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.
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 TiO 2 and bilayer films of Pd/TiO 2 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/TiO 2 -600, with the deposition pressure of 600 mTorr for TiO 2 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.
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.
The selectivity of a SAW (surface acoustic wave) sensor, with a Co3O4 sensitive thin film for NH3 (ammonia) and the influence of SnO2 on its sensitivity, was studied. Thin films were deposited by pulsed laser deposition (PLD) on quartz SAW sensor substrates. Two sensors with different types of sensitive films were developed: a Co3O4 thin film sensor (S1) and a SnO2/Co3O4 thin film sensor (S2). The sensitive films were deposited in conditions which ensured a porous structure. The sensors were tested in the presence of three gases: NH3, methanol, and toluene. The selectivity of Co3O4 for NH3 was determined from the difference in the frequency shifts of the sensor for NH3 and for VOCs (volatile organic compounds). The positive influence of SnO2 on the sensitivity of sensor S2 was observed from the lower limit of detection (LOD) of this sensor and from the differences in frequency shifts between sensor S1 and sensor S2.
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