Sensing of CO2 at room temperature using work function readout of (hetero-)polysiloxanes sensing layers

Organically modified silicates based on primary amino groups are known to be CO₂ sensitive, as they can undergo a reversible acid base reaction. In order to generate detectable CO₂ signals and to limit the cross-sensitivity to humidity, some sources suggest that these materials should be operated at higher temperatures (50-70 °C). In this paper, a new variant of CO₂ sensing is to be presented, namely a combination of work function readout and organically modified silicates, which yields CO₂ detection even at room temperature. Kelvin probe measurements are used for work function readout. The layers are intended to be used in a “Floating Gate Field Effect Transistors” (FGFETs) sensing platform (mySens) by Micronas. The reversible interaction of CO₂ with spin-coated heteropolysiloxane sensitive layers results in changes of the work function with typical signal heights of 15-20 mV (change from 400 to 4000 ppm CO₂) and response times of only a few minutes. Also, results will be presented regarding variations in the chemical nature of the films. The findings summarized in this paper point towards the possibility of a new room temperature CO₂ sensor, which comprises fast response times and sufficient sensitivity for ambient CO₂ variations.     

Carbon dioxide gas sensor using a graphene sheet

In this article, we report on a high-performance graphene carbon dioxide (CO₂) gas sensor fabricated by mechanical cleavage. Unlike other solid-state gas sensors, the graphene sensor can be operated under ambient conditions and at room temperature. Changes in the device conductance are measured for various concentrations of CO₂ gas adsorbed on the surface of graphene. The conductance of the graphene gas sensor increases linearly when the concentration of CO₂ gas is increased from 10 to 100 ppm. The advantages of this sensor are high sensitivity, fast response time, short recovery time, and low power consumption.     

Gas sensing properties of SnO2 nanowires on micro-heater

The SnO₂ nanowires (NWs) network gas sensors were fabricated on a micro-electrode and heater suspended in a cavity. The sensors showed selective detection to C₂H₅OH at a heater power during sensor operation as low as 30-40 mW. The gas response and response speed of the SnO₂ NWs sensor to 100 ppm C₂H₅OH were 4.6- and 4.7-fold greater, respectively, than those of the SnO₂ nanoparticles (NPs) sensor with the same electrode geometry. The reasons for these enhanced gas sensing characteristics are discussed in relation to the sensing materials and sensor structures.     

Structural and properties of nanocrystalline WO3/TiO2-based humidity sensors elements prepared by high energy activation

Nanocrystalline WO₃/TiO₂-based powders have been prepared by the high energy activation method with WO₃ concentration ranging from 1 to 10 mol%. The samples were thermal treated in a microwave oven at 600 °C for 20 min and their structural and micro-structural characteristics were evaluated by X-ray diffraction, Raman spectroscopy, EXAFS measurements at the Ti K-edge, and transmission electron microscopy. Nitrogen adsorption isotherms and H₂ Temperature Programmed Reduction were also carried out for physical characterization. The crystallite and particle mean sizes ranged from 30 to 40 nm and from 100 to 190 nm, respectively. Good sensor response was obtained for samples with at least 5 mol% WO₃ activated for at least 80 min. Ceramics heat-treated in microwave oven for 20 min have shown similar sensor response as those prepared in conventional oven for 120 min, which is highly cost effective. These results indicate that WO₃/TiO₂ ceramics can be used as a humidity sensor element.     

A CO2 sensor based upon a continuous-wave thermoelectrically-cooled quantum cascade laser

A CO₂ sensor based upon a continuous-wave thermoelectrically-cooled distributed feedback quantum cascade laser operating between 2305 and 2310 cm⁻¹ and a 54.2 cm long optical cell has been developed. Two approaches for direct absorption spectroscopy have been evaluated and applied for monitoring of the CO₂ concentration in gas lines and ambient laboratory air. In the first approach optical transmittance was derived from the single channel laser intensity, whilst in the second approach a ratio of signal and reference laser intensities (balanced detection) was used. The optimum residual absorption standard deviation was estimated to be 1.9 × 10⁻⁴ for 100 averages of 1 ms duration and 0.1 cm⁻¹ scans over the P(46) CO₂ absorption line of the ν₃ vibrational band at 2306.926 cm⁻¹. A CO₂ detection limit (1 standard deviation) of 36 ppb was estimated for 0.1 s average and balanced detection.     

Micromachined catalytic combustible hydrogen gas sensor

An integrated catalytic combustion H₂ sensor has been fabricated by using MEMS technology. Both the sensing elements and the reference elements could be integrated into the suspended micro heaters connected in a suitable circuit such as a Wheatstone configuration with low power consumption. Two sensitive elements and two reference sensors were integrated together onto a single chip. The size of chip was 5.76 mm² and the catalytic combustion sensor showed high response to H₂ at operating voltage of 1 V. The response and recovery times to 1000 ppm H₂ were 0.36 s and 1.29 s, respectively.     

Preparation and characterization of unimorph actuators based on piezoelectric Pb(Zr0.52Ti0.48)O3 materials

This paper describes the preparation and characterization of unimorph actuators for deformable mirrors, based on Pb(Zr_0.52Ti_0.48)O₃ (PZT52) thin film. As comparison, two different designs, where the PZT layer in the unimorph actuators was driven by either interdigitated electrodes (IDT-mode) or parallel plate electrodes (d₃₁-mode), were investigated. The actuators utilize a unimorph membrane (diaphragm) structure consisting of an active PZT piezoelectric layer and a passive SiO₂/Si composite layer. To fabricate the diaphragm structures, n-type (1 0 0) silicon-on-insulator (SOI) wafers with 1 μm thermal SiO₂ were used as substrates (for d₃₁-mode actuators, the upper Si part of SOI need to be heavily doped and used as bottom electrodes simultaneously). Sol-gel derived PZT piezoelectric layers with PbTiO₃ (PT) bufferlayer in total of 0.86 μm were then fabricated on them, and 0.15 μm Al reflective layers were deposited and patterned into top electrode geometries, subsequently. The diaphragms were released using orientation-dependent wet etching (ODE) with 5-10 μm residual silicon layers. The complete unimorph actuators comprise 4 × 4 discrete units (4 mm² in size) with patterned PZT films for parallel plate configuration or 3 × 3 individual pixels (2 mm in IDT diameter) with continuous PZT films in graphic region for IDT configuration. The measurement results indicated that both of the two configurations can generate considerable deflections at low voltage. The measured maximum central deflections at 15 V were approximately 2.5 μm and 2.8 μm, respectively. The intrinsic strain conditions shaping the deflection profiles for the diaphragm actuators were also analyzed. In this paper, the behaviors of clamped parallel plate configuration without a diaphragm were also evaluated.     

Improved crystalline structure and H2S sensing performance of CuO-Au-SnO2 thin film using SiO2 additive concentration

In situ SiO₂-doped SnO₂ thin films were successfully prepared by liquid phase deposition. The influence of SiO₂ additive as an inhibitor on the surface morphology and the grain size for the thin film has been investigated. These results show that the morphology of SnO₂ film changes significantly by increasing the concentration of H₂SiF₆ solution which decreases the grain size of SnO₂. The stoichiometric analysis of Si content in the SnO₂ film prepared from various Si/Sn molar ratios has also been estimated. For the sensing performance of H₂S gas, the SiO₂-doped Cu-Au-SnO₂ sensor presents better sensitivity to H₂S gas compared with Cu-Au-SnO₂ sensor due to the fact that the distribution of SiO₂ particles in grain boundaries of nano-crystallines SnO₂ inhibited the grain growth (<6 nm) and formed a porous film. By increasing the Si/Sn molar ratio, the SiO₂-doped Cu-Au-SnO₂ gas sensors (Si/Sn = 0.5) exhibit a good sensitivity (S = 67), a short response time (t_90% < 3 s) and a good gas concentration characteristic (α = 0.6074). Consequently, the improvement of the nano-crystalline structures and high sensitivity for sensing films can be achieved by introducing SiO₂ additive into the SnO₂ film prepared by LPD method.     

Effect of La2CuO4 electrode area on potentiometric NOx sensor response and its implications on sensing mechanism

The intent of this work is to look at the effects of varying the La₂CuO₄ electrode area and the asymmetry between the sensing and counter electrode in a solid state potentiometric sensor with respect to NO_x sensitivity. NO₂ sensitivity was observed at 500-600 °C with a maximum sensitivity of ∼22 mV/decade [NO₂] observed at 500 °C for the sensor with a La₂CuO₄ electrode area of ∼30 mm². The relationship between NO₂ sensitivity and area is nearly parabolic at 500 °C, decreases linearly with increasing electrode area at 600 °C, and was a mixture of parabolic and linear behavior 550 °C. NO sensitivity varied non-linearly with electrode area with a minima (maximum sensitivity) of ∼−22 mV/decade [NO] at 450 °C for the sensor with a La₂CuO₄ electrode area of 16 mm². The behavior at 400 °C was similar to that of 450 °C, but with smaller sensitivities due to a saturation effect. At 500 °C, NO sensitivity decreases linearly with area.We also used electrochemical impedance spectroscopy (EIS) to investigate the electrochemical processes that are affected when the sensing electrode area is changed. Changes in impedance with exposure to NO_x were attributed to either changes in La₂CuO₄ conductivity due to gas adsorption (high frequency impedance) or electrocatalysis occurring at the electrode/electrolyte interface (total electrode impedance). NO₂ caused a decrease in high frequency impedance while NO caused an increase. In contrast, NO₂ and NO both caused a decrease in the total electrode impedance. The effect of area on both the potentiometric and impedance responses show relationships that can be explained through the mechanistic contributions included in differential electrode equilibria.     

Development of SAW-based multi-gas sensor for simultaneous detection of CO2 and NO2

A 440 MHz wireless and passive surface acoustic wave (SAW)-based multi-gas sensor integrated with a temperature sensor was developed on a 41° YX LiNbO₃ piezoelectric substrate for the simultaneous detection of CO₂, NO₂, and temperature. The developed sensor was composed of a SAW reflective delay lines structured by an interdigital transducer (IDT), ten reflectors, a CO₂ sensitive film (Teflon AF 2400), and a NO₂ sensitive film (indium tin oxide). Teflon AF 2400 was used for the CO₂ sensitive film because it provides a high CO₂ solubility, with good permeability and selectivity. For the NO₂ sensitive film, indium tin oxide (ITO) was used. Coupling of mode (COM) modeling was conducted to determine the optimal device parameters prior to fabrication. Using the parameters determined by the simulation results, the device was fabricated and then wirelessly measured using a network analyzer. The measured reflective coefficient S₁₁ in the time domain showed high signal/noise (S/N) ratio, small signal attenuation, and few spurious peaks. The time positions of the reflection peaks were well matched with the predicted values from the simulation. High sensitivity and selectivity were observed at each target gas testing. The obtained sensitivity was 2.12°/ppm for CO₂ and 51.5°/ppm for NO₂, respectively. With the integrated temperature sensor, temperature compensation was also performed during gas sensitivity evaluation process.     

Synthesis and gas sensing properties of bundle-like α-Fe2O3 nanorods

Bundle-like α-Fe₂O₃ nanostructures were successfully synthesized by a simple calcination of β-FeOOH precursor derived from a hydrothermal method in the presence of poly(vinyl pyrrolidone). The as-prepared products were characterized by X-ray power diffraction, field emission scanning electron microscopy, and transmission electron microscopy. The results indicated that bundle-like nanostructures were composed of well-aligned single crystalline nanorods with the diameters of 20-30 nm and the lengths of 200-300 nm. The gas sensing properties of as-prepared products were investigated. It was found that the sensor based on α-Fe₂O₃ nanostructure exhibited high response, quick response-recovery, and good repeatability to acetone at 250 °C.     

Influence of doping BiYO3 and Nb2O5 on PTCR characteristics of BaTiO3 thermistor ceramics

Nb₂O₅-doped (1 − x)Ba_0.96Ca_0.04TiO₃-xBiYO₃ (where x = 0.01, 0.02, 0.03 and 0.04) lead-free PTC thermistor ceramics were prepared by a conventional solid state reaction method. X-ray diffraction, scanning electron microscope, Agilent E4980A and resistivity-temperature measurement instrument, were used to characteristic the lattice distortion, microstructure, temperature dependence of permittivity and resitivity-temperature dependence. It was revealed that the tetragonality c/a of the perovskite lattice, the microstructure and the Curie temperature changed with the BiYO₃ content. In order to decrease the room temperature resistivity, the effect of Nb₂O₅ on the room temperature resistivity was also studied, and its optimal doping content was finally chosen as 0.2 mol%. The 0.97Ba_0.96Ca_0.04TiO₃-0.03BiYO₃-0.002Nb₂O₅ thermistor ceramic exhibited a low ρ_RT of 3.98 × 10³ Ω cm, a typical PTCR effect of ρ_max/ρ_min > 10³ and a T_c of 153 °C.     

Highly sensitive and selective LPG sensor based on α-Fe2O3 nanorods

The α-Fe₂O₃ nanorods were successfully synthesized without any templates by calcining the α-FeOOH precursor in air at 300 °C for 2 h and their LPG sensing characteristics were investigated. The α-FeOOH precursor was prepared through a simple and low cost wet chemical route at low temperature (40 °C) using FeSO₄·7H₂O and CH₃COONa as starting materials. The formation of α-FeOOH precursor and its topotactic transformation to α-Fe₂O₃ upon calcination was confirmed by X-ray diffraction measurement (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis. The α-Fe₂O₃ nanorods exhibited outstanding gas sensing characteristics such as, higher gas response (∼1746-50 ppm LPG at 300 °C), extremely rapid response (∼3-4 s), relatively slow recovery (∼8-9 min), excellent repeatability, good selectivity and lower operating temperature (∼300 °C). Furthermore, the α-Fe₂O₃ nanorods are able to detect up to 5 ppm for LPG with reasonable response (∼15) at the operating temperature of 300 °C and they can be reliably used to monitor the concentration of LPG over the range (5-60 ppm). The experimental results clearly demonstrate the potential of using the α-Fe₂O₃ nanorods as sensing material in the fabrication of LPG sensors. Plausible LP G sensing mechanism of the α-Fe₂O₃ nanorods is also discussed.     

Contact CMOS imaging of gaseous oxygen sensor array

We describe a compact luminescent gaseous oxygen (O₂) sensor microsystem based on the direct integration of sensor elements with a polymeric optical filter and placed on a low power complementary metal-oxide semiconductor (CMOS) imager integrated circuit (IC). The sensor operates on the measurement of excited-state emission intensity of O₂-sensitive luminophore molecules tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) ([Ru(dpp)₃]²⁺) encapsulated within sol-gel derived xerogel thin films. The polymeric optical filter is made with polydimethylsiloxane (PDMS) that is mixed with a dye (Sudan-II). The PDMS membrane surface is molded to incorporate arrays of trapezoidal microstructures that serve to focus the optical sensor signals on to the imager pixels. The molded PDMS membrane is then attached with the PDMS color filter. The xerogel sensor arrays are contact printed on top of the PDMS trapezoidal lens-like microstructures. The CMOS imager uses a 32 × 32 (1024 elements) array of active pixel sensors and each pixel includes a high-gain phototransistor to convert the detected optical signals into electrical currents. Correlated double sampling circuit, pixel address, digital control and signal integration circuits are also implemented on-chip. The CMOS imager data is read out as a serial coded signal. The CMOS imager consumes a static power of 320 μW and an average dynamic power of 625 μW when operating at 100 Hz sampling frequency and 1.8 V DC. This CMOS sensor system provides a useful platform for the development of miniaturized optical chemical gas sensors.     

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).     

Facile synthesis of hierarchical SnO2 semiconductor microspheres for gas sensor application

Hierarchical SnO₂ microspheres were synthesized by a hydrothermal method at 140 °C using stannic chloride hydrate and sodium hydroxide as starting materials. The individual hierarchical SnO₂ microsphere ranged from 700 to 900 nm in diameter. After these microspheres were heated at 600 °C for 2 h, the spheres were cross-linked into clusters by short SnO₂ nanorods as revealed by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Most importantly, SnO₂ hierarchical microsphere sensor exhibits excellent selectivity and fast response to ethanol. Response and recovery times were 0.6 s and 11 s when the sensor was exposed to 50 ppm ethanol at an operating temperature of 300 °C. Thus, hierarchical structures play a significant role in the field of gas sensing.     

An interferometric biosensor composed of a prism-chamber assembly and a composite waveguide with a Ta2O5 nanometric layer

A highly sensitive integrated polarimetric interferometer biosensor with improved long-time stability and simple operation was prepared by using a novel prism-chamber assembly and an inexpensive waveguide made by sputtering a tapered nanometric layer of Ta₂O₅ on a single-mode glass waveguide. By comparing the measured refractive-index (RI) sensitivities with those simulated based on a four-layer homogeneous waveguide, both the equivalent thicknesses (T_eq) for the tapered Ta₂O₅ layers and a severe dependence of RI sensitivity on T_eq were obtained. Addition of 1 g of water in 100 g of a Chinese liquor (alcohol concentration = 46% (v/v)) was easily detected by the sensor. Monitoring of anti-human IgG adsorption with a waveguide of T_eq = 31.99 nm indicates that the antibody coverage required for inducing a phase-different change of Δ? = π is less than 0.012 monolayer. The same waveguide presents a quasi-linear dependence of Δ? on water temperature with the slope of d(Δ?)/dT = −28.50°/°C to which the contribution by the thermo-optical effect of the waveguide is 4.24°/°C, equivalent to a liquid RI change of Δn_c = 1.41 × 10⁻⁵. The interferometer exhibits the promising potential for chemical and biological analyses because of its outstanding characteristics.     

Electrical conductivity dependence of Ni doped Sm0.95Ce0.05FeO3−δ on surface morphology and composition

Sm_0.95Ce_0.05Fe_1−xNi_xO_3−δ materials are considered as candidates for sensing reducing gases. The total electrical conductivity of Ni doped Sm_0.95Ce_0.05FeO_3−δ perovskite materials is discussed in terms of Ni concentration, surface morphology and relative surface atomic ratios. Powders of formula Sm_0.95Ce_0.05Fe_1−xNi_xO_3−δ (x = 0-0.10) were prepared from citrate precursors by using a sol gel method and were then pressed uniaxially and sintered at 1350 °C for 4 h to form pellets. In fresh pellets the relative surface atomic ratios of Sm and Ni increased while that of Fe and Ce decreased as a function of nickel concentration, showing the segregation of samarium species. In contrast, the chemically reduced pellets show Fe rich surfaces. The electrical conductivity of fresh, partially reduced (700 °C under 5% (v/v) H₂/N₂ for 1 h) and fully reduced (1000 °C under 5% (v/v) H₂/N₂ for 1 h) pellets was measured by the four probe DC method.Under air, x = 0.07 and x = 0.10 showed the highest electrical conductivity in the series. Interestingly the x = 0.01-0.05 materials were n-type conductors while x = 0.07-0.10 exhibited p-type behaviour. The reduction treatment at 1000 °C enhanced electrical conductivities up to ∼5000 fold due to changes associated with surface morphology and surface elemental composition. While phase separations are usually detrimental, in this case the reduced sensors are more sensitive without sacrificing reproducibility.     

Nanostructured spinel ZnCo2O4 for the detection of LPG

Nanostrucutred spinel ZnCo₂O₄ (∼26-30 nm) was synthesized by calcining the mixed precursor (consisting of cobalt hydroxyl carbonate and zinc hydroxyl carbonate) in air at 600 °C for 5 h. The mixed precursor was prepared through a low cost and simple co-precipitation/digestion method. The transformation of the mixed precursor into nanostructured spinel ZnCo₂O₄ upon calcinations was confirmed by X-ray diffraction (XRD) measurement, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). To demonstrate the potential applicability of ZnCo₂O₄ spinel in the fabrication of gas sensors, its LPG sensing characteristics were systematically investigated. The ZnCo₂O₄ spinel exhibited outstanding gas sensing characteristics such as, higher gas response (∼72-50 ppm LPG gas at 350 °C), response time (∼85-90 s), recovery time (∼75-80 s), excellent repeatability, good selectivity and relatively lower operating temperature (∼350 °C). The experimental results demonstrated that the nanostructured spinel ZnCo₂O₄ is a very promising material for the fabrication of LPG sensors with good sensing characteristics. Plausible LPG sensing mechanism is also discussed.