Temperature Dependence of Arn+ Cluster Backscattering from Polymer Surfaces: a New Method to Determine the Surface Glass Transition Temperature

In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to study the intensity variations of the backscattered Arn + clusters as a function of temperature for several amorphous polymer surfaces (polyolefins, polystyrene, and polymethyl methacrylate). For all these investigated polymers, our results show a transition of the ratio Ar2 +/(Ar2 + + Ar3 +) when the temperature is scanned from –120 °C to +125 °C (the exact limits depend on the studied polymer). This transition generally spans over a few tens of degrees and the temperature of the inflection point of each curve is always lower than the bulk glass transition temperature (Tg) reported for the considered polymer. Due to the surface sensitivity of the cluster backscattering process (several nanometers), the presented analysis could provide a new method to specifically evaluate a surface transition temperature of polymers, with the same lateral resolution as the gas cluster beam.