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.     

Resonance properties and mass sensitivity of monolithic microcantilever sensors actuated by piezoelectric PZT thick film

The PZT thick film cantilever devices fabricated via MEMS process have much attraction because they are appropriate for biological transducer or sensor, resulting from their large actuating force and relatively high sensitivity especially in liquid. By means of resonance behavior, theoretical calculation and experimental verification of the PZT thick film cantilever devices have not been studied before. Accordingly, we focused on the sensitivity analysis and interpretation of the PZT thick film cantilevers in this study. Especially, the investigation for mass sensitivity of the PZT thick film cantilever is of importance for physical, chemical and biological sensing application. The PZT thick film cantilever devices were constructed on Pt/TiO₂/SiN _X /Si substrates using screen printing method and MEMS process. The harmonic oscillation response (resonance frequency) was measured using an optical laser interferometric vibrometer. The effect of cantilever geometry on the resonance frequency change was investigated. Compared with the theoretical resonant frequency change by mass loading, the experimental resonant frequency change of the PZT micromechanical thick film cantilever shows a variation of less than 2%. Mass sensitivities are estimated to be 30.7, 57.1 and 152.0 pg/Hz for the 400 × 380 μm, 400 × 480 μm and 400 × 580 μm cantilever, respectively.     

Gas sensors: New materials and processing approaches

To satisfy demands for detecting chemicals in the environment, versatile sensors are required to detect a rapidly growing range of chemical species. In this paper, focus is directed on progress being made to develop temperature-independent oxygen sensors based on the perovskite solid solution system SrTi_1−x Fe _x O_3−δ,and on improving the sensitivity of thin film gas sensors integrated on Si-based self heated substrates. A novel strategy to produce macroporous films with high surface area for enhanced chemical activity is described, and how this processing strategy results in markedly improved sensitivity of gas sensors based on a novel material, CaCu₃Ti₄O₁₂, is demonstrated.     

Developing novel gas sensors for NO2 detection based on Ce(1-x)MXO2, {M?=?Ru, In} solid solutions

CeO₂, Ce_(1-x)M_XO₂, {M = Ru, In} compounds with sensing properties were fabricated using the sol–gel route. The main purpose was to compare the efficiency of CeO₂ vs. Ce_(1-x)M_XO₂ doped compounds as gas sensors for NO₂ detection. Characterization was performed by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and surface area determination (BET). Measurements of electrical resistance under different conditions of time, concentration and temperature in the presence of NO₂ were carried out. Ruthenium inclusion increased the CeO₂ sensor response in a great extent, gas response (S) = 1.8 for CeO₂ vs. gas response (S) = 350 for Ce_0.95Ru_0.05O₂ and gas response (S) = 35 for Ce_0.95In_0.05O₂. This behavior is reported by the first time. Our results demonstrate that ruthenium or indium inclusion has been beneficial for CeO₂. Conclusively the materials herein described could be applied as NO₂ gas sensors.     

NOx Sensing Properties of Varistor-Type Gas Sensors Consisting of Micro p-n Junctions

NO _x sensing properties of SnO₂-xCr₂O₃ as a varistor-type gas sensor have been investigated in the temperature range of 200–600°C. The breakdown voltage of SnO₂ shifted to a higher electric field upon exposure to NO₂ at 300–500°C, and the largest breakdown voltage shift, i.e. the highest NO₂ sensitivity was observed at 400°C. In contrast, the direction of the breakdown voltage shift in NO varied with temperature: the breakdown voltage shifted to a lower electric field at 300°C, but to a higher electric field at 500°C, and remained almost unchanged at 400°C. The NO₂ sensitivity of SnO₂ was superior to the NO sensitivity at every temperature, and then the SnO₂ exhibited good selectivity to NO₂ at 400°C. The breakdown voltage of Cr₂O₃ shifted in the reverse direction upon exposure to NO and NO₂, in comparison with those observed with SnO₂, owing to its p-type semiconductivity. Thus, Cr₂O₃ also exhibited certain sensitivity to both NO and NO₂ at 200°C, being more sensitive to NO₂, though the sensitivities decreased drastically at temperatures higher than 300°C. The addition of 5.0 wt% Cr₂O₃ to SnO₂ resulted in a significant improvement of NO and NO₂ sensitivities at 600°C, being accompanied by an increase in the breakdown voltage in air. Especially, the NO sensitivity was superior to the NO₂ sensitivity in the concentration range of 20–100 ppm, and then SnO₂ mixed with 5.0 wt% Cr₂O₃ was found to be the most suitable candidate for a NO sensor among the sensors tested. The increase in the breakdown voltage in air induced by the Cr₂O₃ addition was confirmed to arise from both the decrease in the particle size of SnO₂ and the formation of micro p-n junctions at grain boundaries. The decrease in the particle size was also responsible for the increased NO and NO₂ sensitivities, but the p-n junctions were suggested to play a more important role in promoting and stabilizing the chemisorption of NO at higher temperatures.     

The development of novel trivalent ion conducting solids and their application for gas sensors

An exceptionally high Al³⁺ ion conducting polycrystalline solid based on the NASICON type structure was successfully realized within the system (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃. The partial substitution of the smaller higher valent Nb⁵⁺ ion for Zr⁴⁺ helped stabilize and accommodate the mobile Al³⁺ ion into the NASICON like structure. The addition of boron oxide to the Al³⁺ ion conducting solid electrolyte, as a sintering additive, aided in the achievement of satisfactory mechanical strength and density for practical use. Environmental gas sensors were fabricated by combining the (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid electrolyte with yttria stabilized zirconia (YSZ) and appropriate auxiliary electrodes. The Nernst-like electrochemical sensors demonstrated rapid and reproducible response to CO₂ and NOx, thereby promising excellent potential for environmental monitoring applications.     

Characteristics of thick-film CO2 sensors based on NASICON with Na2CO3-CaCO3 auxiliary phases

Potentiometric CO₂ sensors were fabricated using a NASICON (Na_1+x Zr₂Si_xP_3−x O₁₂) thick film and auxiliary layers. The powder of a precursor of NASICON with high purity was synthesized using the sol-gel method. Using the NASICON paste, an electrolyte was prepared on the alumina substrate through screen printing and then sintered at 1000^∘C for 4 h. In the present study, as new auxiliary phases, a series of Na₂CO₃-CaCO₃ system was deposited on the Pt sensing electrode. The electromotive force (EMF) values were found to be linearly dependent on the logarithm of the CO₂ concentration in the range of 1000–10000 ppm. The device to which Na₂CO₃-CaCO₃ (1:2) was attached showed good sensing properties at low temperatures.     

Pyroelectric infrared sensors made of La-modified PbTiO3 thin films and their applications

Abstract

High sensitive pyroelectric infrared (IR) sensors have been fabricated by using c-axis oriented La-modified PbTiO₃ (Pb_1–xLa_xTi_1?x/4O₃, PLT) thin films. The PLT thin films were deposited on (100)-cleaved MgO single crystal substrates by intermittent rf-magnetron sputtering method. The PLT thin films have high figures of merit for IR sensor without a poling treatment. High performance pyroelectric IR sensors (single element type and linear array type) were fabricated by using PLT (x=0·1, γ=5·5x10^?8 C/cm²K, ?_r=200) thin films. The sensors have remarkably high D* of 3–6x10⁸ cmHz^1/2/W and very fast response. A new compact IR sensing system using the linear array sensor (8 elements) has been developed for a new type of room air-conditioner. This system can measure thermal distribution (8x64) by horizontal scanning of the vertical linear array. Image processing with neural network concept makes possible high-accuracy using a few data from the sensor elements. This sensing system provides ‘‘smart airconditioning'’to improve the comfortable control.     

Resolving the problem of cross sensitivity in fiber Bragggrating sensor based on the principle of polarized-lightinterference

The article introduces an advanced approach of fiber grating strain demodulation based on the principle of polarized-light interference. This method can solve the problem of cross sensitivity in fiber Bragg grating sensor. As for the yttrium vanadate (YVO₄) crystal polarized-light interferometer, if there are two different fiber Bragg gratings that have a π rad phase difference, one is used for strain sensor and the other is used for temperature compensating. Then the problem of cross sensitivity can be overcome. The analyses of the strain demodulation resolution show that with a decrease in crystal thickness the resolution increases. The experiment shows that when the thickness of YVO₄ crystal is 0.5 mm, the effect of cross-sensitivity will be reduced to 0.13 μɛ/°C, which is 1.6% of the effect used by only one fiber Bragg grating for strain measure. And when the thickness is 0.1 mm the cross-sensitivity will be reduced to 0.006 7 μɛ/°C, which is less than 0.08%. Less thickness of crystal is beneficial for the resolution of strain measure, but the machining of small thickness crystal is difficult. To solve this problem, a new scheme of polarized-light interfereometer with the structure of double layer crystal was analyzed. Translated from Acta Optica Sinica, 2006, 26(1): 19–24 [译自: 光学学报]     

Surface acoustic wave sensors to detect volatile gases by measuring output phase shift

This paper presents properties of saw acoustic wave (SAW) gas sensors to detect volatile gases such as acetone, methanol, and ethanol by measuring phase shift. A dual-delay-line saw sensors with a center frequency of 100 MHz were fabricated on 128^∘ Y-Z LiNbO₃ piezoelectric substrate. In order to improve sensitivity of SAW sensors, a thin titanium (Ti) film as mass sensitive layer was deposited using e-beam evaporation on the surface of the SAW sensors. In our investigation the response time and sensitivity of SAW sensors were measured. The response time and sensitivity of SAW sensor with thin Ti film were strongly improved because of changing electrical and mechanical properties in the mass sensitive layer. As a result, high sensitivity and fast response time could be achieved by deposition of thin Ti film as mass sensitive layer on the surface of SAW sensor. It can be applied for high performance electronic nose system by assembling an array of different sensors.     

Ni-Zn ferrite films synthesized from aqueous solution usable for sheet-type conducted noise suppressors in GHz range

Ni_0.2Zn_0.3Fe_2.5O₄ films (1–5 μm thick) were deposited by spin spray ferrite plating from an aqueous solutions onto polyimide sheets at 90^∘C. Their peel test and high-frequency permeability as well as noise suppression effects were investigated. The oxygen plasma treatment on polyimide sheet surface improved the film adhesion. There was not visible crack on the bended film surface for the Ni-Zn ferrite film thinner than 2 μm and was not peeled off even after the bending test of a million times. The films exhibited excellent high-frequency permeability profile and a natural resonance frequency (where the imaginary permeability reaches a maximum) f _r was 370 ± 30 MHz. The transmission loss increased with the film thickness, reaching the maximum Δ P _loss = 70% at 8 GHz for the 5 μm-thick film. The reflection loss in the measured frequency range was S ₁₁ < 10 % which is small enough for films to be used as the conducted noise suppressors. The value of Δ P _loss obtained for the 5-μm thick film was about 15% higher than that (Δ P _loss = 55 %) attained by the commercialized 50-μm thick noise suppressing sheet.     

Structure and dielectric properties of BaTi4O9 thin films for RF-MIM capacitor applications

BaTi₄O₉ thin films were grown on a Pt/Ti/SiO₂/Si substrate using RF magnetron sputtering. A homogeneous BaTi₄O₉ crystalline phase developed in the films deposited at 550^∘C and annealed above 850^∘C. When the thickness of the film was reduced, the capacitance density and leakage current density increased. Furthermore, the dielectric constant was observed to decrease with decreasing film thickness. The BaTi₄O₉ film with a thickness of 62 nm exhibited excellent dielectric and electrical properties, with a capacitance density of 4.612 fF/μm² and a dissipation factor of 0.26% at 100 kHz. Similar results were also obtained in the RF frequency range (1–6 GHz). A low leakage current density of 1.0 × 10⁻⁹ A/cm² was achieved at ± 2 V, as well as small voltage and temperature coefficients of capacitance of 40.05 ppm/V² and –92.157 ppm/^∘C, respectively, at 100 kHz.     

Ferroelectric properties of (Bi3.15 Nd 0.85 )Ti 3 O 12 with decreasing film thickness

Film texture and ferroelectric behaviors of (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNdT) of layered-perovskite structure deposited on Pt/TiO₂/Si substrate are dependent on the film thickness. When the film thickness is reduced from ∼240 to ∼120 nm, BNdT grains evolve from a rod-like morphology to a spherical morphology, accompanied by a decrease in average grain size. At the same time, P-E hysteresis transforms from a square-shaped hysteresis loop (2Pr ∼24.1 μC/cm² at 240 nm) to a relative slimmer hysteresis loop (with a lower 2Pr = 19.8 μC/cm² at 120 nm). The nonvolatile polarization (Δ P) shows a maximum at the film thickness of 160 nm, where Δ P was measured to be 14.7 μC/cm² and 6.8 μC/cm² at 5 V and 3 V, respectively. A small amount of excess bismuth in the film thickness of 130 nm, introduced by co-sputtering, can lead to a much enhanced remanent polarization (2Pr of 21.3 μC/cm² at 5 V and 15.2 μC/cm²at 3 V), which is promising for low voltage FRAM applications.     

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.     

Fabrication and characterization of piezoelectric driven microdiaphragm resonating sensor for a biosensing application

The detection capability of microresonating sensors is decided by the resonant properties (mass sensitivity and quality factor) because the microresonating sensors have detection principle that the target material of small amount quantitatively detect by measuring the resonant properties change of microresonators. Mass sensitivity is important factor to evaluate minimum detectable mass of microresonating sensors. For the biomolecule detection in liquid, microresonaotrs have to keep the quality factor that can discriminate small frequency change when the liquid sample injected on the microresonating sensors. In order to study mass sensitivity and quality factor of the fabricated microdiaphragm sensors, Pt thin film with different thicknesses are deposited on the our Pb(Zr_0.52Ti_0.48)O₃ layer-embedded microdiaphragm sensors. Increasing the mass sensitivity ranging from 1.68 to 36.61 Hz/ng which is found with the decreasing the width of squared microdiaphragms ranging 900 to 300 μm. The mass sensitivity of our microdiaphragm sensor stands comparison with microcantilever sensor of length scale of 200?~?300 μm. Moreover, we find that the quality factor is kept on more than 23 that was ten times better than microcantilever resonating sensor with length scale of 200 μm.     

Fabrication of bulk glass from the eutectic melt in Y2O3-CaO-Al2O3 system

We have studied glass formable region in the Y₂O₃-CaO-Al₂O₃ system. An optimal composition for the amorphous phase formation was found in the pseudo-eutectic 12CaO⋅7Al₂O₃-CaYAlO₄ system. An amorphous bulk plate of 10 × 25 × 1.8 mm was successfully fabricated using a simple molding technique. The fabricated glass plate showed an IR absorption edge at around 5.6 μm. The crystallization of the glass sample was observed above 890^∘C by an X-ray diffraction (XRD) and Thermogravimetry and Differential thermal analysis (TG-DTA).     

PZT thick films by diol chemical solution deposition

Process optimization and properties of lead zirconate titanate (PZT) films for piezoelectric micromachined ultrasonic transducers (pMUTs) for scanning probe devices will be presented. The goal of the work was a replacement of the tetragenic and mutagenic solvent and a decrease of time-consuming PZT 2–methoxy ethanol (2MOE) route. An alternative diol-based solution synthesis process was developed and “Design Of Experiment” (DOE) was used to achieve processing optimization for thick and crack free films. Tight parameter control allowed to develop a highly reproducible PZT diol process. The crystallization behaviour of crack-free PbZr_0.53Ti_0.47O₃ films (1–5 μm) with oriented perovskite structure was examined by X-ray diffraction and surface analysis using scanning electron microscopy. Piezoelectric and dielectric properties were examined. The effective transverse piezoelectric coefficient e _31,f of sol–gel processed films was investigated for 4 μm thick layers. Best properties were achieved with {1 0 0}-textured films, where a remanent e _31,f value of −7.3 C/m² was measured for 4.1 μm thick films.     

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.     

Oxygen permeation properties and surface modification of acceptor-doped CeO2/MnFe2O4 composites

The preparation and oxygen permeation properties of the (Ce_0.8Pr_0.2)O_2−δ − x vol% MnFe₂O₄ composites, where x = 0 to 35, have been investigated. The samples were prepared by the Pechini method. In the case of Ce_0.8Pr_0.2O_2−δ, an oxygen flux density of 6 μmol⋅cm⁻²⋅s⁻¹ (L = 0.0247 cm) and the maximum methane conversion of 50% were attained at 1000^∘C. Unlike composites consisting of Gd-doped CeO₂ and MnFe₂O₄, the oxygen permeability of the (Ce_0.8Pr_0.2)O_2−δ – x vol% MnFe₂O₄ composites was almost constant regardless of the volume fraction of MnFe₂O₄; however, the optimum volume fraction of MnFe₂O₄ was determined to be 5 to 25 in the context of the chemical and mechanical stabilities under methane conversion atmosphere. In addition, the surface modification of the (Ce_0.8Gd_0.2)O_2−δ – 15 vol% MnFe₂O₄ composite was performed by using the FePt nanoparticles. The catalyst loading of 2.8 mg/cm² on the both side of the 0.3 mm-thick (Ce_0.8Gd_0.2)O_2−δ – 15vol% MnFe₂O₄ composite increased the oxygen flux density from 0.30 to 0.76 μmol⋅cm⁻²⋅s⁻¹ in the case of He/air gradients; however, the effect seems to be reduced in the case of high oxygen flux density caused by a large pO₂ gradient. Moreover, the Langmuir-Blodgett film of the FePt nanoparticles were successfully prepared on the tape-cast (Ce_0.8Gd_0.2)O_2−δ – 15vol% MnFe₂O₄ composite. Hydrophobic treatments for the surface of the composite were crucial to achieve high transfer ratio for the deposition of the LB film.     

Preparation and characteristics of LiCoO2 paste electrodes for lithium ion micro-batteries

The thick film electrodes (cathode) have been developed via screen printing using LiCoO₂ paste to improve the discharge capacity of lithium ion micro-batteries. The LiCoO₂ pastes were formulated using the mixtures of LiCoO₂ powder as a functional material, carbon black as a conducting agent, ethyl cellulose and terpineol as a vehicle, and Emphos PS-21A as a dispersant. Depending on the amount of carbon black, the average and maximum surface roughnesses varied from 0.54 to 1.00 μm and 6.2 to 18.7 μm respectively. The internal resistance in the paste electrodes could also be controlled to 120 KΩcm⁻² by the addition of carbon black in the pastes. The thickness of the printed film is independent of the paste composition, but it decreased from 15 to 6 μm with the increase in screen mesh number from 250 to 500. The initial specific discharge capacity of the printed cathode which was prepared using the mixture Ag-coated LiCoO₂ powder improved to 180 μAhcm⁻².