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Over the past four decades, energy microsources based on piezoelectric energy harvesting have been intensively studied for applications in autonomous sensor systems. The research is triggered by the request for replacing standard lead-based piezoelectric ceramics with environmentally friendly lead-free materials and potential deployment of energy-harvesting microsystems in internet of things, internet of health, ‘place and leave’ sensors in infrastructures and agriculture monitoring. Moreover, futher system miniaturization and co-integration of functions are required in line with a desired possibility to increase the harvested power density per material volume. Thus, further research efforts are necessary to develop more sustainable materials/systems with high-performance. This paper gives a comprehensive overview on the processing and functional testing the lead-free bulk materials and thin films and discusses their potential in the applications in the stress- and strain-driven piezoelectric energy harvesting. This includes the methodology of estimation of the substrate clamping and orientation/texture effects in the thin films, and identification of orientations offering high figure of merit. The ability to control film orientation of different lead-free materials is reviewed and the expected piezoelectric performances are compared with the ones reported in literature.

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.

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 (VO

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 β-diketonate fluorinated compounds, with molecular formula "M(hfa)

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, β-NaYF4/TiO2 composite films have been synthetized through a novel sol–gel/spin-coating approach using a mixture of β-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 β-NaYF4/TiO2 composites. The effect of the doped β-NaYF4 phase on the photocatalytic activity of TiO2 for the degradation of methylene blue (MB) has been deeply investigated. In particular, the upconverting TiO2/β-NaYF4: 20%Yb, 2% Gd, x% Tm (x = 0.5 and 1%) and the downshifting TiO2/β-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/β-NaYF4: 10% Eu system after 240 min of UV irradiation.

An easy approach is presented to determine vapor pressures of complexes and thus to evaluate “a priori” their suitability as precursors for AP-MOCVD or spatial ALD. Fluorinated Mg and Ca compounds have been applied to the AP-MOCVD of MF2 films.

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.

A tri-metallic precursor mixture has been used to deposit Bi(1−x)DyxFeO3 film on conductive SrTiO3:Nb(100) substrates. A fine adjustment of the film composition is the key enabling an accurate tuning of the film piezoelectric and optical properties.

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.

International audience; 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.

Mild heating of the Zn(C5F6HO2)(2)center dot 2H(2)O center dot CH3(OCH2CH2)(2)OCH3 precursor allowed MOCVD deposition of ZnO films, in a low-pressure horizontal hot-wall reactor, on ITO substrates. The ZnO films were subsequently implanted with Sb ions. XRD measurements provided evidence that they consist of hexagonal, (002) and (101) oriented, crystals. UV-vis spectra showed that the transmittance of these films in the visible region is about 90%. The Sb implanted ZnO film showed a current-voltage characteristic that resembles that of a rectifying diode. This study represents the first example of Sb-implantation in ZnO films obtained by MOCVD.

A careful engineering of the central metal coordination spheres provides adducts with excellent properties for application as precursors in vapor phase and solution processes. The family of precursors under study concerns the fluorinated metal-organic β-diketonates of alkaline, alkaline-earth and rare-earth metals adducted with a polyether, with general formula M(hfa)n·L (M = Ca, Na, Y, Yb, Er, Tm; Hhfa = 1,1,1,5,5,5 hexafluoroacetylacetone, L = diglyme or tetraglyme). Mass transport properties, such as volatility and thermal stability, of these adducts have been deeply analyzed through thermogravimetric analysis and differential scanning calorimetric measurements. These properties are rationalized in relation to the metal coordination sphere in the precursors and their applications. In particular, the precursors under focus have been applied to metal organic chemical vapor deposition and a combined sol–gel/spin-coating approach. Both methods allow us to obtain selectively and reproducibly CaF2 and NaYF4 phases with several combinations of lanthanide doping ions, using a proper mixture of fluorinated precursors. A careful optimization of both synthetic strategies is the key point for the production of different lanthanide-doped binary and multicomponent fluoride films, i.e., CaF2:Yb3+,Er3+; CaF2:Yb3+,Tm3+; CaF2:Yb3+,Er3+,Tm3+ and NaYF4:Yb3+,Er3+; NaYF4:Yb3+,Tm3+, with suitable morphologies, compositions and crystalline structures. The films show very promising upconversion properties, thus pointing to their appealing applications in photovoltaic systems and white light emission devices.

Increasing awareness of environmental concerns has strongly pushed the scientific community towards the search for new solutions for efficient removal of oils and organic solvents from water. Here, we report the preparation of multifunctional TiO2-coated melamine-formaldehyde (MF) sponges as absorbent material for oils and organic solvents in water. TiO2-coated MF sponges were fabricated through an environmentally friendly approach, consisting in a simple immersion of the sponge into an oleic acid-capped TiO2 nanoparticles dispersion. The adhesion of TiOle coating to the sponge was then improved by the deposition of a low surface energy diamond-like carbon (DLC) thin layer. Our results highlighted that the modified MF sponges possess superhydrophobic and oleophilic behaviour, inertness to corrosive environment, good durability and reusability. Furthermore, the superhydrophobic DLC/TiO2@sponges showed (1) novel self-cleaning properties towards an absorbed commercial organic dye (IR-270BKA, chosen as representative) under visible light irradiation and (2) enhanced flame-retardant behaviour respect to the pristine MF sponge. These findings point out an important added value of DLC/TiOle@sponges making them promising candidates for wastewater treatments.

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 (e′ = 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.

Starting from fluorinated metal–organic β-diketonates, we report the synthesis of undoped and lanthanide-doped alkaline-earth fluoride (Er3+,Tm3+,Yb3+ tri-doped CaF2) thin films through two different chemical approaches: a metal–organic chemical vapor deposition (MOCVD) method and a combined sol–gel/spin-coating procedure. Both chemical approaches have the advantage of being very reliable and reproducible for the fast production of thin films with a high degree of uniformity over large areas. The fluorinated metal precursors act as a single-source in both processes, and an accurate control of the process parameters allows the optimization of the doped CaF2 films. X-ray diffraction, field emission scanning electron microscopy and energy dispersive X-ray analysis have been used to characterize the deposited films. Upconversion emission, typical of the lanthanide ions, in the visible and near infrared regions upon laser excitation at 980 nm is clearly observable. The emissions are in the central region of the CIE1931 color coordinate space.

A new tetraglyme adduct of sodium hexafluoroacetylacetonate [Na(hfa)·tetraglyme] has been synthesized and successfully used, together with the RE(hfa)3·diglyme (RE = Y, Yb, Er) complexes, in the synthesis of hexagonal phase NaYF4:Yb3+,Er3+ upconverting films through a facile sol–gel method.

We report the synthesis of novel heterobimetallic precursors of the formula [RE(hfa)

An innovative sol-gel process, using a mixture of Na(hfa)·tetraglyme and RE(hfa)3·diglyme (RE = Y, Yb, Tm) complexes, has been optimized to produce upconverting β-NaYF4:Yb3+/Tm3+ thin films. The X-ray diffraction (XRD) analysis confirms that the new sol-gel preparation route yields reproducibly and selectively the hexagonal Na(Y1.5Na0.5)F6 structure (β-NaYF4) without any impurity phases, since no peaks of the cubic NaYF4, YOF, Y2O3 or NaF phases were observed. This final goal has been achieved through an accurate optimization of the operative parameters such as the molar ratio of the precursor mixture, the aging time of the sol, the spin coating procedure and the annealing temperature. Field-emission scanning electron microscopy (FE-SEM) images indicate that the morphology of the surfaces, grain dimensions and thickness are strongly related to the processing parameters, with the hexagonal phase films having a very uniform morphology. Energy dispersive X-ray (EDX) analyses established the film composition in terms of dopant ions, which are responsible for the upconverting properties of the material. Luminescence measurements under laser excitation at 980 nm confirmed the promising upconversion properties of the β-NaYF4:Yb3+/Tm3+ films.

A systematic study into the MOCVD of V-O films using the vanadyl-acetylacetonate [VO(acac)2] precursor is carried out. The films are prepared via low pressure MOCVD on Si(001) substrates. The nature and quality of films are examined by varying operational parameters, e.g., deposition temperature, precursor vaporization rate, and flow of oxygen reacting gas. X-ray diffraction data point to the formation of crystalline films in the range 200−550 °C. Outside of this temperature ranges amorphous phases were obtained. Field-emission scanning electron microscope (FESEM) images indicate very homogeneous surfaces with grain shape and dimensions depending on operational conditions. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) analyses point to the absence of any C contamination.

Pr1–xCaxMnO3 thin films have been deposited through an in situ metal organic chemical vapor deposition (MOCVD) process using a molten multi-metal source, consisting of the Pr(hfa)3·diglyme, Ca(hfa)2·tetraglyme, and Mn(tmhd)3 precursor mixture on single crystal substrates such as LaAlO3 (001) and MgO (001). Optimization of processing parameters has allowed the deposition of homogeneous thin films in morphology, composition, and thickness. The effect of substrate has been assessed in relation to structure and morphology. Field emission scanning electron microscope of a Pr0.7Ca0.3MnO3 film deposited at 1000 °C on MgO (001).

International audience; In Accumulated Low Schottky Barrier metal oxide semiconductor field effect transistors (MOSFET) on SOl structures, very thin silicide layers are used for ohmic contacts. Silicide contacts form due to metallurgical reaction of metal with semiconductor. In order to get a broad vision of the most interesting metal/silicide solution several material stacks were evaluated including platinum and iridium. In this work cross-sectional transmission electron microscopy was used to study the process of silicide formation in metal/Si and metal/SiGe/Si structures. Novel structure architectures have been developed. They are mainly based on the use of a very thin film SOl substrate with typical active silicon layer thicknesses ranging between 2 and 20 nm for 10-40 nm gate length MOSFETs. In Accumulation LowSchottky Barrier -SOI MOSFET structures very thin silicides are used for ohmic contacts. Silicide contacts form due to metallurgical reaction of metal with semiconductor.