Chemical Bath Deposition of ZnO on Functionalized Self-Assembled Monolayers: Selective Deposition and Control of Deposit Morphology

We have developed a method by which to selectively and reproducibly deposit ZnO films on functionalized self-assembled monolayers (SAMs) using chemical bath deposition (CBD). The deposition bath is composed of zinc acetate and ethylenediamine. The deposition reaction pathways are shown to be similar to those observed for sulfides and selenides, even though ethylenediamine acts as both an oxygen source and a complexing agent. On -COOH terminated SAMs, Zn-carboxylate surface complexes act as nucleation sites for ion-by-ion growth, leading to the formation of adherent ZnO nanocrystallites. Cluster-by-cluster growth is also observed, which produces weakly adherent micrometer-sized ZnO crystallites. On -CH3 and -OH terminated SAMs, only micrometer-sized ZnO crystallites are observed because Zn2+ does not complex with the SAM terminal group, preventing nucleation of the nanocrystalline phase. The application of either ultrasound ("sonication-assisted CBD") or stirring promotes ion-by-ion ZnO growth on -COOH terminated SAMs. Stirring produces smoother but less reproducible ZnO films than sonication-assisted CBD.