraction, pole figure, and high resolution transmission electron microscopy (HRTEM). The chemical composition, determined by X-ray photoelectron spectroscopy (XPS), was slightly different at early stage depending on the substrate orientation, but it became similar after the longer deposition. Hall measurements indicated that the electrical resistivity of ITO films decreased with increasing the deposition time (or film thickness) irrespective of the film orientation. The ITO film deposited on (1 1 0) YSZ for 10 s showed the highest electrical resistivity. The gas sensor fabricated from the ITO film on (1 1 0) YSZ deposited for 10 s showed the highest NO₂ gas response at relatively low temperature (100 °C), which was attributed to the higher Sn concentration and higher surface roughness of that film.     

Aviation emission inventory development and analysis

An up to date and accurate aviation emission inventory is a prerequisite for any detailed analysis of aviation emission impact on greenhouse gases and local air quality around airports. In this paper we present an aviation emission inventory using real time air traffic trajectory data. The reported inventory is in the form of a 4D database which provides resolution of 1° × 1° × 1000 ft for temporal and spatial emission analysis. The inventory is for an ongoing period of six months starting from October 2008 for Australian Airspace.In this study we show 6 months of data, with 492,936 flights (inbound, outbound and over flying). These flights used about 2515.83 kt of fuel and emitted 114.59 kt of HC, 200.95 kt of CO, 45.92 kt of NO_x, 7929.89 kt of CO₂, and 2.11 kt of SO_x. From the spatial analysis of emissions data, we found that the CO₂ concentration in some parts of Australia is much higher than other parts, especially in some major cities. The emission results also show that NO_x emission of aviation may have a significant impact on the ozone layer in the upper troposphere, but not in the stratosphere.It is expected that with the availability of this real time aviation emission database, environmental analysts and aviation experts will have an indispensable source of information for making timely decisions regarding expansion of runways, building new airports, applying route charges based on environmentally congested airways, and restructuring air traffic flow to achieve sustainable air traffic growth.     

Characterization and optimization to improve uneven surface on MEMS bridge fabrication

This paper presents an optimized fabrication method for developing a freestanding bridge for RF MEMS switches. In this method, the sacrificial layer is patterned and hard baked a 220 °C for 3 min, after filling the gap between the slots of the coplanar waveguide. Measurement results by AFM and SEM demonstrate that this technique significantly improves the planarity of the sacrificial layer, reducing the uneven surface to less than 20 nm, and the homogeneity of the Aluminum thickness across the bridge. Moreover, a mixture of O₂, Ar and CF₄ was used and optimized for dry releasing of the bridge. A large membrane (200 × 100 μm²) was released without any surface bending. Therefore, this method not only simplifies the fabrication process, but also improves the surface flatness and edge smoothness of the bridge. This fabrication method is fully compatible with standard silicon IC technology.     

Characteristics of a Pd–oxide–In0.49Ga0.51P high electron mobility transistor (HEMT)-based hydrogen sensor

An interesting hydrogen sensor based on a high electron mobility transistor (HEMT) device with a Pd–oxide–In_0.49Ga_0.51P gate structure is fabricated and demonstrated. The hydrogen sensing characteristics including hydrogen detection sensitivity and transient responses of the studied device under different hydrogen concentrations and temperature are measured and studied. The hydrogen detection sensitivity is related to a change in the contact potential at the Pd/insulator interface. The kinetic and thermodynamic properties of hydrogen adsorption are also studied. Experimentally, good hydrogen detection sensitivities, large magnitude of current variations (3.96 mA in 9970 ppm H₂/air gas at room temperature) and shorter absorption response time (22 s in 9970 ppm H₂/air gas at room temperature) are obtained for a 1.4 μm × 100 μm gate dimension device. Therefore, the studied device provides a promise for high-performance solid-state hydrogen sensor, integrated circuit (IC) and micro electro-mechanical system (MEMS) applications.     

Investigation of the phase equilibria in Ti-Ni-Hf system using diffusion triples and equilibrated alloys

In present work, the phase equilibrium relations in the Ti-Ni-Hf ternary system, which are of great importance for the design of Ti-Ni based high temperature shape memory alloys, were investigated using diffusion triples and sixteen key equilibrated alloys. Based on the experimental results from electron-probe microscopy analysis (EPMA) and X-ray diffraction (XRD) techniques, two isothermal sections were constructed, which consist of 13 and 12 three-phase regions at 900 °C and 800 °C, respectively. Hf can substitute for Ti in TiNi and Ti₂Ni phases increasing from 30, 62 at% at 800 °C to 36, 64 at% at 900 °C, respectively. The Hf₇Ni₁₀ and Hf₉Ni₁₁ phases show wide ternary composition ranges, while the solubility of Ti in HfNi₅, Hf₂Ni₇, and HfNi phases are relatively limited. A new ternary phase of τ was detected for the first time, and the stoichiometry of τ phase is close to Ni:(Hf,Ti) = 11:14, with Ti substituting for Hf from ～5 at% to ～22 at%. The single-phase region of the τ phase became narrow as the decreasing of annealing temperature. Based on comparison of phase relations at 900 °C and 800 °C, it is speculated there is an invariant reaction TiNi + τ → HfNi + Ti₂Ni at between 900 °C and 800 °C.     

High-precision interferometric monitoring of polymer swelling using a simple optofluidic sensor

The ZnO nanorods (diameter of 40 nm and 100 nm) were modified with Ru(dcbpy)₂(NCS)₂ (RuN3), and their responses to formaldehyde were measured at room temperature. All the results showed that the responses to formaldehyde of modified ZnO were higher than that of bare ZnO; especially the responses of modified ZnO nanorods with diameter of 40 nm–5 ppm formaldehyde was about 200% higher than that of bare ZnO. The UV–vis absorption spectrum and transient photovoltage analysis showed that the high responses of modified ZnO mainly arose from the strong photocatalytic oxidizing effect induced by the increasing of the absorption and photo-generated electron–hole separation. Our results demonstrate that the modification of RuN3 is a promising approach on improving the formaldehyde responses of ZnO nanorods.     

Boosting sensitivity of boron nitride nanotube (BNNT) to nitrogen dioxide by Fe encapsulation

The pristine boron nitride nanotube (BNNT) exhibits a poor chemical reactivity to some adsorbates, thus greatly limiting its application for the gas sensor. In the present work, using density functional theory (DFT) methods, we put forward a novel strategy to enhance the sensitivity of BNNT to nitrogen dioxide (NO₂) by the encapsulation of a single Fe atom inside its cavity. The results suggest that the NO₂ molecule can be only physically adsorbed on the pristine BNNT with a small adsorption energy (−0.10 eV). After the inclusion of the Fe atom inside BNNT (Fe@BNNT), the interaction of NO₂ molecules with this tube is significantly enhanced, leading to a transformation from the physisorption of on pristine BNNT to the current chemisorption. Interestingly, up to five NO₂ molecules can be adsorbed on this encapsulated BNNT along its circumference with the average adsorption energy of −0.52 eV, corresponding to a short recovery time (6 ms). Moreover, 0.38 electrons are transferred from the Fe@BNNT to the adsorbed NO₂ molecules, which is enough to induce the obvious change of its electrical conductance. Thus, we predict that the encapsulation of Fe atom inside BNNT would greatly boosts its sensitivity to NO₂ molecules, indicating its potential application as NO₂ sensors.     

Device characteristics for Pt–Ti–O gate Si–MISFETs hydrogen gas sensors

A novel Pt–Ti–O-gate Si–metal–insulator–semiconductor field-effect transistor (MISFET) hydrogen gas sensor has been proposed by Usagawa and Kikuchi (2010) [1]. The sensors consist of unique gate structures composed of Ti and oxygen accumulated regions around Pt grains on top of a novel mixing layer of nanocrystalline TiO_x and superheavily oxygen-doped amorphous Ti formed on SiO₂/Si substrates. The optimum Pt/Ti thickness and annealing conditions for most hydrogen safety monitoring sensor systems are obtained by annealing Pt(15 nm)/Ti(5 nm)-gate Si–MOS structures in air around 400 °C for 2 h. One of the advantages of the Pt–Ti–O-gate Si–MISFETs after 10 min of air-diluted 1000-ppm hydrogen exposure at 115 °C are reproducible and uniform threshold voltage of V_th in addition to large sensing amplitudes at a practically important hydrogen concentration range between 100 ppm and 1%. The analysis of device characteristics of the Pt–Ti–O-gate Si–MISFETs hydrogen sensors concludes that the oxidation process of the Ti layer is consistently explained by an oxidation model that the oxygen invasion into Ti layer comes from open air through Pt grain boundaries and at the same time Ti will evacuate into the Pt surface through Pt grain boundaries. During the course of this process, the invading oxygen will be balanced with the evacuating Ti so that the Ti layer keeps nearly the same thickness with the as grown states. Ti and oxygen will remains around Pt grains named Ti and oxygen merged corridors.     

Simulation of solid thermal explosion and liquid thermal explosion of dicumyl peroxide using calorimetric technique

Dicumyl peroxide (DCPO), is produced by cumene hydroperoxide (CHP) process, is utilized as an initiator for polymerization, a prevailing source of free radicals, a hardener, and a linking agent. DCPO has caused several thermal explosion and runaway reaction accidents in reaction and storage zone in Taiwan because of its unstable reactive property. Differential scanning calorimetry (DSC) was used to determine thermokinetic parameters including 700 J g^–1 of heat of decomposition (ΔH_d), 110 °C of exothermic onset temperature (T₀), 130 kJ mol^–1 of activation energy (E_a), etc., and to analyze the runaway behavior of DCPO in a reaction and storage zone. To evaluate thermal explosion of DCPO with storage equipment, solid thermal explosion (STE) and liquid thermal explosion (LTE) of thermal safety software (TSS) were applied to simulate storage tank under various environmental temperatures (T_e). T_e exceeding the T₀ of DCPO can be discovered as a liquid thermal explosion situation. DCPO was stored under room temperature without sunshine and was prohibited exceeding 67 °C of self-accelerating decomposition temperature (SADT) for a tank (radius = 1 m and height = 2 m). SADT of DCPO in a box (width, length and height = 1 m, respectively) was determined to be 60 °C. The TSS was employed to simulate the fundamental thermal explosion behavior in a large tank or a drum. Results from curve fitting demonstrated that, even at the earlier stage of the reaction in the experiments, ambient temperature could elicit exothermic reactions of DCPO. To curtail the extent of the risk, relevant hazard information is quite significant and must be provided in the manufacturing process.     

Investigation of spectroscopic properties of Sm-Eu codoped phosphate glasses

Phosphate glasses with chemical compositions of 74.5NaH₂PO₄–20ZnO–5Li₂O–0.5Sm₂O₃ and 74NaH₂PO₄–20ZnO–5Li₂O–0.5Sm₂O₃–0.5Eu₂O₃ were synthetized by melt quenching method. We investigated the influence of Sm³⁺/Eu³⁺ doping on the optical properties of phosphate glasses. X-ray Diffraction indicates that the samples have an amorphous structure. DSC measurements show a good thermal stability of phosphate glasses. Using the absorption spectra, Judd–Ofelt analysis was applied to absorption bands of Sm³⁺ (4f⁵) to carry out the three phenomenological parameters of Judd–Ofelt (JO). According to the obtained values of Ω₂, Ω₄ and Ω₆, some radiative properties were theoretically determined. We report both the photoluminescence (PL) and the PL lifetime measurements of a prominent emission transition ⁴G_5/2 → ⁶H_5/2 (604 nm) of Sm³⁺ both in absence and in presence of Eu³⁺. It is shown that Eu³⁺ ions act as sensitizers for Sm³⁺ ions and contribute largely to the improvement of the radiative properties of phosphate glasses. An improvement of the PL lifetime value after adding Eu³⁺ ions (4.58 ms) is reported. The predicted lifetime (τ_rad) calculated by Judd–Ofelt theory and the experimental lifetime (τ_meas) for the prepared phosphate glasses were compared with those of other works. Photoluminescence (PL) intensity of ⁴G_5/2 → ⁶H_5/2 (604 nm), ⁴G_5/2 → ⁶H_7/2 (567 nm), ⁴G_5/2 → ⁶H_9/2 (650 nm) and ⁴G_5/2 → ⁶H_11/2 (706 nm) and the quantum efficiency (η) for the excited ⁴G_5/2 level were enhanced after adding Eu³⁺. The radiative properties obtained for (Sm, Eu) codoped phosphate glasses suggest that the present material can be a potential candidate for the development of color display devices.     

Theoretical study of the geometries and decomposition energies of CO2 on Al12X: Doping effect of Al12X

The adsorption and decomposition of CO₂ molecule on X-centered icosahedronal Al₁₂X clusters (doping atom X = Al, Be, Zn, Fe, Ni, Cu, B, C, Si, P) were investigated by the DFT methods of PW91 and PWC. Adsorption energies, chemisorption energies and energy barriers of physic- and chemisorptions for CO₂ were determined. It was found that the doping atoms and spin states have important influences on the Al₁₂X geometries, electronic properties and energies of the adsorption processes. CO₂ chemisorption on the Al₁₂C cluster is energetically and kinetically unfavorable. CO₂ decomposition on the metallic doping Al₁₂X (X = Fe, Ni, Cu) clusters has relatively low energy barriers. On contrary, the barriers are large when X = B, C, Si and P. The energy barriers for CO₂ chemisorption and decomposition on the Al₁₂Fe cluster are 5.23 kJ/mol and 38.53 kJ/mol, respectively. These values are the lowest among all the clusters being discussed. The adsorption and decomposition of CO₂ on the Al₁₂X cluster can be tuned by X doping.