Effect of Substrate Geometry on Polymer Molecular Weight and Polydispersity during Surface-Initiated Polymerization

Poly(methyl methacrylate) (PMMA) anchored chains were grown on porous silicon (p-Si) and anodically etched aluminum oxide (AAO) substrates via surface-initiated atom transfer radical polymerization (ATRP). Using hydrogen fluoride, the chains could be cleaved from the substrates, as evidenced by infrared spectroscopy. The molecular weights and molecular weight distributions of PMMA could be analyzed directly on these substrates (after cleaving the chains from the support) using direct ionization mass spectrometry (DIOS-MS) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). Two principal conclusions were drawn from the study. First, matrix-free DIOS-MS was effective at direct analysis of the polymers up to a molecular weight of ≈6 kDa; the signal-to-noise ratio for heavier polymer chains diminished rapidly. Second, under the same polymerization conditions, PMMA grown on both p-Si and AAO substrates had a much lower molecular weight and a broader molecular weight distribution than that grown in solution. Confinement effects imposed by the pores during the polymerization are proposed as the likely mechanism for the reduced growth rates and more polydisperse chains.