NIMP| Adelina STANOIU, Author at NIMP

Projects

1. Sensing mechanism for Sn1-xGdxO(4-x)/2 in relation to the operating temperature, relative air humidity and CO2 concentration

Project Type: PCE, Start Date: 2022-05-03 End Date: 2024-12-31

Publications

1. Influence of Synthesis Method and Electrode Geometry on GHG-Sensing Properties of 5%Gd-Doped SnO₂

Authors: Simion, CE; Mihalcea, CG; Iacoban, AC; Dinu, IV; Predoi, D; Vlaicu, ID; Florea, OG; Stanoiu, A

Published: AUG 2024, CHEMOSENSORS, 12, 148, DOI: 10.3390/chemosensors12080148

This study investigates the influence of synthesis methods and electrode geometry on the physico-chemical properties of 5%Gd-doped SnO2. Two distinct synthesis routes, co-precipitation and hydrothermal growth, were employed, resulting in powders denoted as SnO2: Gd 5%-CP and SnO2: Gd 5%-HT. Morpho-structural and textural analyses reveal a uniform morphology consisting of quasi-spherical nanoparticles with dimensions of similar to 6 nm and mesoporosity for CP and a non-uniform morphology with larger nanoparticles of similar to 42 nm, with irregular shapes and macroporosity for the HT sample, respectively. The powders were deposited onto alumina substrates equipped with platinum interdigital electrodes with alternative gaps of 200 mu m and 100 mu m. The back-side heater allows for variation in the temperature of the layer. Sensing properties assessed under in-field-like atmospheres simulated by a computer-controlled Gas Mixing System reveal higher sensitivity to methane compared to carbon dioxide. Although the sensor signals did not differ quantitatively, they exhibited distinct saturation tendencies with an increasing methane concentration, attributed to the morpho-structure and porosity induced by the synthesis method. Differentiation was achieved by varying the interdigital gap of the electrodes, highlighting different sensor signals and conduction mechanisms, determined by the specific size of the crystallites.

2. Low traces of acetone detection with WO3-based chemical sensors

Authors: Stanoiu, A; Vlaicu, ID; Iacoban, AC; Mihalcea, CG; Ghica, C; Florea, OG; Dinu, IV; Mercioniu, I; Simion, CE

Published: APR 1 2024, MATERIALS CHEMISTRY AND PHYSICS, 316, 129105, DOI: 10.1016/j.matchemphys.2024.129105

This work presents the ability of WO3-based sensors to detect low traces of acetone, specifically within the range of 0.25-5 ppm, specific to the in -field atmosphere. The WO3 powder was synthesised through the hydrothermal method. Morpho-structural investigations showed a monoclinic structure and a good crystallization of the WO3 powder, containing well -grown and faceted grains along low -index crystallographic planes. The paste obtained by mixing the powder with propanediol was screen -printed as a thick layer onto commercial alumina substrates, obtaining the chemical sensors. A dynamic computer -controlled Gas Mixing System was utilized to ensure controlled airflow with variable relative humidity and acetone concentrations. The sensor response was explained based on physico-chemical equations, taking into consideration pre -adsorbed species of oxygen and water, both of which are relevant constituents of atmospheric conditions. The results highlight the applicative potential of WO3, having a good signal-to-noise ratio in relative humidity conditions up to 90% and a pronounced sensitive selectivity to acetone.

3. In-depth insight into the structural properties of nanoparticulate NiO for CO sensing

Authors: Mihalcea, CG; Stefan, M; Ghica, C; Florea, OG; Stanoiu, A; Simion, CE; Somacescu, S; Ghica, D

Published: APR 1 2024, APPLIED SURFACE SCIENCE, 651, 159252, DOI: 10.1016/j.apsusc.2023.159252

The outstanding properties exhibited by the p-type NiO nanostructures can be greatly affected by morpho-structural and defect characteristics with constructive or competing effects. We have conducted an in-depth study on NiO nanoparticles obtained by hydrothermal synthesis and submitted to various thermal treatments, to monitor the evolution of their structural properties and the effect of the thermal history on their CO sensing. Correlated electron paramagnetic resonance and analytical transmission electron microscopy investigations evidenced an amount of up to 1 % metallic nickel clusters close to surface in the NiO nanoparticles calcined at 400 degrees C and 500 degrees C for 8 h. Subsequent annealing in vacuum and in air of the sample calcined at 400 degrees C resulted in different size distributions and morphology of the NiO nanoparticles and an increase/decrease of the nickel phase, respectively. Comparative CO sensing tests on the two pristine samples and on the sample calcined at 400 degrees C and further annealed in air at 500 degrees C for 2 h showed an increase in the baseline resistance of the later due to the decrease of free charge carriers induced by the dissolution of the nickel clusters. The overall CO sensing results show a strong dependence on the samples thermal history.

4. Sensing mechanisms of CO and H2 with NiO material - DRIFTS investigations

Authors: Simion, CE; Junker, B; Weimar, U; Stanoiu, A; Bârsan, N

Published: SEP 1 2023, SENSORS AND ACTUATORS B-CHEMICAL, 390, 134028, DOI: 10.1016/j.snb.2023.134028

The response of nickel oxide gas sensors towards CO and H2 and the underlying gas sensing mechanisms were investigated with special focus on the influence of ambient humidity interference. Surface reactions were tracked by using diffuse reflectance infrared Fourier transformation spectroscopy with simultaneous resistance measurements. The sensor response to both gases is barely influenced by the background humidity. Spectroscopic results reveal that the underlying processes at the surface are almost identical for CO and H2 reception and similar to the effect of the removal of oxygen. Accordingly, the detection of the analytes is based purely on the reduction and oxidation of the oxide material instead of the formation of analyte specific surface species.

5. The influence of the synthesis method on Gd2O3 morpho-structural properties and sensitivity to CO2 under in-field conditions

Authors: Simion, CE; Vlaicu, ID; Iacoban, AC; Mihalcea, CG; Ghica, C; Stanoiu, A

Published: FEB 15 2023, MATERIALS CHEMISTRY AND PHYSICS, 296, 127354, DOI: 10.1016/j.matchemphys.2023.127354

In this study, we report the implications of the synthesis method on Gd2O3 sensitivity to CO2. The rare-earth oxide was prepared by wet chemical co-precipitation and by hydrothermal method. The obtained powders labelled Gd2O3-CoP and Gd2O3-HT were deposited as thick films over commercial Al2O3 substrates provided with Pt electrodes and a back-side heater. Both powders consist of the same crystallographic phase, with a significant difference appearing in selected area electron diffraction patterns, transmission electron microscopy images at higher magnification and X-ray diffraction spectra, with respect to the crystallization degree. The associated role in sensing properties is revealed via electrical resistance variations determined by CO2 concen-trations in the range between 400 and 3000 ppm and variable relative humidity between 0 and 50%RH, similar to the in-field atmosphere. The proposed CO2 interaction mechanism is based on phenomenological in-vestigations which highlight the electronic affinity variation as the effect of dipoles induced by the in-field conditions on the Gd2O3 surface.

6. Influence of relative humidity on CO2 interaction mechanism for Gd-doped SnO2 with respect to pure SnO2 and Gd2O3

Authors: Ghica, C; Mihalcea, CG; Simion, CE; Vlaicu, ID; Ghica, D; Dinu, IV; Florea, OG; Stanoiu, A

Published: OCT 1 2022, SENSORS AND ACTUATORS B-CHEMICAL, 368, 132130, DOI: 10.1016/j.snb.2022.132130

The paper aims to identify the CO2 interaction mechanism for chemical sensors based on Gd-doped SnO2, SnO2 and Gd2O3 powders deposited as thick sensitive layers. The low reactivity of CO2 conferred by the thermodynamic stability and chemical inertia can be offset by the presence of relative humidity. The sensitive powders were prepared by wet chemical co-precipitation method. The Gd concentration was varied from 1% to 20 at% in order to determine the limit for Gd integration as a doping ion prior to chemical segregation as a secondary phase. Analytical transmission electron microscopy points to a homogeneous Gd doping of the nanostructured SnO2 powders for low doping concentrations and the formation of a nanocomposite based on SnO2 as main phase and cubic Gd2O3 as secondary phase for the highly doped samples. The electrical resistance is either influenced by the density of oxygen vacancies, or is the result of compensation for two opposite behaviours into the SnO2- Gd2O3 nanocomposite structures. The CO2 exposure to humid atmosphere determines distinct behaviours cor-responding to SnO2 and Gd2O3 as constitutive elements. The associated CO2 interaction mechanism is based on simultaneous DC electrical resistance and Contact Potential Difference measurements, which allow decoupling the ionosorption from the dipolar processes, thus highlighting specific chemical interactions on the SnO2 and Gd2O3 surfaces.

7. Effects of Calcination Temperature on CO-Sensing Mechanism for NiO-Based Gas Sensors

Authors: Stanoiu, A; Ghica, C; Mihalcea, CG; Ghica, D; Somacescu, S; Florea, OG; Simion, CE

Published: MAY 2022, CHEMOSENSORS, 10, 191, DOI: 10.3390/chemosensors10050191

NiO-sensitive materials have been synthesized via the hydrothermal synthesis route and calcined in air at 400 degrees C and, alternatively, at 500 degrees C. Structural, morphological, and spectroscopic investigations were involved. As such, the XRD patterns showed a higher crystallinity degree for the NiO calcined at 500 degrees C. Such an aspect is in line with the XPS data indicating a lower surface hydroxylation relative to NiO calcined at 400 degrees C. An HRTEM microstructural investigation revealed that the two samples differ essentially at the morphological level, having different sizes of the crystalline nanoparticles, different density of the surface defects, and preferential faceting according to the main crystallographic planes. In order to identify their specific gas-sensing mechanism towards CO exposure under the in-field atmosphere, the simultaneous evaluation of the electrical resistance and contact potential difference was carried out. The results allowed the decoupling of the water physisorption from the chemisorption of the ambient oxygen species. Thus, the specific CO interaction mechanism induced by the calcination temperature of NiO has been highlighted.

8. Insights about CO Gas-Sensing Mechanism with NiO-Based Gas Sensors-The Influence of Humidity

Authors: Simion, CE; Ghica, C; Mihalcea, CG; Ghica, D; Mercioniu, I; Somacescu, S; Florea, OG; Stanoiu, A

Published: SEP 2021, CHEMOSENSORS, 9, DOI: 10.3390/chemosensors9090244

Polycrystalline NiO thick film-based gas sensors have been exposed to different test gas atmospheres at 250 degrees 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.

9. Sensing Properties of NiO Loaded SnO2 Nanoparticles-Specific Selectivity to H2S

Authors: Stanoiu, A; Kuncser, AC; Ghica, D; Florea, OG; Somacescu, S; Simion, CE

Published: JUN 2021, CHEMOSENSORS, 9, DOI: 10.3390/chemosensors9060125

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.

10. CuWO4 with CuO and Cu(OH)(2) Native Surface Layers for H2S Detection under in-Field Conditions

Authors: Somacescu, S; Stanoiu, A; Dinu, IV; Calderon-Moreno, JM; Florea, OG; Florea, M; Osiceanu, P; Simion, CE

Published: JAN 2021, MATERIALS, 14, DOI: 10.3390/ma14020465

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 degrees 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.

11. DEPOSITION AND CHARACTERIZATION OF THIN FILMS BASED ON NANOSTRUCTURED WO3 AS SENSORIAL ELEMENTS FOR DETECTION O F H2S

Authors: Sobetkii, A; Olaru, MT; Cindemir, U; Osterlund, L; Stanoiu, A; Simion, CE; Bejan, SE; Irimescu, RE

Published: 2020, REVISTA ROMANA DE MATERIALE-ROMANIAN JOURNAL OF MATERIALS, 50, 394, DOI:

Thin nanostructured films are the state-of-the-art materials for detection of very low limits of toxic gases. The work presents a comparison between the properties of WO3 thin films obtained by two different deposition techniques: Advanced Gas Deposition (AGD) and DC Reactive Sputtering. Films have been characterized by XRD, SEM and XPS. WO3-based sensors have selective sensitivity in H2S detection at operating temperature of 200 degrees C and relative humidity specific to field applications. The potential interferences with CO2, SO2 and NH3 are negligible, highlighting the application potential of WO3.

12. Low temperature CO sensing under infield conditions with in doped Pd/SnO2

Authors: Stanoiu, A; Ghica, C; Somacescu, S; Kuncser, AC; Vlaicu, AM; Mercioniu, IF; Florea, OG; Simion, CE

Published: APR 1 2020, SENSORS AND ACTUATORS B-CHEMICAL, 308, DOI: 10.1016/j.snb.2020.127717

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 degrees 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.

13. CeO2:Mn3O4 Catalytic Micro-Converters Tuned for CH4 Detection Based on Catalytic Combustion under Real Operating Conditions

Authors: Simion, CE; Florea, OG; Florea, M; Neatu, F; Neatu, S; Trandafir, MM; Stanoiu, A

Published: MAY 2020, MATERIALS, 13, DOI: 10.3390/ma13092196

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, H-2-Temperature Programmed Reduction (H-2-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.

14. Nanostructured Cobalt Doped Barium Strontium Titanate Thin Films with Potential in CO2 Detection

Authors: Ciobota, CF; Piticescu, RM; Neagoe, C; Tudor, IA; Matei, A; Dragut, DV; Sobetkii, A; Anghel, EM; Stanoiu, A; Simion, CE; Florea, OG; Bejan, SE

Published: NOV 2020, MATERIALS, 13, DOI: 10.3390/ma13214797

In this work, (Ba0.75Sr0.25) (Ti0.95Co0.05) O-3 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 degrees C and 1000 degrees 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 degrees C, for a fixed CO2 concentration of 3000 ppm, highlighted specific differences between Co-doped BaSrTiO3 treated at 800 degrees C compared to that treated at 1000 degrees 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.

15. Methane Combustion Using Pd Deposited on CeOx-MnOx/La-Al2O3 Pellistors

Authors: Florea, OG; Stanoiu, A; Gheorghe, M; Cobianu, C; Neatu, F; Trandafir, MM; Neatu, S; Florea, M; Simion, CE

Published: NOV 2020, MATERIALS, 13, DOI: 10.3390/ma13214888

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 degrees C and 550 degrees 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.

16. Humidity-Tolerant Ultrathin NiO Gas-Sensing Films

Authors: Wilson, RL; Simion, CE; Stanoiu, A; Taylor, A; Guldin, S; Covington, JA; Carmalt, CJ; Blackman, CS

Published: MAY 22 2020, ACS SENSORS, 5, 1397, DOI: 10.1021/acssensors.0c00172

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 degrees 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.

17. Bulk Versus Surface Modification of Alumina with Mn and Ce Based Oxides for CH4 Catalytic Combustion

Authors: Neatu, S; Trandafir, MM; Stanoiu, A; Florea, OG; Simion, CE; Leonat, LN; Cobianu, C; Gheorghe, M; Florea, M; Neatu, F

Published: JUN 1 2019, MATERIALS, 12, DOI: 10.3390/ma12111771

This study presents the synthesis and characterization of lanthanum-modified alumina supported cerium-manganese mixed oxides, which were prepared by three different methods (coprecipitation, impregnation and citrate-based sol-gel method) followed by calcination at 500 degrees 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 H-2-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-MnOx catalyst, supported on an optimized amount of 4 wt.% La2O3-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 H-2-TPR and therefore more reactive oxygen species.

18. Conductance Model for Single-Crystalline/Compact Metal Oxide Gas-Sensing Layers in the Nondegenerate Limit: Example of Epitaxial SnO2(101)

Authors: Simion, CE; Schipani, F; Papadogianni, A; Stanoiu, A; Budde, M; Oprea, A; Weimar, U; Bierwagen, O; Barsan, N

Published: SEP 2019, ACS SENSORS, 4, 2428, DOI: 10.1021/acssensors.9b01018

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 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.

19. Nanoclustered Pd decorated nanocrystalline Zn doped SnO2 for ppb NO2 detection at low temperature

Authors: Somacescu, S; Ghica, C; Simion, CE; Kuncser, AC; Vlaicu, AM; Stefan, M; Ghica, D; Florea, OG; Mercioniu, IF; Stanoiu, A

Published: SEP 1 2019, SENSORS AND ACTUATORS B-CHEMICAL, 294, 156, DOI: 10.1016/j.snb.2019.05.033

Nanoclustered Pd (2 mol%) was used to decorate Zn doped SnO2 (10 mol% Zn) in order to increase its sensing performances. Zn doped SnO2 built from nanoparticles was prepared by a hydrothermal method using a nonionic surfactant -Brij52 and Tripropylamine (TPA) as co-templates. The presence of well-dispersed Zn2+ ions in the SnO2 matrix leads to a nonstoichiometric surface. Pd was deposited by subsequent wet impregnation using hydrazine as reducing agent. The as obtained powders were deposited as thick layers onto commercial substrates, in order to obtain the sensitive structures. The coexistence of a mixture of valence states (Pd-0, Pd2+ and Pd4+) was highlighted on the surface of the as prepared layers. Several aspects have been followed regarding the Zn and Pd dispersion into the SnO2 matrix: the large scale and low scale morphology (SEM and TEM/HRTEM) in relation with the synthesis route, the obtained crystallographic phases (XRD, SAED) and the way in which the Zn2+ ions are inserted into the SnO2 structure (XRD, XPS, EPR), the spatial distribution of the added chemical elements, Zn and Pd (SEM, STEM, EDS). All these morphological and structural aspects, as well as the Pd surface chemistry, have been correlated with the sensing properties of the nanostructured materials under controlled gas atmosphere. Through this study, we could harvest the specific role of the aforementioned loadings towards selective detection of low NO2 concentrations, between 350 ppb to 5 ppm, at low operating temperature of 100 degrees C, for infield conditions.

20. The Effect of Film Thickness on the Gas Sensing Properties of Ultra-Thin TiO2 Films Deposited by Atomic Layer Deposition

Authors: Wilson, RL; Simion, CE; Blackman, CS; Carmalt, CJ; Stanoiu, A; Di Maggio, F; Covington, JA

Published: MAR 2018, SENSORS, 18, DOI: 10.3390/s18030735

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 degrees 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.

21. H2S sensing mechanism of SnO2-CuWO4 operated under pulsed temperature modulation

Authors: Simion, CE; Somacescu, S; Teodorescu, VS; Osiceanu, P; Stanoiu, A

Published: APR 15 2018, SENSORS AND ACTUATORS B-CHEMICAL, 259, 268, DOI: 10.1016/j.snb.2017.12.027

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. (c) 2017 Elsevier B.V. All rights reserved.

22. Networked mesoporous SnO2 nanostructures templated by Brij (R) 35 with enhanced H2S selective performance

Authors: Stanoiu, A; Simion, CE; Sackmann, A; Baibarac, M; Florea, OG; Osiceanu, P; Teodorescu, VS; Somacescu, S

Published: NOV 1 2018, MICROPOROUS AND MESOPOROUS MATERIALS, 270, 101, DOI: 10.1016/j.micromeso.2018.05.008

Sensors based networked mesoporous SnO2 nanostructures templated by non-ionic surfactant - Brij (R) 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 (< 5 ppm) under 50% relative humidity (RH). 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.

23. H2S selective sensitivity of Cu doped BaSrTiO3 under operando conditions and the associated sensing mechanism

Authors: Stanoiu, A; Piticescu, RM; Simion, CE; Rusti-Ciobota, CF; Florea, OG; Teodorescu, VS; Osiceanu, P; Sobetkii, A; Badilita, V

Published: JUL 1 2018, SENSORS AND ACTUATORS B-CHEMICAL, 264, 336, DOI: 10.1016/j.snb.2018.03.013

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 (T-op = 250 degrees 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. (C) 2018 Elsevier B.V. All rights reserved.

24. Gas sensing mechanism involved in H2S detection with NiO loaded SnO2 gas sensors

Authors: Simion, CE; Florea, OG; Stanoiu, A

Published: 2017, ROMANIAN JOURNAL OF INFORMATION SCIENCE AND TECHNOLOGY, 20, 425, DOI:

SnO2 loaded with 1 wt.% NiO based gas sensors, have been tested under humid background towards different H2S concentrations when operated at 350 degrees C. Knowing that water dissociation takes place, leading to the formation of strongly bonded surface hydroxyl groups, usually hindering the subsequent gas detection, it is of highly importance to understand the role of NiO as "OH groups trapper" element. By using complementary phenomenological investigations (simultaneous electrical resistance and work function measurements) we could emphasize the role of loading element in mitigating the water effects, further reflected through the different H2S interaction mechanisms. As such, the exposure of the SnO2 - 1 wt.% NiO sensors to different relative humidity levels was mirrored through a decrease in surface band bending due to the water donor effect and to a minor increase in the electronic affinity explained by the low adsorption of surface OH groups.

25. Gas sensing properties of NiO/mesoporous SnO2

Authors: Stanoiu, A; Somacescu, S; Simion, CE; Calderon-Moreno, JM; Florea, OG

Published: 2017, 2017 INTERNATIONAL SEMICONDUCTOR CONFERENCE (CAS), 40TH EDITION, 96, DOI:

NiO/mesoporous SnO2 was deposited by incipient wetness impregnation of the SnO2 powder prepared by hydrothermal synthesis route templated by Brij (R) 35. The sensing properties were acquired and the dependence on the operating temperature of the sensitive material was pointed out. Sensitive selectivity towards H2S detection was highlighted at 350 degrees C.

26. Sensors based on mesoporous SnO2-CuWO4 with high selective sensitivity to H2S at low operating temperature

Authors: Stanoiu, A; Simion, CE; Calderon-Moreno, JM; Osiceanu, P; Florea, M; Teodorescu, VS; Somacescu, S

Published: JUN 5 2017, JOURNAL OF HAZARDOUS MATERIALS, 331, 160, DOI: 10.1016/j.jhazmat.2017.02.038

Development of new sensitive materials by different synthesis routes in order to emphasize the sensing properties for hazardous H2S detection is one of a nowadays challenge in the field of gas sensors. In this study we obtained mesoporous SnO2-CuWO4 with selective sensitivity to H2S by an inexpensive synthesis route with low environmental pollution level, using tripropylamine (TPA) as template and polyvinylpyrrolidone (PVP) as dispersant/stabilizer. In order to bring insights about the intrinsic properties, the powders were characterized by means of a variety of complementary techniques such as: X-Ray Diffraction, XRD; Transmission Electron Microscopy, TEM; High Resolution TEM, HRTEM; Raman Spectroscopy, RS; Porosity Analysis by N-2 adsorption/desorption, BET; Scanning Electron Microscopy, SEM and X-ray Photoelectron Spectroscopy, XPS. The sensors were fabricated by powders deposition via screen printing technique onto planar commercial Al2O3 substrates. The sensor signals towards H2S exposure at low operating temperature (100 degrees C) reaches values from 10(5) (for SnWCu600) to 10(6) (for SnWCu800) over the full range of concentrations (5-30 ppm). The recovery processes were induced by a short temperature trigger of 500 degrees C. The selective sensitivity was underlined with respect to the H2S, relative to other potential pollutants and relative humidity (10-70% RH). (C) 2017 Elsevier B.V. All rights reserved.

27. AMMONIA SENSING WITH 5 MOL% LANTHANUM DOPED BARIUM STRONTIUM TITANATE UNDER HUMID AIR BACKGROUND

Authors: Simion, CE; Stanoiu, A; Teodorescu, VS; Rusti, CF; Piticescu, RM; Vasile, E; Vasile, E; Tudor, IA

Published: FEB 2016, REVUE ROUMAINE DE CHIMIE, 61, +, DOI:

Nanostructured Ba0.7Sr0.3TiO3 (BST) with 5 molar % of Lanthanum (La) have been synthesized using a high pressure hydrothermal chemical route. The structural and morphological investigations were performed. Termogravimetry/differential scanning calorimetry and Raman investigations have been also employed to analyse the as-prepared material. The gas sensing investigations have indicated the ability of La doped BST to detect ammonia, when operated at room temperature in humid background. The obtained results were discussed with respect to the possible gas-sill-face interaction mechanism. In addition, the said material showed low cross-sensitivity to other possible interfering gases: methane, carbon monoxide, nitrogen dioxide, sulphur dioxide and hydrogen sulphide.

28. Low level NO2 detection under humid background and associated sensing mechanism for mesoporous SnO2

Authors: Stanoiu, A; Somacescu, S; Calderon-Moreno, JM; Teodorescu, VS; Florea, OG; Sackmann, A; Simion, CE

Published: AUG 2016, SENSORS AND ACTUATORS B-CHEMICAL, 231, 174, DOI: 10.1016/j.snb.2016.02.137

Mesoporous SnO2 prepared by a hydrothermal synthesis route assisted by the ionic surfactant Cetyltrimethylammonium bromide, has rutile-type tetragonal symmetry, small homogeneous nanocrystallite size of similar to 4 nm and good thermal stability. Porosity analysis revealed high surface area similar to 127 m(2)/g and a narrow pore size distribution, with an average pore diameter similar to 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 NO2 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 degrees C, were the sensor signal towards NO2 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 NO2. (C) 2016 Elsevier B.V. All rights reserved.

29. Room temperature ammonia sensing with barium strontium titanate under humid air background

Authors: Simion, CE; Sackmann, A; Teodorescu, VS; Rusti, CF; Stanoiu, A

Published: DEC 1 2015, SENSORS AND ACTUATORS B-CHEMICAL, 220, 1246, DOI: 10.1016/j.snb.2015.07.045

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. (C) 2015 Elsevier B.V. All rights reserved.

30. Tuned Sensitivity Towards H2S and NH3 with Cu Doped Barium Strontium Titanate Materials

Authors: Simion, CE; Sackmann, A; Teodorescu, VS; Rusti, CF; Piticescu, RM; Stanoiu, A

Published: 2014, ELECTROCERAMICS XIV CONFERENCE, 1627, 97, DOI: 10.1063/1.4901664

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 degrees C) under humid conditions (50% RH). The presence of humidity clearly enhances the gas sensitivity to NH3 and H2S detection.

31. Mesopororous (Sn0.9-xIn0.1CuxO2-delta)-O-(I) gas sensors with selectivity to H2S working under humid air conditions

Authors: Somacescu, S; Osiceanu, P; Calderon-Moreno, JM; Sackmann, A; Simion, CE; Stanoiu, A

Published: OCT 2014, MICROPOROUS AND MESOPOROUS MATERIALS, 197, 71, DOI: 10.1016/j.micromeso.2014.06.001

(Sn0.9-xIn0.1CuxO2-delta)-O-(I) (x = 0.02; 0.03 and 0.05 mol%) mesoarchitectures have been synthesized using an ionic surfactant (CTAB) as template for sensing applications. The procedure implies a facile, hydrothermal synthesis route in order to obtain mesoarchitectures built from nanoparticles. The sensors were obtained by screen-printing deposition onto planar Al2O3 substrates provided with interdigitated Pt electrodes on one side and a Pt heater on the back side. The assessment of the well organized porous structure, for the sensitive materials, as specific surface area and uniform pore size distributions were revealed by N-2 adsorption/desorption. The morphological and structural features of the resultant material were investigated by scanning electron microscopy (SEM), Raman spectroscopy and X-ray diffraction (XRD), while the surface chemistry was closely monitored by X-ray photoelectron spectroscopy (XPS). Thus, the incorporation of Cu1+ and In3+ into SnO2 lattice inducing the formation of oxygen vacancies combined with hydroxyl groups adsorbed on the outermost surface layer enhanced the sensitivity and selectivity of our sensing material. The sensors have been tested for NO2, CH4, CO, H2S target gases under humid air conditions very close to real working conditions. The sample with x = 0.05 mol% exhibits very attractive sensing properties for application as selective, low operating temperature (100 degrees C), low cost H2S sensor. With a deeper understanding of the underlying mechanisms and further improvement of the synthesis one can foresee promising applications in catalysis. (C) 2014 Elsevier Inc. All rights reserved.

32. NO2 sensing mechanism of ZnO-Eu2O3 binary oxide under humid air conditions

Authors: Stanoiu, A; Simion, CE; Somacescu, S

Published: SEP 2013, SENSORS AND ACTUATORS B-CHEMICAL, 186, 694, DOI: 10.1016/j.snb.2013.06.083

In order to understand the role of ambient humidity on NO2 detection, electrical resistance and work function changes were recorded simultaneously on ZnO-Eu2O3 material. Thus, surface band bending and electron affinity could be evaluated, according to the Schottky model. The lack of electron affinity changes during NO2 exposure in dry air conditions, reveals that only the free charge concentration is affected. Exposure to NO2 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 NO2 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 NO2 exposure. A gas-sensing interaction mechanism has been proposed. (C) 2013 Elsevier B.V. All rights reserved.

33. NO2 sensing properties of Cr2O3 highlighted by work function investigations

Authors: Stanoiu, A; Simion, CE; Diamandescu, L; Tarabasanu-Mihaila, D; Feder, M

Published: NOV 1 2012, THIN SOLID FILMS, 522, 400, DOI: 10.1016/j.tsf.2012.09.003

Gas sensing peculiarities of chromiumoxide (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 degrees 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 degrees 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. (C) 2012 Elsevier B.V. All rights reserved.

34. Hydrothermal synthesis of ZnO-Eu2O3 binary oxide with straight strips morphology and sensitivity to NO2 gas

Authors: Somacescu, S; Dinescu, A; Stanoiu, A; Simion, CE; Moreno, JMC

Published: DEC 15 2012, MATERIALS LETTERS, 89, 222, DOI: 10.1016/j.matlet.2012.08.100

ZnO-x%Eu2O3 (x=5 wt.%) binary oxide with straight strips morphology was successfully synthesized by hydrothermal route, using cetyltrimethylammonium bromide (CTAB) as template ZnSO4. Eu(NO3)(3)center dot 5H(2)O as inorganic precursors and ammonium hydroxide solution 28% NH3 for adjusting the pH to 11 value. The morphology, structure, photoluminescence and surface chemistry were investigated. The results highlighted that ZnO-Eu2O3 binary oxide shows straight strip morphology and crystalline framework indexed to wurtzite ZnO while Eu2O3 was detected as secondary phase. Surface chemistry revealed the presence of Eu3+. High sensor signal to 3 ppm NO2 together with its low sensitivity towards CO recommend this material as a good candidate in selective detection of NO2. (C) 2012 Elsevier B.V. All rights reserved.

35. Influence of humidity on CO sensing with p-type CuO thick film gas sensors

Authors: Hubner, M; Simion, CE; Tomescu-Stanoiu, A; Pokhrel, S; Barsan, N; Weimar, U

Published: APR 20 2011, SENSORS AND ACTUATORS B-CHEMICAL, 153, 353, DOI: 10.1016/j.snb.2010.10.046

A model for the detection of CO in the presence of humidity is proposed for thick porous film gas sensors based on p-type CuO. The sensing mechanism is investigated by means of simultaneous DC electrical resistance and work function changes measurements combined with appropriate modeling of the conduction in the polycrystalline sensing film. The experiments were performed at 150 degrees C in dry and humid air backgrounds. The conclusion is that, very similarly to the case of undoped SnO2, the explanation of the cross-interference of water in the CO detection is the fact that both react with pre-adsorbed oxygen ions. (C) 2010 Elsevier B.V. All rights reserved.

36. DIFFERENCES IN THE GAS SENSING PROPERTIES READOUT WITH N AND P-TYPE MOX MATERIALS

Authors: Simion, CE; Tomescu-Stanoiu, A

Published: 2010, 2010 INTERNATIONAL SEMICONDUCTOR CONFERENCE (CAS), VOLS 1 AND 2, 204, DOI:

The way in which surface changes are transduced into a variation of an electrical parameter (often electrical resistance) depends on the surface oxidation level, material morphology its semiconductor behaviour, etc. Therefore, if one wants to understand more about the way in which gas-surface interactions affect the gas sensing properties of material, complex phenomenological and spectroscopic investigations are needed. Herein, by simultaneous DC and relative work function investigations we could explain the differences induced by the MOX semiconductor character (n and p-type) to the surface phenomena transduction mechanism.

Dr. Adelina STANOIU

Scientific Researcher I