MEMS-based microheaters integrated gas sensors

Abstract

In the present work efforts have been made to develop microheater integrated gas sensors with low power consumption. The design and simulation of a single-cell microheater is carried out using ANSYS. Low power consumption (<35?mW) platinum micro-heater has been fabricated using bulk micromachining technique on silicon dioxide membrane (1.5?μm thin), which provided improved thermal isolation of the active area of 250?×?250?μm². The micro-heater has achieved a maximum temperature of ～950?°C at an applied dc voltage of 2.5 V. Fabricated mircro-heater has been integrated with SnO₂ based gas sensors for the efficient detection of H₂ and NO₂ gases. The developed sensors were found to yield the maximum sensing response of ～184 and ～2.1 with low power consumption of 29.18 and 34.53?mW towards the detection of 1?ppm of NO₂ gas and 500?ppm of H₂ gas, respectively.     

Low operating temperature CO sensor prepared using SnO<Subscript>2</Subscript> nanoparticles

A low operating temperature CO (carbon monoxide) sensor was fabricated from a nanometer-scale SnO₂ (tin oxide) powder. The SnO₂ nanoparticles in a size range 10–20 nm were synthesized as a function of surfactant (tri-n-octylamine, TOA) addition (0–1.5 mol%) via a simple thermal decomposition method. The resulting SnO₂ nanoparticles were first screen-printed onto an electrode patterned substrate to be a thick film. Subsequently, the composite film was heat-treated to be a device for sensing CO gas. The thermal decomposed powders were characterized by field-emission scanning electron microscopy (FESEM), X-ray diffractometry (XRD), and surface area measurements (BET). The CO-sensing performance of all the sensors was investigated. The experimental results showed that the TOA addition significantly decreased the particle size of the resulting SnO₂ nanoparticle. However, the structure of the powder coating was crucial to their sensing performance. After heat-treatment, the smaller particle tended to cause the formation of agglomeration, resulting in the decline of surface area and reducing the reaction site during sensing. However, the paths for the sensed gas entering between the agglomerated structure may influence the sensing performance. As a CO sensing material, the SnO₂ nanoparticle (~12 nm in diameter) prepared with 1.25 mol% TOA addition exhibited most stable electrical performance. The SnO₂ coating with TOA addition >0.75 mol% exhibited sensor response at a relatively low temperature of <50°C.     

Effects of different morphologies of ZnO films on hydrogen sensing properties

This paper describes the characteristics of chemiresistor hydrogen (H₂) sensors with different ZnO film structures in which ZnO dense films, nanoparticles (NPs), and nanorods (NRs) were prepared by RF magnetron sputtering, the sol–gel method, and the hydrothermal method, respectively. These were decorated with a Pt NP catalyst to investigate the performance of devices comprised of these structures. The effects of the ZnO morphology and operating temperature on the gas sensing behavior of the sensor are reported in detail. The various ZnO film morphologies, which contributed significantly to differences between sensors, play a very important role in enhancement of the supported Pt catalyst area and initial oxygen absorption on the ZnO surface. ZnO dense films prepared by sputtering showed the fastest response with a 13.5 % resistance variation at 1,000 ppm H₂ because gas adsorption occurred only on the film surface. The sensor with ZnO NRs showed a slower response, but the highest change in resistance of 65.5 % occurred at 1,000 ppm H₂ at room temperature. H₂ sensing performance of the chemiresistor sensors was improved due to the Pt catalyst, which was more efficient in dissociating H₂ gas molecules even at low temperature. The best chemiresistor sensor was fabricated using ZnO NRs and had a response time of approximately 10 s, a 27 s recovery time, and an 81.5 % change in resistance at 200 °C.     

WO3/BTO heterostructures based NO2 sensor with enhanced response characteristics

Abstract

In the present work, an efficient NO₂ gas sensor has been realised using single phase Barium titanate, BaTiO₃, (BTO) thin film, grown by chemical solution deposition technique (CSD). The gas sensing characteristics of BTO thin film were enhanced by integrating WO₃ modifier in the form of uniformly distributed circular nano-clusters and continuous overlayer. The WO₃ nanoclusters/BTO sensing element exhibited enhanced sensor response (～156) with fast response speed (16?s) at a relatively low operating temperature (140?°C) towards 50?ppm NO₂ gas. An attempt has been made to explain the sensing mechanism involving the twin effect of “Fermi-level exchange mechanism” and “spill over mechanism” upon interaction with target NO₂ gas. The obtained results in the present work are encouraging for the realization of hand-held NO₂ gas sensor.     

Preparation and evaluation of temperature-sensitive magnetic film with low Curie temperature

Up to now, only bulk materials and thick films were available for use as temperature-sensitive substances. However, due to the high heat capacity of these substances, their sensitivity is too low for the detection of minute temperature variations. General trends toward the miniaturization and weight reduction of electronic equipment necessitate development of thin films having magnetic properties. No technology for the preparation of temperature-sensitive magnetic thin films (TMF) has existed so far because of difficulties related to the adjustment of the mixture ratio of TMF materials composed of Fe, Mn, and Zn oxides. The authors investigated a method of fabrication of TMF by annealing of the film formed by the sputtering of a target consisting of temperature-sensitive ferrites with low Curie temperature. This method involves a two-step processing: depositing the metal components of temperature-sensitive ferrites on a substrate by sputtering and a high-temperature annealing treatment performed in a flow of argon gas in a tank containing oxygen. As a result, a ferrite thin film (thickness 1.5 μm) with spinel structure can be fabricated. The TMF characteristics closely reproduce parameters of the temperature-sensitive ferrites used in the target. The TMF so obtained also have an exceptional temperature dependence and a low heat capacity, thus providing for a prompt response to minute temperature variations of the order of 10^–1 °C. Therefore, the TMF are expected to find use in such applications as pyromagnetic sensors, optimized artificial sensors, and biosensors. © 1999 Scripta Technica, Electr Eng Jpn, 129(4): 17–23, 1999     

Structure and Dielectric Properties of Heteroepitaxial PMNT Thin Films

Thin films of PbMg_1/3 Nb_2/3O₃(PMN) and (1 ? x)PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMNT) with x = 0.1 to 0.3 were epitaxially grown on (100) MgO and (100) SrTiO₃ (ST) substrates by magnetron sputtering. Typical film thickness was 300 to 900 nm. Pyrochlore free (001) PMN and (001) PMNT thin films were grown on the ST and MgO substrates at narrow temperature window of 500 ± 20°C. The cross-sectional TEM image showed that the sputtered PMN and PMNT thin films comprised high density and continuous structure. These sputtered films showed 3-dimensional epitaxy. The dielectric response of the sputtered thin films showed frequency dispersion similar to bulk relaxor-like behavior with a broad temperature anomaly. PMN-23PT (x = 0.23) thin films showed the temperature of maximum, Tm, at 80°C. The Tm coincided with that of corresponding bulk materials. However, the obtained maximum dielectric permittivity, ?_m, ?_m = 900 to 1000, was considerably smaller than that in the bulk. The relatively low dielectric permittivity was probably due to the presence of strained hetero-epitaxial layer having temperature independent dielectric properties.     

Influence of Annealing Temperature on Structural,Morphological and NH3 Sensing Properties of Nanostructured WO3 Porous Films

The tungsten trioxide (WO₃) precursor was prepared by sol-gel method with tungsten powder as the raw material, and the WO₃ gas sensing films were obtained by a dip coating method and annealing precursor in air. X-ray diffraction (XRD) spectra indicate that with increasing annealing temperature the triclinic structure of as-prepared sample was transformed into monoclinic or orthorhombic phase. The images of scanning electron microscopy (SEM) exhibit that the WO₃ grain sizes increase from less than 100 nm to several micrometers with increasing annealing temperature. The influences of applied frequency, annealing and operating temperature on NH₃ gas sensing properties of the nanostructured WO₃ porous films were investigated. The results indicate that the gas sensing film annealed at 500°C express high sensitivity, fast response and recovery speed to NH₃ at operating temperature 250°C.     

A magnetic semiconductor protective device with built-in multifunction sensors

This paper describes protectors and multisensors using ferrite-magnetic semiconductor (FMS). Useful FMS devices with Curie temperature from ?15° to 300°C, in which the ferromagnetic properties below are retained below the Curie temperature, can be produced. The magnetic and electrical properties of FMS depend on temperature, humility, and gas concentration and can perform a switching function. The magnetic reluctance increases with temperature and approaches a maximum at the Curie temperature, but is independent of humidity or the concentration of combustible gases. The semiconducting resistance decreases from 225 to 170 kω as the humidity changes from 50 to 90 percent The FMS's specific dielectric constant above 900 is dependent on temperature, humidity, and the concentrations of combustible gases, including acetone, methanol, and ammonia In methanol, the capacitance increases from 0.18 to 0.5 nF as the concentration rises from 0 to 850 ppm. Bidirectional switching characteristics appear at voltages above 250 V. These characteristics should have practical applications in protective and measuring instruments. An overheating/overvoltage protector with temperatwe/humidity/gas concentration sensors composed of two annular FMSs is described.     

Modelling of chemical surface acoustic wave sensors and comparative analysis of new sensing materials

Comparative analysis of different, new gas sensing materials in surface acoustic wave chemical sensors is presented. Different gas sensing materials as polyaniline (PANI), Teflon AF 2400, polyisobutylene (PIB), polyepichlorohydrin (PECH) are considered. They are chosen according to the type of gas to be detected and the desired accuracy: Teflon AF 2400 thin film for the detection of CO₂, PANI nanocomposites film that belongs to the group of conductive polymers for the detection of CO, NO₂ and phosgene (COCl₂), and PECH and PIB for the detection of dichloromethane (CH₂Cl₂, DCM). In the analysis, the simple and useful method of the complete analyses of gas chemical sensors is used. The method is based on the electrical equivalent circuit of the surface acoustic wave sensor. The method is very efficient and can be used for the optimal design of CO₂ sensors. The results are compared with those presented in public literature and good agreement is obtained, demonstrating the validity of modelling. Copyright © 2012 John Wiley & Sons, Ltd.     

Performance of surface ionic conduction single chamber fuel cell prepared by the sol gel method

The performance of surface ionic conduction single chamber fuel cell (SIC‐SCFC) prepared by the sol gel method was studied on electric characteristics due to the differences of the operating temperature and humidity, the electrode distance and electrolyte film depth, and multiple cells with the series and parallel connections. The SIC–SCFC was arranged the both anode of Pt and cathode of Au on the boehmite electrolyte. The open circuit voltage (OCV) of single cell achieved a maximum of 530mV in the dry gas mixtures of O₂/H₂=50% in room temperature operation, and but it became decrease as over 60%. The OCV was maintained the constant value between operating temperatures of 30°C to 80°C, and but it was decreased sharply at over 90°C because a humidity on the cell became lower as increasing operating temperature. Then, the cell property was improved to 120°C by adding to the humidity of 70% using a humidifier. The electrode distance and the electrolyte film depth of SIC‐SCFC found to be contributed to the reductions of the cell resistance and the surface roughness on the electrode, respectively. Moreover, the power property of SIC‐SCFC was significantly improved by cell stacks comprised of the series or parallel connection of a cell.     

Nanostructured TiO2-based mixed metal oxides prepared using microemulsions for carbon monoxide detection

Nanostructured powders of Nb-doped TiO₂ (TN) and SnO₂ mixed with Nb-doped TiO₂ in two different atomic ratios—10 to 1 (TSN 101) and 1 to 1 (TSN 11)—were synthesized using the reverse micelle microemulsion of a nonionic surfactant (brine solution/1-hexanol/Triton X-100/cyclohexane). The powders were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Thick films were fabricated for gas sensors and characterized by XRD analysis and field emission scanning electron microscopy (FE-SEM). The effects of the film morphology and firing temperature in the range 650–850 °C on CO sensitivity were studied. The best gas response, expressed as the ratio between the resistance in air and the resistance under gas exposure (R _air/R _gas), was measured for TSN 11 at 11 for 1,000 ppm CO exposure. All types of sensors showed good thermal stability. The electrochemical impedance spectroscopy (EIS) measurements were performed in different gas atmospheres (air, O₂, CO and NO₂) to better understand the electrical properties of the nanostructured mixed metal oxides.     

Pulsed Laser Deposited Ba(Mg1/3Ta2/3)O3 Microwave Dielectric Thin Films

Ba(Mg_1/3Ta_2/3)O₃ (BMT) microwave dielectric thin films were successfully synthesized by a modified pulsed laser deposition (PLD) process, which includes low temperature (200°C) deposition and high temperature (>500°C) annealing. Crystalline structured BMT thin films were obtained when the PLD-deposited films were post-annealed at a temperature higher than 500°C in oxygen atmosphere. The characteristics of BMT thin film, including crystallinity, grain size, film roughness, and dielectric properties were improved with annealing temperature, achieving dielectric constant K = 23.5 and dissipation factor tan δ = 0.015 (at 1 MHz) for the 800°C-annealed films.     

Fabrication and evaluation of LaCrO3 thin film heaters

Lanthanum chromium oxide (LaCrO₃) has excellent high‐temperature properties. LaCrO₃ doped with alkaline earth metals also has high electric conductivity. The purpose of this study is to fabricate thin film heaters using LaCrO₃ doped with Ca by RF magnetron sputtering method. The crystal structure of thin films was evaluated and the surface form was studied. The results show that the thin film deposited on Si(100) single crystal and quartz glass substrates in Ar gas had a strong orientation and that its surface form was comparatively smooth. The crystal structure of the thin films deposited on Si(100) and quartz glass substrate at temperatures of 700 and 800 °C by sputtering in a mixture of Ar and O₂ gases was the same as the crystal structure of LaCrO₃. The heating characteristics of a thin film heater on Si(100) substrate with Pt electrodes were evaluated by measurement of the equilibrium temperature‐current (T–I) and resistance‐equilibrium temperature (R–T) characteristics. The maximum equilibrium heating temperature was about 1100 °C. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 139(3): 18–25, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.1156     

Dielectric properties of zinc titanate thin films prepared by Rf magnetron sputtering

Zinc titanate thin films of ~500 nm in thickness were synthesized by an RF magnetron sputtering using a sintered ceramic target. After annealing in temperature ranges of 300–800 °C, their phase transition and dielectric properties were investigated as a function of annealing temperature. Crystalline ZnTiO₃ phase was first detected at the annealing temperature of 500 °C within XRD detection limit though the sputtered film was mainly amorphous. ZnTiO₃ still remained as a main phase although the slight decomposition of ZnTiO₃ into Zn₂TiO₄ and TiO₂ occurred in association with the increase of annealing temperature. Dielectric properties were apparently improved with increase of annealing temperature and showed maximum value at 650 °C. Further higher temperature annealing caused inferior dielectric property. These results were explained in terms of the presence of TiO₂ (rutile) phase, resulting from the decomposition of ZnTiO₃ phase, and the morphology of the thin film.     

Thin pyroelectric PLZT film obtained with sol-gel technology

The sol-gel technology (J. Zarzycki in J.Sol-Gel Sci. Technol. 8:17–22, 1997) and the spin coating were employed for the production of PLZT 12/40/60 pyroelectric film. The starting materials were: lead acetate, lanthanum nitrate, metallo-organic compounds of zirconium and titanium and acetic acid. An alumina substrate with pre-deposited lanthanum-strontium cobalt oxide (LSCO) (H. Takahashi, et al in Phys. Rev. B. 57:15211–15218, 1998) bottom electrode was spin-coated with a sol several times. Following, the film was rapidly thermally processed. To obtain a continuous PLZT film these two operations were repeated a few times. The top electrode, made from LSCO, was subsequently applied on the PLZT film. The produced film has a lower pyroelectric coefficient than bulk ceramics and thick films formerly produced. Figure of merit F _v relating to the voltage responsivity is higher than those of the two earlier materials, due to much lower relative permittivity. The important advantage of applied method is that it requires much lower processing temperature (680°C) than that (1,150°C) needed to produce bulk and thick-film sensors.     

Thin ferroelectric films for thermal detector applications

Abstract

The deposition of thin films of lead scandium tantalate (Pb(Sc_1/2Ta_1/2O₃) have been investigated by two processing routes. In the first, progress is reviewed for chemical vapour deposition in a purpose built low pressure reactor, utilising suitable modified proprietary precursors. Deposition has been studied over the temperature range 400–800°C and, in general, amorphous films result which convert to crystalline perovskites on subsequent annealing. However, inclusion of hydroxy compounds in the vapour train catalyses the crystallisation process and enhances the growth rate at above 600°C. It was found that the best thin films, in terms of density and morphology, are formed at low deposition rates 1–2μm/hr. The perovskite phase is obtained if the gas phase composition is controlled throughout growth. The choice of precursors, gas compositions and growth conditions will be described. In the second process, lead scandium tantalate thin films (1μm) were deposited using a modified sol-gel solution route. This was achieved by spin-coating a solution of metallo-organic compounds of scandium and tantalum followed by lead, onto suitable substrates and firing and annealing the films at 800–1000°C. These firing temperatures gave films with grain sizes ranging from 0.5–4μm, which are single phase perovskite. Permittivity, dielectric loss and field induced pyro-electricity have been measured against field and temperature to assess the pyroelectric figure-of-merit, F_D of films obtained from both film deposition process. The F_D for sol-derived films indicates a performance similar to that of bulk ceramic material.     

Fabrication and characterization of co-planar type MEMS structures on SiO2 /Si 3 N 4 membrane for gas sensors with dispensing method guided by micromachined wells

MEMS structures for micro gas sensors had advantage for lower power consumption, reducing size, and easily making cavity structures. Also, co-planar type MEMS structures (CPMS) for gas sensors with low power consumption heater and dispensed sensing materials were newly proposed and investigated. CPMS, which were formed with micro heater and sensing electrodes at the same layer, to reduce process steps, diffusions between upper layer and lower layer, and thermal differences between the center and the periphery of the sensing layer compared with stacked structure. Dispensing method guided by back-side etched well was good for forming sensing material on sensing electrode and had advantage that various sensing materials could be applied for array type sensors. CPMS were fabricated on four-inch diameter and double side polished (100) silicon wafers and using anisotropic bulk silicon micromachining for membrane formation and etched well. A size of chips with 1.15 mm × 1.15 mm membrane was 4.8 mm × 4.8 mm. And co-planar type sensing electrodes were located in the middle of low stress SiO₂/Si₃N₄ (400 nm /1 μm) membranes. Membranes are thermally isolated from the chip frame because they have low thermal conductivity, generally. Temperatures were measured using IR thermometer with linearly increasing applied power. Power consumption at 400^∘C was 150 mW. Membranes of CPMS were withstood up to 730^∘C at the power of 350 mW. Characteristics of micro heaters for various heater widths of 50 μm, 75 μm, 100 μm and ratios of membrane dimension to heater dimension were measured. Sensing materials guided by micromachined well were dispensed on sensing electrodes. CPMS were mounted on a TO-8 package. From these results, fabricated and characterized CPMS could be used for applications in portable gas sensors for detection of CO, NO_x, CH_x, H₂S, and so on.     

Improvement of heating characteristics of molybdenum silicide thin film electric heaters

Molybdenum silicide (MoSi₂) has an electrical conductivity as high as that of a metal, and greater chemical stability than that of, for example, SiC, in various atmospheres. Therefore, many kinds of MoSi₂ bulk‐type heaters are used in practical operations up to 1800^°C, which is higher than the temperature of SiC heaters. However, MoSi₂ is fragile at room temperature and has low creep resistance at high temperature. The purpose of this study is to fabricate heaters using thin films of MoSi₂ deposited on alumina substrates and crucibles by RF magnetron sputtering and to evaluate their characteristics. MoSi₂ thin film was deposited on the outside of an alumina crucible without heating the substrate and then Pt wire was attached using a Pt paste with sintering in a vacuum. This MoSi₂ thin film heater showed almost linear resistance–temperature (R–T) characteristics and a uniform heating state. It also showed good controllability of voltage and stability in the power–T characteristics for operations up to 1000^°C. However, at a heating temperature of 1300^°C, the heating area of MoSi₂ thin film decreased because of the reaction between Pt and MoSi₂ in the case of long‐term heating. Thus, Mo thin film was deposited as a buffer layer between Pt and MoSi₂ thin film to prevent such a reaction. This thin film heater showed good linear R–T characteristics up to 1200^°C. However, the temperature coefficient of resistance changed with repeated heating operation as a result of the diffusion of Mo atoms into MoSi₂. Thus, a thin film heater was fabricated with Mo₃Si, having a higher Mo content than MoSi₂. This heater showed a low degree of diffusion of Mo or Pt atoms into the thin film and had excellent practical characteristics up to 1000^°C. © 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 168(2): 11–19, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20806     

Influence of Water Vapor on the Response of Mg-Doped SrTio3 Ceramic Oxygen Sensors

Mg-doped SrTio₃ thick film sensors fabricated by screen-printing proved to be very promising for the use as oxygen sensors. A study of the influence of water on the response of these sensors gives an important basis for understanding their behavior in practical applications. The influence of water on the sensor response was measured in the oxygen partial pressure region from air (0.21 bar) to pure N₂ (2.5 × 10^–5)and the temperature range from 600 to 800°C. The relative humidity was varied from 1 to 95% RH. The resistance variation as a function of temperature and the activation energy were evaluated under different dry and wet conditions. The results obtained show that the resistance of these sensors generally decreases with increasing water content in the carrier gas and that the effect of water was strongest at lower temperatures as well as at lower oxygen pressures. To explain this behavior, it is proposed that a partial proton conduction is introduced in the water-containing atmospheres and that this contributes to the total conductivity leading to a reduction of the total resistance. Finally, the measurements also show that the response of these sensors still depends on the oxygen partial pressure according to the standard expression even in the presence of water vapor. Therefore, these sensors can still be used as oxygen sensors in humid atmospheres.     

Resistive states in strontium titanate thin films: Bias effects and mechanisms at high and low temperature

A study on charge transport properties of thin film Fe-doped SrTiO₃ epitaxially grown on Nb-doped SrTiO₃ is reported. Electric measurements between 350 °C and 750 °C show a transition from predominant ionic to electronic conduction and lower conductivity of the thin films compared to the bulk of polycrystalline samples. Defect chemical changes at elevated temperature were investigated by applying a bias voltage. A model is described which successfully predicts additional features such as inductive loops or extra semicircles measureable by impedance spectroscopy as well as the complicated time dependence of electric DC-measurements. With this model it is also possible to calculate the negligibly small ionic conductivity next to the dominating electronic conductivity in the high temperature regime. The ionic conductivity is referenced by oxygen isotope depth profiling. Changes of resistive states in Fe-doped SrTiO₃ thin films at high temperature and moderate fields are compared to room temperature resistive switching phenomena at high electric fields. A conductive filament based switching process is observed at room temperature, and the capability for forming such filaments and their electric properties is further analysed using microelectrodes.