Surface functionalization and imaging using monolayers and surface-graftedpolymer layers

Citation
Mdk. Ingall et al., Surface functionalization and imaging using monolayers and surface-graftedpolymer layers, J AM CHEM S, 121(15), 1999, pp. 3607-3613
Citations number
67
Categorie Soggetti
Chemistry & Analysis",Chemistry
Journal title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN journal
00027863 → ACNP
Volume
121
Issue
15
Year of publication
1999
Pages
3607 - 3613
Database
ISI
SICI code
0002-7863(19990421)121:15<3607:SFAIUM>2.0.ZU;2-C
Abstract
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.