Adjusting surface coverage of Pt nanocatalyst decoration for selectivity control in CMOS-integrated SnO2 thin film gas sensors

Abstract

Smart gas-sensor devices are of crucial importance for emerging consumer electronics and Internet-of-Things (IoT) applications, in particular for indoor and outdoor air quality monitoring (e.g., CO₂ levels) or for detecting pollutants harmful for human health. Chemoresistive nanosensors based on metal-oxide semiconductors are among the most promising technologies due to their high sensitivity and suitability for scalable low-cost fabrication of miniaturised devices. However, poor selectivity between different target analytes restrains this technology from broader applicability. This is commonly addressed by chemical functionalisation of the sensor surface via catalytic nanoparticles. Yet, while the latter led to significant advances in gas selectivity, nanocatalyst decoration with precise size and coverage control remains challenging. Here, we present CMOS-integrated gas sensors based on tin oxide (SnO₂) films deposited by spray pyrolysis technology, which were functionalised with platinum (Pt) nanocatalysts. We deposited size-selected Pt nanoparticles (narrow size distribution around 3 nm) by magnetron-sputtering inert-gas condensation, a technique which enables straightforward surface coverage control. The resulting impact on SnO₂ sensor properties for CO and volatile organic compound (VOC) detection via functionalisation was investigated. We identified an upper threshold for nanoparticle deposition time above which increased surface coverage did not result in further CO or VOC sensitivity enhancement. Most importantly, we demonstrate a method to adjust the selectivity between these target gases by simply adjusting the Pt nanoparticle deposition time. Using a simple computational model for nanocatalyst coverage resulting from random gas-phase deposition, we support our findings and discuss the effects of nanoparticle coalescence as well as inter-particle distances on sensor functionalisation.

Fig. 1. (a) Fabrication steps for the realisation of CMOS-integrated SnO₂ thin films sensors. (b) Scanning electron microscopy image of typical device. The sensor structure is integrated on a suspended microhotplate mechanically connected via four arms. (c) Schematic of sensor functionalisation via magnetron-sputtering inert-gas condensation. (d) Chemoresistive signal of a pristine SnO₂-based gas sensor at 50% relative humidity and an operation temperature of 200 °C.

Fig. 2. (a) High-resolution TEM micrographs of Pt nanoparticles, showing crystalline structure and surface faceting (scale bars: 1 nm). (b) Size distribution of Pt nanoparticles (normal distribution) obtained by TEM imaging and automated image analysis, assuming circular nanoparticle diameters.

Fig. 3. Low-magnification TEM micrographs of Pt nanoparticles deposited for (a) 10 min, (b) 20 min, and (c) 30 min.

Fig. 4. Sensor response S to CO (left) and VOC (right) of pristine and Pt-decorated SnO₂ sensors (nanoparticle deposition times 10 min, 20 min, 30 min) at 50% relative humidity (rH) and operation temperatures of 200 °C (top row) and 350 °C (bottom row). The relative selectivity (averaged in the concentration range 5–60 ppm) of CO response over VOC response is shown in the right graph.