Heavyweight dendritic inks for positive microcontact printing

Poly(propylene imine) dendrimers with dialkyl sulfide end groups were prepared and developed as inks for positive microcontact printing ((+)uCP) on gold. Long (C10H21-S-C10H20-), medium (C3H7-S-C4H8-), and short (CH3-S-CH2-) dialkyl sulfide end groups were attached to second- and third-generation PPI dendrimers to create a family of dendritic sulfides. The dendritic inks flatten upon adsorption and form monolayers on gold. (+)uCP was performed on gold using commercially available poly(dimethylsiloxane) as stamp material and n-octadecanethiol as etch resist. The gold beneath the dendrimers was selectively etched away with an acidic Fe(NO3)3/thiourea solution to give the positive copy of the original master pattern. The multivalent sulfide attachment and the relatively high molecular mass of these dendrimers ensured minimal lateral ink spreading and thus optimal feature reproducibility. Contact times were varied to analyze the spreading rates of the dendritic inks. The spreading rates of the dendritic inks were found to be much lower than that of pentaerythritol tetrakis(3-mercaptopropionate). (+)uCP with the new inks was extended to submicrometer features. Optical microscopy, scanning electron microscopy, and atomic force microscopy were used to characterize the etched samples. Lines with a width of 100 nm were faithfully replicated with the third-generation dendrimers bearing medium (C3-S-C4-) end groups.