We present a microcontact
printing (μCP) routine suitable
to introduce defined (sub-) microscale patterns on surface substrates
exhibiting a high capillary activity and receptive to a silane-based
chemistry. This is achieved by transferring functional trivalent alkoxysilanes,
such as (3-aminopropyl)-triethoxysilane (APTES) as a low-molecular
weight ink via reversible covalent attachment to polymer brushes grafted
from elastomeric polydimethylsiloxane (PDMS) stamps. The brushes consist
of poly{
N
-[tris(hydroxymethyl)-methyl]acrylamide}
(PTrisAAm) synthesized by reversible addition–fragmentation
chain-transfer (RAFT)-polymerization and used for immobilization of
the alkoxysilane-based ink by substituting the alkoxy moieties with
polymer-bound hydroxyl groups. Upon physical contact of the silane-carrying
polymers with surfaces, the conjugated silane transfers to the substrate,
thus completely suppressing ink-flow and, in turn, maximizing printing
accuracy even for otherwise not addressable substrate topographies.
We provide a concisely conducted investigation on polymer brush formation
using atomic force microscopy (AFM) and ellipsometry as well as ink
immobilization utilizing two-dimensional proton nuclear Overhauser
enhancement spectroscopy (
1
H–
1
H-NOESY-NMR).
We analyze the μCP process by printing onto Si-wafers and show
how even distinctively rough surfaces can be addressed, which otherwise
represent particularly challenging substrates.
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