Bottom-Up Assembly of Molecular Nanostructures by Means of Ferroelectric Lithography.

Here, we report on the photochemical deposition of Rhodamine 6G (Rh6G) and Alexa647 molecules from aqueous and methanolic solution along 180° ferroelectric (FE) domain walls (DWs) of z-cut lithium niobate (LNO) single crystals. Molecules and FE domains were investigated by means of dynamic-mode AFM, piezoresponse force microscopy (PFM), and confocal scanning fluorescence microscopy. A high deposition affinity for 180° DWs on the LNO surface is observed, leading to the formation of molecular nanowires. Additionally, a more complex deposition pattern for Rh6G adsorbed to the domain areas of freshly poled samples was equally observed, being associated with the DW dynamics. These results are explained by considering contributions from screening-charge-dependent photochemistry as confined to the DWs, UV-induced DW motion, and transient electrostatic fields arising from the metastable defect distribution shortly after poling. Hence, tuning these effects offers the possibility for accurately controlling the complex bottom-up assembly of functional molecular nanostructures through domain-structured ferroelectric templates.