In dip‐pen nanolithography, molecules are “written” onto substrates using an atomic force microscope tip. It is shown here that nanostructures generated using this technique can be used as resists for generating three‐dimensional multilayered solid‐state structures such as that shown in the Figure (a Au/Ti/Si trilayer nanoscale pillar) via wet chemical etching (see also cover).

This article describes novel phase-separation behavior by a binary mixture of alkanethiols when deposited onto a gold surface using micro- and nanodeposition tools, such as microcontact printing (muCP) and dip-pen nanolithography (DPN). This behavior is significantly different than that observed in the bulk. We demonstrate this behavior using three model compounds: 16-mercaptohexadecanoic acid (MHA), 1-octadecanethiol (ODT), and CF3(CF2)11(CH2)2SH (PFT). The identity of the resulting segregated structure is confirmed by lateral force microscopy (LFM) and by selective metal-organic coordination chemistry. Importantly, this phenomenon can be exploited to print sub-100 nm wide alkanethiol lines via conventional muCP and to form sub-15 nm features using DPN, which is below the ultimate resolution of both these techniques. We also demonstrate that these nano-patterned materials can serve as templates for constructing more complex architectures.

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By controlling the extent of oxidation of the polymeric forms of the new class of isolable, polymerizable terthienyl Ru(II) complexes 1, one can modulate both the binding strength of the polymer backbone for Ru(II) and the electronic nature of the bound metal centers.