The Effect of Silver and Samarium on the Properties of Bioglass Coatings Produced by Pulsed Laser Deposition and Spin Coating.

The current study reports the use of silver (Ag) and samarium (Sm) as dopants to improve the properties of standard bioglass in terms of biological performance. This experiment considers thin films of doped bioglass obtained by pulsed laser deposition (PLD) and spin coating (SC). For both methods, some parameters were gradually varied, as the main objective was to produce a bioglass that could be used in biomedical fields. In order to study the morphology, the phase composition and other properties, the samples obtained were subjected to multiple analyses, such as thermal analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Fourier-transform infrared (FT-IR), Raman spectroscopy, and x-ray diffraction (XRD). Furthermore, the in vitro bioactivity of the samples, as assessed through simulated body fluid (SBF) immersion, as well as immunocytochemistry and evaluation of actin filaments, assessed through fluorescence microscopy, are reported. The results confirmed the formation of the designed vitreous target employed as the source of material in the PLD experiments only at sintering temperatures below 800 °C; this vitreous nature was preserved in the grown film as well. The presence of Ag and Ce dopants in the parent glassy matrix was validated for all stages, from powder, to target, to PLD/SC-derived coatings. Additionally, it was demonstrated that the surface topography of the layers can be adjusted by using substrates with different roughness or by modulating the processing parameters, such as substrate temperature and working pressure in PLD, rotation speed, and number of layers in SC. The developed material was found to be highly bioactive after 28 days of immersion in SBF, but it was also found to be a potential candidate for inhibiting the growth of Gram-negative bacteria and a suitable support for cell growth and proliferation.

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.

SAW Hydrogen Sensors with Pd/SnO2 Layers.

Pd/SnO2 bilayers for surface acoustic wave (SAW) sensors were obtained using pulsed laser deposition (PLD). Bilayers were made at several deposition pressures in order to observe the influence of the morphology of the sensitive films on the response of the sensors. The morphological properties were analyzed by scanning electron microscopy (SEM). The SnO2 monolayers were initially deposited on quartz substrates at 100, 400 and 700 mTorr, to observe their morphology at these pressures. The Pd/SnO2 bilayer depositions were made at 100 and 700 mTorr. The sensors realized with these sensitive films were tested at different hydrogen concentrations, in the range of 0.2-2%, at room temperature. In order to establish selectivity, tests for hydrogen, nitrogen, oxygen and carbon dioxide were carried out with SnO2-700, Pd-100/SnO2-700 and Pd-700/SnO2-700 sensors. The sensor with the most porous sensitive film (both films deposited at 700 mTorr) had the best results: a sensitivity of 0.21 Hz/ppm and a limit of detection (LOD) of 142 ppm. The morphology of the SnO2 film is the one that has the major influence on the sensor results, to the detriment of the Pd morphology. The use of Pd as a catalyst for hydrogen improved the sensitivity of the film considerably and the selectivity of the sensors for hydrogen.

Effect of Pd/ZnO Morphology on Surface Acoustic Wave Sensor Response.

Laser deposition was used to obtain Pd/ZnO bilayers, which were used as sensing layers in surface acoustic wave (SAW) sensors. The effect of laser deposition parameters such as deposition pressure, laser energy per pulse, laser wavelength or pulse duration on the porosity of the Pd and ZnO films used in the sensors was studied. The effect of the morphology of the Pd and ZnO components on the sensor response to hydrogen was assessed. Deposition conditions producing more porous films lead to a larger sensor response. The morphology of the ZnO component of the bilayer is decisive and has an influence on the sensor properties in the same order of magnitude as the use of a bilayer instead of a single Pd or ZnO layer. The effect of the Pd film morphology is considerably smaller than that of ZnO, probably due to its smaller thickness. This has implications in other bilayer material combinations used in such sensors and for other types of analytes.

Synthesis Methods of Obtaining Materials for Hydrogen Sensors.

The development of hydrogen sensors has acquired a great interest from researchers for safety in fields such as chemical industry, metallurgy, pharmaceutics or power generation, as well as due to hydrogen's introduction as fuel in vehicles. Several types of sensors have been developed for hydrogen detection, including resistive, surface acoustic wave, optical or conductometric sensors. The properties of the material of the sensitive area of the sensor are of great importance for establishing its performance. Besides the nature of the material, an important role for its final properties is played by the synthesis method used and the parameters used during the synthesis. The present paper highlights recent results in the field of hydrogen detection, obtained using four of the well-known synthesis and deposition methods: sol-gel, co-precipitation, spin-coating and pulsed laser deposition (PLD). Sensors with very good results have been achieved by these methods, which gives an encouraging perspective for their use in obtaining commercial hydrogen sensors and their application in common areas for society.

ZnO Metal Oxide Semiconductor in Surface Acoustic Wave Sensors: A Review.

Surface acoustic wave (SAW) gas sensors are of continuous development interest to researchers due to their sensitivity, short detection time, and reliability. Among the most used materials to achieve the sensitive film of SAW sensors are metal oxide semiconductors, which are highlighted by thermal and chemical stability, by the presence on their surface of free electrons and also by the possibility of being used in different morphologies. For different types of gases, certain metal oxide semiconductors are used, and ZnO is an important representative for this category of materials in the field of sensors. Having a great potential for the development of SAW sensors, the discussion related to the development of the sensitivity of metal oxide semiconductors, especially ZnO, by the synthesis method or by obtaining new materials, is suitable and necessary to have an overview of the latest results in this domain.

Development of Pd/TiO2 Porous Layers by Pulsed Laser Deposition for Surface Acoustic Wave H2 Gas Sensor.

The influence of sensitive porous films obtained by pulsed laser deposition (PLD) on the response of surface acoustic wave (SAW) sensors on hydrogen at room temperature (RT) was studied. Monolayer films of TiO2 and bilayer films of Pd/TiO2 were deposited on the quartz substrates of SAW sensors. By varying the oxygen and argon pressure in the PLD deposition chamber, different morphologies of the sensitive films were obtained, which were analyzed based on scanning electron microscopy (SEM) images. SAW sensors were realized with different porosity degrees, and these were tested at different hydrogen concentrations. It has been confirmed that the high porosity of the film and the bilayer structure leads to a higher frequency shift and allow the possibility to make tests at lower concentrations. Thus, the best sensor, Pd-1500/TiO2-600, with the deposition pressure of 600 mTorr for TiO2 and 1500 mTorr for Pd, had a frequency shift of 1.8 kHz at 2% hydrogen concentration, a sensitivity of 0.10 Hz/ppm and a limit of detection (LOD) of 1210 ppm. SAW sensors based on such porous films allow the detection of hydrogen but also of other gases at RT, and by PLD method such sensitive porous and nanostructured films can be easily developed.

Hydrogen Detection with SAW Polymer/Quantum Dots Sensitive Films.

Regarding the use of hydrogen as a fuel, it is necessary to measure its concentration in air at room temperature. In this paper, sensitive composite films have been developed for surface acoustic wave (SAW) sensors, using quantum dots (QDs) and polymers. Si/SiO2 QDs were used due to having a high specific surface area, which considerably improves the sensitivity of the sensors compared to those that only have a polymer. Si/SiO2 QDs were obtained by laser ablation and analyzed by X-ray diffraction and transmission electron microscopy (TEM). Two types of polymers were used: polydimethylsiloxane (PDMS) and polymethylmethacrylate (PMMA). Polymer and polymer with QDs compositions were deposited on the sensor substrate by drop casting. A heat treatment was performed on the films at 80 °C with a thermal dwell of two hours. The sensors obtained were tested at different hydrogen concentrations at room temperature. A limit of detection (LOD) of 452 ppm was obtained by the sensor with PDMS and Si/SiO2 QDs, which was heat treated. The results demonstrated the potential of using QDs to improve the sensitivity of the SAW sensors and to achieve a heat treatment that increases its adsorption capacity of the gas molecules.

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.