Highly stable CsPbBr3 perovskite phases from new lead ß-diketonate glyme adducts.

Lead is one of the key metals of the all-inorganic lead halide perovskites. This work tailors novel architectures of lead's coordination sphere using a ß-diketone (H-hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione) and a glyme (monoglyme, diglyme, triglyme, or tetraglyme) ligand. The coordination chemistry and thermal behaviour of these "Pb(hfa)2·glyme" adducts have been analysed through FT-IR spectroscopy, 1H and 13C NMR analyses, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Single-crystal X-ray diffraction studies provide evidence of the formation of a monomeric Pb(hfa)2·monoglyme structure. In order to validate the potentiality of these "Pb(hfa)2·glyme" precursors for the fabrication of Pb-based halide perovskites, a facile, one-step and low-temperature solution approach has been applied to prepare CsPbBr3 microcrystals with a process carried out in air under atmospheric pressure. Pure stoichiometric CsPbBr3 powders, obtained using Cs(hfa) and Br2 as cesium and bromide sources, respectively, show excellent stability under atmospheric conditions. Better results are obtained in terms of yield and stability from the diglyme and tetraglyme lead adducts. Field emission scanning electron microscopy (FE-SEM) indicates a good uniform morphology of cubic grains, while the structure and the 1 : 1 : 3 stoichiometry of Cs : Pb : Br are confirmed by X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX), respectively. Tauc plots derived from absorption spectroscopy point to optical energy band-gaps (Eg) in the 2.21-2.27 eV range, in agreement with literature data. The present research elucidates the potential of these novel "Pb(hfa)2·glyme" adducts as promising lead precursors for CsPbBr3 perovskite synthesis, paving the way for their implementation in various technological applications.

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.

Fabrication of Europium-Doped CaF2 Films via Sol-Gel Synthesis as Down-Shifting Layers for Solar Cell Applications.

In the present work, an in-depth study on the sol-gel process for the fabrication of Eu-doped CaF2 materials in the form of thin films has been addressed for the production of down-shifting layers. Fine-tuning of the operative parameters, such as the annealing temperature, substrate nature and doping ion percentage, has been finalized in order to obtain Eu(III)-doped CaF2 thin films via a reproducible and selective solution process for down-shifting applications. An accurate balance of such parameters allows for obtaining films with high uniformity in terms of both their structural and compositional features. The starting point of the synthesis is the use of a mixture of Ca(hfa)2•diglyme•H2O and Eu(hfa)3•diglyme adducts, with a suited ratio to produce 5%, 10% and 15% Eu-doped CaF2 films, in a water/ethanol solution. A full investigation of the structural, morphological and compositional features of the films, inspected using X-ray diffraction analysis (XRD), field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray analysis (EDX), respectively, has stated a correlation between the annealing temperature and the structural characteristics and morphology of the CaF2 thin films. Interestingly, crystalline CaF2 films are obtained at quite low temperatures of 350-400 °C. The down-shifting properties, validated by taking luminescence measurements under UV excitation, have allowed us to correlate the local environment in terms of the degree of symmetry around the europium ions with the relative doping ion percentages.

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.

Sensing enhancement of a Fabry-Perot THz cavity using switchable VO2 mirrors.

We experimentally investigate the sensing properties of an open cavity operating in the THz regime and realized by employing as mirrors two thin vanadium dioxide (VO2) films grown on silicon parallel plates and separated by a variable length. The phase transition of VO2 is used to control the behavior of the system between two different responses: a high transmission mode to the incident radiation (VO2 in the insulating state) and a high sensitivity to tiny changes in the cavity refractive index (VO2 in the conducting state). In the first state, the low loss regime enables to adjust the cavity length and easily optimize the resonances due to the Fabry-Perot (FP) effect in the Si plates and in the cavity volume. The activation of the metallic-like state instead, by damping the FP oscillations in the plates, promotes the onset of a comb-like spectrum that can be exploited as a versatile tool for accurate sensing applications. Using both an analytical model and full-wave simulations, we estimate the device response to variation in the refractive index of the cavity volume, showing that the proposed structure can achieve sensitivity values among the highest reported for THz sensors.

Sodium ß-Diketonate Glyme Adducts as Precursors for Fluoride Phases: Synthesis, Characterization and Functional Validation.

Very few sodium complexes are available as precursors for the syntheses of sodium-based nanostructured materials. Herein, the diglyme, triglyme, and tetraglyme (CH3O(CH2CH2O)nCH3, n = 2-4) adducts of sodium hexafluoroacetylacetonate were synthesized in a single-step reaction and characterized by IR spectroscopy, 1H, and 13C NMR. Single-crystal X-ray diffraction studies provide evidence of the formation of the ionic oligomeric structure [Na4(hfa)6]2-•2[Na(diglyme2]+ when the diglyme is coordinated, while a mononuclear seven-coordinated complex Na(hfa)•tetraglyme is formed with the tetraglyme. Reaction with the monoglyme (CH3OCH2CH2OCH3) does not occur, and the unadducted polymeric structure [Na(hfa)]n forms, while the triglyme gives rise to a liquid adduct, Na(hfa)•triglyme•H2O. Thermal analysis data reveal great potentialities for their applications as precursors in metalorganic chemical vapor deposition (MOCVD) and sol-gel processes. As a proof-of-concept, the Na(hfa)•tetraglyme adduct was successfully applied to both the low-pressure MOCVD and the sol-gel/spin-coating synthesis of NaF films.

Luminescent 1,10-Phenanthroline ß-Diketonate Europium Complexes with Large Second-Order Nonlinear Optical Properties.

Substitution of the diglyme ligand of [Eu(hfa)3(diglyme)] (where hfa is hexafluoroacetylacetonate) with a simple 1,10-phenanthroline leads to a six-fold increase of the product µßEFISH, as measured by the Electric-Field-Induced Second Harmonic generation (EFISH) technique. Similarly, [Eu(tta)3(1,10-phenanthroline)] (where Htta is 2-thenoyltrifluoroacetone) is characterized by a large second-order NLO response. Both 1,10-phenanthroline europium complexes have great potential as multifunctional materials for photonics.

Synthesis, characterization and photocatalytic properties of nanostructured lanthanide doped ß-NaYF4/TiO2 composite films.

The photocatalytic approach is known to be one of the most promising advanced oxidation processes for the tertiary treatment of polluted water. In this paper, ß-NaYF4/TiO2 composite films have been synthetized through a novel sol-gel/spin-coating approach using a mixture of ß-diketonate complexes of Na and Y, and Yb3+, Tm3+, Gd3+, Eu3+ as doping ions, together with the TiO2 P25 nanoparticles. The herein pioneering approach represents an easy, straightforward and industrially appealing method for the fabrication of doped ß-NaYF4/TiO2 composites. The effect of the doped ß-NaYF4 phase on the photocatalytic activity of TiO2 for the degradation of methylene blue (MB) has been deeply investigated. In particular, the upconverting TiO2/ß-NaYF4: 20%Yb, 2% Gd, x% Tm (x = 0.5 and 1%) and the downshifting TiO2/ß-NaYF4: 10% Eu composite films have been tested on MB degradation both under UV and visible light irradiation. An improvement up to 42.4% in the degradation of MB has been observed for the TiO2/ß-NaYF4: 10% Eu system after 240 min of UV irradiation.

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.

Lead-Free LiNbO3 Thick Film MEMS Kinetic Cantilever Beam Sensor/Energy Harvester.

In this paper, we present integrated lead-free energy converters based on a suitable MEMS fabrication process with an embedded layer of LiNbO3. The fabrication technology has been developed to realize micromachined self-generating transducers to convert kinetic energy into electrical energy. The process proposed presents several interesting features with the possibility of realizing smaller scale devices, integrated systems, miniaturized mechanical and electromechanical sensors, and transducers with an active layer used as the main conversion element. When the system is fabricated in the typical cantilever configuration, it can produce a peak-to-peak open-circuit output voltage of 0.208 V, due to flexural deformation, and a power density of 1.9 nW·mm-3·g-2 at resonance, with values of acceleration and frequency of 2.4 g and 4096 Hz, respectively. The electromechanical transduction capability is exploited for sensing and power generation/energy harvesting applications. Theoretical considerations, simulations, numerical analyses, and experiments are presented to show the proposed LiNbO3-based MEMS fabrication process suitability. This paper presents substantial contributions to the state-of-the-art, proposing an integral solution regarding the design, modelling, simulation, realization, and characterization of a novel transducer.

Oregano and Thyme Essential Oils Encapsulated in Chitosan Nanoparticles as Effective Antimicrobial Agents against Foodborne Pathogens.

The use of natural compounds with biocidal activity to fight the growth of bacteria responsible for foodborne illness is one of the main research challenges in the food sector. This study reports the preparation and physicochemical characterization of chitosan nanoparticles loaded with Thymus capitatus (Th-CNPs) and Origanum vulgare (Or-CNPs) essential oils. The nanosystems were obtained by ionotropic gelation technique with high encapsulation efficiency (80-83%) and loading capacity (26-27%). Nanoparticles showed a spherical shape, bimodal particle size distribution, and good stability (zeta potential values > 40 mV). The treatment of the nanosuspensions at different temperatures (4 and 40 °C) and storage times (7, 15, 21, and 30 days) did not affect their physicochemical parameters and highlights their reservoir ability for essential oils also under stressful conditions. Both Or-CNPs and Th-CNPs exhibited an enhanced bactericidal activity against foodborne pathogens (S. aureus, E. coli, L. monocytogenes) than pure essential oils. These ecofriendly nanosystems could represent a valid alternative to synthetic preservatives and be of interest for health and food safety.

A Facile One-Pot Approach to the Synthesis of Gd-Eu Based Metal-Organic Frameworks and Applications to Sensing of Fe3+ and Cr2O72- Ions.

Gadolinium metal-organic frameworks (Gd-MOFs) and Eu-doped Gd-MOFs have been synthesized through a one-pot green approach using commercially available reagents. The 1,4-benzenedicarboxylic acid (H2-BDC) and 2,6-naphthalenedicarboxylic acid (H2-NDC) were chosen as ditopic organic linkers to build the 3D structure of the network. The Gd-MOFs were characterized using powder X-ray diffraction (XRD), FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM) and N2 adsorption-desorption analysis. The Gd-MOF structures were attributed comparing the XRD patterns, supported by the FT-IR spectra, with data reported in the literature for Ln-MOFs of similar lanthanide ionic radius. FE-SEM characterization points to the effect of the duration of the synthesis to a more crystalline and organized structure, with grain dimensions increasing upon increasing reaction time. The total surface area of the MOFs has been determined from the application of the Brunauer-Emmett-Teller method. The study allowed us to correlate the processing conditions and ditopic linker dimension to the network surface area. Both Gd-MOF and Eu-doped Gd-MOF have been tested for sensing of the inorganic ions such as Fe3+ and Cr2O72-.

Microwave based regenerating permeable reactive barriers (MW-PRBs): Proof of concept and application for Cs removal.

The present study evaluates the concept of permeable reactive barrier (PRB) coupled with microwaves (MWs) as in situ-regenerating technology with focus on Cs-contaminated water. Experimental and modelling results data from batch and column tests were carried out, evaluating several chemical-physical and environmental parameters. Main results showed a very rapid increase in GAC temperature during MW irradiation up to ∼680 °C. This highlights the GAC strong ability to transform MW power into heat due to GAC excellent dielectric properties (ε' = 13.8). Physical characterization revealed that GAC pore volume and specific surface area change with the number of regeneration cycles. GAC regeneration efficiency variation reflects this behaviour with a maximum value of ∼112% (5th cycle). The final GAC weight loss of ∼7% further demonstrates GAC life span preservation during MW irradiation. Results from column tests confirms that GAC can be regenerated by MW also in dynamic condition, due to sublimation/vaporization and vapour stripping Cs removal mechanisms and that the regeneration effectiveness is time-dependent. The breakthrough curve shape confirms significant benefits from MW irradiation. Overall, obtained finding demonstrated the feasibility of the proposed concept, also providing essential data to guide its scaling-up application.

Piezoelectric BiFeO3 Thin Films: Optimization of MOCVD Process on Si.

This paper presents a simple and optimized metal organic chemical vapor deposition (MOCVD) protocol for the deposition of perovskite BiFeO3 films on silicon-based substrates, in order to move toward the next generation of lead-free hybrid energy harvesters. A bi-metal mixture that is composed of Bi(phenyl)3, and Fe(tmhd)3 has been used as a precursor source. BiFeO3 films have been grown by MOCVD on IrO2/Si substrates, in which the conductive IrO2 functions as a bottom electrode and a buffer layer. BiFeO3 films have been analyzed by X-ray diffraction (XRD) for structural characterization and by field-emission scanning electron microscopy (FE-SEM) coupled with energy dispersive X-ray (EDX) analysis for the morphological and chemical characterizations, respectively. These studies have shown that the deposited films are polycrystalline, pure BiFeO3 phase highly homogenous in morphology and composition all over the entire substrate surface. Piezoelectric force microscopy (PFM) and Piezoelectric Force Spectroscopy (PFS) checked the piezoelectric and ferroelectric properties of the film.

Facile synthesis of novel lithium ß-diketonate glyme adducts: the effect of molecular engineering on the thermal properties.

Novel adducts of lithium hexafluoroacetylacetonato {Li(hfa)} with polyethers (monoglyme = {CH3OCH2CH2OCH3}, diglyme = {CH3O(CH2CH2O)2CH3}, triglyme = {CH3O(CH2CH2O)3CH3} and tetraglyme {CH3O(CH2CH2O)4CH3} have been synthesized through a single step reaction and characterized by FT-IR spectroscopy, 1H, and 13C NMR, single crystal X-ray diffraction studies along with thermal analysis.

Heterobimetallic Sodium Rare-Earth Complexes: "Third-Generation" MOCVD Precursors for the Deposition of NaREF4 (RE = Y, Gd) Films.

We report the synthesis of novel heterobimetallic precursors of the formula [RE(hfa)4]-[Na·tetraglyme]+ [RE = Y, Gd; Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = 2,5,8,11,14-pentaoxapentadecane], which can be efficiently used as a single source for the metal-organic chemical vapor deposition of NaREF4 films.

Vapochromic and chemiresistive characteristics of a nanostructured molecular material composed of a zinc(ii)-salophen complex.

The vapochromic and chemiresistive properties of a nanofibrillar molecular material composed of an amphiphilic ZnII Schiff-base complex, 1, are explored with the aim to obtain new materials with multifunctional properties. The solid 1 is characterized by the existence of two stable dimorphs, both exhibiting a nanofibrillar morphology. The thermal annealing of the ground solid 1 induces an irreversible lamellar-to-square columnar structural phase transition, as assessed by differential scanning calorimetry and X-ray diffraction analysis. When exposed to vapours of a Lewis base, spin coated films of the square columnar dimorph exhibit a marked change of both the optical absorption spectrum and the resistance, because of chemisorption of the Lewis base with the formation of 1·Lewis base adducts. The chemisorbed material is easily restored by thermal heating (150 °C), inducing desorption of the Lewis base. The changes of the properties are reproducible in successive cycles of exposure/restoring. Therefore, the present contribution provides new insights into the properties of this molecular material, potentially useful as a sensor for volatile organic Lewis bases.