RESUMO
Understanding nanoscale mechanisms responsible for the recently discovered ferroelectric nematics can be helped by direct visualization of self-assembly of strongly polar molecules. Here, we report on scanning tunneling microscopy studies of monomolecular layers of a ferroelectric nematic liquid crystal on a reconstructed Au(111) surface. The monolayers are obtained by deposition from a solution at ambient conditions. The adsorbed ferroelectric nematic molecules self-assemble into regular rows with tilted orientation, resembling a layered structure of a smectic C. Remarkably, each molecular dipole in this architecture is oriented along the same direction giving rise to polar ferroelectric ordering.
RESUMO
Combining STM measurements on three different substrates (HOPG, MoS2, and Au[111]) together with DFT calculations allow for analysis of the origin of the self-assembly of 4-cyano-4'-n-decylbiphenyl (10CB) molecules into kinked row structures using a previously developed phenomenological model. This molecule has an alkyl chain with 10 carbons and a cyanobiphenyl group with a particularly large dipole moment. 10CB represents a toy model that we use here to unravel the relationship between the induced kinked structure, in particular the corresponding chirality expression, and the balanced intermolecular/molecule-substrate interaction. We show that the local ordered structure is driven by the typical alkyl chain/substrate interaction for HOPG and Au[111] and the cyanobiphenyl group/substrate interaction for MoS2. The strongest molecule/substrate interactions are observed for MoS2 and Au[111]. These strong interactions should have led to non-kinked, commensurate adsorbed structures. However, this latter appears impossible due to steric interactions between the neighboring cyanobiphenyl groups that lead to a fan-shape structure of the cyanobiphenyl packing on the three substrates. As a result, the kink-induced chirality is particularly large on MoS2 and Au[111]. A further breaking of symmetry is observed on Au[111] due to an asymmetry of the facing molecules in the rows induced by similar interactions with the substrate of both the alkyl chain and the cyanobiphenyl group. We calculate that the overall 10CB/Au[111] interaction is of the order of 2 eV per molecule. The close 10CB/MoS2 interaction, in contrast, is dominated by the cyanobiphenyl group, being particularly large possibly due to dipole-dipole interactions between the cyanobiphenyl groups and the MoS2 substrate.
RESUMO
The light-induced and STM-tip-induced switching of photochromic thiol functionalized terphenylthiazole-based diarylethene self-assembly on Au(111) has been investigated in ambient conditions. For such a purpose, we took advantage of the formation of highly ordered domains of opened-ring (1o) or closed-ring (1c) diarylethene isomers. We evidenced a STM-tip-induced switching for the 1o isomer characterized by a tip bias threshold of 1000 mV above which switching of all molecules of the ordered 1o domains occurs into the 1c isomer. In contrast, switching from 1c form into 1o form is not observed at the same tunnelling conditions within a domain formed by ordered 1c molecules. We compared tip-induced switching of ordered 1o domains and switching of single 1o isomers embedded in 1c domains. This led to the demonstration that the process of switching of the 1o isomer is determined by geometry of the molecules but also that the stability of the switched 1c isomer depends on the nature of the surrounding isomers. We also compare tip-induced switching and switching under the action of external UV light irradiation of ordered 1o domains. In contrast with STM tip-induced switching, the UV light induces switching of 1o domains into their stable 1c form, in agreement with a collective switching under irradiation, which cannot occur under the action of STM tip.
