Capillary bridge rupture in dip-pen nanolithography

Here, we explore fluid transfer from a nanoscale tip to a surface and elucidate the role of fluid flows in dip-pen nanolithography (DPN) of liquid inks. We find that while fluid transfer in this context is affected by dwell time and tip retraction speed from the substrate, their specific roles are dictated by the contact angle of the ink on the surface. This is shown by two observations: (1) the power law scaling of transferred fluid with dwell time depends on contact angle, and (2) slower retraction speeds result in more transfer on hydrophilic surfaces, but less transfer on hydrophobic surfaces. These trends, coupled with the observation of a transition from quasi-static to dynamic capillary rupture at a capillary number of 6 x 10(-6), show that the transfer process is a competition between surface energy and viscosity. Based on this, we introduce retraction speed as an important parameter in DPN and show that it is possible to print polymer features as small as 14 nm. Further explorations of this kind may provide a useful platform for studying capillary phenomena at the nanoscale.