LiNbO3 Thin Films through a Sol-Gel/Spin-Coating Approach Using a Novel Heterobimetallic Lithium-Niobium Precursor.

Lithium niobate is a lead-free material which has attracted considerable attention due to its excellent optical, piezoelectric, and ferroelectric properties. This research is devoted to the synthesis through an innovative sol-gel/spin-coating approach of polycrystalline LiNbO3 films on Si substrates. A novel single-source hetero-bimetallic precursor containing lithium and niobium was synthesized and applied to the sol-gel synthesis. The structural, compositional, and thermal characteristics of the precursor have been tested through attenuated total reflection, X-ray photoelectron spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The LiNbO3 films have been characterized from a structural point of view with combined X-ray diffraction and Raman spectroscopy. Field-emission scanning electron microscopy, energy dispersive X-ray analysis, and X-ray photoelectron spectroscopy have been used to study the morphological and compositional properties of the deposited films.

Stimuli-Responsive Properties of a Zinc(II) Salen-Type Schiff-Base Complex and Vapochromic Detection of Volatile Organic Compounds.

This contribution reports, through a combined thermogravimetric analysis, differential scanning calorimetry, UV-vis, powder X-ray diffraction, and Rietveld refinement analysis, on the stimuli-responsive chromic properties of a substituted Zn(salmal) Schiff-base Lewis acidic complex with unique and distinct thermo- and vapochromic characteristics. The solid complex obtained in air or by evaporation of the solvent from their THF solutions shows a marked thermochromism associated with a phase transition, unusually triggered by the reversible desorption/adsorption of one lattice water molecule. In contrast, the anhydrous solid, achieved from THF solutions of the complex by evaporation of the solvent under anhydrous conditions, behaves very differently as it does not show any absorption of water or thermochromism and exhibits varied vapochromic properties. Detection of volatile organic compounds having Lewis basicity is demonstrated by using the anhydrous solid or the related cast films on glass or paper substrates. In both cases, a marked vapochromism is observed upon exposure to vapors of various volatile species and involves well-defined optical absorptions and naked-eye color changes, also allowing the discrimination of primary aliphatic amines. Vapochromic behavior with the formation of stable, stoichiometric adducts is also demonstrated for both the solid obtained in air and the anhydrous solid or for the related cast films after exposure to vapors of pyridine.

Self-assembled BiFeO3@MIL-101 nanocomposite for antimicrobial applications under natural sunlight.

In this paper, we report on the synthesis of a new hybrid photocatalytic material activated by natural sunlight irradiation. The material consists of multiferroic nanoparticles of bismuth ferrite (BFO) modified through the growth of the Fe-based MIL-101 framework. Material characterization, conducted using various techniques (X-ray diffraction, transmission electron microscopy, FTIR, and X-ray photoelectron spectroscopies), confirmed the growth of the MIL-101 metal-organic framework on the BFO surface. The obtained system possesses the intrinsic photo-degradative properties of BFO nanoparticles significantly enhanced by the presence of MIL-101. The photocatalytic activity of this material was tested in antibacterial experiments conducted under natural sunlight exposure within the nanocomposite concentration range of 100-0.20 µg/ml. The MIL-modified BFO showed a significant decrease in both Minimum Inhibiting Concentration and Minimum Bactericide Concentration values compared to bare nanoparticles. This confirms the photo-activating effect of the MIL-101 modification. In particular, they show an increased antimicrobial activity against the tested Gram-positive species and the ability to begin to inhibit the growth of the four Escherichia coli strains, although at the maximum concentration tested. These results suggest that the new nanocomposite BiFeO3@MOF has been successfully developed and has proven to be an effective antibacterial agent against a wide range of microorganisms and a potential candidate in disinfection processes.

Green Ultrasound-Assisted Synthesis of Rare-Earth-Based MOFs.

Rare-earth (RE)-based metal organic frameworks (MOFs) are quickly gaining popularity as flexible functional materials in a variety of technological fields. These MOFs are useful for more than just conventional uses like gas sensors and catalyst materials; in fact, they also show significant promise in emerging technologies including photovoltaics, optical, and biomedical applications. Using yttrium and europium as ionic host centres and dopants, respectively, and 1,3,5-benzenetricarboxylic acid (H3-BTC) as an organic linker, we describe a simple and green approach for the fabrication of RE-MOFs. Specifically, Y-BTCs and Eu-doped Y-BTCs MOFs have been synthesised in a single step using an eco-friendly method that makes use of ultrasound technology. To establish a correlation between the morphological and structural properties and reaction conditions, a range of distinct reaction periods has been employed for the synthetic processes. Detailed analyses of the synthesised samples through powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM), and Fourier-transform infrared spectroscopy (FT-IR) have confirmed the phase formation. Furthermore, thermal analyses such as thermogravimetric analysis (TGA) have been employed to evaluate the thermal stability and structural modifications of the Y-BTC and Eu-doped Y-BTC samples. Finally, the luminescent properties of the synthesised samples doped with Eu3+ have been assessed, providing an evaluation of their characteristics. As a proof of concept, an Eu-doped Y-BTC sample has been applied for the sensing of nitrobenzene as a molecule test of nitro derivatives.

Highly Tunable MOCVD Process of Vanadium Dioxide Thin Films: Relationship between Structural/Morphological Features and Electrodynamic Properties.

The monoclinic structures of vanadium dioxide are widely studied as appealing systems due to a plethora of functional properties in several technological fields. In particular, the possibility to obtain the VO2 material in the form of thin film with a high control of structure and morphology represents a key issue for their use in THz devices and sensors. Herein, a fine control of the crystal habit has been addressed through an in-depth study of the metal organic chemical vapor deposition (MOCVD) synthetic approach. The focus is devoted to the key operative parameters such as deposition temperature inside the reactor in order to stabilize the P21/c or the C2/m monoclinic VO2 structures. Furthermore, the compositional purity, the morphology and the thickness of the VO2 films have been assessed through energy dispersive X-ray (EDX) analyses and field-emission scanning electron microscopy (FE-SEM), respectively. THz time domain spectroscopy is used to validate at very high frequency the functional properties of the as-prepared VO2 films.

Metalorganic Chemical Vapor Deposition Approach to the Synthesis of Perovskite BaCeO3 and BaCe0.8Y0.2O3 Thin Films.

In the present energetic scenario, the development of materials with high potentiality in the technological fields of energy conversion processes, production and storage of hydrogen, are of great interest in the scientific community. In particular, we report for the first time the fabrication of crystalline and homogeneous barium-cerate-based materials in the form of thin films on various substrates. Starting from the ß-diketonate precursor sources Ce(hfa)3diglyme, Ba(hfa)2tetraglyme and Y(hfa)3diglyme (Hhfa = 1,1,1,5,5,5-hexafluoroacetylacetone; diglyme = bis(2-methoxyethyl)ether; tetraglyme = 2,5,8,11,14-pentaoxapentadecane), a metalorganic chemical vapor deposition (MOCVD) approach has been successfully applied to the fabrication of BaCeO3 and doped BaCe0.8Y0.2O3 systems in the form of thin films. Structural, morphological and compositional analyses allowed for an accurate determination of the properties of deposited layers. The present approach represents a simple, easily scalable, and industrially appealing process for the production of compact and homogeneous barium cerate thin films.

A Low Temperature Growth of Cu2O Thin Films as Hole Transporting Material for Perovskite Solar Cells.

Copper oxide thin films have been successfully synthesized through a metal-organic chemical vapor deposition (MOCVD) approach starting from the copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), Cu(tmhd)2, complex. Operative conditions of fabrication strongly affect both the composition and morphologies of the copper oxide thin films. The deposition temperature has been accurately monitored in order to stabilize and to produce, selectively and reproducibly, the two phases of cuprite Cu2O and/or tenorite CuO. The present approach has the advantages of being industrially appealing, reliable, and fast for the production of thin films over large areas with fine control of both composition and surface uniformity. Moreover, the methylammonium lead iodide (MAPI) active layer has been successfully deposited on the ITO/Cu2O substrate by the Low Vacuum Proximity Space Effusion (LV-PSE) technique. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM) analyses have been used to characterize the deposited films. The optical band gap (Eg), ranging from 1.99 to 2.41 eV, has been determined through UV-vis analysis, while the electrical measurements allowed to establish the p-type conductivity behavior of the deposited Cu2O thin films with resistivities from 31 to 83 Ω cm and carrier concentration in the order of 1.5-2.8 × 1016 cm-3. These results pave the way for potential applications of the present system as a hole transporting layer combined with a perovskite active layer in emergent solar cell technologies.

Journey of a molecule from the solid to the gas phase and vice versa: direct estimation of vapor pressure of alkaline-earth metalorganic precursors for atmospheric pressure vapor phase deposition of fluoride films.

Atmospheric pressure (AP) vapor phase processes such as spatial atomic layer deposition (S-ALD) and AP-metalorganic chemical vapor deposition (AP-MOCVD) are becoming increasingly appealing for their use in a variety of academic and industrial applications. Evaluation of precursor vapour pressures is crucial for their application in AP processes and to this aim the Langmuir equation has been applied as a simple and straightforward method for estimating the vapor pressure and vaporization enthalpy of various metalorganic precursors. Using benzoic acid as a calibration reference, the vapour pressure-temperature curves for several alkaline-earth ß-diketonate fluorinated compounds, with molecular formula "M(hfa)2·L" (with M = Mg, Ca, Sr, Ba; Hhfa = 1,1,1,5,5,5-hexafluoroacetylacetone and L = diglyme, triglyme, and tetraglyme) are derived from their termogravimetric curves. Thus, the enthalpy of vaporization of all complexes has been estimated using the Clausius-Clapeyron equation. As a proof of concept, preliminary results on the use of [Mg(hfa)2·2H2O]·2diglyme and [Ca(hfa)2·diglyme·H2O] or [Ca(hfa)2·triglyme] as precursors for AP-MOCVD deposition of MgF2 and CaF2 in the form of thin films are presented. This approach may be used to easily determine vapor pressures of complexes and thus evaluate "a priori" the suitability of a compound as precursor for AP-MOCVD and/or spatial ALD.

Synthesis of MIL-Modified Fe3O4 Magnetic Nanoparticles for Enhancing Uptake and Efficiency of Temozolomide in Glioblastoma Treatment.

A nanometric hybrid system consisting of a Fe3O4 magnetic nanoparticles modified through the growth of Fe-based Metal-organic frameworks of the MIL (Materials Institute Lavoiser) was developed. The obtained system retains both the nanometer dimensions and the magnetic properties of the Fe3O4 nanoparticles and possesses increased the loading capability due to the highly porous Fe-MIL. It was tested to load, carry and release temozolomide (TMZ) for the treatment of glioblastoma multiforme one of the most aggressive and deadly human cancers. The chemical characterization of the hybrid system was performed through various complementary techniques: X-ray-diffraction, thermogravimetric analysis, FT-IR and X-ray photoelectron spectroscopies. The nanomaterial showed low toxicity and an increased adsorption capacity compared to bare Fe3O4 magnetic nanoparticles (MNPs). It can load about 12 mg/g of TMZ and carry the drug into A172 cells without degradation. Our experimental data confirm that, after 48 h of treatment, the TMZ-loaded hybrid nanoparticles (15 and 20 µg/mL) suppressed human glioblastoma cell viability much more effectively than the free drug. Finally, we found that the internalization of the MIL-modified system is more evident than bare MNPs at all the used concentrations both in the cytoplasm and in the nucleus suggesting that it can be capable of overcoming the blood-brain barrier and targeting brain tumors. In conclusion, these results indicate that this combined nanoparticle represents a highly promising drug delivery system for TMZ targeting into cancer cells.

One-Pot Synthesis of TiO2-rGO Photocatalysts for the Degradation of Groundwater Pollutants.

A non-conventional approach to prepare titanium dioxide-reduced graphene oxide (TiO2-rGO) nanocomposites based on solar photoreduction is here presented. The standard hydro-solvothermal synthesis of the TiO2-rGO composites requires high temperatures and several steps, whereas the proposed one-pot preparation allows one to obtain the photocatalysts with a simple and green procedure, by exploiting the photocatalytic properties of titania activated by the solar irradiation. The TiO2-rGO catalysts were tested in the solar photodegradation of a widely adopted toxic herbicide (2,4-Dichlorophenoxyacetic acid, 2,4-D), obtaining the 97% of degradation after 3 h of irradiation. The as-prepared TiO2-rGO composites were more active compared to the same photocatalysts prepared through the conventional thermal route. The structural, optical, and textural properties of the composites, determined by Raman, Photoluminescence, Fourier Transform InfraRed (FTIR), UV-vis diffuse reflectance (DRS) spectroscopies, and N2 absorption-desorption measurements, showed as the solar irradiation favors the reduction of graphene oxide with higher efficiency compared to the thermal-driven synthesis. Furthermore, the possible toxicity of the as-synthesized composites was measured exposing nauplii of microcrustacean Artemia sp. to solutions containing TiO2-rGO. The good results in the 2,4-D degradation process and the easiness of the TiO2-rGO synthesis allow to consider the proposed approach a promising strategy to obtain performing photocatalysts.