Phase of molecular ink in nanoscale direct deposition processes.

We report the first observation of a phase transition in a nanoscale direct deposition process. This transition involves the melting of molecular ink layers in dip-pen nanolithography, and it is observed by measuring the temperature dependence of the growth rate of the deposited pattern. The results are interpreted using a diffusion equation approach in conjunction with a "double-molecular-layer" model of the adsorbed molecules on the atomic force microscope tip. The theory provides a qualitative explanation for the dependence of the pattern growth rate on solvent and adsorbed water as well as on temperature.