Heats of adsorption of Pb on pristine and electron-irradiated poly(methyl methacrylate) by microcalorimetry

The heat of adsorption and sticking probability were measured for Pb gas atoms adsorbing onto clean poly(methyl methacrylate) (PMMA) and electron-irradiated PMMA. The Pb atoms interact very weakly with the outgassed pristine PMMA surface, with a sticking probability of 0.02 ± 0.02. They deposit a heat into the PMMA of 12.7 ± 0.7 kJ/mol of dosed Pb, independent of Pb exposure up to 10 ML. This is slightly less than would be expected even if no Pb atoms stuck to the PMMA, but if they completely thermally accommodated to the substrate temperature during their collision with the surface. This proves that thermal accommodation is incomplete, highlighting the weakness of the Pb–PMMA interaction. Damaging the PMMA surface with electrons causes an increase in reactivity with Pb, as shown by increases in the initial heat of adsorption up to 134.0 ± 0.7 kJ/mol and the initial sticking probability up to 0.51 ± 0.01. These both increase with increasing coverage toward the values expected for Pb adsorption onto a bulk Pb surface with coverage dependences suggesting that metal islands nucleate at electron-induced defects, and grow into large 3D islands of low number density. This is the first calorimetric measurement of any metal adsorption energy onto any polymer surface wherein the sticking probability of the metal also was measured. The PMMA film was spin coated directly onto the heat detector, a pyroelectric polymer foil (polyvinylidene fluoride—PVDF) precoated on both sides with thin metal electrodes. It provides a detector sensitivity of ∼450 V/J with a pulse-to-pulse standard deviation of 1.2 kJ/mol and absolute accuracy within 2%.