Zinc Titanate Nanoarrays with Superior Optoelectrochemical Properties for Chemical Sensing.

In this report, the gas sensing performance of zinc titanate (ZnTiO3) nanoarrays (NAs) synthesized by coating hydrothermally formed zinc oxide (ZnO) NAs with TiO2 using low-temperature chemical vapor deposition is presented. By controlling the annealing temperature, diffusion of ZnO into TiO2 forms a mixed oxide of ZnTiO3 NAs. The uniformity and the electrical properties of ZnTiO3 NAs made them ideal for light-activated acetone gas sensing applications for which such materials are not well studied. The acetone sensing performance of the ZnTiO3 NAs is tested by biasing the sensor with voltages from 0.1 to 9 V dc in an amperometric mode. An increase in the applied bias was found to increase the sensitivity of the device toward acetone under photoinduced and nonphotoinduced (dark) conditions. When illuminated with 365 nm UV light, the sensitivity was observed to increase by 3.4 times toward 12.5 ppm acetone at 350 °C with an applied bias of 9 V, as compared to dark conditions. The sensor was also observed to have significantly reduced the adsorption time, desorption time, and limit of detection (LoD) when excited by the light source. For example, LoD of the sensor in the dark and under UV light at 350 °C with a 9 V bias is found to be 80 and 10 ppb, respectively. The described approach also enabled acetone sensing at an operating temperature down to 45 °C with a repeatability of >99% and a LoD of 90 ppb when operated under light, thus indicating that the ZnTiO3 NAs are a promising material for low concentration acetone gas sensing applications.

Physisorption-Based Charge Transfer in Two-Dimensional SnS2 for Selective and Reversible NO2 Gas Sensing.

Nitrogen dioxide (NO2) is a gas species that plays an important role in certain industrial, farming, and healthcare sectors. However, there are still significant challenges for NO2 sensing at low detection limits, especially in the presence of other interfering gases. The NO2 selectivity of current gas-sensing technologies is significantly traded-off with their sensitivity and reversibility as well as fabrication and operating costs. In this work, we present an important progress for selective and reversible NO2 sensing by demonstrating an economical sensing platform based on the charge transfer between physisorbed NO2 gas molecules and two-dimensional (2D) tin disulfide (SnS2) flakes at low operating temperatures. The device shows high sensitivity and superior selectivity to NO2 at operating temperatures of less than 160 °C, which are well below those of chemisorptive and ion conductive NO2 sensors with much poorer selectivity. At the same time, excellent reversibility of the sensor is demonstrated, which has rarely been observed in other 2D material counterparts. Such impressive features originate from the planar morphology of 2D SnS2 as well as unique physical affinity and favorable electronic band positions of this material that facilitate the NO2 physisorption and charge transfer at parts per billion levels. The 2D SnS2-based sensor provides a real solution for low-cost and selective NO2 gas sensing.

Optical gas sensing properties of nanoporous Nb2O5 films.

Nanoporous Nb2O5 has been previously demonstrated to be a viable electrochromic material with strong intercalation characteristics. Despite showing such promising properties, its potential for optical gas sensing applications, which involves the production of ionic species such as H(+), has yet to be explored. Nanoporous Nb2O5 can accommodate a large amount of H(+) ions in a process that results in an energy bandgap change of the material which induces an optical response. Here, we demonstrate the optical hydrogen gas (H2) sensing capability of nanoporous anodic Nb2O5 with a large surface-to-volume ratio prepared via a high temperature anodization method. The large active surface area of the film provides enhanced pathways for efficient hydrogen adsorption and dissociation, which are facilitated by a thin layer of Pt catalyst. We show that the process of H2 sensing causes optical modulations that are investigated in terms of response magnitudes and dynamics. The optical modulations induced by the intercalation process and sensing properties of nanoporous anodic Nb2O5 shown in this work can potentially be used for future optical gas sensing systems.

Hydrothermally formed functional niobium oxide doped tungsten nanorods.

Nanorod forms of metal oxides are recognized as one of the most remarkable morphologies. Their structure and functionality have driven important advancements in a vast range of electronic devices and applications. In this work, we postulate a novel concept to explain how numerous localized surface states can be engineered into the bandgap of niobium oxide nanorods using tungsten. We discuss their contributions as local state surface charges for the modulation of a Schottky barrier height, the relative dielectric constant and their respective conduction mechanisms. Their effects on hydrogen gas molecule interaction mechanisms are also examined herein. We synthesized niobium tungsten oxide (Nb17W2O25) nanorods via a hydrothermal growth method and evaluated the Schottky barrier height, ideality factor, dielectric constant and trap energy level from the measured I-V versus temperature characteristics in the presence of air and hydrogen to show the validity of our postulations.

Gas sensing studies of pulsed laser deposition deposited WO3 nanorod based thin films.

WO3 nanorod based thin films were deposited via pulsed laser deposition onto quartz conductometric transducers with pre-patterned gold interdigitated transducers (IDT) employing the shortest wavelength (193 nm) ArF excimer laser. Micro-characterization techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were employed to study surface morphology and crystal structure. It was observed that the fabricated films showed nanocolumnar features perpendicular to the surface. The measured sizes of the nanorods were found to be approximately -50 nm in diameter. The high resolution TEM (HRTEM) image of the nanorods based WO3 showed the WO3 lattice spacing of 3.79 angstroms corresponding to the (020) plane of monoclinic WO3. Gas sensing characterizations of the developed sensors were tested towards hydrogen and ethanol at temperatures between room and 400 degrees C. The sensor exhibited high response towards H2 and ethanol at operating temperatures of 170 and 400 degrees C, respectively. The excellent sensing characteristics of WO3 films towards ethanol and H2 at low concentrations offer great potential for low cost and stable gas sensing.

Self-assembled 3D ZnO porous structures with exposed reactive {0001} facets and their enhanced gas sensitivity.

Complex three-dimensional structures comprised of porous ZnO plates were synthesized in a controlled fashion by hydrothermal methods. Through subtle changes to reaction conditions, the ZnO structures could be self-assembled from 20 nm thick nanosheets into grass-like and flower-like structures which led to the exposure of high proportions of ZnO {0001} crystal facets for both these materials. The measured surface area of the flower-like and the grass, or platelet-like ZnO samples were 72.8 and 52.4 m2∙g-1, respectively. Gas sensing results demonstrated that the porous, flower-like ZnO structures exhibited enhanced sensing performance towards NO2 gas compared with either grass-like ZnO or commercially sourced ZnO nanoparticle samples. The porous, flower-like ZnO structures provided a high surface area which enhanced the ZnO gas sensor response. X-ray photoelectron spectroscopy characterization revealed that flower-like ZnO samples possessed a higher percentage of oxygen vacancies than the other ZnO sample-types, which also contributed to their excellent gas sensing performance.

Interaction of hydrogen with zinc oxide nanorods: why the spacing is important.

Hydrothermally grown ZnO nanorods show high interaction rates with H2 when the spacing between adjacent nanorods decreases. Density functional theory calculations showed the interaction between nanorod surfaces in-registry is attractive at separations < 5 Å, while it is repulsive for out-of-registry alignments, indicating that uniform nanorods grown with their faces aligned out-of-registry are not likely to fuse due to the repulsion between the surfaces. The separation of 5 Å was found to be sufficient for H2 to adsorb between the surfaces, resulting in a transfer of charge from H(2) to the surface, consistent with the measured increase in conductivity. This explains the ability of hydrogen to adsorb on closely spaced nanorods.

Synthesis of nanometre-thick MoO3 sheets.

The formation of MoO(3) sheets of nanoscale thickness is described. They are made from several fundamental sheets of orthorhombic alpha-MoO(3), which can be processed in large quantities via a low cost synthesis route that combines thermal evaporation and mechanical exfoliation. These fundamental sheets consist of double-layers of linked distorted MoO(6) octahedra. Atomic force microscopy (AFM) measurements show that the minimum resolvable thickness of these sheets is 1.4 nm which is equivalent to the thickness of two double-layers within one unit cell of the alpha-MoO(3) crystal.

High-temperature anodized WO3 nanoplatelet films for photosensitive devices.

Anodization at elevated temperatures in nitric acid has been used for the production of highly porous and thick tungsten trioxide nanostructured films for photosensitive device applications. The anodization process resulted in platelet crystals with thicknesses of 20-60 nm and lengths of 100-1000 nm. Maximum thicknesses of approximately 2.4 microm were obtained after 4 h of anodization at 20 V. X-ray diffraction analysis revealed that the as-prepared anodized samples contain predominantly hydrated tungstite phases depending on voltage, while films annealed at 400 degrees C for 4 h are predominantly orthorhombic WO3 phase. Photocurrent measurements revealed that the current density of the 2.4 microm nanostructured anodized film was 6 times larger than the nonanodized films. Dye-sensitized solar cells developed using these films produced 0.33 V and 0.65 mA/cm2 in open- and short-circuit conditions.

Anodization of Ti thin film deposited on ITO.

We have investigated several key aspects for the self-organization of nanotubes in RF sputtered titanium (Ti) thin films formed by the anodization process in fluoride-ion-containing neutral electrolytes. Ti films were deposited on indium tin oxide (ITO) glass substrates at room temperature and 300 degrees C, and then anodized. The films were studied using scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis spectrometry before and after anodization. It was observed that anodization of high temperature deposited films resulted in nanotube type structures with diameters in the range of 10-45 nm for an applied voltage of 5-20 V. In addition, the anatase form of TiO(2) is formed during the anodization process which is also confirmed using photocurrent measurements. However, the anodization of room temperature deposited Ti films resulted in irregular pores or holes.