In this paper, the relationship between the surface structures
of spin-coated fluorinated polymer films and their corresponding film-formation
solution/air interface structures was investigated. Film-forming poly(n-alkyl methacrylate) end-capped with 2-perfluorooctylethyl
methacrylate (FMA; PFMA
y
-ec-PnAMA
x
-ec-PFMA
y
) was
synthesized via a controlled/living atom-transfer radical polymerization
(ATRP) technique. The structures both at solution interface and on
the spin-coated film surface for these polymers were studied by X-ray
photoelectron spectroscopy (XPS), sum frequency spectroscopy (SFG),
and surface tension measurements. The results showed that, with increasing
polymerization degree of PnAMA, the fluorinated moieties in PFMA
y
-ec-PnAMA
x
-ec-PFMA
y
adsorbed at the solution/air interface were
gradually completely replaced by PnAMA segments, resulting in an increase
in corresponding solution surface tension until it was equal to that
of poly(n-alkyl methacrylate) solution. Additionally,
it was observed for the first time that the surface F/C ratios of
spin-coated films decreased linearly with increasing surface tension
of the corresponding film-formation polymer solution. Overall, the
results indicate that the ultimate surface composition of spin-coated
films of these fluorinated methacrylates was mainly dominated by their
corresponding film-formation solution/air interfacial structure. This
work provides a fundamental understanding of the formation of film
surface structures from fluorinated polymer solution to the resulting
solid film.
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