Ammonia gas sensors based on undoped and Ca-doped ZnO nanoparticles

Due to its large use in different industrial sectors, high toxicity, and corrosion, the demand for sensing techniques towards ammonia gas has become urgent. In this study we report on the sensing performances of a conductometric sensor for NH₃ gas based on Ca-doped ZnO nanoparticles with different calcium concentrations (0, 1, and 3 at%) synthesized using the sol-gel process under supercritical dry conditions of ethanol. All samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier-transform infrared (FTIR) spectroscopy. Pure and Ca-doped ZnO are polycrystalline and well crystallized in the hexagonal wurtzite structure. TEM images revealed that pure ZnO is composed of spherical particles with dimensions in the nanometer range. Larger particles were observed after the incorporation of Ca ions. The average crystallite size, estimated by the Williamson-Hall method, was 43, 80, and 96 nm for pure, Ca-1 at% and Ca-3 at%, respectively. Furthermore, FTIR spectroscopy was used to prove the formation of ZnO and the incorporation of calcium ions in the Ca-doped ZnO samples. The gas sensing performances towards ammonia gas clearly ameliorated after the addition of Ca ions in the ZnO structure. The gas response to NH₃, R₀/R_g, of the 1% Ca-doped ZnO sensor reached a value of 33 for 4000 ppm of ammonia at T = 300 °C with good selectivity compared to other gases such as CO, CO₂, and NO₂. The response and recovery times were 5 s and 221 s, respectively. The reported good sensing performances indicate the potential application of Ca-doped ZnO as a sensor material for ammonia detection.