Thermodynamic assessments of the Ni–Pt and Al–Ni–Pt systems

The Ni–Pt system is assessed using the CALPHAD method. The four fcc-based phases, i.e. disordered solid solution phase, Ni₃Pt–L1₂, NiPt–L1₀ and NiPt₃–L1₂, are described by a four-sublattice model. The calculated thermodynamic properties and order/disorder phase transformations are in good agreement with the experimental data. In order to facilitate the assessment, first-principles pseudopotential calculations are also performed to calculate the enthalpy of formation at 0 K, and comparison with the assessed values is discussed. By combining the assessments of Al–Ni and Al–Pt, the Al–Ni–Pt ternary system is assessed within a narrow temperature range, focusing on the fcc-based phases and their phase equilibria with B2 phase.     

Pulsed laser deposited Y-doped BaZrO3 thin films for high temperature humidity sensors

Pulsed laser deposited (PLD) Y-doped BaZrO₃ thin films (BaZr_1-xY_xO_3-y/2, x = 0.2, y > 0), were investigated as to their viability for reliable humidity microsensors with long-term stability at high operating temperatures (T > 500 °C) as required for in situ point of source emissions control as used in power plant combustion processes. Defect chemistry based models and initial experimental results in recent humidity sensor literature [1] and [2]. indicate that bulk Y-doped BaZrO₃ could be suitable for use in highly selective, high temperature compatible humidity sensors. In order to accomplish faster response and leverage low cost batch microfabrication technologies we have developed thin film deposition processes, characterized layer properties, fabricated and tested high temperature humidity micro sensors using these thin films. Previously published results on sputtering Y-doped BaZrO₃ thin films have confirmed the principle validity of our approach [3]. However, the difficulty in controlling the stoichiometry of the films and their electrical properties as well as mud flat cracking of the films occurring either at films thicker than 400 nm or at annealing temperature above 800 °C have rendered sputtering a difficult process for the fabrication of reproducible and reliable thin film high temperature humidity microsensors, leading to the evaluation of PLD as alternative deposition method for these films.X-ray Photoelectron Spectroscopy (XPS) data was collected from as deposited samples at the sample surface as well as after 4 min of Ar⁺ etching. PLD samples were close to the desired stoichiometry. X-ray diffraction (XRD) spectra from all as deposited BaZrO₃:Y films show that the material is polycrystalline when deposited at substrate temperatures of 800 °C. AFM results revealed that PLD samples have a particle size between 32 nm and 72 nm and root mean square (RMS) roughness between 0.2 nm and 1.2 nm. The film conductivity increases as a function of temperature (from 200 °C to 650 °C) and upon exposure to a humid atmosphere, supporting our hypothesis of a proton conduction based conduction and sensing mechanism. Humidity measurements are presented for 200–500 nm thick films from 500 °C to 650 °C at vapor pressures of between 0.05 and 0.5 atm, with 0.03–2% error in repeatability and 1.2–15.7% error in hysteresis during cycling for over 2 h. Sensitivities of up to 7.5 atm⁻¹ for 200 nm thick PLD samples at 0.058 atm partial pressure of water were measured.     

Comparative study on TeO2 and TeO3 thin film for γ-ray sensor application

Tellurium trioxide (TeO₃) and tellurium dioxide (TeO₂) thin film has been deposited by rf sputtering. The influence of γ-radiation doses (in the range 10–50 Gy) on the optical and electrical properties of as-deposited films were studied. Optical band gap values were found to decrease with increasing radiation dose whereas electrical conductivity was increased by about five orders in magnitude. Monotonic decrease in the values of dielectric constant for the deposited TeO₃ films with increase in radiation dose was observed. The γ-ray response behavior of TeO₃ and TeO₂ thin films are compared, and TeO₃ thin film is found to be more suitable in amorphous form for γ-ray detection.     

Influence of Cs doping in spray deposited SnO2 thin films for LPG sensors

Detection of low concentrations of petroleum gas was achieved using transparent conducting SnO₂ thin films doped with 0–4 wt.% caesium (Cs), deposited by spray pyrolysis technique. The electrical resistance change of the films was evaluated in the presence of LPG upon doping with different concentrations of Cs at different working temperatures in the range 250–400 °C. The investigations showed that the tin oxide thin film doped with 2% Cs with a mean grain size of 18 nm at a deposition temperature of 325 °C showed the maximum sensor response (93.4%). At a deposition temperature of 285 °C, the film doped with 3% Cs with a mean grain size of 20 nm showed a high response of 90.0% consistently. The structural properties of Cs-doped SnO₂ were studied by means of X-ray diffraction (XRD); the preferential orientation of the thin films was found to be along the (3 0 1) directions. The crystallite sizes of the films determined from XRD are found to vary between 15 and 60 nm. The electrical investigations revealed that Cs-doped SnO₂ thin film conductivity in a petroleum gas ambience and subsequently the sensor response depended on the dopant concentration and the deposition temperature of the film. The sensors showed a rapid response at an operating temperature of 345 °C. The long-term stability of the sensors is also reported.     

Structural, optical and electrical properties of CdO/Cd(OH)2 thin films grown by the SILAR method

Successive Ionic Layer Adsorption and Reaction (SILAR) was used to form Cd(OH)₂ thin films from aqueous cadmium–ammonia complex on glass substrates at room temperature and the thermal annealing effect on thin films was studied. The as-deposited films were annealed at 200, 300 and 400 °C for 1 h in an oxygen atmosphere for conversion from Cd(OH)₂ to CdO and change in the structural, optical and electrical properties of the films and the effect of the light on the electrical properties of the films were investigated. The structural and surface morphological properties of the films were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that Cd(OH)₂ phase is converted into the cubic CdO films by annealing. The band gap energy values of films decreased from 3.59 to 2.13 eV through increasing annealing temperature. It was found that the current increased with increasing light intensity and CdO films were more conductive than the as-deposited films.     

Self-assembly of polyelectrolytic multilayer thin films of polyelectrolytes on quartz crystal microbalance for detecting low humidity

Low-humidity sensors were made by layer-by-layer (LBL) self-assembly of poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA) or poly(styrenesulfonic acid) sodium salt (PSS) and poly(allylamine hydrochloride) (PAH) into multilayer thin films on a gold electrode of quartz crystal microbalance (QCM). The thin films were characterized by QCM and atomic force microscopy (AFM). The effects of maleic acid (MA) in PSSMA, the number of layers and the ionic strength on the low-humidity sensing properties (sensitivity) were compared with those of PSS. The sensitivity of the PSSMA/PAH multilayer thin film exceeded that of the PSS/PAH multilayer thin film when the multilayered thin films of polyelectrolytes were prepared from solutions without NaCl. The sensitivity of both PSSMA/PAH and PSS/PAH multilayered thin films was increased by increasing the number of layers and by adding salt to the deposition solution. The PSS/PAH multilayered thin film that was prepared from the solutions with NaCl had the highest sensitivity (1.923 −ΔHz/Δppm_v at 27.5 ppm_v) and a short response time. Spin-coating was also adopted to fabricate PSS-based low-humidity sensors for comparison.     

Corrosion resistant and adsorbent plasma polymerized thin film

Adsorbent and corrosion resistant films are useful for sensor development. Therefore, the aim of this work is the production and characterization of plasma polymerized fluorinated organic ether thin films for sensor development. The polymerized reactant was methyl nonafluoro(iso)butyl ether. Infrared Spectroscopy showed fluorinated species and eventually CO but CH_n is a minor species. Contact angle measurements indicated that the film is hydrophobic and organophilic but oleophobic. Optical microscopy reveals not only a good adherence on metals and acrylic but also resistance for organic solvents, acid and basic aqueous solution exposure. Double layer and intermixing are possible and might lead to island formation. Quartz Crystal Microbalance showed that 2-propanol permeates the film but there is no sensitivity to n-hexane. The microreactor manufactured using a 73 cm long microchannel can retain approximately 9 × 10⁻⁴ g/cm² of 2-propanol in vapor phase. Therefore, the film is a good candidate for preconcentration of volatile organic compounds even in corrosive environment.     

A large-displacement 65Pb(Mg1/3Nb2/3)O3–35PbTiO3/Pt bimorph actuator prepared by screen printing

In this paper we present a novel approach to preparing large-displacement 65Pb(Mg_1/3Nb_2/3)O₃–35PbTiO₃/Pt (65/35 PMN–PT/Pt) bimorph actuators. These “substrate-free”, bending-type actuators were prepared by screen-printing the 65/35 PMN–PT and Pt thick-film pastes as the electrodes on alumina substrates. After this screen printing and the subsequent firing the 65/35 PMN–PT/Pt composites were peeled off from the substrates. Displacements of nearly 100 μm at 18 V were achieved for actuators with dimensions of 1.8 cm × 2.5 mm × 50 μm for the 65/35 PMN–PT layer. The normalized displacement (the displacement per unit length) was 40 μm/cm at 18 V. The experimental results together with a computation procedure were used to obtain the material parameters for a finite-element analysis of the 65/35 PMN–PT/Pt bimorph actuators.     

New gas sensitive MIS structures Pt/Al2O3(M = Pt, Rh)/Si with a granular dielectric layer

New gas sensitive MIS structures Pt/Al₂O₃(M)/p-Si, where M = Pt, Rh, with granular dielectric Al₂O₃ layers doped with noble metals were obtained by an aerosol pyrolysis method. Surface morphology and composition of the structures were studied by TEM, AFM and EPMA. Sensor properties of the MIS structures were studied towards reducing gases (1000 ppm H₂, 300 ppm CO, 1000 ppm CH₄ in air) at 100 and 200 °C. The Pt/Al₂O₃(M = Pt, Rh)/Si structures showed a very high sensor response to reducing gases. A shift of C–V characteristics was up to 2.5 V under CO, 2.2 V under hydrogen and 0.7 V under methane. High values of shift of C–V curves can be related with cooperative influence of a change of surface state density in dielectric layer, reduction of platinum electrode and dipole layer formation.     

Using a PEDOT:PSS modified electrode for detecting nitric oxide gas

PEDOT:PSS thick films, prepared by the drop-coated method, were used in this study for sensing nitric oxide (NO) gas. The thickness of PEDOT-PSS film was controlled by dropping different volumes of PEDOT-PSS solution to improve the response of PEDOT-PSS film. Due to its porous structure, the thicker the PEDOT-PSS film is, the higher the noticeable surface area. Thus, a larger response is found. However, since the concentration of NO gas used was low (10 ppm), the effect of the surface area was not noticeable when the thickness of the film was greater than 5 μm. In the range of 2.5–10 ppm NO, the relationship between the response of the PEDOT-PSS film and the NO concentration was linear. The limit of detection (S/N = 3), response time (t₉₅), and recovery time (t₉₅) were about 350 ppb, 527 s, and 1780 s, respectively. The response of PEDOT-PSS film to 10 ppm NO gas was dramatically affected by the presence of either O₂ or CO. The standard deviation, with respect to the sensitivity of the NO gas sensor based on PEDOT:PSS film, was 2.2%. The sensitivity of the sensor remained at about 74.5% that of a fresh one.     

Development of novel PZT thin films for active sliders based on head load/unload on demand systems

 Micromachined active sliders based on head load/unload on demand systems is an interesting concept technology for ultra-high magnetic recording density of more than 100 Gb/in². The active sliders that we proposed use PZT thin films as a microactuator and control the slider flying height of less than 10 nm. It is necessary to develop high performance microactuators in order to achieve active sliders operating at very low applied voltage. This paper describes the development of novel PZT thin films for active sliders. The sol–gel fabrication process for PZT thin films is developed and the fundamental characteristics for the PZT thin films are investigated. It is confirmed that the PZT thin films have good ferroelectric properties. Furthermore, novel thin film microactuators are proposed. The feature is that the sol–gel PZT thin films (thickness 540 nm) are deposited on the sputtered PZT thin films (thickness 300 nm) fabricated on bottom Pt/Ti electrodes. Therefore, the novel thin films consist of a thermal SiO₂ layer and the sputtered and sol–gel PZT thin films layers sandwiched with upper Pt and bottom Pt/Ti electrodes on a Si slider material. Fabricating the diaphragm microactuator, the piezoelectric properties for the novel composite PZT thin films are studied. As a result, the piezoelectric strain constant d ₃₁ for the novel PZT thin films is identified to be 130 × 10⁻¹² m/V. This value is higher than conventional monolithic PZT thin films and it is found that the novel composite PZT thin films have the good piezoelectric properties. This suggests the feasibility of realizing active sliders operating at lower voltage under about 10 V. Received: 22 June 2001/Accepted: 17 October 2001     

Tetrakis(alkylthio)-substituted lutetium bisphthalocyanines for sensing NO2 and O3

In this study, the nitrogen dioxide (NO₂) and ozone (O₃) sensing properties of a series bis[tetrakis(alkylthio) phthalocyaninato] lutetium(III) complexes [(C_nH_2n+1S)₄Pc]₂Lu(III) (n = 6, 10, 16) are investigated as a function of concentration in the temperature range between 25 °C and 150 °C. The concentration ranges were 1–10 ppm for NO₂, and 50 ppb–1 ppm for O₃. The response time and the sensor response to NO₂ are measured for approximately 1 min and 100% ppm⁻¹, respectively, for compound 1 at room temperature. At room temperature, all compounds are in the solid phase. The response time decreases to a few seconds with increasing operation temperature to 150 °C. At this temperature, all compounds are in the liquid crystal phase. The fastest response to oxidizing gases is observed at the liquid crystal phase of the Pcs. It has also been observed that the response time and the sensor response depend on the alkyl chain lengths of the Pcs. The doping effect of oxygen has been determined under high purity nitrogen N₂ flow, after exposure to dry air, at a different period of time and after annealing. It has been found that the conductivities of [(C_nH_2n+1S)₄Pc]₂Lu(III) thin films increased after exposure to dry air and the conduction mechanism also changed from ohmic behavior to space-charge-limited conduction.     

Optical humidity sensor using porphyrin immobilized Nafion composite films

A Nafion–TMPyP composite film was used in an optical humidity sensor. The composites were prepared with various molar ratios between the sulfonic groups and TMPyP molecules, R = [–SO₃H]/[TMPyP]. The UV–vis measurement of the composite films suggested that the TMPyP molecules were well dispersed at in the range of R = 60–100, but formed aggregates at R ≤ 20. Furthermore, the FTIR indicated that sulfonic group interacted with TMPyP. The reflectance change with relative humidity (%RH) occurred at 426.4 and 465.4 nm with the isosbestic point at 437.5 nm, and also in the Q-band region. The sensors of R = 30 and 40 sensitively responded to humidity in the lower humidity region (10–20%RH), but saturated or even decreased with further increase in humidity. At R = 60, the sensitivity slightly decreased but a measurable range was extended to around 70%RH. Remarkable deterioration in sensitivity occurred at R = 100. The TMPyP molecules were stably immobilized on a Nafion matrix, even in liquid water, without solving out.     

Flexible H2 sensor fabricated by layer-by-layer self-assembly of thin films of polypyrrole and modified in situ with Pt nanoparticles

A novel flexible H₂ gas sensor was fabricated by the layer-by-layer (LBL) self-assembly of a polypyrrole (PPy) thin film on a polyester (PET) substrate. A Pt-based complex was self-assembled in situ on the as-prepared PPy thin film, which was reduced to form a Pt-PPy thin film. Microstructural observations revealed that Pt nanoparticles formed on the surface of the PPy film. The sensitivity of the PPy thin film was improved by the Pt nanoparticles, providing catalytically active sites for H₂ gas molecules. The interfering gas NH₃ affected the limit of detection (LOD) of a targeted H₂ gas in a real-world binary gas mixture. A plausible H₂ gas sensing mechanism involves catalytic effects of Pt particles and the formation of charge carriers in the PPy thin film. The flexible H₂ gas sensor exhibited a strong sensitivity that was greater than that of sensors that were made of Pd-MWCNTs at room temperature.     

Ab initio calculation of the BCC Fe–Al–Mo (Iron–Aluminum–Molybdenum) phase diagram: Implications for the nature of the phase

The metastable phase diagram of the BCC-based ordering equilibria in the Fe–Al–Mo system has been calculated via a truncated cluster expansion, through the combination of Full-Potential-Linear augmented Plane Wave (FP-LAPW) electronic structure calculations and of Cluster Variation Method (CVM) thermodynamic calculations in the irregular tetrahedron approximation. Four isothermal sections at 1750 K, 2000 K, 2250 K and 2500 K are calculated and correlated with recently published experimental data on the system. The results confirm that the critical temperature for the order–disorder equilibrium between Fe₃Al–D0₃ and FeAl–B2 is increased by Mo additions, while the critical temperature for the FeAl–B2/A2 equilibrium is kept approximately invariant with increasing Mo contents. The stabilization of the Al-rich A2 phase in equilibrium with overstoichiometric B2–(Fe,Mo)Al is also consistent with the attribution of the A2 structure to the τ₂ phase, stable at high temperatures in overstoichiometric B2–FeAl.     

A differential capacitive thin film hydrogen sensor

A compact, differential, hydrogen-specific sensor based on the lattice expansion of LaAl_0.3Ni_4.7 metal hydride thin films has been fabricated and characterized. Characterization of LaAl_0.3Ni_4.7 films performed using a capacitance dilatometer revealed that the lattice expansion was proportional to the partial pressure of H₂ over the range 0.01–1.3 atm used in this experiment. The films were mechanically robust to cycling between vacuum and partial pressures of H₂ up to 1.3 atm and were not poisoned by exposure to atmosphere's containing up to 24% carbon monoxide. A wafer level process has been established for the fabrication of the differential hydrogen sensor which includes both an active LaAl_0.3Ni_4.7 sensing capacitor and an inert Au reference capacitor. A minimum sensitivity of 400 ppm hydrogen is calculated for the differential device.     

Thin film polypyrrole/SWCNTs nanocomposites-based NH3 sensor operated at room temperature

A PPY/SWCNTs nanocomposite-based sensor with relatively high sensitivity and fast response–recovery was developed for detection of NH₃ gas at room temperature. The gas-sensitive composite thin film was prepared using chemical polymerization and spin-coating techniques, and characterized by Fourier transformed infrared spectra and field-emission scanning electron microscopy. The results reveal that the conjugated structure of the PPY layer was formed and the functionalized SWCNTs were well-embedded. The effects of film thickness, annealing temperature, and SWCNTs content on gas-sensing properties of the composite thin film were investigated to optimize the gas-sensing performance. The as-prepared thin film PPY/SWCNTs composite sensor with optimized process parameters had a response of 26–276% upon exposure to NH₃ gas concentration from 10 to 800 ppm, and their response and recovery times were around 22 and 38 s, respectively.     

Zeolite cover layer for selectivity enhancement of p-type semiconducting hydrocarbon sensors

Screen-printed thick films of the p-type semiconducting materials family SrTi_1−xFe_xO_3−δ have been investigated for hydrocarbon sensing. Among the different compositions tested, the formulations containing 10 and 20% of iron are found to perform best for this purpose. A pronounced cross-interference of NO persisted at operating temperatures of about 400 °C. In order to eliminate this problem, the application of a zeolite cover layer was studied. The properties of this cover layer were optimized with respect to layer thickness and Pt content. Using initial results of a catalytic study on the zeolite powder in addition to a simple diffusion–reaction model, the effect of the zeolite layer with respect to NO cross-interference could be explained satisfactorily.     

Highly sensitive SnO2 thin film with low operating temperature prepared by sol–gel technique

Sol–gel dip coating technique was employed to prepare Cu-doped SnO₂ thin films, which were able to detect H₂S gas at room temperature with high sensitivity and revealed fast response characteristics. The highest sensor response (the ratio of resistance in air versus in H₂S) was 3648 under H₂S concentration of 68.5 ppm at room temperature. Recoverability of the thin films appeared when the temperature raised to 50 °C. The films were analyzed by means of XRD and the dried gel powder was studied by TG-DTA test. Influences of sintering temperature and doping level on the H₂S response are discussed. The average grain size of the SnO₂ was about 25 nm.