Layered Sol-Gel Deposition of a Sn, Ti, Zn, and Pr Mixed Oxide Thin Film with Electrical Properties for Gas Sensing.

This article presents a layered mixed oxide thin film composed of Sn, Ti, Zn, and Pr obtained by sol-gel deposition for gas sensing applications. The film was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, UV-Vis spectroscopy, Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), and Electrochemical impedance spectroscopy (EIS). X-ray diffraction results showed the presence of a single crystalline phase with a cassiterite-like structure. Raman spectroscopy revealed characteristic bands of oxygen-deficient SnO2-based nanocrystallites. The band gap energy calculated from UV-Vis spectroscopy is Eg = 3.83 eV. The XPS proved the presence on the surface of all elements introduced by the inorganic precursors as well as their oxidation states. Thus, Sn4+, Ti4+, Zn2+, and Pr3+ were detected on the surface. Moreover, by XPS, we highlighted the presence of OH groups and water adsorbed on the surface. SEM showed the five-layer morphology of the film after five successive depositions. Electrochemical properties were determined by EIS-impedance spectroscopy. The selectivity for gas sensing was also investigated for methane, propane, and formaldehyde and the gas sensing mechanism was explained. The results indicated that the mixed oxide thin film exhibited high sensitivity and selectivity towards specific gases.

Influence of the Deposition Parameters on the Properties of TiO2 Thin Films on Spherical Substrates.

Wastewater treatment targeting reuse may limit water scarcity. Photocatalysis is an advanced oxidation process that may be employed in the removal of traces of organic pollutants, where the material choice is important. Titanium dioxide (TiO2) is a highly efficient photocatalyst with good aqueous stability. TiO2 powder has a high surface area, thus allowing good pollutant adsorption, but it is difficult to filter for reuse. Thin films have a significantly lower surface area but are easier to regenerate and reuse. In this paper, we report on obtaining sol-gel TiO2 thin films on spherical beads (2 mm diameter) with high surface area and easy recovery from wastewater. The complex influence of the substrate morphology (etched up to 48 h in concentrated H2SO4), of the sol dilution with ethanol (1:0 or 1:1), and the number of layers (1 or 2) on the structure, morphology, chemical composition, and photocatalytic performance of the TiO2 thin films is investigated. Etching the substrate for 2 h in H2SO4 leads to uniform, smooth surfaces on which crystalline, homogeneous TiO2 thin films are grown. Films deposited using an undiluted sol are stable in water, with some surface reorganization of the TiO2 aggregates occurring, while the films obtained using diluted sol are partially washed out. By increasing the film thickness through the deposition of a second layer, the roughness increases (from ~50 nm to ~100 nm), but this increase is not high enough to promote higher adsorption or overall photocatalytic efficiency in methylene blue photodegradation (both about 40% after 8 h of UV-Vis irradiation at 55 W/m2). The most promising thin film, deposited on spherical bead substrates (etched for 2 h in H2SO4) using the undiluted sol, with one layer, is highly crystalline, uniform, water-stable, and proves to have good photocatalytic activity.

Chemiresistors with In2O3 Nanostructured Sensitive Films Used for Ozone Detection at Room Temperature.

Detection of greenhouse gases is essential because harmful gases in the air diffuse rapidly over large areas in a short period of time, causing air pollution that will induce climate change with catastrophic consequences over time. Among the materials with favorable morphologies for gas detection (nanofibers, nanorods, nanosheets), large specific surfaces, high sensitivity and low production costs, we chose nanostructured porous films of In2O3 obtained by the sol-gel method, deposited on alumina transducers, with gold (Au) interdigitated electrodes (IDE) and platinum (Pt) heating circuits. Sensitive films contained 10 deposited layers, involving intermediate and final thermal treatments to stabilize the sensitive film. The fabricated sensor was characterized using AFM, SEM, EDX and XRD. The film morphology is complex, containing fibrillar formations and some quasi-spherical conglomerates. The deposited sensitive films are rough, thus favoring gas adsorption. Ozone sensing tests were performed at different temperatures. The highest response of the ozone sensor was recorded at room temperature, considered to be the working temperature for this specific sensor.

Effect of Al Incorporation on the Structural and Optical Properties of Sol-Gel AZO Thin Films.

ZnO and Al-doped ZnO (AZO) thin films were prepared using the sol-gel method and deposited on a Silicon (Si(100)) substrate using the dipping technique. The structure, morphology, thickness, optical constants in the spectral range 300-1700 nm, bandgap (Eg) and photoluminescence (PL) properties of the films were analyzed using X-ray diffractometry (XRD), X-ray fluorescence (XRF), atomic force microscopy (AFM), scanning electron microscopy (SEM), spectroscopic ellipsometry (SE), Raman analysis and PL spectroscopy. The results of the structure and morphology analyses showed that the thin films are polycrystalline with a hexagonal wurtzite structure, as well as continuous and homogeneous. The PL background and broader peaks observable in the Raman spectra of the AZO film and the slight increase in the optical band gap of the AZO thin film, compared to undoped ZnO, highlight the effect of defects introduced into the ZnO lattice and an increase in the charge carrier density in the AZO film. The PL emission spectra of the AZO thin film showed a strong UV line corresponding to near-band-edge ZnO emission along with weak green and red emission bands due to deep-level defects, attributed to the oxygen-occupied zinc vacancies (OZn lattice defects).

Antibacterial Activity of ZnSe, ZnSe-TiO2 and TiO2 Particles Tailored by Lysozyme Loading and Visible Light Irradiation.

ZnSe, ZnSe-TiO2 microspheres and nanostructured TiO2 obtained by hydrothermal and sol-gel methods were tested against Staphylococcus aureus ATCC 25923 and Micrococcus lysodeikticus ATCC 4698 before and after lysozyme (Lys) loading. Morphological characterization of inorganic matrices and hybrid organic-inorganic complexes were performed by microscopy techniques (SEM, AFM and Dark Field Hyperspectral Microscopy). Light absorption properties of ZnSe, ZnSe-TiO2 and TiO2 powders were assessed by UV-visible spectroscopy and their ability to generate reactive oxygen species (•OH and O2•-) under visible light irradiation was investigated. Antibacterial activity of ZnSe, ZnSe-TiO2, TiO2, Lys/ZnSe, Lys/ZnSe-TiO2 and Lys/TiO2 samples under exposure to visible light irradiation (λ > 420 nm) was tested against Staphylococcus aureus and Micrococcus lysodeikticus and correlated with ROS photogeneration.

Structural, Optical, and Sensing Properties of Nb-Doped ITO Thin Films Deposited by the Sol-Gel Method.

The aim of the present study was the development of Nb-doped ITO thin films for carbon monoxide (CO) sensing applications. The detection of CO is imperious because of its high toxicity, with long-term exposure having a negative impact on human health. Using a feasible sol-gel method, the doped ITO thin films were prepared at room temperature and deposited onto various substrates (Si, SiO2/glass, and glass). The structural, morphological, and optical characterization was performed by the following techniques: X-ray diffractometry (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV/Vis/NIR spectroscopic ellipsometry (SE). The analysis revealed a crystalline structure and a low surface roughness of the doped ITO-based thin films. XTEM analysis (cross-sectional transmission electron microscopy) showed that the film has crystallites of the order of 5-10 nm and relatively large pores (around 3-5 nm in diameter). A transmittance value of 80% in the visible region and an optical band-gap energy of around 3.7 eV were found for dip-coated ITO/Nb films on SiO2/glass and glass supports. The EDX measurements proved the presence of Nb in the ITO film in a molar ratio of 3.7%, close to the intended one (4%). Gas testing measurements were carried out on the ITO undoped and doped thin films deposited on glass substrate. The presence of Nb in the ITO matrix increases the electrical signal and the sensitivity to CO detection, leading to the highest response for 2000 ppm CO concentration at working temperature of 300 °C.

Cobalt- and Copper-Based Chemiresistors for Low Concentration Methane Detection, a Comparison Study.

Methane is a colorless/odorless major greenhouse effect gas, which can explode when it accumulates at concentrations above 50,000 ppm. Its detection cannot be performed without specialized equipment, namely sensing devices. A series of MOX sensors (chemiresistors type), with CoO and CuO sensitive films were obtained using an eco-friendly and low-cost deposition technique (sol-gel). The sensing films were characterized using AFM and SEM as thin film. The transducers are based on an alumina wafer, with Au or Pt interdigital electrodes (IDE) printed onto the alumina surface. The sensor response was recorded upon sensor exposure to different methane concentrations (target gas) under lab conditions (dried target and carrier gas from gas cylinders), in a constant gas flow, with target gas concentrations in the 5-2000 ppm domain and a direct current (DC) applied to the IDE as sensor operating voltage. Humidity and cross-sensitivity (CO2) measurements were performed, along with sensor stability measurements, to better characterize the obtained sensors. The obtained results emphasize good 3-S sensor parameters (sensitivity, partial selectivity and stability) and also short response time and complete sensor recovery, completed by a low working temperature (220 °C), which are key factors for further development of a new commercial chemiresistor for methane detection.

Bioactive Coatings Based on Nanostructured TiO2 Modified with Noble Metal Nanoparticles and Lysozyme for Ti Dental Implants.

This work presents the synthesis of nanostructured TiO2 modified with noble metal nanoparticles (Au, Ag) and lysozyme and coated on titanium foil. Moreover, the specific structural and functional properties of the resulting inorganic and hybrid materials were explored. The purpose of this study was to identify the key parameters for developing engineered coatings on titanium foil appropriate for efficient dental implants with intrinsic antibacterial activity. TiO2 nanoparticles obtained using the sol-gel method were deposited on Ti foil and modified with Au/Ag nanoparticles. Morphological and structural investigations (scanning electron and atomic force microscopies, X-ray diffraction, photoluminescence, and UV-Vis spectroscopies) were carried out for the characterization of the resulting inorganic coatings. In order to modify their antibacterial activity, which is essential for safe dental implants, the following aspects were investigated: (a) singlet oxygen (1O2) generation by inorganic coatings exposed to visible light irradiation; (b) the antibacterial behavior emphasized by titania-based coatings deposited on titanium foil (TiO2/Ti foil; Au-TiO2/Ti foil, Ag-TiO2/Ti foil); (c) the lysozyme bioactivity on the microbial substrate (Micrococcus lysodeicticus) after its adsorption on inorganic surfaces (Lys/TiO2/Ti foil; Lys/Au-TiO2/Ti foil, Lys/Ag-TiO2/Ti foil); (d) the enzymatic activity of the above-mentioned hybrids materials for the hydrolysis reaction of a synthetic organic substrate usually used for monitoring the lysozyme biocatalytic activity, namely, 4-Methylumbelliferyl ß-D-N,N',N″-triacetylchitotrioside [4-MU-ß- (GlcNAc)3]. This was evaluated by identifying the presence of a fluorescent reaction product, 7-hydroxy-4-metyl coumarin (4-methylumbelliferone).

Multifunctional Zn-Doped ITO Sol-Gel Films Deposited on Different Substrates: Application as CO2-Sensing Material.

Undoped and Zn-doped ITO (ITO:Zn) multifunctional thin films were successfully synthesized using the sol-gel and dipping method on three different types of substrates (glass, SiO2/glass, and Si). The effect of Zn doping on the optoelectronic, microstructural, and gas-sensing properties of the films was investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), spectroscopic ellipsometry (SE), Raman spectroscopy, Hall effect measurements (HE), and gas testing. The results showed that the optical constants, the transmission, and the carrier numbers were correlated with the substrate type and with the microstructure and the thickness of the films. The Raman study showed the formation of ITO films and the incorporation of Zn in the doped film (ITO:Zn), which was confirmed by EDX analysis. The potential use of the multifunctional sol-gel ITO and ITO:Zn thin films was proven for TCO applications or gas-sensing experiments toward CO2. The Nyquist plots and equivalent circuit for fitting the experimental data were provided. The best electrical response of the sensor in CO2 atmosphere was found at 150 °C, with activation energy of around 0.31 eV.

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

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.

Eco-friendly synthesized spherical ZnO materials: Effect of the core-shell to solid morphology transition on antimicrobial activity.

ZnO materials with spherical morphology, core-shell and solid, disperse or interconnected, were obtained by a completely green synthesis via a carbohydrate-template route. Morphology, structure and optical properties, as well as antimicrobial potential and cytocompatibility were investigated. The antimicrobial efficiency of the obtained materials was screened against a large spectrum of reference and clinical microbial strains, both susceptible and exhibiting resistance phenotypes of clinical and epidemiological interest, in planktonic and biofilm state. Their biocidal activity is strongly dependent of material's characteristics and target microorganism. One of the most valuable findings of our study is the good antibiofilm activity of the obtained nanostructures, which in some cases was superior to that noted against planktonic cells, despite the well-known high tolerance of biofilm-embedded cells to different stressor agents. Another important finding is the excellent efficiency against three Gram-negative, respectively Pseudomonas aeruginosa, Acinetobacter baumannii, and Klebsiella pneumoniae and two Gram-positive species, i.e. Staphylococcus aureus and Enteroccus faecium included in the ESKAPE list of the most dangerous resistant pathogens, requiring global surveillance and urgent need for the development of novel antimicrobial agents. Our study offers the first insight regarding the high therapeutic potential of ZnO nanoparticles against the fearful nosocomial pathogen A. baumannii. The cytocompatibility of the developed materials in terms of cell morphology, viability and proliferation, revealed a comparable dose-dependent cellular response, at the active antimicrobial concentrations, only a low effect on cell viability is evidenced. Overall, our data demonstrated the potential of the materials for antimicrobial applications and also that their biotoxicity can be modulated directly through their morpho-structural characteristics.

Tubular and Spherical SiO2 Obtained by Sol Gel Method for Lipase Immobilization and Enzymatic Activity.

A wide range of hybrid biomaterials has been designed in order to sustain bioremediation processes by associating sol-gel SiO2 matrices with various biologically active compounds (enzymes, antibodies). SiO2 is a widespread, chemically stable and non-toxic material; thus, the immobilization of enzymes on silica may lead to improving the efficiency of biocatalysts in terms of endurance and economic costs. Our present work explores the potential of different hybrid morphologies, based on hollow tubes and solid spheres of amorphous SiO2, for enzyme immobilization and the development of competitive biocatalysts. The synthesis protocol and structural characterization of spherical and tubular SiO2 obtained by the sol gel method were fully investigated in connection with the subsequent immobilization of lipase from Rhizopus orizae. The immobilization is conducted at pH 6, lower than the isoelectric point of lipase and higher than the isoelectric point of silica, which is meant to sustain the physical interactions of the enzyme with the SiO2 matrix. The morphological, textural and surface properties of spherical and tubular SiO2 were investigated by SEM, nitrogen sorption, and electrokinetic potential measurements, while the formation and characterization of hybrid organic-inorganic complexes were studied by UV-VIS, FTIR-ATR and fluorescence spectroscopy. The highest degree of enzyme immobilization (as depicted from total organic carbon) was achieved for tubular morphology and the hydrolysis of p-nitrophenyl acetate was used as an enzymatic model reaction conducted in the presence of hybrid lipase⁻SiO2 complex.

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

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 N2 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°C) reaches values from 105 (for SnWCu600) to 106 (for SnWCu800) over the full range of concentrations (5-30ppm). The recovery processes were induced by a short temperature trigger of 500°C. The selective sensitivity was underlined with respect to the H2S, relative to other potential pollutants and relative humidity (10-70% RH).

Nanostructured SnO2-ZnO composite gas sensors for selective detection of carbon monoxide.

A series of SnO2-ZnO composite nanostructured (thin) films with different amounts of SnO2 (from 0 to 50 wt %) was prepared and deposited on a miniaturized porous alumina transducer using the sol-gel and dip coating method. The transducer, developed by our research group, contains Au interdigital electrodes on one side and a Pt heater on the other side. The sensing films were characterized using SEM and AFM techniques. Highly toxic and flammable gases (CO, CO2, CH4, and C3H8) were tested under lab conditions (carrier gas was dry air) using a special gas sensing cell developed by our research group. The gas concentrations varied between 5 and 2000 ppm and the optimum working temperatures were in the range of 210-300 °C. It was found that the sensing performance was influenced by the amount of oxide components present in the composite material. Improved sensing performance was achieved for the ZnO (98 wt %)-SnO2 (2 wt %) composite as compared to the sensors containing only the pristine oxides. The sensor response, cross-response and recovery characteristics of the analyzed materials are reported. The high sensitivity (RS = 1.21) to low amounts of CO (5 ppm) was reported for the sensor containing a composite sensitive film with ZnO (98 wt %)-SnO2 (2 wt %). This sensor response to CO was five times higher as compared to its response to CO2, CH4, and C3H8, thus the sensor is considered to be selective for CO under these test conditions.

Tunable ZnO spheres with high anti-biofilm and antibacterial activity via a simple green hydrothermal route.

A family of distinct ZnO morphologies - hollow, compartmented, core-shell and full solid ZnO spheres, dispersed or interconnected - is obtained by a simple hydrothermal route, in the presence of the starch biopolymer. The zinc-carbonaceous precursors were characterized by infrared spectroscopy, thermal analysis and scanning electron microscopy, while the ZnO spheres, obtained after the thermal processing, were investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, UV-VIS spectroscopy, photoluminescence measurements, antimicrobial, anti-biofilm and flow cytometry tests. The formation mechanism proposed for this versatile synthesis route is based on the gelling ability of amylose, one of the starch template constituents, responsible for the effective embedding of zinc cations into starch prior to its hydrothermal carbonization. The simple variation of the raw materials concentration dictates the type of ZnO spheres. The micro-sized ZnO spheres exhibit high antibacterial and anti-biofilm activity against Gram-positive (Staphylococcus aureus, Bacillus subtilis) and Gram-negative (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa) reference and methicillin resistant clinical strains especially for Gram-negative biofilms (P. aeruginosa), demonstrating great potential for new ZnO anti-biofilm formulations.

Biological Behaviour and Enhanced Anticorrosive Performance of the Nitrided Superelastic Ti-23Nb-0.7Ta-2Zr-0.5N Alloy.

The influence of gas nitriding surface treatment on the superelastic Ti-23Nb-0.7Ta-2Zr-0.5N alloy was evaluated. A thorough characterization of bare and nitrided Ti-based alloy and pure Ti was performed in terms of surface film composition and morphology, electrochemical behaviour, and short term osteoblast response. XPS analysis showed that the nitriding treatment strongly influenced the composition (nitrides and oxynitrides) and surface properties both of the substrate and of the bulk alloy. SEM images revealed that the nitrided surface appears as a similar dotted pattern caused by the formation of N-rich domains coexisting with less nitrided domains, while before treatment only topographical features could be observed. All the electrochemical results confirmed the high chemical stability of the nitride and oxynitride coating and the superiority of the applied treatment. The values of the corrosion parameters ascertained the excellent corrosion resistance of the coated alloy in the real functional conditions from the human body. Cell culture experiments with MG63 osteoblasts demonstrated that the studied biomaterials do not elicit any toxic effects and support cell adhesion and enhanced cell proliferation. Altogether, these data indicate that the nitrided Ti-23Nb-0.7Ta-2Zr-0.5N alloy is the most suitable substrate for application in bone implantology.

Quaternary Ti-20Nb-10Zr-5Ta alloy during immersion in simulated physiological solutions: formation of layers, dissolution and biocompatibility.

Samples of the quaternary Ti-20Nb-10Zr-5Ta alloy were immersed in Hanks' simulated physiological solution and in minimum essential medium (MEM) for 25 days. Samples of Ti metal served as controls. During immersion, the concentration of ions dissolved in MEM was measured by inductively coupled plasma mass spectrometry, while at the end of the experiment the composition of the surface layers was analyzed by X-ray photoelectron spectroscopy, and their morphology by scanning electron microscopy equipped for chemical analysis. The surface layer formed during immersion was comprised primarily of TiO2 but contained oxides of alloying elements as well. The degree of oxidation differed for different metal cations; while titanium achieved the highest valency, tantalum remained as the metal or is oxidized to its sub-oxides. Calcium phosphate was formed in both solutions, while formation of organic-related species was observed only in MEM. Dissolution of titanium ions was similar for metal and alloy. Among alloying elements, zirconium dissolved in the largest quantity. The long-term effects of alloy implanted in the recipient's body were investigated in MEM, using two types of human cells-an osteoblast-like cell line and immortalized pulmonary fibroblasts. The in vitro biocompatibility of the quaternary alloy was similar to that of titanium, since no detrimental effects on cell survival, induction of apoptosis, delay of growth, or change in alkaline phosphatase activity were observed on incubation in MEM.

Structure and surface chemistry in crystalline mesoporous (CeO(2-δ))-YSZ.

Mesoporous metal oxides (CeO(2-δ))-YSZ have been synthesized by a versatile direct synthesis method using ionic cetyltrimethylammonium bromide (CTAB) and different nonionic (block copolymers) as surfactants and urea as hydrolyzing agent. The synthesis was realized at pH=9 using tetraethylammonium hydroxide (TEAOH) as pH mediator. Calcination at 550 °C led to the formation of crystalline metal oxides with uniform mesoporosity. The obtained materials have been characterized by thermogravimetric analysis (TG-DTG), wide and small-angle X-ray diffraction (XRD), Raman spectroscopy, Brunauer, Emmett and Teller (BET) surface area analysis, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). All the obtained materials exhibits mesoporous structure, crystalline structure indexed in a cubic symmetry, showing a high surface area, a uniform and narrow pore size distribution, spherical morphology typical for the mesoporous materials. The crystalline and mesoporous structures, surface chemistry and stoichiometry for the samples synthesized using ionic and nonionic surfactants have been discussed.