Sol-Gel Multilayered Niobium (Vanadium)-Doped TiO2 for CO Sensing and Photocatalytic Degradation of Methylene Blue.

Multilayered TiO2 films doped either with Niobium or Vanadium (1.2 at. %) were deposited by the sol-gel dip coating method on c-Si and glass substrates. The films on glass substrates were tested for CO sensing and photocatalytic degradation of methylene blue. X-ray diffraction data analysis showed that all the TiO2:Nb(V) films were nanocrystalline in the anatase phase, with a uniform and compact microstructure and a homogeneous superficial structure of small grains with diameters in the range of 13-19 nm. For the electrical characterization, the TiO2:Nb(V) films were incorporated in Metal-Insulator-Semiconductor (MIS) structures. The specific resistivity is of the order of 104 Ωcm and its value decreases with increasing the electrical field, which testifies to the injection of electrons into these layers. From the analysis of the current-voltage curves taken at different temperature- and frequency-dependent capacitance-voltage and conductance-voltage characteristics, the density and parameters of deep levels in these TiO2 films are evaluated and the electron charge transport mechanism is established. It was shown that the current in these TiO2:Nb(V)-Si MIS structures is mainly carried out by inter-trap tunneling via deep levels energetically distributed in the TiO2 bandgap. Testing these sol-gel TiO2:Nb(V) layers for gas sensing and photocatalytic capabilities proved that they could serve such purposes. In particular, the results of the V-doped sol-gel TiO2 film confirm its CO detection capability, which is rarely reported in the literature. For the photodegradation of methylene blue, the Nb-doped TiO2 samples were superior, with nearly double the photocatalytic efficiency of undoped TiO2.

Advanced Nanostructured Coatings Based on Doped TiO2 for Various Applications.

For many years, TiO2-based materials and improving their properties in order to expand their application areas have been the focus of numerous research groups. Various innovative approaches have been proposed to improve the photocatalytic and gas-sensing properties of TiO2 nanostructures. In this review, we aim to synthesize the available information in the literature, paying special attention to the sol-gel technology, which is one of the most frequently used methods for TiO2 synthesis. The influence of dopants on the structural, morphological, optical, and electrical properties of TiO2 and the way to modify them in a controlled manner are briefly discussed. The role of shallow and/or deep energy levels within the TiO2 bandgap in the electron transport behavior of doped TiO2 is emphasized. Selected research on photocatalytic applications in water disinfection, wastewater treatment, and self-sterilizing coatings that contribute to improving the quality of human life and environmental preservation is highlighted. A survey of biosensors that are closely related to medical applications such as cancer detection, implantology, and osteogenesis is also provided. Finally, the pressing problems that need to be solved in view of the future development of TiO2-based nanostructures are listed.

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.

Various Applications of ZnO Thin Films Obtained by Chemical Routes in the Last Decade.

This review addresses the importance of Zn for obtaining multifunctional materials with interesting properties by following certain preparation strategies: choosing the appropriate synthesis route, doping and co-doping of ZnO films to achieve conductive oxide materials with p- or n-type conductivity, and finally adding polymers in the oxide systems for piezoelectricity enhancement. We mainly followed the results of studies of the last ten years through chemical routes, especially by sol-gel and hydrothermal synthesis. Zinc is an essential element that has a special importance for developing multifunctional materials with various applications. ZnO can be used for the deposition of thin films or for obtaining mixed layers by combining ZnO with other oxides (ZnO-SnO2, ZnO-CuO). Also, composite films can be achieved by mixing ZnO with polymers. It can be doped with metals (Li, Na, Mg, Al) or non-metals (B, N, P). Zn is easily incorporated in a matrix and therefore it can be used as a dopant for other oxidic materials, such as: ITO, CuO, BiFeO3, and NiO. ZnO can be very useful as a seed layer, for good adherence of the main layer to the substrate, generating nucleation sites for nanowires growth. Thanks to its interesting properties, ZnO is a material with multiple applications in various fields: sensing technology, piezoelectric devices, transparent conductive oxides, solar cells, and photoluminescence applications. Its versatility is the main message of this review.

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).

Multi-Parametric Exploration of a Selection of Piezoceramic Materials for Bone Graft Substitute Applications.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties-piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of ~50%), which yielded a promising compressive strength of ~20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

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.

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.

Alkali Niobate Powder Synthesis Using an Emerging Microwave-Assisted Hydrothermal Method.

For more than five decades, alkali niobate-based materials (KxNa1-xNbO3) have been one of the most promising lead-free piezoelectric materials researched to be used in electronics, photocatalysis, energy storage/conversion and medical applications, due to their important health and environmentally friendly nature. In this paper, our strategy was to synthetize the nearest reproductible composition to KxNa1-xNbO3 (KNN) with x = 0.5, placed at the limit of the morphotropic phase boundary (MPB) with the presence of both polymorphic phases, orthorhombic and tetragonal. The wet synthesis route was chosen to make the mix crystal powders, starting with the suspension preparation of Nb2O5 powder and KOH and NaOH alkaline solutions. Hydrothermal microwave-assisted maturation (HTMW), following the parameter variation T = 200-250 °C, p = 47-60 bar and dwelling time of 30-90 min, was performed. All powders therefore synthesized were entirely KxN1-xNbO3 solid solutions with x = 0.06-0.69, and the compositional, elemental, structural and morphological characterization highlighted polycrystalline particle assemblage with cubic and prismatic morphology, with sizes between 0.28 nm and 2.95 µm and polymorphic O-T phase coexistence, and a d33 piezoelectric constant under 1 pC/N of the compacted unsintered and unpoled discs were found.

GeSn/SiO2 Multilayers by Magnetron Sputtering Deposition for Short-Wave Infrared Photonics.

The development of short-wave infrared (SWIR) photonics based on GeSn alloys is of high technological interest for many application fields, such as the Internet of things or pollution monitoring. The manufacture of crystalline GeSn is a major challenge, mainly because of the low miscibility of Ge and Sn. The use of embedded GeSn nanocrystals (NCs) by magnetron sputtering is a cost-effective and efficient method to relax the growth conditions. We report on the use of GeSn/SiO2 multilayer deposition as a way to control the NC size and their insulation. The in situ prenucleation of NCs during deposition was followed by ex situ rapid thermal annealing. The nanocrystallization of 20×(11nm_Ge0.865Sn0.135/1.5nm_SiO2) multilayers leads to formation of GeSn NCs with ∼16% Sn concentration and ∼9 nm size. Formation of GeSn domes that are vertically correlated contributes to the nanocrystallization process. The absorption limit of ∼0.4 eV in SWIR found by ellipsometry is in agreement with the spectral photosensitivity. The ITO/20×(GeSn NC/SiO2)/p-Si/Al diodes show a maximum value of the SWIR photosensitivity at a reverse voltage of 0.5 V, with extended sensitivity to wavelengths longer than 2200 nm. The multilayer diodes have higher photocurrent efficiency compared to diodes based on a thick monolayer of GeSn NCs.

The Effect of Different Coupling Agents on Nano-ZnO Materials Obtained via the Sol-Gel Process.

Hybrid nanomaterials based on zinc oxide were synthesized via the sol-gel method, using different silane coupling agents: (3-glycidyloxypropyl)trimethoxysilane (GPTMS), phenyltriethoxysilane (PhTES), octyltriethoxysilane (OTES), and octadecyltriethoxysilane (ODTES). Morphological properties and the silane precursor type effect on the particle size were investigated using dynamic light scattering (DLS), environmental scanning electron microscopy (ESEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). The bonding characteristics of modified ZnO materials were investigated using Fourier transform infrared spectroscopy (FTIR). The final solutions were deposited on metallic substrate (aluminum) in order to realize coatings with various wettability and roughness. The morphological studies, obtained by ESEM and TEM analysis, showed that the sizes of the ZnO nanoparticles are changed as function of silane precursor used in synthesis. The thermal stability of modified ZnO materials showed that the degradation of the alkyl groups takes place in the 300-500 °C range. Water wettability study revealed a contact angle of 142 ± 5° for the surface covered with ZnO material modified with ODTES and showed that the water contact angle increases as the alkyl chain from the silica precursor increases. These modified ZnO materials, therefore, can be easily incorporated in coatings for various applications such as anti-corrosion and anti-icing.