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.

Laser Processed Hybrid Lead-Free Thin Films for SAW Sensors.

In this study we report the specific interaction of various gases on the modified surface of acoustic wave devices for gas sensor applications, using the piezoelectric ceramic material BaSrTiO3 (BST), with different concentrations of Sr. For enhancing the sensitivity of the sensor, the conductive polymer polyethylenimine (PEI) was deposited on top of BST thin films. Thin films of BST were deposited by pulsed laser deposition (PLD) technique and integrated into a test heterostructure with PEI thin films deposited by matrix assisted pulsed laser evaporation (MAPLE) and interdigital Au electrodes (IDT). Further on, the layered heterostructures were incorporated into surface acoustic wave (SAW) devices, in order to measure the frequency response to various gases (N2, CO2 and O2). The frequency responses of the sensors based on thin films of the piezoelectric material deposited at different pressures were compared with layered structures of PEI/BST, in order to observe differences in the frequency shifts between sensors. The SAW tests performed at room temperature revealed different results based on deposition condition (pressure of oxygen and the percent of strontium in BatiO3 structure). Frequency shift responses were obtained for all the tested sensors in the case of a concentration of Sr x = 0.75, for all the analysed gases. The best frequency shifts among all sensors studied was obtained in the case of BST50 polymer sensor for CO2 detection.

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)).

MAPLE Assembled Acetylcholinesterase⁻Polyethylenimine Hybrid and Multilayered Interfaces for Toxic Gases Detection.

Developing a controlled method for obtaining hybrid enzymatic-based interfaces for sensing application require the use of a multiuse, reusable sensor. By controlling the interface characteristics in terms of the surface chemistry, thickness, and roughness, a tailored response toward various toxic compounds can be obtained, regarding both materials used as active surfaces and fabrication methods. Herein, we report a preliminary study on using a laser-based method (i.e., matrix-assisted pulsed laser evaporation, or MAPLE) for obtaining active polymeric⁻enzymatic interfaces as hybrid or layered coatings for detecting toxic vapors. The MAPLE fabrication consisted of the simultaneous alternating evaporation of layers of polyethylenimine (PEI) and acetylcholinesterase (AchE) in order to obtain active surfaces as both hybrid PEI-AchE and a PEI/AchE layered coating, respectively. The deposition processes of the polymer and enzyme were carried out using a double-target system and a Nd:YAG pulsed laser, operating at 0.45 J/cm² fluences with a wavelength of 266 nm and a repetition rate of 10 Hz. Fourier transform infrared spectroscopy revealed no significant changes in the functional groups of both hybrid and layered coatings compared with the initial material. The thickness and roughness, as well as the morphologies of the coatings revealed by atomic force microscopy and scanning electron microscopy showed coatings thicker than two µm that had smooth surfaces and average roughness values below six nm. The sensors were tested with simulants for nerve gases and pesticides containing phosphonate ester groups, namely dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP), and a different sensitivity was shown to the selected chemical agents for each of the sensors. The best sensitivities for DMMP and DIMP obtained by using a PEI-AchE coated sensor are 65 kHz and 200 kHz, respectively, whereas the best sensitivity when using multilayered interfaces is 30 kHz and 10 KHz for DIMP and DMMP, respectively.

Nanostructuring of GeTiO amorphous films by pulsed laser irradiation.

Laser pulse processing of surfaces and thin films is a useful tool for amorphous thin films crystallization, surface nanostructuring, phase transformation and modification of physical properties of thin films. Here we show the effects of nanostructuring produced at the surface and under the surface of amorphous GeTiO films through laser pulses using fluences of 10-30 mJ/cm(2). The GeTiO films were obtained by RF magnetron sputtering with 50:50 initial atomic ratio of Ge:TiO2. Laser irradiation was performed by using the fourth harmonic (266 nm) of a Nd:YAG laser. The laser-induced nanostructuring results in two effects, the first one is the appearance of a wave-like topography at the film surface, with a periodicity of 200 nm and the second one is the structure modification of a layer under the film surface, at a depth that is related to the absorption length of the laser radiation. The periodicity of the wave-like relief is smaller than the laser wavelength. In the modified layer, the Ge atoms are segregated in spherical amorphous nanoparticles as a result of the fast diffusion of Ge atoms in the amorphous GeTiO matrix. The temperature estimation of the film surface during the laser pulses shows a maximum of about 500 °C, which is much lower than the melting temperature of the GeTiO matrix. GeO gas is formed at laser fluences higher than 20 mJ/cm(2) and produces nanovoids in the laser-modified layer at the film surface. A glass transition at low temperatures could happen in the amorphous GeTiO film, which explains the formation of the wave-like topography. The very high Ge diffusivity during the laser pulse action, which is characteristic for liquids, cannot be reached in a viscous matrix. Our experiments show that the diffusivity of atomic and molecular species such as Ge and GeO is very much enhanced in the presence of the laser pulse field. Consequently, the fast diffusion drives the formation of amorphous Ge nanoparticles through the segregation of Ge atoms in the GeTiO matrix. The nanostructuring effects induced by the laser irradiation can be used in functionalizing the surface of the films.