Monolayer-Directed Electrodeposition of Oxide Thin Films: Surface Morphology versus Chemical Modification

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Abstract

In this paper we describe the general role that surface morphology and chemical nature play in guiding the cathodic deposition of oxide thin films onto electrode surfaces. By use of a “featureless” stamp for microcontact printing (μCP), the pregrooved microfeatures (“mountains” and “valleys” representing the track trails) of recordable compact disc (CD-R) gold substrates can be selectively modified with OH- or CH3-terminated self-assembled monolayers (SAMs). For comparison, “flat” gold substrates were patterned with the above SAMs in parallel “microstrips” that are analogous to the CD-R substrate (but no height differences). Electrochemical deposition of zirconia thin films showed that, on the CD-R substrates, surface morphology (height difference) dominates over the blocking effects of the SAMs; that is, deposition occurred primarily on the mountains despite these sites being modified with organic monolayers. For flat gold substrates it was found that n-alkanethiolate SAMs block deposition in modified areas while directing the deposition to regions of the bare surface. When flat gold substrates were modified with CH3- and OH-terminated SAMs in alternating microstrips, deposition was confined to “narrower” regions that are different from the periodicity on the stamp. The type of microstructures and feature sizes of the zirconia thin film were dependent on scan rate, number of cycles, and terminal groups of the SAM to a lesser extent.

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