A strategy has been developed for the grafting of poly(ethylene glycol) (PE
G) monolayers onto the atomically flat Si(111) surface. This process involv
es the direct interaction of the HO-functional group on PEG with a chlorine
-terminated silicon surface. The resulting monolayers show exceptional flat
ness, with mean roughness on the angstrom scale. Film thickness is determin
ed by ellipsometry, X-ray photoelectron spectroscopy, and atomic force micr
oscopy. Results for different molecular weights reveal that the grafted PEG
molecules are in a brushlike configuration at low molecular weight (MW = 2
00, 300) and a more coil-like configuration at higher molecular weight (MW
= 1000, 2000). The surface density of grafted PEG molecules is significantl
y higher than those reported in the literature and decreases with increasin
g molecular weight, from 92% at MW = 300 to 35% at MW = 2000. Both the brus
hlike and the coil-like configurations show excellent properties of protein
resistance.