Electrospinning is reported in this paper as a new coating approach for surface acoustic wave (SAW) sensor in order to enhance its chemical detection capability. Ultrafine (100–300 nm) polyethylene oxide (PEO) fibrous film with controlled thickness and porosity were electrospun-coated on the surface of a ST-X quartz based SAW sensor. Compared to the conventional solid thin film coating techniques, the nanofiber-coated SAW sensor shows a higher sensitivity and faster response. A theoretical analysis was performed to characterize the SAW sensor response with nanofibrous film coating. The nanofibrous film provides a high surface area to volume ratio, which can not only offer more adsorption sites for vapor molecules, but also shortens the diffusion length of vapor molecules into polymer material. It is concluded that the nanofiber film holds a great potential in enhancing SAW sensor performance for trace level detection of chemical analytes.

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