Chemiresistive vapor sensing with microscale films of gold monolayer protected clusters

Here we report the stability, conductivity, and vapor-sensing properties of microcontact-printed films of 1.6-nm average diameter hexanethiolate-coated gold monolayer protected clusters (C6 Au MPCs). The C6 Au MPCs were stamped into parallel lines (approximately 1.2 microm wide and 400 nm thick) across two Au electrodes separated by a 1-microm gap. The chemiresistive vapor-sensing properties were measured for saturated toluene and 2-propanol vapors. As-prepared patterned Au MPC films were unstable in the presence of saturated toluene vapor, and their current response was irreversible. Chemically linking the films with vapor-phase hexanedithiol greatly improves their stability and leads to reversible responses. The extent of Au MPC cross-linking and vapor response to organic vapors varies with different exposure times to dithiol vapor. The response to toluene changed from 61 to 8% for exposures of 1 and 60 min, respectively, which is likely due to greater film flexibility with less dithiol exposure. The current measured through the films varies from 10(-11) to 10(-3) Angstroms as a function of the temperature between 250 and 320 degrees C, which correlates with the loss of organic material as measured by FT-IR spectroscopy and the change in thickness and width of the film as measured by atomic force microscopy. The vapor-sensing properties vary with temperature, current, and organic content in the film, which are all interrelated. Response to toluene decreased with increasing temperature and conductivity, while the response to 2-propanol was less predictable. Reducing the size of vapor-sensing devices based on Au MPCs is important for creating highly portable devices that can simultaneously detect multiple analytes. This work demonstrates a simple method for reducing the size of such devices down to the microscale and describes methods for maximizing response, stability, and reversibility.