Role of absorbed solvent in polymer pen lithography

We report on the dynamic role of solvents in molecular printing and show that material transport can be mediated by both environmental solvent (i.e., humidity) and solvent absorbed in the pen. To explore the transport of materials in the absence of environmental solvent, a hydrophobic polymer was patterned using a polydimethylsiloxane (PDMS) pen array that had been soaked in undecane, a nonpolar solvent that readily absorbs into PDMS. We also explored the patterning of the hydrophilic polymer polyethylene glycol (PEG) and found that, even though PDMS only absorbs trace amounts of water, soaking a PDMS pen array in water enables PEG deposition in completely dry environments for over 2 h. We find that the length of time one can pattern in a dry environment is determined by the availability of absorbed solvent, a relationship that we elucidate by comparing the performance of pens with varying ability to absorb water. Furthermore, a calculation accounting for the dynamics of retained water captures these effects completely, allowing for generalization of this result to other solvents and providing a way to tune the desired solvent retention profile. Taken together, this work explores the subtle and dynamic role of solvent on molecular printing and provides an alternative to strict environmental humidity control for reliable molecular printing.