Achieving Humidity-Independent Dimethyl Methylphosphonate Response in Surface Acoustic Wave Sensors through ZrO₂...

Surface acoustic wave (SAW) sensors are widely employed for detecting dimethyl methylphosphonate (DMMP, a simulant of the chemical warfare agent sarin) due to their wireless and passive monitoring capability, digital output, and cost-effectiveness. Zirconium dioxide (ZrO₂) nanoparticles are considered one of the most promising sensing materials for DMMP detection owing to their unique and strong surface interactions with phosphorus-containing compounds, as well as their excellent chemical and thermal stability. However, the practical deployment of ZrO₂ SAW sensors faces significant challenges, as atmospheric humidity severely degrades their performance, causing substantial sensitivity drift and even polarity reversal. This work reports a strategy involving the modification of ZrO₂ nanoparticle surfaces with hydrophobic functional groups (-Si(CH₃)₃). This approach successfully transformed the inherently superhydrophilic ZrO₂ material (water contact angle, WCA = 19°) into a hydrophobic state (WCA = 136°). For SAW sensors based on this hydrophobized ZrO₂, the initial frequency drift induced by humidity was suppressed by 92.6 at 85% relative humidity (RH). More importantly, across the dynamic humidity range of 20-85% RH, the DMMP response remained stable at approximately -325 Hz/ppm (fluctuation <6%). This performance is significantly superior to that of unmodified ZrO₂ SAW sensors, whose responses fluctuated drastically between -1030 Hz/ppm and +1141 Hz/ppm under identical conditions. The mechanisms underlying the humidity-induced sensitivity drift in ZrO₂ SAW sensors were elucidated using in situ infrared absorption spectroscopy and X-ray photoelectron spectroscopy techniques. This study not only provides a straightforward strategy for imparting hydrophobicity to ZrO₂ but also offers novel insights for addressing the issue of frequency drift in SAW sensors caused by atmospheric moisture.