Mdk. Ingall et al., Surface functionalization and imaging using monolayers and surface-graftedpolymer layers, J AM CHEM S, 121(15), 1999, pp. 3607-3613
A method of surface functionalization of ceramics with monolayers and surfa
ce grafted polymer layers is described. A phenylsilane monolayer is created
on the substrate's oxide surface by using phenyltrichlorosilane as the sil
ane coupling agent. To control the formation of the monolayer and ensure th
e growth of a dense, homogeneous layer, the ceramic surface is first dried
and then a controlled amount of water is adsorbed onto it, and a hindered o
rganic base is added to the phenyltrichlorosilane solution to absorb acid g
enerated in the reaction of the silane coupling agent with hydroxyl groups
on the ceramic surface. This procedure results in dense homogeneous phenyls
ilane monolayers on a variety of surfaces, including silicon, Pt/PtO, and q
uartz. These layers can now be functionalized by addition of triflic acid,
which removes the phenyl ring as benzene, and introduction of a nucleophile
. Monolayers of -C=CH, -OCH2CF3, [(OCH2CH2)(2)O], -OCH2CF2CF3, and -O(CH2)(
6)NH2 were generated in this fashion, all proving to be continuous and homo
geneous. In addition, the cationic silyl triflate site generated by the rem
oval of the phenyl ring is capable of initiating polymerization to form cov
alently bound polymer layers on the surface. Polymer layers of poly(methyl
methacrylate), poly(propylene oxide), and poly(dimethylsiloxane) were gener
ated in this manner; in the case of poly (dimethylsiloxane), layers up to 3
00 Angstrom thick were formed. Anionic initiation of polymerization is also
possible, using a bromopropyl trichlorosilane coupling agent to form the i
nitial monolayer, followed by lithiation with lithium di-tert-butylbiphenyl
. Acrylonitrile can be anionically polymerized to films of up to 2450 Angst
rom in thickness. The monolayers and polymer layers were characterized by X
PS, AFM, contact angle measurements, and profilometry and were found to be
continuous. The initial phenylsilane monolayer can be lithographically patt
erned by using 193 nm Light to cleave the surface phenyl groups; the remain
ing groups can then be functionalized as discussed above to create surface-
grafted patterned polymer layers.