Microwave irradiation-assisted method for the deposition of adherent oxide films on semiconducting and dielectric substrates

We report a method for the deposition of thin films and thick coatings of metal oxides through the liquid medium, involving the micro waveirradiation of a solution of a metal-organic complex in a suitable dielectric solvent. The process is a combination of sol-gel and dip-coating methods, wherein coatings can be obtained on nonconducting and semiconducting substrates, within a few minutes. Thin films of nanostructured ZnO (wurtzite) have been obtained on Si(100), glass and polymer substrates, the nanostructure determined by process parameters The coatings are strongly adherent and uniform over 15 mm x 15 mm, the growth rate similar to 0.25 mu m/min Coatings of nanocrystalline Fe2O3 and Ga2O3 have also been obtained The method is scalable to larger substrates, and is promising as a low temperature technique for coating dielectric substrates, including flexible polymers. (C) 2010 Elsevier B.V. All rights reserved.

Microstructural characterization of electron beam evaporated tungsten oxide films for gas sensing applications

Tungsten trioxide is one of the potential semiconducting materials used for sensing NH3, CO, CH4 and acetaldehyde gases. The current research aims at development, microstructural characterization and gas sensing properties of thin films of Tungsten trioxide (WO3). In this paper, we intend to present the microstructural characterization of these films as a function of post annealing heat treatment. Microstructural and elemental analysis of electron beam evaporated WO3 thin films and iron doped WO3 films (WO3:Fe) have been carried out using analytical techniques such as Transmission electron microscopy, Rutherford Backscattered Spectroscopy and XPS analysis. TEM analysis revealed that annealing at 300oC for 1 hour improves cyrstallinity of WO3 film. Both WO3 and WO3:Fe films had uniform thickness and the values corresponded to those measured during deposition. RBS results show a fairly high concentration of oxygen at the film surface as well as in the bulk for both films, which might be due to adsorption of oxygen from atmosphere or lattice oxygen vacancy inherent in WO3 structure. XPS results indicate that tungsten exists in 4d electronic state on the surface but at a depth of 10 nm, both 4d and 4f electronic states were observed. Atomic force microscopy reveals nanosize particles and porous structure of the film. This study shows e-beam evaporation technique produces nanoaparticles and porous WO3 films suitable for gas sensing applications and doping with iron decreases the porosity and particle size which can help improve the gas selectivity.

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.

Preparation and characterization of tin oxide nanowires on SiC

Interest in nanowires of metal oxide oxides has been exponentially growing in the last years, due to the attracting potential of application in electronic, optical and sensor field. We have focused our attention on the sensing properties of semiconducting nanowires as conductometric and optical gas sensors. Single crystal tin dioxide nanostructures were synthesized to explore and study their capability in form of multi-nanowires sensors. The nanowires of SnO2 have been used to produce a novel gas sensor based on Pt/oxide/SiC structure and operating as Schottky diode. For the first time, a reactive oxide layer in this device has been replaced by SnO2 nanowires. Proposed sensor has maintained the advantageous properties of known SiC- based MOS devices, that can be employed for the monitoring of gases (hydrogen and hydrocarbons) emitted by industrial combustion processes.

Voltammetric, spectroscopic, and microscopic investigations of electrocrystallized forms of semiconducting AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) exhibiting different morphologies and colors

Chemically synthesized AgTCNQ exists in two forms that differ in their morphologies (needles and microcrystals) and colors (red and blue). It is now shown that both forms exhibit essentially indistinguishable X-ray diffraction, spectroscopic, and thermochemical data, implying that they are not separate phases, as implied in some literature. Electrochemical reduction of TCNQ((MeCN)) in the presence of Ag+((MeCN)) generates both red and blue AgTCNQ. On glassy carbon, platinum, or indium tin oxide electrodes and at relatively positive deposition potentials, slow growth of high aspect ratio, red needle AgTCNQ crystals occurs. After longer times and at more negative deposition potentials, blue microcrystalline AgTCNQ thin films are favored. Blue AgTCNQ is postulated to be generated via reduction of a Ag+\[(TCNQ(center dot-))(TCNQ)]((MeCN)) intermediate. At even more negative potentials, Ag-(metal) formation inhibits further growth of AgTCNQ. On a gold electrode, Ag-(metal)) deposition occurs at more positive potentials than on the other electrode materials examined. However, surface plasmon resonance data indicate (hat a small potential region is available between the stripping of Ag-(metal)) and the oxidation of TCNQ(center dot-)(MeCN) back to TCNQ(MeCN) where AgTCNQ may form. AgTCNQ in both the red and blue forms also can be prepared electrochemically on a TCNQ((s)) modified electrode in -0.1 M AgNO3(aq) where deposition of Ag(m,,,I) onto the TCNQ((s)) crystals allows a charge transfer process to occur. However, the morphology formed in this solid-solid phase transformation is more difficult to control.

Deterministic surface growth of single-crystalline iron oxide nanostructures in nonequilibrium plasma

An innovative approach to precise tailoring of surface density, shapes, and sizes of single-crystalline α-Fe 2O 3 nanowires and nanobelts by controlling interactions of reactive oxygen plasma-generated species with the Fe surface is proposed. This strongly nonequilibrium, rapid, almost incubation-free, high-rate growth directly from the solid-solid interface can also be applied to other oxide materials and is based on deterministic control of the density of oxygen species and the surface conditions, which determine the nanostructure nucleation and growth.

Reversible Conversion of Dominant Polarity in Ambipolar Polymer/Graphene Oxide Hybrids

The possibility to selectively modulate the charge carrier transport in semiconducting materials is extremely challenging for the development of high performance and low-power consuming logic circuits. Systematical control over the polarity (electrons and holes) in transistor based on solution processed layer by layer polymer/graphene oxide hybrid system has been demonstrated. The conversion degree of the polarity is well controlled and reversible by trapping the opposite carriers. Basically, an electron device is switched to be a hole only device or vice versa. Finally, a hybrid layer ambipolar inverter is demonstrated in which almost no leakage of opposite carrier is found. This hybrid material has wide range of applications in planar p-n junctions and logic circuits for high-throughput manufacturing of printed electronic circuits.

A Method for the Deposition of Transparent Conducting Thin-Films of Tin Oxide

A modified method has been developed for the deposition of transparent semiconducting thin films of tin oxide, involving the chemical vapour phase oxidation of tin iodide. These films show sheet resistances greater than 100 Ω/□ and an average optical transmission in the visible range exceeding 80%. The method avoids uncontrolled contamination, resulting in better reproducibility of the films. The films showed direct and indirect transitions and the possibility of an indirect forbidden transition. X-ray diffraction studies reveal that the films are polycrystalline. The low mobility values of the films have been attributed to the grain boundary scattering effect.

Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification

Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

Zinc oxide nanowire networks for macroelectronic devices

Highly transparent zinc oxide (ZnO) nanowire networks have been used as the active material in thin film transistors (TFTs) and complementary inverter devices. A systematic study on a range of networks of variable density and TFT channel length was performed. ZnO nanowire networks provide a less lithographically intense alternative to individual nanowire devices, are always semiconducting, and yield significantly higher mobilites than those achieved from currently used amorphous Si and organic TFTs. These results suggest that ZnO nanowire networks could be ideal for inexpensive large area electronics. © 2009 American Institute of Physics.

Electrical actuation and readout in a nanoelectromechanical resonator based on a laterally suspended zinc oxide nanowire.

In this paper, we present experimental results describing enhanced readout of the vibratory response of a doubly clamped zinc oxide (ZnO) nanowire employing a purely electrical actuation and detection scheme. The measured response suggests that the piezoelectric and semiconducting properties of ZnO effectively enhance the motional current for electromechanical transduction. For a doubly clamped ZnO nanowire resonator with radius ~10 nm and length ~1.91 µm, a resonant frequency around 21.4 MHz is observed with a quality factor (Q) of ~358 in vacuum. A comparison with the Q obtained in air (~242) shows that these nano-scale devices may be operated in fluid as viscous damping is less significant at these length scales. Additionally, the suspended nanowire bridges show field effect transistor (FET) characteristics when the underlying silicon substrate is used as a gate electrode or using a lithographically patterned in-plane gate electrode. Moreover, the Young's modulus of ZnO nanowires is extracted from a static bending test performed on a nanowire cantilever using an AFM and the value is compared to that obtained from resonant frequency measurements of electrically addressed clamped–clamped beam nanowire resonators.

Strong carrier lifetime enhancement in GaAs nanowires coated with semiconducting polymer.

The ultrafast charge carrier dynamics in GaAs/conjugated polymer type II heterojunctions are investigated using time-resolved photoluminescence spectroscopy at 10 K. By probing the photoluminescence at the band edge of GaAs, we observe strong carrier lifetime enhancement for nanowires blended with semiconducting polymers. The enhancement is found to depend crucially on the ionization potential of the polymers with respect to the Fermi energy level at the surface of the GaAs nanowires. We attribute these effects to electron doping by the polymer which reduces the unsaturated surface-state density in GaAs. We find that when the surface of nanowires is terminated by native oxide, the electron injection across the interface is greatly reduced and such surface doping is absent. Our results suggest that surface engineering via π-conjugated polymers can substantially improve the carrier lifetime in nanowire hybrid heterojunctions with applications in photovoltaics and nanoscale photodetectors.

Top down scale-up of semiconducting nanostructures for large area electronics

In this paper, we present a study on electrical and optical characteristics of n-type tin-oxide nanowires integrated based on top-down scale-up strategy. Through a combination of contact printing and plasma based back-channel passivation, we have achieved stable electrical characteristics with standard deviation in mobility and threshold voltage of 9.1% and 25%, respectively, for a large area of 1× 1 cm2 area. Through use of contact printing, high alignment of nanowires was achieved thus minimizing the number of nanowire-nanowire junctions, which serve to limit carrier transport in the channel. In addition, persistent photoconductivity has been observed, which we attribute to oxygen vacancy ionization and subsequent elimination using a gate pulse driving scheme. © 2014 IEEE.

A thermalization energy analysis of the threshold voltage shift in amorphous indium gallium zinc oxide thin film transistors under simultaneous negative gate bias and illumination

It has been previously observed that thin film transistors (TFTs) utilizing an amorphous indium gallium zinc oxide (a-IGZO) semiconducting channel suffer from a threshold voltage shift when subjected to a negative gate bias and light illumination simultaneously. In this work, a thermalization energy analysis has been applied to previously published data on negative bias under illumination stress (NBIS) in a-IGZO TFTs. A barrier to defect conversion of 0.65-0.75 eV is extracted, which is consistent with reported energies of oxygen vacancy migration. The attempt-to-escape frequency is extracted to be 10 6-107 s-1, which suggests a weak localization of carriers in band tail states over a 20-40 nm distance. Models for the NBIS mechanism based on charge trapping are reviewed and a defect pool model is proposed in which two distinct distributions of defect states exist in the a-IGZO band gap: these are associated with states that are formed as neutrally charged and 2+ charged oxygen vacancies at the time of film formation. In this model, threshold voltage shift is not due to a defect creation process, but to a change in the energy distribution of states in the band gap upon defect migration as this allows a state formed as a neutrally charged vacancy to be converted into one formed as a 2+ charged vacancy and vice versa. Carrier localization close to the defect migration site is necessary for the conversion process to take place, and such defect migration sites are associated with conduction and valence band tail states. Under negative gate bias stressing, the conduction band tail is depleted of carriers, but the bias is insufficient to accumulate holes in the valence band tail states, and so no threshold voltage shift results. It is only under illumination that the quasi Fermi level for holes is sufficiently lowered to allow occupation of valence band tail states. The resulting charge localization then allows a negative threshold voltage shift, but only under conditions of simultaneous negative gate bias and illumination, as observed experimentally as the NBIS effect. © 2014 AIP Publishing LLC.