The integration of porous thin films using microelectronic compatible processes sometimes requires the protection of the interior of the pores during the critical integration steps. In this paper, the polymerization of neo‐pentyl methacrylate (npMA) is performed via initiated chemical vapor deposition (iCVD) on a porous organosilicate (SiOCH) and on a dense SiOCH. The characterizations by Fourier‐transform infrared spectroscopy, spectroscopic ellipsometry, and time‐of‐flight secondary ion mass spectrometry of the different stacks show that iCVD is a powerful technique to polymerize npMA in the nanometric pores and thus totally fill them with a polymer. The study of the pore filling for very short iCVD durations shows that the polymerization in the pores is complete in less than ten seconds and is uniform in depth. Then, the poly(npMA) film growth continues on top of the filled SiOCH layer. These characteristics make iCVD a straightforward and very promising alternative to other infiltration techniques in order to fill the porosity of microporous thin films.

investigate the influence of the molecular weight of poly(methyl methacrylate) (PMMA) thin films coated on silicon wafer on the time-of-flight secondary ion mass spectrometry (ToF-SIMS) sputtering mechanisms and kinetics during depth profiling using low-energy monoatomic caesium ions. The sputtering yield volumes are determined as function of molecular weight, film thickness and beam energy. The results show that the sputtering yield volume decreases with increasing molecular weight M w down to a threshold value below which it becomes nearly constant, as previously observed with argon cluster ions. The relevance of physical parameters such as the glass transition temperature T g -determined here from ellipsometry measurements-and the entanglement of the polymer chains to account for this behaviour is discussed. The variation of the sputtering yield was also found to vary logarithmically with the primary beam energy. In addition, preliminary experiments carried out using a low molecular weight PMMA (4 kg/mol) evidenced a nanoconfinement effect similar to that observed with argon cluster sputtering but of lower magnitude.