Toward SERS based localized thermometry of Polymer-Supported silver and gold nanostructures

In order to accurately account for the contribution of different plasmon mediated phenomena when developing materials for applications in photothermal therapy, photovoltaics, or photocatalysis reliable, precise, and localized temperature measurements are required. In this work we applied two surface-enhanced Raman scattering (SERS) spectroscopy based methods to measure the local temperature increase due to the thermoplasmonic effect in gold and silver nanoparticles on thin polystyrene films. The first method relies on the temperature dependence of the anti-Stokes to Stokes Raman bands intensity ratio for a label Rhodamine 6G deposited on the nanostructures. We found that the method enables good measurements in the 20-60 °C temperature range but becomes less reliable at higher temperatures when the system undergoes transformations and the plasmonic response of the nanoparticles changes with heating. The second method makes use of the temperature dependent adsorption geometry of phenyl isocyanide (PIC) and a corresponding shift of ν(C≡N) vibration. The method demonstrates greater temperature sensitivity of gold nanoparticles than silver. The difference in sensing capability is related to the difference in molecular adsorption geometry of PIC on Au compared to Ag. We conclude that for universal thermometry of the nanoparticle/ thin film composite a combination of the two methods provides more precise localized temperature measurements.