Alternating LB film of ferric oxide nanoparticles-copper phthalocyanine derivative and its gas sensitivity

Nanoparticulate ferric oxide - tris - (2,4-di-t-amylphenoxy) - (8-quinolinolyl) copper phthalocyanine Langmuir-Blodgett Z-type multilayers were obtained by using monodisperse nanoparticle ferric oxide hydrosol as the subphase. XPS data reveal that the nanoparticle ferric oxide exist as alpha -Fe2O3 phase in the films. Transition electron microscopic (TEM) image of the alternating monolayer shows that the film was highly covered by the copper phthalocyanine derivative and the nanoparticles were arranged rather closely. IR and visible spectra all give the results that the nanoparticles were deposited onto the substrate with the copper phthalocyanine derivative. The gas-sensing measurements show that the alternating LB film had very fast response-recovery characteristic to 2 ppm C2H5OH gas, and also sensitive to larger than 200 ppm NH3.

Electrochemical oxidation of nitrite and the oxidation and reduction of NO2 in the room temperature ionic liquid [C(2)mim][NTf2]

The electrochemical oxidation of potassium nitrite has been studied in the room temperature ionic liquid (RTIL) [C(2)mim][NTf2] by cyclic voltammetry at platinum electrodes. A chemically irreversible oxidation peak was observed, and a solubility of 7.5(+/- 0.5) mM and diffusion coefficient of 2.0(+/- 0.2) x 10(-11) m(2) s(-1) were calculated from potential step chronoamperometry on the microdisk electrode. A second, and sometimes third, oxidation peak was also observed when the anodic limit was extended, and these were provisionally assigned to the oxidation of nitrogen dioxide (NO2) and nitrate (NO3-), respectively. The electrochemical oxidation of nitrogen dioxide gas (NO2) was also studied by cyclic voltammetry in [C(2)mim][NTf2] on Pt electrodes of various size, giving a solubility of ca. 51(+/- 0.2) mM and diffusion coefficient of 1.6(+/- 0.05) x 10(-10) m(2) s(-1) (at 25 degrees C). It is likely that NO2 exists predominantly as its dimer, N2O4, at room temperature. The oxidation mechanism follows a CE process, which involves the initial dissociation of the dimer to the monomer, followed by a one-electron oxidation. A second, larger oxidation peak was observed at more positive potentials and is thought to be the direct oxidation of N2O4. In addition to understanding the mechanisms of NO2- and NO2 oxidations, this work has implications in the electrochemical detection of nitrite ions and of NO2 gas in RTIL media, the latter which may be of particular use in gas sensing.

Monitoring microbial sulfate reduction in porous media using multi-purpose electrodes

There is growing interest in the application of electrode-based measurements for monitoring microbial processes in the Earth using biogeophysical methods. In this study, reactive electrode measurements were combined to electrical geophysical measurements during microbial sulfate reduction occurring in a column of silica beads saturated with natural river water. Electrodic potential (EP), self potential (SP) and complex conductivity signals were recorded using a dual electrode design (Ag/AgCl metal as sensing/EP electrode, Ag/AgCl metal in KCl gel as reference/SP electrode). Open-circuit potentials, representing the tendency for electrochemical reactions to occur on the electrode surfaces, were recorded between sensing/EP electrode and reference/SP electrode and showed significant spatiotemporal variability associated with microbial activity. The dual electrode design isolates the microbial driven sulfide reactions to the sensing electrode and permits removal of any SP signal from the EP measurement. Based on the known sensitivity of a Ag electrode to dissolved sulfide, we interpret EP signals exceeding 550 mV recorded in this experiment in terms of bisulfide (HS-) concentration near multiple sensing electrodes. Complex conductivity measurements capture an imaginary conductivity (s?) signal interpreted as the response of microbial growth and biomass formation in the column. Our results suggest that the implementation of multipurpose electrodes, combining reactive measurements with electrical geophysical measurements, could improve efforts to monitor microbial processes in the Earth using electrodes.

Effect of plasticizer-polymer compatibility on the response characteristics of optical thin CO2 and O-2 sensing films

A homologous family of dialkyl phthalates has been used to investigate the effect of plasticizer/polymer compatibility on the response characteristics of transparent, plastic, thin optical gas sensing films for CO2 and oxygen. Plasticizer/polymer compatibilities were determined through the value of the difference in solubility parameter, i.e. Delta delta, for the plasticizer and polymer with a Delta delta value of zero indicating high compatibility. A strong correlation was found between plasticizer/polymer compatibility and sensitivity in phenol red/ethyl cellulose CO2-sensitive films and this relationship extended to CO2-sensitive films based on other polymers such as polystyrene and poly(methyl methacrylate). It extended also to optical O-2-sensitive films implying that the relationship is general for thin-film optical sensors. Other results from the CO2-sensitive films in different polymers indicated that the film sensitivity is largely independent of the polymer matrix regardless of its inherent gas permeability, when a sufficient quantity of compatible plasticizer is present. (C) 1998 Elsevier Science B.V.

Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases

One of the main challenges in the development of metal-oxide gas sensors is enhancement of selectivity to a particular gas. Currently, two general approaches exist for enhancing the selective properties of sensors. The first one is aimed at preparing a material that is specifically sensitive to one compound and has low or zero cross-sensitivity to other compounds that may be present in the working atmosphere. To do this, the optimal temperature, doping elements, and their concentrations are investigated. Nonetheless, it is usually very difficult to achieve an absolutely selective metal oxide gas sensor in practice. Another approach is based on the preparation of materials for discrimination between several analyte in a mixture. It is impossible to do this by using one sensor signal. Therefore, it is usually done either by modulation of sensor temperature or by using sensor arrays. The present work focus on the characterization of n-type semiconducting metal oxides like Tungsten oxide (WO3), Zinc Oxide (ZnO) and Indium oxide (In2O3) for the gas sensing purpose. For the purpose of gas sensing thick as well as thin films were fabricated. Two different gases, NO2 and H2S gases were selected in order to study the gas sensing behaviour of these metal oxides. To study the problem associated with selectivity the metal oxides were doped with metals and the gas sensing characteristics were investigated. The present thesis is entitled “Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases” and consists of six chapters.

Influence of ambient gas on the growth and properties of porous tin-doped indium oxide thin films made by pulsed laser deposition

The laser ablation method was used for depositing porous nanocrystalline indium-tin oxide thin films for gas sensing applications. Samples were prepared at different pressures using three gases (O-2, 0.8N(2):0.2O(2), N-2) and heat-treated in the same atmosphere used for the ablation process. X-ray diffraction results show that the films are not oriented and the grain sizes are in the range between 15 and 40 nm. The grains are round shaped for all samples and the porosity of the films increases with the deposition pressure. The degree of sintering after heat treatment increases for lower oxygen concentrations, generating fractures on the surface of the samples. Film thicknesses are in the range of I pm for all gases as determined from scanning electron microscopy cross-sections. Electrical resistance varies between 36.3 ohm for the film made at 10 Pa pressure in N-2 until 9.35 x 10(7) ohm for the film made at 100 Pa in O-2. (C) 2007 Elsevier B.V. All rights reserved.

A new method to control particle size and particle size distribution of SnO2 nanoparticles for gas sensor applications

The controlled growth of SnO2 nanoparticles for gas sensor applications is reported by these authors. Nb2O5 additive is used to control nucleation and growth of the SnO2 (see Figure), which is synthesized by the polymeric precursor method. Preliminary gas sensing measurements are performed and it is demonstrated that the response time of the Nb2O5-doped SnO2 is faster than that of the undoped material.

Impedance spectroscopy analysis of TiO(2) thin film gas sensors obtained from water-based anatase colloids

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optimized design of substrate-integrated hollow waveguides for mid-infrared gas analyzers

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Gas sensor properties of zno nanorods grown by chemical bath deposition

The present work shows a study about the growing of ZnO nanorods by chemical bath deposition (CBD) and its application as gas sensor. It was prepared ZnO nanorods and Au decorated ZnO nanorods and the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and gas sensing response measurements. The results obtained by XRD show the growth of ZnO phase. It was possible to observe the formation of uniform dense well-aligned ZnO nanorods. The results obtained also revealed that Ag nanoparticles have decorated the surface of ZnO nanorods successfully. Au nanoparticles with diameter of a few nanometers were distributed over the ZnO surface nanorods. The gas sensing response measurements showed a behavior of n type semiconductor. Furthermore, the Au-functionalized ZnO nanorods gas sensors showed a considerably enhanced response at 250 and 300 °C.

An easy method of preparing ozone gas sensors based on ZnO nanorods

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Photoconductivity and Electro-Optical Properties of Wide Band Gap Metal Oxides

The PhD activity described in this Thesis was focused on the study of metal-oxide wide-bandgap materials, aiming at fabricating new optoelectronic devices such as solar-blind UV photodetectors, high power electronics, and gas sensors. Photocurrent spectroscopy and DC photocurrent time evolution were used to investigate the performance of prototypes under different atmospheres, temperatures and excitation wavelengths (or dark conditions). Cathodoluminescence, absorption spectroscopy, XRD and SEM were used to assess structural, morphologic, electrical and optical properties of materials. This thesis is divided into two main sections, each describing the work done on a different metal-oxide semiconductor. 1) MOVPE-grown Ga2O3 thin films for UV solar-blind photodetectors and high power devices The semiconducting oxides, among them Ga2O3, have been employed for several decades as transparent conducting oxide (TCO) electrodes for fabrication of solar cells, displays, electronic, and opto-electronic devices. The interest was mainly confined to such applications, as these materials tend to grow intrinsically n-type, and attempts to get an effective p-type doping has consistently failed. The key requirements of TCO electrodes are indeed high electrical conductivity and good transparency, while crystallographic perfection is a minor issue. Furthermore, for a long period no high-quality substrates and epi-layers were available, which in turn impeded the development of a truly full-oxide electronics. Recently, Ga2O3 has attracted renewed interest, as large single crystals and high-quality homo- and hetero-epitaxial layers became available, which paved the way to novel application areas. Our research group spent the last two years in developing a low temperature (500-700°C) MOVPE growth procedure to obtain thin films of Ga2O3 on different substrates (Dept. of Physics and IMEM-CNR at UNIPR). We obtained a significant result growing on oriented sapphire epitaxial films of high crystalline, undoped, pure phase -Ga2O3 (hexagonal). The crystallographic properties of this phase were investigated by XRD, in order to clarify the lattice parameters of the hexagonal cell. First design and development of solar blind UV photodetectors based on -phase was carried out and the optoelectronic performance is evaluated by means of photocurrent spectroscopy. The UV-response is adequately fast and reliable to render this unusual phase a subject of great interest for future applications. The availability of a hexagonal phase of Ga2O3 stable up to 700°C, belonging to the same space group of gallium nitride, with high crystallinity and tunable electrical properties, is intriguing in view of the development of nitride-based devices, by taking advantage of the more favorable symmetry and epitaxial relationships with respect to the monoclinic β-phase. In addition, annealing at temperatures higher than 700°C demonstrate that the hexagonal phase converts totally in the monoclinic one. 2) ZnO nano-tetrapods: charge transport mechanisms and time-response in optoelectronic devices and sensors Size and morphology of ZnO at the nanometer scale play a key role in tailoring its physical and chemical properties. Thanks to the possibility of growing zinc oxide in a variety of different nanostructures, there is a great variety of applications, among which gas sensors, light emitting diodes, transparent conducting oxides, solar cells. Even if the operation of ZnO nanostructure-based devices has been recently demonstrated, the mechanisms of charge transport in these assembly is still under debate. The candidate performed an accurate investigation by photocurrent spectroscopy and DC-photocurrent time evolution of electrical response of both single-tetrapod and tetrapod-assembly devices. During the research done for this thesis, a thermal activation energy enables the performance of samples at high temperatures (above about 300°C). The energy barrier is related to the leg-to-leg interconnection in the assembly of nanotetrapods. Percolation mechanisms are responsible for both the very slow photo-response (minutes to hours or days) and the significant persistent photocurrent. Below the bandgap energy, electronic states were investigated but their contribution to the photocurrent are two-three order of magnitude lower than the band edge. Such devices are suitable for employ in photodetectors as well as in gas sensors, provided that the mechanism by which the photo-current is generated and gas adsorption on the surface modify the conductivity of the material are known.

Low temperature CO sensitive nanostructured WO3 thin films doped with Fe

Nanostructured tungsten oxide thin film based gas sensors have been developed by thermal evaporation method to detect CO at low operating temperatures. The influence of Fe-doping and annealing heat treatment on microstructural and gas sensing properties of these films have been investigated. Fe was incorporated in WO3 film by co-evaporation and annealing was performed at 400oC for 2 hours in air. AFM analysis revealed a grain size of about 10-15 nm in all the films. GIXRD analysis showed that as-deposited films are amorphous and annealing at 400oC improved the crystallinity. Raman and XRD analysis indicated that Fe is incorporated in the WO3 matrix as a substitutional impurity, resulting in shorter O-W-O bonds and lattice cell parameters. Doping with Fe contributed significantly towards CO sensing performance of WO3 thin films. A good response to various concentrations (10-1000 ppm) of CO has been achieved with 400oC annealed Fe-doped WO3 film at a low operating temperature of 150oC.

Low temperature response of nanostructured tungsten oxide thin films toward hydrogen and ethanol

Semiconducting metal oxide based gas sensors usually operate in the temperature range 200–500 °C. In this paper, we present a new WO3 thin film based gas sensor for H2 and C2H5OH, operating at 150 °C. Nanostructured WO3 thin films were synthesized by thermal evaporation method. The properties of the as-deposited films were modified by annealing in air at 300 °C and 400 °C. Various analytical techniques such as AFM, TEM, XPS, XRD and Raman spectroscopy have been employed to characterize their properties. A clear indication from TEM and XRD analysis is that the as-deposited WO3 films are highly amorphous and no improvement is observed in the crystallinity of the films after annealing at 300 °C. Annealing at 400 °C significantly improved the crystalline properties of the films with the formation of about 5 nm grains. The films annealed at 300 °C show no response to C2H5OH (ethanol) and a little response to H2, with maximum response obtained at 280 °C. The films annealed at 400 °C show a very good response to H2 and a moderate response to C2H5OH (ethanol) at 150 °C. XPS analysis revealed that annealing of the WO3 thin films at 400 °C produces a significant change in stoichiometry, increasing the number of oxygen vacancies in the film, which is highly beneficial for gas sensing. Our results demonstrate that gas sensors with significant performance at low operating temperatures can be obtained by annealing the WO3 films at 400 °C and optimizing the crystallinity and nanostructure of the as-deposited films.

A hydrogen/methane sensor based on niobium tungsten oxide nanorods synthesised by hydrothermal method

An investigation on hydrogen and methane sensing performance of hydrothermally formed niobium tungsten oxide nanorods employed in a Schottky diode structure is presented herein. By implementing tungsten into the surface of the niobium lattice, we create Nb5+ and W5+ oxide states and an abundant number of surface traps, which can collect and hold the adsorbate charge to reinforce a greater bending of the energy bands at the metal/oxide interface. We show experimentally, that extremely large voltage shifts can be achieved by these nanorods under exposure to gas at both room and high temperatures and attribute this to the strong accumulation of the dipolar charges at the interface via the surface traps. Thus, our results demonstrate that niobium tungsten oxide nanorods can be implemented for gas sensing applications, showing ultra-high sensitivities.