Gas sensing characteristics of Fe-doped tungsten oxide thin films

This study reports on the gas sensing characteristics of Fe-doped (10 at.%) tungsten oxide thin films of various thicknesses (100–500 nm) prepared by electron beam evaporation. The performance of these films in sensing four gases (H2, NH3, NO2 and N2O) in the concentration range 2–10,000 ppm at operating temperatures of 150–280 °C has been investigated. The results are compared with the sensing performance of a pure WO3 film of thickness 300 nm produced by the same method. Doping of the tungsten oxide film with 10 at.% Fe significantly increases the base conductance of the pure film but decreases the gas sensing response. The maximum response measured in this experiment, represented by the relative change in resistance when exposed to a gas, was ΔR/R = 375. This was the response amplitude measured in the presence of 5 ppm NO2 at an operating temperature of 250 °C using a 400 nm thick WO3:Fe film. This value is slightly lower than the corresponding result obtained using the pure WO3 film (ΔR/R = 450). However it was noted that the WO3:Fe sensor is highly selective to NO2, exhibiting a much higher response to NO2 compared to the other gases. The high performance of the sensors to NO2 was attributed to the small grain size and high porosity of the films, which was obtained through e-beam evaporation and post-deposition heat treatment of the films at 300 °C for 1 h in air.

Thermally evaporated tungsten oxide (WO3) thin films for gas sensing applications

In this thesis, the author proposed and developed gas sensors made of nanostructured WO3 thin film by a thermal evaporation technique. This technique gives control over film thickness, grain size and purity. The device fabrication, nanostructured material synthesis, characterization and gas sensing performance have been undertaken. Three different types of nanostructured thin films, namely, pure WO3 thin films, iron-doped WO3 thin films by co-evaporation and Fe-implanted WO3 thin films have been synthesized. All the thin films have a film thickness of 300 nm. The physical, chemical and electronic properties of these films have been optimized by annealing heat treatment at 300ºC and 400ºC for 2 hours in air. Various analytical techniques were employed to characterize these films. Atomic Force Microscopy and Transmission Electron Microscopy revealed a very small grain size of the order 5-10 nm in as-deposited WO3 films, and annealing at 300ºC or 400ºC did not result in any significant change in grain size. X-ray diffraction (XRD) analysis revealed a highly amorphous structure of as-deposited films. Annealing at 300ºC for 2 hours in air did not improve crystallinity in these films. However, annealing at 400ºC for 2 hours in air significantly improved the crystallinity in pure and iron-doped WO3 thin films, whereas it only slightly improved the crystallinity of iron-implanted WO3 thin film as a result of implantation. Rutherford backscattered spectroscopy revealed an iron content of 0.5 at.% and 5.5 at.% in iron-doped and iron-implanted WO3 thin films, respectively. The RBS results have been confirmed using energy dispersive x-ray spectroscopy (EDX) during analysis of the films using transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) revealed significant lowering of W 4f7/2 binding energy in all films annealed at 400ºC as compared with the as-deposited and 300ºC annealed films. Lowering of W 4f7/2 is due to increase in number of oxygen vacancies in the films and is considered highly beneficial for gas sensing. Raman analysis revealed that 400ºC annealed films except the iron-implanted film are highly crystalline with significant number of O-W-O bonds, which was consistent with the XRD results. Additionally, XRD, XPS and Raman analyses showed no evidence of secondary peaks corresponding to compounds of iron due to iron doping or implantation. This provided an understanding that iron was incorporated in the host WO3 matrix rather than as a separate dispersed compound or as catalyst on the surface. WO3 thin film based gas sensors are known to operate efficiently in the temperature range 200ºC-500 ºC. In the present study, by optimizing the physical, chemical and electronic properties through heat treatment and doping, an optimum response to H2, ethanol and CO has been achieved at a low operating temperature of 150ºC. Pure WO3 thin film annealed at 400ºC showed the highest sensitivity towards H2 at 150ºC due to its very small grain size and porosity, coupled with high number of oxygen vacancies, whereas Fe-doped WO3 film annealed at 400ºC showed the highest sensitivity to ethanol at an operating temperature of 150ºC due to its crystallinity, increased number of oxygen vacancies and higher degree of crystal distortions attributed to Fe addition. Pure WO3 films are known to be insensitive to CO, but iron-doped WO3 thin film annealed at 300ºC and 400ºC showed an optimum response to CO at an operating temperature of 150ºC. This result is attributed to lattice distortions produced in WO3 host matrix as a result of iron incorporation as substitutional impurity. However, iron-implanted WO3 thin films did not show any promising response towards the tested gases as the film structure has been damaged due to implantation, and annealing at 300ºC or 400ºC was not sufficient to induce crystallinity in these films. This study has demonstrated enhanced sensing properties of WO3 thin film sensors towards CO at lower operating temperature, which was achieved by optimizing the physical, chemical and electronic properties of the WO3 film through Fe doping and annealing. This study can be further extended to systematically investigate the effects of different Fe concentrations (0.5 at.% to 10 at.%) on the sensing performance of WO3 thin film gas sensors towards CO.

The correlation between electric field emission phenomenon and Schottky contact reverse bias characteristics in nanostructured systems

Two different morphologies of nanotextured molybdenum oxide were deposited by thermal evaporation. By measuring their field emission (FE) properties, an enhancement factor was extracted. Subsequently, these films were coated with a thin layer of Pt to form Schottky contacts. The current-voltage (I-V) characteristics showed low magnitude reverse breakdown voltages, which we attributed to the localized electric field enhancement. An enhancement factor was obtained from the I-V curves. We will show that the enhancement factor extracted from the I-V curves is in good agreement with the enhancement factor extracted from the FE measurements.

Pt/Nanostructured RuO2/SiC Schottky Diode based hydrogen gas sensors

In this paper, we report the development of novel Pt/nanostructured RuO2/SiC Schottky diode based sensors for hydrogen gas applications. The nanostructured ruthenium oxide thin films were deposited on SiC substrates using radio frequency sputtering technique. Scanning electron microscopy revealed the sputtered RuO2 layer consists of nano-cubular structures with dimensions ranging between 10 and 50 nm. X-ray diffraction confirmed the presence of tetragonal ruthenium (IV) oxide, with preferred orientation along the (101) lattice plane. The current-voltage characteristics of the sensors were investigated towards hydrogen gas in synthetic air at different temperatures from 25 °C to 240 °C. The dynamic responses of the sensors were studied at an optimum temperature of 240 °C and a voltage shift of 304 mV was recorded toward 1% hydrogen gas.

Oriented graphitic carbon films for hydrogen gas sensors

An oriented graphitic nanostructured carbon film has been employed as a conductometric hydrogen gas sensor. The carbon film was energetically deposited using a filtered cathodic vacuum arc with a -75 V bias applied to a stainless steel grid placed 1cm from the surface of the Si substrate. The substrate was heated to 400°C prior to deposition. Electron microscopy showed evidence that the film consisted largely of vertically oriented graphitic sheets and had a density of 2.06 g/cm3. 76% of the atoms were bonded in sp2 or graphitic configurations. A change in the device resistance of >; 1.5% was exhibited upon exposure to 1 % hydrogen gas (in synthetic, zero humidity air) at 100°C. The time for the sensor resistance to increase by 1.5 % under these conditions was approximately 60 s and the baseline (zero hydrogen exposure) resistance remained constant to within 0.01% during and after the hydrogen exposures.

Exploiting the facile oxidation of evaporated gold films to drive electroless silver deposition for the creation of bimetallic Au/Ag surfaces

Gold is often considered as an inert material but it has been unequivocally demonstrated that it possesses unique electronic, optical, catalytic and electrocatalytic properties when in a nanostructured form.[1] For the latter the electrochemical behaviour of gold in aqueous media has been widely studied on a plethora of gold samples, including bulk polycrystalline and single-crystal electrodes, nanoparticles, evaporated films as well as electrodeposited nanostructures, particles and thin films.[1b, 2] It is now well-established that the electrochemical behaviour of gold is not as simple as an extended double-layer charging region followed by a monolayer oxide-formation/-removal process. In fact the so-called double-layer region of gold is significantly more complicated and has been investigated with a variety of electrochemical and surface science techniques. Burke and others[3] have demonstrated that significant processes due to the oxidation of low lattice stabilised atoms or clusters of atoms occur in this region at thermally and electrochemically treated electrodes which were confirmed later by Bond[4] to be Faradaic in nature via large-amplitude Fourier transformed ac voltammetric experiments. Supporting evidence for the oxidation of gold in the double-layer region was provided by Bard,[5] who used a surface interrogation mode of scanning electrochemical microscopy to quantify the extent of this process that forms incipient oxides on the surface. These were estimated to be as high as 20% of a monolayer. This correlated with contact electrode resistance measurements,[6] capacitance measurements[7] and also electroreflection techniques...

Gas sensing of ruthenium implanted tungsten oxide thin films

Different amounts of Ru were implanted into thermally evaporated WO3 thin films by ion implantation. The films were subsequently annealed at 600oC for 2 hours in air to remove defects generated during the ion implantation. The Ru concentrations of four samples have been quantified by Rutherford Backscattering Spectrometry as 0.8, 5.5, 9 and 11.5 at%. The un-implanted WO3 films were highly porous but the porosity decreased significantly after ion implantation as observed by Transmission Electron Microscopy and Scanning Electron Microscopy. The thickness of the films also decreased with increasing Ru-ion dose, which is mainly due to densification of the porous films during ion implantation. From Raman spectroscopy two peaks at 408 and 451 cm-1 (in addition to the typical vibrational peaks of the monoclinic WO3 phase) associated with Ru were observed. Their intensity increased with increasing Ru concentration. X-Ray Photoelectron Spectroscopy showed a metallic state of Ru with binding energy of Ru 3d5/2 at 280.1 eV. This peak position remained almost unchanged with increasing Ru concentration. The resistances of the Ru-implanted films were found to increase in the presence of NO2 and NO with higher sensor response to NO2. The effect of Ru concentration on the sensing performance of the films was not explicitly observed due to reduced film thickness and porosity with increasing Ru concentration. However, the results indicate that the implantation of Ru into WO3 films with sufficient film porosity and film thickness can be beneficial for NO2 sensing at temperatures in the range of 250°C to 350°C.

Conductometric gas sensors based on nanostrutured WO3 thin films

Nanostructured WO3 thin films have been prepared bythermal evaporation to detect hydrogen at low t emperatures. The influence of heat treatment on the physical, chemical and electronic properties of these films has been investigated. The films were annealed at 400oC for 2 hours in air. AFM and TEM analysis revealed that the as-deposited WO3 film is high amorphous and made up of cluster of particles. Annealing at 400oC for 2 hours in air resulted in very fine grain size of the order of 5 nm and porous structure. GIXRD and Raman analysis revealed that annealing improved the crystallinity of WO3 film. Gas sensors based on annealed WO3 films have shown a high response towards various concentrations (10-10000 ppm) H2 at an operating temperature of 150oC. The improved sensing performance at low operating temperature is due to the optimum physical, chemical and electronic properties achieved in the WO3 film through annealing. - See more at: http://dl4.globalstf.org/?wpsc-product=conductometric-gas-sensors-based-on-nanostructured-wo3-thin-films-2#sthash.IrfhlZ6H.dpuf

Effective control of nanostructured phases in rapid, room-temperature synthesis of nanocrystalline Si in high-density plasmas

An innovative and effective approach based on low-pressure, low-frequency, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to synthesize device-quality nanocrystalline silicon (nc-Si) thin films at room temperature and with very competitive growth rates. The crystallinity and microstructure properties (including crystal structure, crystal volume fraction, surface morphology, etc.) of this nanostructured phase of Si can be effectively tailored in broad ranges for different device applications by simply varying the inductive rf power density from 25.0 to 41.7 mW/cm3. In particular, at a moderate rf power density of 41.7 mW/cm3, the nc-Si films feature a very high growth rate of 2.37 nm/s, a high crystalline fraction of 86%, a vertically aligned columnar structure with the preferential (111) growth orientation and embedded Si quantum dots, as well as a clean, smooth and defect-free interface. We also propose the formation mechanism of nc-Si thin films which relates the high electron density and other unique properties of the inductively coupled plasmas and the formation of the nanocrystalline phase on the Si surface.

Reactive oxygen plasma-enabled synthesis of nanostructured CdO : tailoring nanostructures through plasma–surface interactions

Plasma-assisted synthesis of nanostructures is one of the most precise and effective approaches used in nanodevice fabrication. Here we report on the innovative approach of synthesizing nanostructured cadmium oxide films on Cd substrates using a reactive oxygen plasma-based process. Under certain conditions, the surface morphology features arrays of crystalline CdO nano/micropyramids. These nanostructures grow via unconventional plasma-assisted oxidation of a cadmium foil exposed to inductively coupled plasmas with a narrow range of process parameters. The growth of the CdO pyramidal nanostructures takes place in the solid-liquid-solid phase, with the rates determined by the interaction of plasma-produced oxygen atoms and ions with the surface. It is shown that the size of the pyramidal structures can be effectively controlled by the fluxes of oxygen atoms and ions impinging on the cadmium surface. The unique role of the reactive plasma environment in the controlled synthesis of CdO nanopyramidal structures is discussed as well.

Numerical simulation of nanoparticle-generating electronegative plasmas in the PECVD of nanostructured silicon film

The results of numerical simulation of the equilibrium parameters of a low pressure nanopowder-generating discharge in silane for the plasma enhanced chemical vapor deposition (PECVD) of nanostructured silicon-based films are presented. It is shown that a low electron temperature and a low density of negative SiH3 - ions are favorable for the PECVD process. This opens a possibility to predict the main parameters of the reactive plasma and plasma-nucleated nanoparticles, and hence, to control the quality of silicon nanofilms.

Fabrication and characterization of plasma polymer thin films from monoterpene alcohols for applications in organic electronics and biotechnology

After more than twenty years of basic and applied research, the use of nanotechnology in the design and manufacture of nanoscale materials is rapidly increasing, particularly in commercial applications that span from electronics across renewable energy areas, and biomedical devices. Novel polymers are attracting significant attention for they promise to provide a low−cost high−performance alternative to existing materials. Furthermore, these polymers have the potential to overcome limitations imposed by currently available materials thus enabling the development of new technologies and applications that are currently beyond our reach. This work focuses on the development of a range of new low−cost environmentally−friendly polymer materials for applications in areas of organic (flexible) electronics, optics, and biomaterials. The choice of the monomer reflects the environmentally−conscious focus of this project. Terpinen−4−ol is a major constituent of Australian grown Melaleuca alternifolia (tea tree) oil, attributed with the oil's antimicrobial and anti−inflammatory properties. Plasma polymerisation was chosen as a deposition technique for it requires minimal use of harmful chemicals and produces no hazardous by−products. Polymer thin films were fabricated under varied process conditions to attain materials with distinct physico−chemical, optoelectrical, biological and degradation characteristics. The resultant materials, named polyterpenol, were extensively characterised using a number of well−accepted and novel techniques, and their fundamental properties were defined. Polyterpenol films were demonstrated to be hydrocarbon rich, with variable content of oxygen moieties, primarily in the form of hydroxyl and carboxyl functionalities. The level of preservation of original monomer functionality was shown to be strongly dependent on the deposition energy, with higher applied power increasing the molecular fragmentation and substrate temperature. Polyterpenol water contact angle contact angle increased from 62.7° for the 10 W samples to 76.3° for the films deposited at 100 W. Polymers were determined to resist solubilisation by water, due to the extensive intermolecular and intramolecular hydrogen bonds present, and other solvents commonly employed in electronics and biomedical processing. Independent of deposition power, the surface topography of the polymers was shown to be smooth (Rq <0.5 nm), uniform and defect free. Hardness of polyterpenol coatings increased from 0.33 GPa for 10 W to 0.51 GPa for 100 W (at 500 μN load). Coatings deposited at higher input RF powers showed less mechanical deformation during nanoscratch testing, with no considerable damage, cracking or delamination observed. Independent of the substrate, the quality of film adhesion improved with RF power, suggesting these coatings are likely to be more stable and less susceptible to wear. Independent of fabrication conditions, polyterpenol thin films were optically transparent, with refractive index approximating that of glass. Refractive index increased slightly with deposition power, from 1.54 (10 W) to 1.56 (100 W) at 500 nm. The optical band gap values declined with increasing power, from 2.95 eV to 2.64 eV, placing the material within the range for semiconductors. Introduction of iodine impurity reduced the band gap of polyterpenol, from 2.8 eV to 1.64 eV, by extending the density of states more into the visible region of the electromagnetic spectrum. Doping decreased the transparency and increased the refractive index from 1.54 to 1.70 (at 500 nm). At optical frequencies, the real part of permittivity (k) was determined to be between 2.34 and 2.65, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies, where permittivity increased with input RF energy – from 2.32 to 2.53 (at 10 GHz ) and from 2.65 to 2.83 (at 20 GHz). At low frequencies, the dielectric constant was determined from current−voltage characteristics of Al−polyterpenol−Al devices. At frequencies below 100 kHz, the dielectric constant varied with RF power, from 3.86 to 4.42 at 1 kHz. For all samples, the resistivity was in order of 10⁸−10⁹ _m (at 6 V), confirming the insulating nature of polyterpenol material. In situ iodine doping was demonstrated to increase the conductivity of polyterpenol, from 5.05 × 10⁻⁸ S/cm to 1.20 × 10⁻⁶ S/cm (at 20 V). Exposed to ambient conditions over extended period of time, polyterpenol thin films were demonstrated to be optically, physically and chemically stable. The bulk of ageing occurred within first 150 h after deposition and was attributed to oxidation and volumetric relaxation. Thermal ageing studies indicated thermal stability increased for the films manufactured at higher RF powers, with degradation onset temperature associated with weight loss shifting from 150 ºC to 205 ºC for 10 W and 100 W polyterpenol, respectively. Annealing the films to 405 °C resulted in full dissociation of the polymer, with minimal residue. Given the outcomes of the fundamental characterisation, a number of potential applications for polyterpenol have been identified. Flexibility, tunable permittivity and loss tangent properties of polyterpenol suggest the material can be used as an insulating layer in plastic electronics. Implementation of polyterpenol as a surface modification of the gate insulator in pentacene-based Field Effect Transistor resulted in significant improvements, shifting the threshold voltage from + 20 V to –3 V, enhancing the effective mobility from 0.012 to 0.021 cm²/Vs, and improving the switching property of the device from 10⁷ to 10⁴. Polyterpenol was demonstrated to have a hole transport electron blocking property, with potential applications in many organic devices, such as organic light emitting diodes. Encapsulation of biomedical devices is also proposed, given that under favourable conditions, the original chemical and biological functionality of terpinen−4−ol molecule can be preserved. Films deposited at low RF power were shown to successfully prevent adhesion and retention of several important human pathogens, including P. aeruginosa, S. aureus, and S. epidermidis, whereas films deposited at higher RF power promoted bacterial cell adhesion and biofilm formation. Preliminary investigations into in vitro biocompatibility of polyterpenol demonstrated the coating to be non−toxic for several types of eukaryotic cells, including Balb/c mice macrophage and human monocyte type (HTP−1 non-adherent) cells. Applied to magnesium substrates, polyterpenol encapsulating layer significantly slowed down in vitro biodegradation of the metal, thus increasing the viability and growth of HTP−1 cells. Recently, applied to varied nanostructured titanium surfaces, polyterpenol thin films successfully reduced attachment, growth, and viability of P. aeruginosa and S. aureus.