Ternary holey carbon nanohorns/TiO2/PVP nanohybrids as sensing films for resistive humidity sensors

Abstract

In this paper, we present the relative humidity (RH) sensing response of a chemiresistive sensor, employing sensing layers based on a ternary nanohybrids comprised of holey carbon nanohorns (CNHox), titanium (IV) oxide, and polyvinylpyrrolidone (PVP) at 1/1/1/(T1), 2/1/1/(T2), and with 3/1/1 (T3) mass ratios. The sensing device is comprised of a silicon-based substrate, a SiO2 layer, and interdigitated transducer (IDT) electrodes. The sensitive layer was deposited via the drop-casting method on the sensing structure, followed by a two-step annealing process. The structure and composition of the sensing films were investigated through scanning electron microscopy (SEM), Raman spectroscopy, and X-ray diffraction (XRD). The resistance of the ternary nanohybrid-based sensing layer increases when H increases between 0% and 80%. A different behavior of the sensitive layers is registered when the humidity increases from 80% to 100%. Thus, the resistance of the T1 sensor slightly decreases with increasing humidity, while the resistance of sensors T2 and T3 register an increase in resistance with increasing humidity. The T2 and T3 sensors demonstrate a good linearity for the entire (0–100%) RH range, while for T1, the linear behavior is limited to the 0–80% range. Their overall room temperature response is comparable to a commercial humidity sensor, characterized by a good sensitivity, a rapid response, and fast recovery times. The functional role for each of the components of the ternary CNHox/TiO2/PVP nanohybrid is explained by considering issues such as their electronic properties, affinity for water molecules, and internal pore accessibility. The decreasing number of holes in the carbonaceous component at the interaction with water molecules, with the protonic conduction (Grotthus mechanism), and with swelling were analyzed to evaluate the sensing mechanism. The hard–soft acid-base (HSAB) theory also has proven to be a valuable tool for understanding the complex interaction of the ternary nanohybrid with moisture.