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The synthesis of grafted PMMA homopolymer films is reported using a surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization from a RAFT-agent immobilized on a silanized stainless steel surface. Therefore, stainless steel surfaces were hydroxylated with piranha solution followed by silanization with 3-aminopropylsilane (APS). The pendant primary amino groups of the cross-linked polysiloxane layer were reacted with 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid N-hydroxysuccinimide ester to produce a surface with covalently immobilized RAFT agents. PMMA homopolymers of different molecular weights between 13 060 and 45 000 g/mol were then prepared by a surface-initiated RAFT polymerization. Molecular weight (MW) and polydispersity index (PDI) were determined from sacrificial polymerization in solution. The different steps of stainless steel surface modification and the ultrathin films were investigated using atomic force microscopy (AFM), static, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance infrared spectroscopy (ATR-IR), and ellipsometry.

We describe the controlled assembly of silane-based copolymers on various interfaces that have surface silanol groups. This assembly occurs as a result of the formation of very robust siloxane bonds (Si-O-Si) due to a condensation reaction between the alkoxysilane groups of the polymers and surface hydroxyl groups of the substrates. Deposition of these copolymers is not self-limiting; therefore, they could not be assembled into discrete monolayers. However, UV-visible data collected as a function of deposition cycle reveals a linear relationship, confirming the deposition of a constant amount of polymer in each deposition cycle. A linear variation of layer thickness with deposition cycles is also observed. The assembled polymer layers are found to be very robust and resistant even when exposed to piranha solution for several hours.

It has been found that a common shipping and packaging material for commercial AFM cantilever tips, poly(dimethylsiloxane) (PDMS), causes a thin layer of silicone oil contamination on AFM cantilever tips. Due to the similarity of elemental compositions between silicone oils and AFM cantilevers (both contain silicon and oxygen), it is difficult to detect such contaminants with the widely used surface characterization technique, X-ray photoelectron spectroscopy (XPS), since XPS provides mainly elemental and short-range chemical information. However, by using static time-of-flight secondary-ion mass spectrometry (TOF-SIMS), a technique that is extremely surface-sensitive, silicone oils on AFM cantilevers can easily be identified by their molecular fragments. A simple dip cleaning procedure using a mixture of concentrated sulfuric acid and hydrogen peroxide (piranha solution) was found to be an easy and effective way to remove organic contamination, including silicone oils, from AFM cantilever tips. It has al...