We describe a new patterning technique that employs microcontact printing to replace preformed labile self-assembled monolayers (SAMs) selectively; we call this "microdisplacement printing". We demonstrate that this technique results in ordered molecular regions of both the patterning ("displacing") molecule as well as the remnant labile film, here 1-adamantanethiolate. The existence of the 1-adamantanethiolate SAM before patterning hinders lateral surface diffusion of the patterning molecules, and therefore permits the use of molecules that are otherwise too mobile to pattern by other methods.
We have investigated the transport mechanism of the inks most typically used in dip-pen nanolithography by patterning both 16-mercaptohexadecanoic acid (MHDA) and 1-octadecanethiol (ODT) on the same Au{111} substrate. Several pattern geometries were used to probe ink transport from the tip to the sample during patterning of both dots (stationary tip) and lines (moving tip). When ODT was written on top of a pre-existing MHDA structure, the ODT was observed at the outsides of the MHDA structure, and the transport rate increased. In the reverse case, the MHDA was also observed on the outsides of the previously patterned ODT features; however, the transport rate was reduced. Furthermore, the shapes of pre-existing patterns of one ink were not changed by deposition of the other ink. These results highlight the important role hydrophobicity plays, both of the substrate as well as of the inks, in determining transport properties and thereby patterns produced in dip-pen nanolithography.
Here we demonstrate the versatility of “microdisplacement printing,” a soft lithographic patterning technique that employs microcontact printing to replace pre-formed self-assembled monolayers (SAMs) selectively. We use molecules that are common in microcontact printing as well as low-molecular-weight molecules that cannot be patterned by traditional methods. Multiple component SAMs were fabricated by additional processing steps, extending microdisplacement printing to more complex patterns.
The surface area of electrodeposited thin films of Ni, Co, and NiCo was evaluated using electrochemical double-layer capacitance, electrochemical area measurements using the [Ru(NH)]/[Ru(NH)] redox couple, and topographic atomic force microscopy (AFM) imaging. These three methods were compared to each other for each composition separately and for the entire set of samples regardless of composition. Double-layer capacitance measurements were found to be positively correlated to the roughness factors determined by AFM topography. Electrochemical area measurements were found to be less correlated with measured roughness factors as well as applicable only to two of the three compositions studied. The results indicate that in situ double-layer capacitance measurements are a practical, versatile technique for estimating the accessible surface area of a metal sample.
By patterning with dip-pen nanolithography using tip dwell times ranging from 15 s to 2 h over a period of 19 h, we show that the transport rate for smaller patterns is different than for larger ones. This transport behavior is found for both 1-octadecanethiol (ODT) and 16-mercaptohexadecanoic acid (MHDA) inks on gold substrates. Additionally, MHDA shows an overall decrease in transport rate as a function of total writing time during such experiments. These results indicate that measurements with short dwell times are insufficient to determine transport rates for larger features.
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