Lead-Free Perovskite Thin Films with Tailored Pockels-Kerr Effects for Photonics.

Pockels and Kerr effects are linear and nonlinear electro-optical effects, respectively, used in many applications. The modulation of the refractive index is employed in different photonic circuits. However, the greatest challenge is in photonic elements for quantum computing at room temperature. For this aim, materials with strong Pockels/Kerr effects and χ(2)/χ(3) nonlinear susceptibilities are necessary. Here, we demonstrate composition-modulated strong electro-optical response in epitaxial films of (Ba,Ca)(Ti,Zr)O3 perovskite titanate. These films are grown by pulsed laser deposition on SrTiO3. Depending on the ratios of Ca/Ba and Ti/Zr, films show high Pockels or Kerr optical nonlinearities. We relate the variable electro-optic response to the occurrence of nanopolar domains with different symmetries in a selected composition range. These findings open the route to easily implement nonlinear optical elements in integrated photonic circuits.

Mo-LDH-GO Hybrid Catalysts for Indigo Carmine Advanced Oxidation.

This paper is focused on the utilization of hybrid catalysts obtained from layered double hydroxides containing molybdate as the compensation anion (Mo-LDH) and graphene oxide (GO) in advanced oxidation using environmentally friendly H2O2 as the oxidation agent for the removal of indigo carmine dye (IC) from wastewaters at 25 °C using 1 wt.% catalyst in the reaction mixture. Five samples of Mo-LDH-GO composites containing 5, 10, 15, 20, and 25 wt% GO labeled as HTMo-xGO (where HT is the abbreviation used for Mg/Al in the brucite type layer of the LDH and x stands for the concentration of GO) have been synthesized by coprecipitation at pH 10 and characterized by XRD, SEM, Raman, and ATR-FTIR spectroscopy, determination of the acid and base sites, and textural analysis by nitrogen adsorption/desorption. The XRD analysis confirmed the layered structure of the HTMo-xGO composites and GO incorporation in all samples has been proved by Raman spectroscopy. The most efficient catalyst was found to be the catalyst that contained 20%wt. GO, which allowed the removal of IC to reach 96.6%. The results of the catalytic tests indicated a strong correlation between catalytic activity and textural properties as well as the basicity of the catalysts.

Lead-Free Perovskite Thin Films for Gas Sensing through Surface Acoustic Wave Device Detection.

Thin film technology shows great promise in fabricating electronic devices such as gas sensors. Here, we report the fabrication of surface acoustic wave (SAW) sensors based on thin films of (1 - x) Ba(Ti0.8Zr0.2)O3-x(Ba0.7Ca0.3)TiO3 (BCTZ50, x = 50) and Polyethylenimine (PEI). The layers were deposited by two laser-based techniques, namely pulsed laser deposition (PLD) for the lead-free material and matrix assisted pulsed laser evaporation (MAPLE) for the sensitive polymer. In order to assay the impact of the thickness, the number of laser pulses was varied, leading to thicknesses between 50 and 350 nm. The influence of BCTZ film's crystallographic features on the characteristics and performance of the SAW device was studied by employing substrates with different crystal structures, more precisely cubic Strontium Titanate (SrTiO3) and orthorhombic Gadolinium Scandium Oxide (GdScO3). The SAW sensors were further integrated into a testing system to evaluate the response of the BCTZ thin films with PEI, and then subjected to tests for N2, CO2 and O2 gases. The influence of the MAPLE's deposited PEI layer on the overall performance was demonstrated. For the SAW sensors based on BCTZ/GdScO3 thin films with a PEI polymer, a maximum frequency shift of 39.5 kHz has been obtained for CO2; eight times higher compared to the sensor without the polymeric layer.

Kaolinite Thin Films Grown by Pulsed Laser Deposition and Matrix Assisted Pulsed Laser Evaporation.

In this work, thin films of lamellar clays were deposited by laser techniques (matrix assisted pulsed laser evaporation (MAPLE) and pulsed laser deposition (PLD)). The focus of this paper is the optimization of deposition parameters for the production of highly oriented crystalline films. The films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). Contact angle measurements were employed to identify the wetting properties of the deposited thin films. Hydrophobic to superhydrophilic films can be prepared by using different deposition techniques and deposition parameters. MAPLE led to superhydrophilic films with contact angles in the range 4°-8°, depending on the microstructure and surface roughness at micro and nano scale. The 1064 nm PLD had a high deposition rate and produced a textured film while at λ = 193 nm an extremely thin and amorphous layer was depicted. Oriented kaolinite films were obtained by MAPLE even at 5 wt.% kaolinite in the target.

The Influence of the Preparation Method on the Physico-Chemical Properties and Catalytic Activities of Ce-Modified LDH Structures Used as Catalysts in Condensation Reactions.

Mechanical activation and mechanochemical reactions are the subjects of mechanochemistry, a special branch of chemistry studied intensively since the 19th century. Herein, we comparably describe two synthesis methods used to obtain the following layered double hydroxide doped with cerium, Mg3Al0.75Ce0.25(OH)8(CO3)0.5·2H2O: the mechanochemical route and the co-precipitation method, respectively. The influence of the preparation method on the physico-chemical properties as determined by multiple techniques such as XRD, SEM, EDS, XPS, DRIFT, RAMAN, DR-UV-VIS, basicity, acidity, real/bulk densities, and BET measurements was also analyzed. The obtained samples, abbreviated HTCe-PP (prepared by co-precipitation) and HTCe-MC (prepared by mechanochemical method), and their corresponding mixed oxides, Ce-PP (resulting from HTCe-PP) and Ce-MC (resulting from HTCe-MC), were used as base catalysts in the self-condensation reaction of cyclohexanone and two Claisen-Schmidt condensations, which involve the reaction between an aromatic aldehyde and a ketone, at different molar ratios to synthesize compounds with significant biologic activity from the flavonoid family, namely chalcone (1,3-diphenyl-2-propen-1-one) and flavone (2-phenyl-4H-1benzoxiran-4-one). The mechanochemical route was shown to have indisputable advantages over the co-precipitation method for both the catalytic activity of the solids and the costs.

Thickness-Dependent Photoelectrochemical Water Splitting Properties of Self-Assembled Nanostructured LaFeO3 Perovskite Thin Films.

Tuning the intrinsic structural and stoichiometric properties by different means is used for increasing the green energy production efficiency of complex oxide materials. Here, we report on the formation of self-assembled nanodomains and their effects on the photoelectrochemical (PEC) properties of LaFeO3 (LFO) epitaxial thin films as a function of layer's thickness. The variation with the film's thickness of the structural parameters such as in-plane and out-of-plane crystalline coherence length and the coexistence of different epitaxial orientation-<100>SrTiO3//<001> LFO, <100>SrTiO3//<110> LFO and [110] LFO//[10] STO, as well as the appearance of self-assembled nanodomains for film's thicknesses higher than 14 nm, is presented. LFO thin films exhibit different epitaxial orientations depending on their thickness, and the appearance of self-assembled nanopyramids-like domains after a thickness threshold value has proven to have a detrimental effect on the PEC functional properties. Using Nb:SrTiO3 as conductive substrate and 0.5 M NaOH aqueous solution for PEC measurements, the dependence of the photocurrent density and the onset potential vs. RHE on the structural and stoichiometric features exhibited by the LFO photoelectrodes are unveiled by the X-ray diffraction, high-resolution transmission electron microscopy, ellipsometry, and Rutherford backscattering spectroscopy results. The potentiodynamic PEC analysis has revealed the highest photocurrent density Jphotocurrent values (up to 1.2 mA/cm2) with excellent stability over time, for the thinnest LFO/Nb:SrTiO3 sample, both cathodic and anodic behavior being noticed. Noticeably, the LFO thin film shows unbiased hydrogen evolution from water, as determined by gas chromatography in aqueous 0.5 M NaOH solution under constant illumination.

The Influence of the Structural and Morphological Properties of WO3 Thin Films Obtained by PLD on the Photoelectrochemical Water-Splitting Reaction Efficiency.

Due to its physical and chemical properties, the n-type tungsten oxide (WO3) semiconductor is a suitable photoanode for water decomposition reaction. The responses of the photoelectrochemical PEC water-splitting properties as an effect of structural and optical changes of WO3 thin films, as well as the nature of electrolyte solutions, were studied in this work. The WO3 thins films have been obtained by pulsed laser deposition (PLD) on silicon (Si(001)) covered with platinum substrates using three different laser wavelengths. As the XRD (X-ray diffraction) and XTEM (cross-section transmission electron microscopy) analysis shows, the formation of highly crystalline monocline WO3 phase is formed for the film deposited at 1064 nm wavelength and poor crystalline phases with a large ordering anisotropy, characteristic of 2D structures for the films deposited at 355 nm and 193 nm wavelengths, respectively. The photogenerated current densities Jph depend on the laser wavelength, in both alkaline and acidic electrolyte. The maximum values of the photocurrent density have been obtained for the sample prepared with laser emitting at 355 nm. This behavior can be correlated with the coherent crystallized atomic ordering that appear for long distances (10-15 nm) in the (001) plane of the monoclinic WO3 phase structure films obtained at 355 nm laser wavelength. All the samples show poor current density in dark conditions and they are very stable in both acidic and alkaline solutions. The highest photocurrent density value is obtained in acidic solution for the WO3 thin film prepared by 355 nm laser (29 mA/cm2 at 1.6 V vs. RHE (1.35 V vs. Ag/AgCl)).

Stearic Acid/Layered Double Hydroxides Composite Thin Films Deposited by Combined Laser Techniques.

We report on the investigation of stearic acid-layered double hydroxide (LDH) composite films, with controlled wettability capabilities, deposited by a combined pulsed laser deposition (PLD)-matrix-assisted pulsed laser evaporation (MAPLE) system. Two pulsed lasers working in IR or UV were used for experiments, allowing the use of proper deposition parameters (wavelength, laser fluence, repetition rate) for each organic and inorganic component material. We have studied the time stability and wettability properties of the films and we have seen that the morphology of the surface has a low effect on the wettability of the surfaces. The obtained composite films consist in stearic acid aggregates in LDH structure, exhibiting a shift to hydrophobicity after 36 months of storage.

Self-assembled zinc oxide hierarchical structures with enhanced antibacterial properties from stacked chain-like zinc oxalate compounds.

Single ZnO crystallites assembled into porous hierarchical structures have been prepared by topotactic thermal decomposition of in situ obtained zinc oxalate precursors, whose synthesis involves a redox reaction between 1,2-ethanediol and nitrate ion. For the first time it was demonstrated that post-synthesis protocols of the precursors (e.g. ultrasound irradiation, hydrolytic decomposition) master the hydrogen bonds formed between oxalate chains, allowing that way the adjustment of materials properties (morphology, porosity and optical) and a rational introduction of different dopants (Eu3+/Er3+). The ZnO surface reactivity is confirmed by the significant biocidal activity of the obtained materials against Gram-positive and Gram-negative planktonic and biofilm-embedded cells, superior to those reported in the literature for other ZnO-based materials or antibiotics, associated also with a good biocompatibility.

Zinc Oxide Spherical-Shaped Nanostructures: Investigation of Surface Reactivity and Interactions with Microbial and Mammalian Cells.

Two ZnO materials of spherical hierarchical morphologies, with hollow (ZnOHS) and solid cores (ZnOSS), were obtained through the hydrolysis of zinc acetylacetonate in 1,4-butanediol. The nature of the defects and surface reactivity for the two ZnO materials were investigated through photoluminescence, X-ray photoelectron spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy proving the coexistence of shallow and deep defects and, also, the presence of polyol byproducts adsorbed on the outer layers of the ZnO samples. The EPR spectroscopy coupled with the spin-trapping technique showed that the surface of the ZnO samples generates reactive oxygen species (ROS) like hydroxyl (•OH) and singlet oxygen (1O2) as well as carbon-centered radicals. The ZnO materials exhibited a wide spectrum of antimicrobial activity, being active against Gram-positive, Gram-negative, and fungi strains, both in planktonic and, more importantly, adherent growth states. The decrease of antimicrobial efficiency in the presence of a ROS scavenger (mannitol) and the decrease of the cell viability with the ROS level suggest that one of the mechanisms that governs both the antimicrobial and cytotoxic activities on human liver cells is ROS-mediated. However, at active antimicrobial concentrations, the biocompatibility of the tested materials is very good.

Cellulose defibrillation and functionalization by plasma in liquid treatment.

Submerged liquid plasma (SLP) is a new and promising method to modify powder materials. Up to now, this technique has been mostly applied to carbonaceous materials, however, SLP shows great potential as a low-cost and environmental-friendly method to modify cellulose. In this work we demonstrate the modification of microcrystalline cellulose (MCC) by applying the SLP combined with ultrasonication treatments. The plasma generated either in an inert (argon) or reactive (argon: oxygen or argon:nitrogen) gas was used in MCC dispersions in water or acetonitrile:water mixtures. An enhanced defibrillation of MCC has been observed following the application of SLP. Furthermore, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy have been applied to investigate the surface functionalization of MCC with oxygen or nitrogen moieties. Depending on the plasma treatment applied, poly (3-hydroxybutyrate) composites fabricated with the plasma modified cellulose fibers showed better thermal stability and mechanical properties than pristine PHB. This submerged liquid plasma processing method offers a unique approach for the activation of cellulose for defibrillation and functionalization, aiming towards an improved reinforcing ability of biopolymers.

Surface Acoustic Wave Hydrogen Sensors Based on Nanostructured Pd/WO3 Bilayers.

The effect of nanostructure of PLD (Pulsed Laser Deposition)-deposited Pd/WO3 sensing films on room temperature (RT) hydrogen sensing properties of SAW (Surface Acoustic Wave) sensors was studied. WO3 thin films with different morphologies and crystalline structures were obtained for different substrate temperatures and oxygen deposition pressures. Nanoporous films are obtained at high deposition pressures regardless of the substrate temperature. At lower pressures, high temperatures lead to WO3 c-axis nanocolumnar growth, which promotes the diffusion of hydrogen but only once H2 has been dissociated in the nanoporous Pd layer. XRD (X-ray Diffraction) analysis indicates texturing of the WO3 layer not only in the case of columnar growth but for other deposition conditions as well. However, it is only the predominantly c-axis growth that influences film sensing properties. Bilayers consisting of nanoporous Pd layers deposited on top of such WO3 layers lead to good sensing results at RT. RT sensitivities of 0.12⁻0.13 Hz/ppm to hydrogen are attained for nanoporous bilayer Pd/WO3 films and of 0.1 Hz/ppm for bilayer films with a nanocolumnar WO3 structure. SAW sensors based on such layers compare favorably with WO3-based hydrogen detectors, which use other sensing methods, and with SAW sensors with dense Pd/WO3 bilayers.

Impact of thickness variation on structural, dielectric and piezoelectric properties of (Ba,Ca)(Ti,Zr)O3 epitaxial thin films.

It is shown that the dielectric and piezoelectric properties of Ba(Ti0.8Zr0.2)O3-x(Ba0.7Ca0.3)TiO3 (x = 0.45) (BCTZ 45) epitaxial thin films have a nontrivial dependence on film thickness. BCTZ 45 epitaxial films with different thicknesses (up to 400 nm) have been deposited on SrTiO3 by pulsed laser deposition and investigated by different combined techniques: conventional and off-axis X-ray diffraction, high resolution transmission electron microscopy and dielectric and piezoforce microscopy. The changes occurring in epitaxial films when their thickness increases have been attributed to a partial relaxation of misfit strain, driving the induced tetragonal symmetry in very thin films to the original rhombohedral symmetry of the bulk material in the thickest film, which influences directly and indirectly the dielectric and piezoelectric properties.

Facile, high yield ultrasound mediated protocol for ZnO hierarchical structures synthesis: Formation mechanism, optical and photocatalytic properties.

Hierarchical flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method performed in a ordinary ultrasonic bath using an ammonia solution and zinc acetate, in the absence of any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the materials obtained at different ultrasound irradiation times were characterized by infrared, UV-Vis and photoluminescence spectroscopy, X-ray diffraction, scanning and transmission electron microscopy investigations. It was proved that the ultrasound irradiation time manipulates both the defect content (implicit the photoluminescent properties) and morphology of the ZnO materials: shorter irradiation times leads to the synthesis of high-defected ZnO structures of flower morphology with triangular-shaped petals, while higher irradiation times favours the formation of low-defected ZnO structures with tipped rod-like petals. A plausible growth mechanism of the architectures that implies aggregation via oriented attachment followed by an Ostwald ripening is advanced based on these results. The ZnO flower-like structures present high photocatalytic activities, a total phenol mineralization being registered in the case of visible light experiments. Electron-spin resonance measurements demonstrate the generation of reactive oxygen species, namely hydroxyl radicals but also C centred radicals adducts derived most probable from the residual acetate adsorbed on ZnO surface.

Sustainable one-pot integration of ZnO nanoparticles into carbon spheres: manipulation of the morphological, optical and electrochemical properties.

ZnO-carbon composite spheres were synthesized via starch hydrothermal carbonization (HTC) in the presence of a soluble zinc salt (acetate), followed by thermal processing under an argon atmosphere. Besides sustainability, the one-pot procedure represents a scalable synthesis of tailored carbon-metal oxide spheres with a structurally-ordered carbon matrix obtained at a relatively low temperature (700 °C). The ability of zinc cations to develop different linkages with starch's hydrophilic functional groups and to act as external nucleators determines an increase in HTC yield; the effect is obvious even in the presence of small concentrations of zinc in the reaction medium (0.005 M), thus providing a way to improve the carbonization process efficiency. It is also shown that zinc content is the control vector of the spherical composite's properties: a variation from 0.3 to 4.8 at% not only induces a variation in their size (200 nm-10 µm), interconnectivity (from disperse spheres to necklace-like aggregations), surface area and connected porosity (from micro- to mesoporosity), but also of their electrochemical and white light adsorption and emission features. Since the variation in zinc content is made by a simple adjustment of the raw material concentrations, the functionality of these carbon-based materials can be modulated in a straightforward manner.

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.

High Permittivity (1 - x)Ba(Zr(0.2)Ti(0.8))O3 - x(Ba(0.7)Ca(0.3))TiO3 (x = 0.45) Epitaxial Thin Films with Nanoscale Phase Fluctuations.

Epitaxial (1 - x)Ba(Ti0.8Zr0.2)TiO3 - x(Ba0.7Ca0.3)TiO3, x = 0.45 (BCZT 45), thin films have been deposited on (001) SrTiO3 (STO) and (001/100) SrLaAlO4 (SLAO) substrates by pulsed laser deposition. X-ray diffraction and high-resolution transmission electron microscopy (HRTEM) confirmed the epitaxial growth of the films. A high structural quality has been evidenced for the BCZT/STO films. Geometric phase analysis (GPA) associated with the HRTEM enabled us to obtain microstrain analysis and the in-plane and out-of-plane lattice parameter variation on different areas. Tetragonality ratio fluctuations at nanoscale level which are relevant for the existence of nanodomains have been evidenced on the BCZT/STO films. The in-plane dielectric constant has been measured on interdigital electrodes deposited by lift-off technique on the top of the films. High values of dielectric permittivity (>3000) combined with low dielectric loss (<0.01) are obtained for BCZT 45 film deposited on STO substrate, showing nearly constant values between 1 kHz and 10 MHz. The high dielectric permittivity of BCZT thin films was attributed to their high structural quality and to the loss of rotation stability of the polarization associated with the presence of nanodomains. This results into a divergence of fluctuations of polarization direction and a peak of dielectric susceptibility. The enhanced switching of such nanodomain configuration was probed by piezoforce microscopy, by writing and reading domains during topography scanning.

A general, eco-friendly synthesis procedure of self-assembled ZnO-based materials with multifunctional properties.

A bioinspired one-pot approach for the synthesis of ZnO-carbohydrate hierarchical architectures was developed. The synergy between a saccharide (mono-, di- or polysaccharide) that contains d-glucose units and triethanolamine is the key parameter of the synthetic methodology. The morphology of the ZnO composites is dictated by the saccharide used, and rod, spindle, solid and hollow spherical-like ZnO structures are obtained by varying the carbohydrate. The synthesized composites present good photocatalytic and antimicrobial activity.