Metal-modified and vertically aligned carbon nanotube sensors array for landfill gas monitoring applications

Vertically aligned carbon nanotube (CNT) layers were synthesized on Fe-coated low-cost alumina substrates using radio-frequency plasma enhanced chemical vapour deposition (RF-PECVD) technology. A miniaturized CNT-based gas sensor array was developed for monitoring landfill gas (LFG) at a temperature of 150 degrees C. The sensor array was composed of 4 sensing elements with unmodified CNT, and CNT loaded with 5 nm nominally thick sputtered nanoclusters of platinum (Pt), ruthenium (Ru) and silver (Ag). Chemical analysis of multicomponent gas mixtures constituted of CO(2), CH(4), H(2), NH(3), CO and NO(2) has been performed by the array sensor responses and pattern recognition based on principal component analysis (PCA). The PCA results demonstrate that the metal-decorated and vertically aligned CNT sensor array is able to discriminate the NO(2) presence in the multicomponent mixture LFG. The NO(2) gas detection in the mixture LFG was proved to be very sensitive, e.g.: the CNT:Ru sensor shows a relative change in the resistance of 1.50% and 0.55% for NO(2) concentrations of 3.3 ppm and 330 ppb dispersed in the LFG, respectively, with a wide NO(2) gas concentration range measured from 0.33 to 3.3 ppm, at the sensor temperature of 150 degrees C. The morphology and structure of the CNT networks have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. A forest-like nanostructure of vertically aligned CNT bundles in the multi-walled form appeared with a height of about 10 microm and a single-tube diameter varying in the range of 5-35 nm. The intensity ratio of the Raman spectroscopy D-peak and G-peak indicates the presence of disorder and defects in the CNT networks. The size of the metal (Pt, Ru, Ag) nanoclusters decorating the CNT top surface varies in the range of 5-50 nm. Functional characterization based on electrical charge transfer sensing mechanisms in the metal-modified CNT-chemoresistor array demonstrates high sensitivity by providing minimal sub-ppm level detection, e.g., download up to 100 ppb NO(2), at the sensor temperature of 150 degrees C. The gas sensitivity of the CNT sensor array depends on operating temperature, showing a lower optimal temperature of maximum sensitivity for the metal-decorated CNT sensors compared to unmodified CNT sensors. Results indicate that the recovery mechanisms in the CNT chemiresistors can be altered by a rapid heating pulse from room temperature to about 110 degrees C. A comparison of the NO(2) gas sensitivity for the chemiresistors based on disorderly networked CNTs and vertically aligned CNTs is also reported. Cross-sensitivity towards relative humidity of the CNT sensors array is investigated. Finally, the sensing properties of the metal-decorated and vertically aligned CNT sensor arrays are promising to monitor gas events in the LFG for practical applications with low power consumption and moderate sensor temperature.