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When the gas sensor active layer film thickness is decreased, increased sensitivity to changes in the adsorbate concentration is expected when measuring the resistance of the layer, in particular when this thickness is on the order of the Debye length of the material (one–tens of nanometers); however, this is demonstrated only for a limited number of materials. Herein, ultrathin NiO films of different thicknesses (8–21 nm) have been deposited via chemical vapor deposition to fabricate gas sensor devices. Sensor performance for a range of NO2 concentrations (800 part-per-billion to 7 part-per-million) was evaluated and an optimum operating temperature of 125 °C determined. The dependence of the potential relative changes with respect to the NO2 concentration and of the sensor signal with respect to the geometrical parameters was qualitatively evaluated to derive a transduction model capable of fitting the experimental results. The selective sensitivity toward NO2 was confirmed by the limited response for different reducing gases, CO, CH4, NH3, and SO2, under optimum operating conditions, and the sensor signal toward NO2 increased with decreasing thickness, demonstrating that the concept of a Debye length dependence of sensitivity is applicable for the p-type semiconductor NiO. In addition, these NiO sensors were exposed to different relative levels of humidity over a wide range of operating temperatures and were found to display humidity tolerance far superior to those in previous reports on SnO2 materials.

Polycrystalline NiO thick film-based gas sensors have been exposed to different test gas atmospheres at 250 °C and measured via simultaneous electrical resistance and work function investigations. Accordingly, we decoupled different features manifested toward the potential changes, i.e., work function, band-bending, and electron affinity. The experimental results have shown that the presence of moisture induces an unusual behavior toward carbon monoxide (CO) detection by considering different surface adsorption sites. On this basis, we derived an appropriate detection mechanism capable of explaining the lack of moisture influence over the CO detection with NiO-sensitive materials. As such, CO might have both chemical and dipolar interactions with pre-adsorbed or lattice oxygen species, thus canceling out the effect of moisture. Additionally, morphology, structure, and surface chemistry were addressed, and the results have been linked to the sensing properties envisaging the role played by the porous quasispherical–hollow structures and surface hydration.

NiO-loaded SnO2 powders were prepared involving two chemical procedures. The mesoporous SnO2 support was synthesized by a hydrothermal route using Brij 35 non-ionic surfactant as a template. The nickel loadings of 1 and 10 wt.%. NiO were deposited by the wet impregnation method. The H2S sensing properties of xNiO-(1-x)SnO2 (x = 0, 1, 10%) thick layers deposited onto commercial substrates have been investigated with respect to different potential interfering gases (NO2, CO, CO2, CH4, NH3 and SO2) over a wide range of operating temperatures and relative humidity specific for in-field conditions. Following the correlation of the sensing results with the morphological ones, 1wt.% NiO/SnO2 was selected for simultaneous electrical resistance and work function investigations. The purpose was to depict the sensing mechanism by splitting between specific changes over the electron affinity induced by the surface coverage with hydroxyl dipoles and over the band bending induced by the variable surface charge under H2S exposure. Thus, it was found that different gas-interaction partners are dependent upon the amount of H2S, mirrored through the threshold value of 5 ppm H2S, which from an applicative point of view, represents the lower limit of health effects, an eight-hour TWA.

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)2 have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)2 native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 °C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.

In this work, (Ba0.75Sr0.25) (Ti0.95Co0.05) O3 perovskite nanostructured material, denoted subsequently as Co-doped BaSrTiO3, was synthesized in a one-step process in hydrothermal conditions. The obtained powder was heat-treated at 800 &deg, C and 1000 &deg, C, respectively, in order to study nanostructured powder behavior during thermal treatment. The Co-doped BaSrTiO3 powder was pressed into pellets of 5.08 cm (2 inches) then used for thin film deposition onto commercial Al2O3 substrates by RF sputtering method. The microstructural, thermal, and gas sensing properties were investigated. The electrical and thermodynamic characterization allowed the evaluation of thermodynamic stability and the correlation of structural features with the sensing properties revealed under real operating conditions. The sensing behavior with respect to the temperature range between 23 and 400 &deg, C, for a fixed CO2 concentration of 3000 ppm, highlighted specific differences between Co-doped BaSrTiO3 treated at 800 &deg, C compared to that treated at 1000 &deg, C. The influence of the relative humidity level on the CO2 concentrations and the other potential interfering gases was also analyzed. Two possible mechanisms for CO2 interaction were then proposed. The simple and low-cost technology, together with the high sensitivity when operating at room temperature corresponding to low power consumption, suggests that Co-doped BaSrTiO3 has a good potential for use in developing portable CO2 detectors.

Pd deposited on CeOx-MnOx/La-Al2O3 has been prepared as a sensitive material for methane (CH4) detection. The effect of different amounts (1.25%, 2.5% and 5%) of Pd loading has been investigated. The as prepared materials were deposited on Pt microcoils using a drop-coating method, as a way of developing pellistors operated using a Wheatstone bridge configuration. By spanning the operating temperature range between 300 &deg, C and 550 &deg, C, we established the linearity region as well as the maximum sensitivity towards 4900 ppm of CH4. By making use of the sigmoid dependence of the output voltage signal from the Wheatstone bridge, the gas surface reaction and diffusion phenomena have been decoupled. The pellistor with 5% Pd deposited on CeOx-MnOx/La-Al2O3 exhibited the highest selective-sensitivity in the benefit of CH4 detection against threshold limits of carbon monoxide (CO), sulfur dioxide (SO2) and hydrogen sulfide (H2S). Accordingly, adjusting the percent of Pd makes the preparation strategies of pellistors good candidates towards CH4 detection.

Mesoporous CeO2:Mn3O4 materials (3:7 and 7:3 molar ratio) were prepared by co-precipitation and deposited as porous thick films over alumina (Al2O3) planar substrate provided with Pt meander. The aim was oriented towards detecting low levels methane (CH4) at moderate operating temperatures. Herein we demonstrated that the sensitivity of catalytic micro-converters (CMCs) towards a given peak of CH4 concentration corresponds to specific gas-surface interaction phenomena. More precisely, a transition from thermal conductivity to combustion rate is likely to occur when CMCs are operated under real atmospheric conditions (normal pressure, presence of relative humidity, and constant operating temperature). The response to CH4 was analyzed over different gas flows and different gas concentrations under the same operating regime. The materials were fully characterized by adsorption-desorption isotherms, H2-Temperature Programmed Reduction (H2-TPR), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), and Raman spectroscopies. Thus, the applicative aspect of using CeO2:Mn3O4 as moderate temperature CMC for CH4 detection is brought to the fore.

Semiconducting metal oxide (SMOX)-based gas sensors are indispensable for safety and health applications, for example, explosive, toxic gas alarms, controls for intake into car cabins, and monitor for industrial processes. In the past, the sensor community has been studying polycrystalline materials as sensors where the porous and random microstructure of the SMOX does not allow a separation of the phenomena involved in the sensing process. This led to conduction models that can model and predict the behavior of the overall response, but they were not capable of giving fundamental information regarding the basic mechanisms taking place. The study of epitaxial layers is a definite improvement, allowing clarifying the different aspects and contributions of the sensing mechanisms. A detailed analytical model of the transduction function for n-A nd p-type single-crystalline/compact metal oxide gas sensors was developed that directly relates the conductance of the sample with changes in the surface electrostatic potential. Combined dc resistance and work function measurements were used in a compact SnO2(101) layer in operando conditions that allowed us to check the validity of our model in the region where Boltzmann approximation holds to determine the surface and bulk properties of the material. Fil: Simion, Cristian Eugen. Institut de Physique Des Matériaux, Bucarest-magurele; Rumania Fil: Schipani, Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina Fil: Papadogianni, Alexandra. Paul Drude Institut Fur Festkorperelektronik; Alemania Fil: Stanoiu, Adelina. Institut de Physique Des Matériaux, Bucarest-magurele; Rumania Fil: Budde, Melanie. Paul Drude Institut Fur Festkorperelektronik; Alemania Fil: Oprea, Alexandru. Universität Tübingen; Alemania Fil: Weimar, Udo. Universität Tübingen; Alemania Fil: Bierwagen, Oliver. Paul Drude Institut Fur Festkorperelektronik; Alemania Fil: Barsan, Nicolae. Universität Tübingen; Alemania

Sensors based networked mesoporous SnO2 nanostructures templated by non-ionic surfactant - Brij® 35 were prepared via hydrothermal chemistry route. Specific patterns of the structure, morphology, surface chemistry and sensing properties were obtained by pH and autogenous pressure tuning. Consequently, the as-obtained SnO2 powders were subjected to extensive BET, Raman, TEM, HRTEM and XPS complementary investigations. The sensitive films were obtained by screen printing deposition of the powders onto commercial Al2O3 substrates. The gas sensing properties were assessed towards different hazardous gas species: CO, CH4, NH3, NO2, SO2 and H2S over a wide range of operating temperatures. Our particular SnO2 – HP sensor synthesized at high autogenous pressure showed the highest selective-sensitivity to H2S ( The enhancement in the H2S sensitivity at low operating temperature under infield conditions was found to be closely connected to the morphological aspects and surface chemistry, peculiarities that can be assessed as consequences of the chemical tuning.

This paper reports the sensing mechanism of SnO2-CuWO4 mixed oxides towards H2S detection revealed through Pulsed Temperature Mode (PTM). After thick film deposition onto commercial substrates, the final annealing temperature enhances the material reliability through the changes occurred during the experimental conditions. PTM approach represents a tradeoff in terms of sensing mechanism versus sensing performance, in order to get insights about the fundamental aspects. The measurements have been done under dynamic gas flow conditions, in the presence of 50% relative humidity (RH). The gas sensors based on SnO2-CuWO4 exhibit sensor signals higher than 100 to 10 ppm H2S, low cross-sensitivity to common gaseous interfering agents (CO, CH4, NH3, SO2), average selective sensitivity of 8.64 towards the main interfering NO2 gas, moderate response (4 min)/recovery (5 min) transients and power consumption. In order to emphasize the role of moisture towards H2S detection mechanism, the photoacoustic spectroscopic insights were correlated with Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy results. Such approach has shown promising aspects towards further operational sensitive devices.

Semiconducting metal oxide (SMOX)-based gas sensors are indispensable for safety and health applications, for example, explosive, toxic gas alarms, controls for intake into car cabins, and monitor for industrial processes. In the past, the sensor community has been studying polycrystalline materials as sensors where the porous and random microstructure of the SMOX does not allow a separation of the phenomena involved in the sensing process. This led to conduction models that can model and predict the behavior of the overall response, but they were not capable of giving fundamental information regarding the basic mechanisms taking place. The study of epitaxial layers is a definite improvement, allowing clarifying the different aspects and contributions of the sensing mechanisms. A detailed analytical model of the transduction function for n- and p-type single-crystalline/compact metal oxide gas sensors was developed that directly relates the conductance of the sample with changes in the surface electrostatic potential. Combined dc resistance and work function measurements were used in a compact SnO

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)2 have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)2 native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 °C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.

Mesoporous SnO 2 prepared by a hydrothermal synthesis route assisted by the ionic surfactant Cetyltrimethylammonium bromide, has rutile-type tetragonal symmetry, small homogeneous nanocrystallite size of ∼4 nm and good thermal stability. Porosity analysis revealed high surface area ∼127 m 2 /g and a narrow pore size distribution, with an average pore diameter ∼4 nm. The mesoporous structure is likewise advantageous towards enhancing the surface reactivity and subsequent gas sensing performances. The role played by the surface hydroxylation on the NO 2 sensing mechanism was discussed with respect to the associated photoelectron spectral components. Under humid air, associated with the in-field conditions, the highest sensitivity was attained at 150 °C, were the sensor signal towards NO 2 is 4 times higher than the one recorded in dry air. This feature has been experimentally demonstrated by simultaneous electrical resistance and work function changes measurements conducted in the range of 400–5000 ppb NO 2 .

Within the field of chemical gas sensing, ammonia detection represents one of the nowadays challenges, due to its adverse effects for human health. Real operating investigations are imposed by the high solubility potential of NH3 at room temperature. Thick films of Ba0.75Sr0.25TiO3 material have been investigated by means of electrical resistance and capacitance changes and correlated with the photoacoustic outputs. The experimental findings have been discussed in terms of Grotthuss mechanism, with respect to the ionic/electronic conduction within BST, toward ammonia detection enhanced by the presence of water vapors when operated at room temperature. So an appropriate NH3 sensing mechanism was proposed.

A one-step method assisted by hydrothermal treatment was approached to obtain nanocrystalline 1 and 10 mol.% In doped 2 mol.% Pd-SnO2 powders using a non-ionic surfactant Brij52 and Polyethylene glycol 6000 (PEG) as templates. Depending on In content, the samples were labeled as Pd1InSn and Pd10InSn. The obtained materials consist of nanosized crystallites packed into micrometric grains with a high porosity, as revealed by the morphological and structural investigations (SEM, TEM). A dependence of the grain size with respect to the In content has been revealed i.e. the sample Pd1InSn was showing an average grain size of around 10 nm, whilst for the sample Pd10InSn the average grain size was found to be around 5 nm. The XPS investigations highlighted the differences occurred in the surface chemistry in terms of surface hydroxylation as well as the chemical states of Pd. The sensing properties towards different CO concentrations have been examined under infield background conditions, at low operating temperature of 50 °C. The sensing mechanism model for CO was discussed in detail according to the possible interplay between oxygen and water related species based on the experimentally results acquired through simultaneous electrical resistance and work function measurements.

Analyte sensitivity for gas sensors based on semiconducting metal oxides should be highly dependent on the film thickness, particularly when that thickness is on the order of the Debye length. This thickness dependence has previously been demonstrated for SnO2 and inferred for TiO2. In this paper, TiO2 thin films have been prepared by Atomic Layer Deposition (ALD) using titanium isopropoxide and water as precursors. The deposition process was performed on standard alumina gas sensor platforms and microscope slides (for analysis purposes), at a temperature of 200 °C. The TiO2 films were exposed to different concentrations of CO, CH4, NO2, NH3 and SO2 to evaluate their gas sensitivities. These experiments showed that the TiO2 film thickness played a dominant role within the conduction mechanism and the pattern of response for the electrical resistance towards CH4 and NH3 exposure indicated typical n-type semiconducting behavior. The effect of relative humidity on the gas sensitivity has also been demonstrated.

Nanostructured Cu mol. 5% doped perovskite material Ba0.75Sr0.25TiO3 was synthesized under hydrothermal conditions and further on deposited via RF sputtering technique onto commercial Al2O3 substrates provided with Au interdigital electrodes and Pt heater. The obtained thin films have been analyzed by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM, TEM), X-ray photoelectron spectroscopy (XPS), Differential Scanning Calorimetry-Thermogravimetry (DSC-TG) and electrical investigations. The H2S (5–90 ppm) gas-surface interaction at moderate operating temperature (Top = 250 °C) associated with the interplay between the pre-adsorbed oxygen species and surface dipolar hydroxyl groups, has been highlighted by simultaneous work function and electrical resistance measurements. By correlation with the XPS spectra, the dominant role of surface hydroxylation was revealed and the subsequent gas sensing mechanism under operando conditions has been addressed.

NiO/mesoporous SnO 2 was deposited by incipient wetness impregnation of the SnO 2 powder prepared by hydrothermal synthesis route templated by Brij® 35. The sensing properties were acquired and the dependence on the operating temperature of the sensitive material was pointed out. Sensitive selectivity towards H 2 S detection was highlighted at 350 °C.

This study presents the synthesis and characterization of lanthanum-modified alumina supported cerium&ndash, manganese mixed oxides, which were prepared by three different methods (coprecipitation, impregnation and citrate-based sol-gel method) followed by calcination at 500 &deg, C. The physicochemical properties of the synthesized materials were investigated by various characterization techniques, namely: nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and H2&ndash, temperature programmed reduction (TPR). This experimental study demonstrated that the role of the catalytic surface is much more important than the bulk one. Indeed, the incipient impregnation of CeO2&ndash, MnOx catalyst, supported on an optimized amount of 4 wt.% La2O3&ndash, Al2O3, provided the best results of the catalytic combustion of methane on our catalytic micro-convertors. This is mainly due to: (i) the highest pore size dimensions according to the Brunauer-Emmett-Teller (BET) investigations, (ii) the highest amount of Mn4+ or/and Ce4+ on the surface as revealed by XPS, (iii) the presence of a mixed phase (Ce2MnO6) as shown by X-ray diffraction, and (iv) a higher reducibility of Mn4+ or/and Ce4+ species as displayed by H2&ndash, TPR and therefore more reactive oxygen species.

In order to understand the role of ambient humidity on NO 2 detection, electrical resistance and work function changes were recorded simultaneously on ZnO–Eu 2 O 3 material. Thus, surface band bending and electron affinity could be evaluated, according to the Schottky model. The lack of electron affinity changes during NO 2 exposure in dry air conditions, reveals that only the free charge concentration is affected. Exposure to NO 2 in humid background leads to an increase in sensor signals and a significant change in the electron affinity as well. This effect suggests an interaction between NO 2 and surface hydroxyl species; thereby additional charge carriers are involved in the overall sensing process. High resolution XPS analysis proves the presence of Eu solely in the 3 + oxidation state before and after NO 2 exposure. A gas-sensing interaction mechanism has been proposed.

ZnO– x %Eu 2 O 3 ( x =5 wt.%) binary oxide with straight strips morphology was successfully synthesized by hydrothermal route, using cetyltrimethylammonium bromide (CTAB) as template ZnSO 4 , Eu(NO 3 ) 3 ·5H 2 O as inorganic precursors and ammonium hydroxide solution 28% NH 3 for adjusting the pH to 11 value. The morphology, structure, photoluminescence and surface chemistry were investigated. The results highlighted that ZnO–Eu 2 O 3 binary oxide shows straight strip morphology and crystalline framework indexed to wurtzite ZnO while Eu 2 O 3 was detected as secondary phase. Surface chemistry revealed the presence of Eu 3+ . High sensor signal to 3 ppm NO 2 together with its low sensitivity towards CO recommend this material as a good candidate in selective detection of NO 2.

Development of new sensitive materials by different synthesis routes in order to emphasize the sensing properties for hazardous H

Gas sensing peculiarities of chromium oxide (Cr2O3) nanoparticles, obtained by hydrothermal reaction at moderate temperature and subsequent thermal annealing, were studied. The structure and morphology of the obtained Cr2O3 samples were investigated by X-ray diffraction and transmission electron microscopy techniques. Gas sensing measurements revealed their selective sensitivity to nitrogen dioxide (NO2) at 200 °C relative to carbon monoxide (CO), both in dry and humid air. Higher selectivity towards NO2 is attributed to the material surface reactivity even at low operating temperatures. This property was experimentally highlighted by work function changes, as a complementary investigation method to basic electrical resistance. Thus, it was observed that the surface reactivity of Cr2O3 (calcinated at 1000 °C) towards NO2 is higher compared to CO and less influenced by the relative humidity of the surrounding atmosphere. The present study reveals possible applications in the selective detection of NO2 based on Cr2O3.

The different amount of Cu-doped Barium Strontium Titanate (BST) thick film materials have been tested for their gas-sensing performances towards NH3 and H2S under dry and 50% relative humidity (RH) background conditions. The optimum NH3 sensitivity was attained with 0.1mol% Cu-doped BST whereas the selective detection of H2S was highlighted using 5mol% Cu-doped BST material. No cross-sensitivity effects to CO, NO2, CH4 and SO2 were observed for all tested materials operated at their optimum temperature (200°C) under humid conditions (50% RH). The presence of humidity clearly enhances the gas sensitivity to NH3 and H2S detection.