Negative printing by soft lithography

In inkless microcontact printing (IμCP) by soft lithography, the poly(dimethylsiloxane) (PDMS) stamp transfers uncured polymer to a substrate corresponding to its pattern. The spontaneous diffusion of PDMS oligomers to the surface of the stamp that gives rise to this deleterious side effect has been leveraged to fabricate a variety of devices, such as organic thin film transistors, single-electron devices, and biomolecular chips. Here we report an anomalous observation on a partially cured PDMS stamp where the transfer of oligomers onto Au occurred on regions that were not in contact with the stamp, while the surface in contact with the stamp was pristine with no polymer. On the SiO2 surface of the same chip, as expected, the transfer of PDMS occurred exclusively on regions in contact with the stamp. The printing on Au was quantified by a novel method where the submonolayer of PDMS transfer was measured by probing the local electrochemical passivation of the Au. The local transfer of polymer on SiO2 (and also Au) was measured by selective deposition of Au nanoparticle necklaces that exclusively deposited on PDMS at submonolayer sensitivity. It was discovered that the selectivity and sharpness of PDMS deposition on Au for inkless printing (i.e., negative) is significantly better than the traditional (positive) microcontact printing where the stamp is "inked" with low molecular weight PDMS.