M. Mikula

Hydrogen gas sensors based on nanocrystalline TiO2 thin films

Titanium dioxide thin films are extensively studied for applications in solid state gas sensor devices. Their gas sensing properties are strongly dependent on deposition technique, annealing temperature, film thickness and consequent properties like crystalline structure, grain size or amount of defects and impurities. In this work we report the gas sensing properties of TiO2 thin films prepared by reactive magnetron sputtering technique and subsequently annealed at temperatures 600°C and 900°C. The films were exposed to different concentrations of H2 gas up to 10 000 ppm. Their sensitivity to gas at various operating temperatures, ranging from 250°C to 450°C, was obtained by measuring their resistance.

Effect of Post-Deposition Annealing Treatment on the Structural, Optical and Gas Sensing Properties of TiO2 Thin Films

One of the potential applications of TiO2 is its use in gas sensor technology. The aim of this work was to study the gas sensing properties of TiO2 thin films in combination with the effect of post-deposition annealing treatment. Titanium dioxide thin films with thickness 100 nm were prepared by the reactive dc magnetron sputtering. The thin films were deposited on sapphire substrate from a titanium target in an oxygen atmosphere. The samples were then post-annealed in air in the temperature range 600 °C 1000 °C. Crystal structure, surface topography and absorption edge of the thin films have been studied by X-ray Diffraction technique, Atomic Force Microscopy and UV-VIS Spectroscopy. It was found that the phase gradually changed from anatase to rutile, the grain size and roughness tended to increase with increasing post-annealing temperature. The effect of these factors on gas sensing properties was discussed. For electrical measurements comb-like Pt electrodes were prepared by standard photolithography and the films were exposed to different concentrations of H2 gas up to 10000 ppm in synthetic air at various operating temperatures from 200 °C to 350 °C.

Experimental and computational studies on toughness enhancement in Ti-Al-Ta-N quaternaries

Design of hard ceramic material coatings with enhanced toughness, which prevents crack formation/propagation leading to brittle failure during application, is a primary industrial requirement. In this work, experimental methods supported by ab initio density functional theory (DFT) calculations and electronic structure analyses are used to investigate the mechanical behavior of magnetron sputtered Ti-Al-Ta-N hard coatings. The as-deposited Ti1-x-yAlxTayN (y = 0–0.60) films exhibit a single phase cubic sodium chloride (B1) structure identified as TiAl(Ta)N solid solutions. While the hardness H of Ti0.46Al0.54N (32.5 ± 2 GPa) is not significantly affected by alloying with TaN (H of the quaternary nitrides varies between 26 ± 2 and 35 ± 4 GPa), the elastic stiffness monotonically decreases from 442 to 354 GPa with increasing Ta contents, which indicates improved toughness in TiAlTaN. Consistent with the experimental findings, the DFT results show that Ta substitutions in TiAlN reduce the shear resistance due...

Thermally induced age hardening in tough Ta-Al-N coatings via spinodal decomposition

We combine experiments and ab initio density functional theory calculations to investigate the evolution in structural and mechanical properties of TaAlN coatings as a function of the annealing temperature T. Formation of coherent cubic TaN- and AlN-rich nanometer-size domains, occurring during the initial stage of thermally induced phase separation within cubic NaCl-type (B1) TaAlN solid solutions, yields a monotonic increase in hardness from 29 GPa (as deposited coatings) up to a maximum of 35 GPa (+17%) reached after annealing at 1000 °C. Further thermal treatment at T > 1000 °C leads to the transformation of metastable cubic domains into stable hexagonal TaNx and wurtzite AlN phases, thus resulting in hardness reductions. A comparison of our results with those reported in the literature reveals that TaAlN coatings are at least as hard while considerably less stiff (lower elastic moduli) than TiAlN coatings, thus indicating a substantial increase in toughness achieved upon replacing Ti with Ta in the h...

Studies of YBa2Cu3O6+x degradation and surface conductivity properties by Scanning Spreading Resistance Microscopy

Local surface conductivity properties and surface degradation of c-axis oriented YBa2Cu3O6+x (YBCO) thin films were studied by Scanning Spreading Resistance Microscopy (SSRM). For the surface degradation studies, the YBCO surface was cleaned by ion beam etching and the SSRM surface conductivity map has been subsequently repeatedly measured over several hours in air and pure nitrogen. Average surface conductivity of the scanned area was gradually decreasing over time in both cases, faster in air. This was explained by oxygen out-diffusion in both cases and chemical reactions with water vapor in air. The obtained surface conductivity images also revealed its high inhomogenity on micrometer and nanometer scale with numerous regions of highly enhanced conductivity compared to the surroundings. Furthermore, it has been shown that the size of these conductive regions considerably depends on the applied voltage. We propose that such inhomogeneous surface conductivity is most likely caused by varying thickness of degraded YBCO surface layer as well as varying oxygen concentration (x parameter) within this layer, what was confirmed by scanning Auger electron microscopy (SAM). In our opinion the presented findings might be important for analysis of current–voltage and differential characteristics measured on classical planar junctions on YBCO as well as other perovskites.

Structure of Hydrogen Gas Sensing TiO2 Thin Films Prepared by Sol-Gel Method and their Comparison with Magnetron Sputtered Films

TiO2 thin films with a thickness of about 150 nm were deposited by spin coating method on sapphire substrate from a sol-gel system. The hydrogen sensing properties of TiO2 films annealed at various temperatures were studied and correlated with their structure, optical and electrical properties. The annealing temperatures in the range of 600 800 °C lead to anatase films with a roughness in the range of 0.6 0.9 nm. Their sensitivity towards hydrogen is low. The thin films annealed at temperatures in the range 900 1000 °C consist of rutile phase and their roughness increased to 11.7 13.5 nm. They showed good hydrogen sensitivity with optimal operating temperature 200 250 °C. The structure and sensing properties of the prepared films are compared with those synthesized with magnetron sputtering. The maximum of sensitivity was measured on the thin films with diameter of the grains about 100 nm in both cases, i.e. on thin films prepared by sol-gel method as well as on thin films prepared by magnetron sputtering. The maximum sensitivity correlates with the diameter of the grains and dont depend on the allotropy of the titanium dioxide anatase or rutile.

Metal oxide gas sensors on the nanoscale

Low cost, low power and highly sensitive gas sensors operating at room temperature are very important devices for controlled hydrogen gas production and storage. One of the disadvantages of chemosensors is their high operating temperature (usually 200 – 400 °C), which excludes such type of sensors from usage in explosive environment. In this report, a new concept of gas chemosensors operating at room temperature based on TiO2 thin films is discussed. Integration of such sensor is fully compatible with sub-100 nm semiconductor technology and could be transferred directly from labor to commercial sphere.

Properties of Metal Oxide Gas Sensors with Electrodes Placed below the Sensing Layer

In this work, we investigate the influence of position of electrodes on the sensitivity of hydrogen gas sensors based on TiO2 thin films. We have prepared two types of sensors with platinum comb-like electrodes deposited on top and under the TiO2 layer. Response of these sensors to hydrogen gas in the concentration range of 0 10 000 ppm at temperature of 350 °C has been studied. The sensors with electrodes placed under the TiO2 layer showed two orders of magnitude lower sensitivity for 10 000 ppm compared to sensors with electrodes on top of the layer, but it was considerably increased when thickness of the TiO2 layer was lowered. This gives a possibility to improve the sensitivity of gas sensors in which the electrodes must be placed below the sensing layer for their protection from harsh environment.

Optical studies of nanocrystalline and amorphous TiO2 thin films deposited by HiTUS technique

TiO2 thin films were deposited on glass substrates by HiTUS (high target utilization sputtering) technique. Structural studies of TiO2 thin films of different thickness were performed by X-ray diffraction. Refractive index and extinction coefficient were measured by spectroscopic ellipsometer. Transmission spectra of TiO2 thin films were investigated in the temperature interval 77-300 K. The temperature behaviour of Urbach absorption edge for TiO2 thin film was studied. The effect of temperature on the optical parameters and order-disorder processes in TiO2 thin films was analysed.

Influence of structural disorder on the optical properties of non-stoichiometric Cu6Ps5I-based thin films

Cu6PS5I-based thin films were deposited onto silicate glass substrates by magnetron sputtering. Chemical composition of the thin films was determined by energy-dispersive X-ray spectroscopy. With increasing Cu content, a red shift of the exponential absorption edge energy position as well as a decrease of the Urbach energy are observed. Optical transmission spectra of Cu8.05P0.68S3.54I0.73 thin film were investigated in the temperature interval 77–300 K; the temperature behaviour of the optical absorption spectra and the refractive index dispersion was studied. Temperature dependences of the energy position of the absorption edge, the Urbach energy, and the refractive index of the Cu8.05P0.68S3.54I0.73 thin film were analysed. The influence of structural disorder on the optical properties of the Cu6PS5Ibased thin films is discussed.