Sol–gel grown Pd modified WO3 thin film based methanol sensor and the effect of annealing temperatures

In this paper, Pd modified WO₃ thin film methanol sensor has been developed by sol–gel method. WCl₆ chemical compound is used as a precursor. Spin coating method is employed for the preparation of the WO₃ thin film on the Si substrate. The crystalline structure of the WO₃ thin film is analyzed by scanning electron microscopy and X-ray diffraction techniques. The thin film sensor is fabricated at different annealing temperatures (400, 600 and 800 °C). The response magnitude of the WO₃ thin film is studied at different operating temperatures (100–300 °C). It is observed that the operating temperature of Pd modified thin film sensor is 200 °C. It is also noticed that the maximum response magnitude of Pd modified WO₃ thin film sensor is found at the annealing temperature of 600 °C. It is found that Pd modified WO₃ thin film sensor are suitable for methanol vapour detection compare to unmodified WO₃ thin film senor.

     

Hydrogen incorporation in gasochromic coloration of sol-gel WO3 thin films

In the present work, nanostructured WO₃ films were prepared by the sol-gel spin coating method. The as-prepared films were annealed at different temperatures and their structures were characterized by field-emission scanning electron microscopy and X-ray diffraction. A layer of platinum (Pt) was then sputtered onto the surface of WO₃ films. The gasochromic properties of the prepared Pt/WO₃ thin films were examined by use of optical transmittance under alternate exposures to various H₂-N₂ gas mixture and air. The results indicated that the sol-gel derived WO₃ films with amorphous structure exhibited excellent gasochromic performance with good coloration change and fast response rate under ambient condition. The coloration kinetics was well fitted by exponential equation, indicating the coloration was a surface reaction-controlled process. A new model based on double-injection concept is proposed. According to the model, it is found that the hydrogen insertion coefficient (x) in the gasochromic colored tungsten bronze state (H_xWO₃) of the studied sol-gel WO₃ films is about 0.29, which is similar to the reported gasochromic and electrochromic studies.     

Gas sensing properties of ZnO thin films prepared by microcontact printing

In situ patterned zinc oxide (ZnO) thin films were prepared by precipitation of Zn(NO₃)₂/urea aqueous solution and by microcontact printing of self-assembled monolayers (SAMs) on Al/SiO₂/Si substrates. The visible precipitation of Zn(OH)₂ from the urea containing Zn(NO₃)₂ solution was enhanced by increasing the reaction temperature and the amount of urea. The optimized condition for the ZnO thin films was found to be the Zn(NO₃)₂/urea ratio of 1/8, the precipitation temperature of 80 °C, the precipitation time of 1 h and the annealing temperature of 600 °C, respectively. SAMs are formed by exposing Al/SiO₂/Si to solutions comprising of hydrophobic octadecylphosphonic acid (OPA) in tetrahydrofuran and hydrophilic 2-carboxylethylphosphonic acid (CPA) in ethanol. The ZnO thin film was then patterned with the heat treatment of Zn(OH)₂ precipitated on the surface of hydrophilic CPA. The ZnO gas sensor was exposed to different concentrations of C₃H₈ (5000 ppm), CO (250 ppm) and NO (1000 ppm) at elevated temperatures to evaluate the gas sensitivity of ZnO sensors. The optimum operating temperatures of C₃H₈, CO and NO gases showing the highest gas sensitivity were determined to be 350, 400 and 200 °C, respectively.     

Au-doped WO3-based sensor for NO2 detection at low operating temperature

Pure and Au-doped WO₃ powders for NO₂ gas detection were prepared by a colloidal chemical method, and characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The NO₂ sensing properties of the sensors based on pure and Au-doped WO₃ powders were investigated by HW-30A gas sensing measurement. The results showed that the gas sensing properties of the doped WO₃ sensors were superior to those of the undoped one. Especially, the 1.0 wt% Au-doped WO₃ sensor possessed larger response, better selectivity, faster response/recovery and better longer term stability to NO₂ than the others at relatively low operating temperature (150 °C).     

Low temperature carbon nanotube and hexagonal diamond deposition with photo-enhanced chemical vapor deposition

Deposition of carbon nanotube and hexagonal diamond thin films at low substrate temperature with photo-enhanced chemical vapor deposition is described here. Extensive experimentation is conducted to optimize the catalyst layer utilized for deposition by varying Al/Ni/Al metal layer thicknesses on SiO₂ coated Si substrates. The coated substrates are annealed to transform the thin metal layers into nanoparticles. Suitable catalyst layer thicknesses obtained are 3/2/3, 5/1/5 and 5/3/5 nm for Al/Ni/Al sandwich metal layers. Suitable annealing conditions are in the range of 350–450 °C for substrate temperature and from 0.22 to 10 Torr for chamber pressure in ammonia ambient for 25 min. Carbon tetrachloride (CCl₄) is used as a carbon precursor in this work. Argon to CCl₄ flow ratio is varied in 1.5–19 range, chamber pressure is varied in 3–10 Torr range, and the substrate temperature is varied in 350–450 °C range. Carbon nanotubes (CNT) growth is observed at lower chamber pressure, lower partial pressure of CCl₄, lower substrate temperature and for thin Ni catalyst layer. The optimal CNT deposition condition observed is 5 Torr total chamber pressure, 9:1 partial pressure ratio of Ar to CCl₄, 400 °C substrate temperature and 5/1/5 nm thick Al/Ni/Al catalyst layers. The hexagonal diamond deposition is observed at a higher chamber pressure, higher partial pressure of CCl₄, higher substrate temperature and for a thicker Ni catalyst layer. The optimal condition for hexagonal diamond deposition observed is 10 Torr total chamber pressure, 7:3 partial pressure ratio of Ar to CCl₄, 450 °C substrate temperature and 5/3/5 nm thick Al/Ni/Al catalyst sandwich layers.     

MEMS-based microthruster with integrated platinum thin film resistance temperature detector (RTD), heater meander and thermal insulation for operation up to 1,000°C

We have fabricated microthruster chip pairs—one chip with microthruster structures such as injection capillaries, combustion chamber and converging/diverging nozzle machined using the deep reactive ion etching process, the other chip with sputtered platinum (Pt) thin film devices such as resistance temperature detectors (RTDs) and a heater. To our knowledge, this is the first microelectromechanical systems-based microthruster with fully integrated temperature sensors. The effects of anneal up to 1,050°C on the surface morphology of Pt thin films with varied geometry as well as with/without PECVD-SiO₂ coating were investigated in air and N₂ and results will also be presented. It was observed that by reducing the lateral scale of thin films the morphology change can be suppressed and their adhesion on the substrate can be enhanced. Chemical analysis with X-ray photoelectron spectroscopy showed that no diffusion took place between neighboring layers during annealing up to 1?h at 1,050°C in air. Electrical characterization of sensors was carried out between room temperature and 1,000°C with a ramp of ±5?Kmin^?1 in air and N₂. In N₂, the temperature-resistance characteristics of sensors had stabilized to a large extent after the first heating. After stabilization the sensors underwent up to eight further temperature cycles. The maximum drift of the sensor signal was observed for temperatures above 950°C and was less than 8.5?K in N₂. To reduce the loss of combustion heat, chip material around microthruster structures was partially removed with laser ablation. The effects of thermal insulation were investigated with microthruster chip pairs which were clamped together mechanically. The heater was operated with up to 20?W and the temperature distribution in the chip pairs with/without thermal insulation was monitored with seven integrated RTDs. The experiments showed that a thermal insulation allows the maximum temperature as well as the temperature gradient within the microthruster chip pairs to be increased.     

Temperature dependent H2S and Cl2 sensing selectivity of Cr2O3 thin films

The conductometric gas sensing characteristics of Cr₂O₃ thin films - prepared by electron-beam deposition of Cr films on quartz substrate followed by oxygen annealing - have been investigated for a host of gases (CH₄, CO, NO₂, Cl₂, NH₃ and H₂S) as a function of operating temperature (between 30 and 300 °C) and gas concentration (1-30 ppm). We demonstrate that these films are highly selective to H₂S at an operating temperature of 100 °C, while at 220 °C the films become selective to Cl₂. This result has been explained on the basis of depletion of chemisorbed oxygen from the surface of films due to temperature and/or interaction with Cl₂/H₂S, which is supported experimentally by carrying out the work function measurements using Kelvin probe method. The temperature dependent selectivity of Cr₂O₃ thin films provides a flexibility to use same film for the sensing of Cl₂ as well as H₂S.     

Humidity-insensitive and low oxygen dependence tungsten oxide gas sensors

Gas sensing characteristics of WO₃ powder and its physical properties under different heat treatment conditions have been investigated. The WO₃ powder was synthesized by wet process from ammonium tungstate parapentahydrate and nitric solution. The precipitated product was then calcined at 300–800 °C for 2–12 h. The physical properties of the products were characterized by using X-ray diffractometer (XRD), scanning electron microscope (SEM), and BET method. It was found that the crystallite size, particle size and surface area of the WO₃ powders were in the range of 30–45 nm, 0.1–3.0 μm and 1.2–3.7 m²/g, respectively. Calcination at higher temperature and longer time led to the increase of particle size by more than 300%, and reduction in specific surface area by more than 60%. However, the crystallite size was found to increase only by ∼30% under identical heat treatment. These results inferred that such heat treatment had more profound effect on crystallite aggregation than on crystallite growth. Gas sensing measurement showed that the largest change of output voltage to both ethyl alcohol and ammonia was obtained from the sensor calcined at 600 °C for 2 h, which had the highest surface area. However, the highest sensitivity which is defined as the ratio of sensor's resistance in air to that in the sample gas, R_air/R_gas, was obtained from the sensor calcined at 600 °C for 6 h due to its highest background resistance in air. Moreover, it was also found that the sensors were less sensitive to the oxygen content in the carrier gas and did not sensitive at all to water vapor.     

NOx adsorption behavior of LaFeO3 and LaMnO3+δ and its influence on potentiometric sensor response

NO_x adsorption behavior on LaFeO₃ (LFO) and LaMnO_3+δ (LMO) was characterized using temperature controlled methods and mass spectrometry. Temperature program desorption revealed decomposition of complex surface species formation when NO or NO₂ was adsorbed on LFO and LMO. LFO exhibited higher adsorption capacity for NO_x species than LMO and was shown to be more active for NO_x surface conversion. Both effects were attributed to the different B-site cations, with iron in LFO in the 3+ valence state, and manganese in LMO in the 3+ and 4+ valence states. Results from diffuse reflectance infrared spectroscopy were used to identify specific nitrite and nitrate species that are formed on the surfaces of LFO and LMO at room temperature. Temperature programmed reaction revealed a complex NO₂ decomposition mechanism to NO and O₂ for LFO and LMO in which the formation of nitrite and nitrate species serve as intermediates below ∼600 °C. NO_x sensing mechanisms were considered and predicted based on the types and quantities of surface species formed.     

Annealing effect of low‐temperature (<150°C) Cat‐CVD gate dielectric silicon nitride films diluted with atomic hydrogen

Abstract— The effect of in‐situ hydrogen pretreatment on dielectric properties of silicon nitride (SiN^x) thin films for a gate dielectric layer has been studied. SiN^xthin films were grown at a low temperature (150°C) by Catalytic CVD followed by conventional furnace annealing at 150°C for 2 hours. The in‐situ hydrogen pretreatment was performed without vacuum break before the sample was transferred to the furnace for thermal annealing. Capacitance—voltage (C‐V) and current‐density—voltage (J‐V) measurement showed that the hydrogen pretreatment was effective in reducing the hysteresis in the C‐V curve and in increasing the breakdown voltage. Without the treatment, the 150°C annealing failed to produce reliable C‐V and I‐V characteristics. The C‐V hysteresis and the threshold voltage shift of SiN^x were improved by furnace annealing as the hydrogen dilution ratio increased. Also, addition of hydrogen to the deposition gas mixture helped to improve the dielectric properties of the SiN^x films after thermal annealing. The combination of hydrogen dilution of the source gas and the in‐situ hydrogen treatment was successful in producing low‐temperature SiN^x films applicable to a‐Si TFTs. The TFT fabricated by using these films showed a field‐effect mobility of 0.23 cm²/V‐sec and a Vth of 3.1 V.     

Semi-physical mean-value NOx model for diesel engine control

A semi-physical model has been developed to predict nitrogen oxide (NO_x) emissions produced by diesel engines. This model is suitable for online NO_x estimation and for model-based engine control. It is derived from a zero-dimensional thermodynamic model which was simplified by only retaining main phenomena contributing to NO_x formation. The crank angle evolution of the burned gas temperature, which has a strong impact on NO_x formation rate, is described by a semi-empirical model whose key variable is the maximum burned gas temperature. This variable presents a good correlation with the molar fraction of NO_x at the end of combustion and can be expressed as a function of the intake burned gas ratio and the start of combustion. The maximum burned gas temperature sub-model is then coupled to an averaged NO_x formation kinetic model (based on the Zeldovich mechanism) to form a mean-value model for NO_x computation. This latter model was validated using data sets recorded in two diesel engines for steady-state operating conditions as well as for several driving cycles including parametric variations of the engine calibration.     

Sensitivity and selectivity improvement of rf sputtered WO3 microhotplate gas sensors

Active layers consisting of rf sputtered WO₃ were deposited on microhotplate substrates. The films were doped with seven different materials (Pt, Au, Ag, Ti, SnO₂, ZnO and ITO (indium tin oxide)). The eight types of sensors (including pure tungsten oxide ones) were tested in the presence of ammonia, hydrogen sulphide, nitrogen dioxide, carbon monoxide and methane. It was found that gold improved the sensitivity to H₂S. On the other hand, doping with Ag and Pt led to higher responses to NO₂ and NH₃, respectively. No response to CH₄ was observed. The sensitivity to CO was very low. The influence of the working temperature on the sensor response was also studied. Our study proves that selective gas detection is possible combining a few tungsten oxide sensors with different dopants.     

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.     

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.     

Ion sensitive field effect transistor with amorphous tungsten trioxide gate for pH sensing

In this study, the pH sensitive properties of the amorphous tungsten trioxide (a-WO₃) thin films by rf sputtering system from a-WO₃ target have been investigated. The a-WO₃ thin films with 600–4750 Å thickness were deposited on the electrolyte–insulator–semiconductor (EIS) structure maintained at room temperature and a total pressure of 30 mTorr in Ar mixed O₂ gas for 0.5–2 h, and we could obtain the electrical resistivity of the a-WO₃ films, was about 7.8×10⁵–4.5×10⁹ Ω-cm. The EIS structure with a-WO₃ thin films can be used to detect the ion sensitivity and can be explained by C–V curve in the different acidic buffer solutions (pH=1–7) using the C–V measurement. In addition, the a-WO₃ thin films were also deposited on the double layer structure of a-WO₃/SiO₂ gate ion sensitive field effect transistor (ISFET), and these devices were packaged with epoxy. Then, we can obtain the shift of the linear region threshold voltage (ΔV_T) of the ISFET devices in the acidic solutions (pH=1–7). The a-WO₃ materials exhibited a fairly high response, and the sensitivity was about 50 mV/pH.     

Comparison of classical and fluctuation-enhanced gas sensing with PdxWO3 nanoparticle films

Nanoparticle films of Pd_xWO₃, with x being 0.01 or 0.12, were made by dual-beam gas evaporation. The stochastic signal component (fluctuation-enhanced signal) originating from resistance fluctuations and the dc resistance (classical sensor signal) were measured during exposure to ethanol and hydrogen gas. For ethanol concentrations exceeding 50 ppm, changes in the resistance fluctuations gave 300 times larger detection sensitivity than changes in the dc resistance.     

Metal oxide gas sensor for high temperature application

 The present study is focused on the development of a gas sensor for application in a high temperature environment. The sensor has been realised using thin films prepared on silicon substrates including a high temperature stable heating and wiring system. TiO₂ acts as sensitive layer. Measurements have been carried out in synthetic gas mixtures as well as in gases in a given application. Neural networks and multivariate data analysis have been used for determining the gas concentrations. The capability to detect CO, NO _x , and toluene is shown. Received: 3 February 2000/Accepted: 3 February 2000     

In2O3 + xBaO (x = 0.5-5 at.%) - A novel material for trace level detection of NOx in the ambient

Indium oxide (In₂O₃) doped with 0.5-5 at.% of Ba was examined for their response towards trace levels of NO_x in the ambient. Crystallographic phase studies, electrical conductivity and sensor studies for NO_x with cross interference for hydrogen, petroleum gas (PG) and ammonia were carried out. Bulk compositions with x ≤ 1 at.% of Ba exhibited high response towards NO_x with extremely low cross interference for hydrogen, PG and ammonia, offering high selectivity. Thin films of 0.5 at.% Ba doped In₂O₃ were deposited using pulsed laser deposition technique using an excimer laser (KrF) operating at a wavelength of (λ) 248 nm with a fluence of ∼3 J/cm² and pulsed at 10 Hz. Thin film sensors exhibited better response towards 3 ppm NO_x quite reliably and reproducibly and offer the potential to develop NO_x sensors (Threshold limit value of NO₂ and NO is 3 and 25 ppm, respectively).     

Amorphous‐silicon thin‐film transistors made at 280°C on clear‐plastic substrates by interfacial stress engineering

Abstract— A process temperature of ～300°C produces amorphous‐silicon (a‐Si) thin‐film transistors (TFTs) with the best performance and long‐term stability. Clear organic polymers (plastics) are the most versatile substrate materials for flexible displays. However, clear plastics with a glass‐transition temperature (T_g) in excess of 300°C can have coefficients of thermal expansion (CTE) much larger than that of the silicon nitride (SiN^x) and a‐Si in TFTs deposited by plasma‐enhanced chemical vapor deposition (PECVD). The difference in the CTE that may lead to cracking of the device films can limit the process temperature to well below that of the T_g of the plastic. A model of the mechanical interaction of the TFT stack and the plastic substrate, which provides design guidelines for avoid cracking during TFT fabrication, is presented. The fracture point is determined by a critical interfacial stress. The model was used to successfully fabricate a‐Si TFTs on novel clear‐plastic substrates with a maximum process temperature of up to 280°C. The TFTs made at high temperatures have higher mobility, lower leakage current, and higher stability than TFTs made on conventional low‐T_g clear‐plastic substrates.     

Fluorescence detection of nitrogen dioxide with perylene/PMMA thin films

Thin films of polymethylmethacrylate (PMMA) doped with perylene provide selective, robust and easily prepared optical sensor films for NO₂ gas with suitable response times for materials aging applications. The materials are readily formed as 200 nm thin spin cast films on glass from chlorobenzene solution. The fluorescence emission of the films (λ_max=442 nm) is quenched upon exposure to NO₂ gas through an irreversible reaction forming non-fluorescent nitroperylene. Infrared, UV–VIS and fluorescence spectroscopies confirmed the presence of the nitro adduct in the films. In other atmospheres examined, such as air and 1000 ppm concentrations of SO₂, CO, Cl₂ and NH₃, the films exhibited no loss of fluorescence intensity over a period of days to weeks. Response curves were obtained for 1000, 100 and 10 ppm NO₂ at room temperature with equilibration times varying from hours to weeks. The response curves were fit using a numerical solution to the coupled diffusion and a nonlinear chemical reaction problem assuming that the situation is reaction limiting. The forward reaction constant fitted to experimental data was k_f∼0.06 (ppm min)⁻¹.