3D Orientational Control in Self‐Assembled Thin Films with Sub‐5 nm Features by Light

While self‐assembled molecular building blocks could lead to many next‐generation functional organic nanomaterials, control over the thin‐film morphologies to yield monolithic sub‐5 nm patterns with 3D orientational control at macroscopic length scales remains a grand challenge. A series of photoresponsive hybrid oligo(dimethylsiloxane) liquid crystals that form periodic cylindrical nanostructures with periodicities between 3.8 and 5.1 nm is studied. The liquid crystals can be aligned in‐plane by exposure to actinic linearly polarized light and out‐of‐plane by exposure to actinic unpolarized light. The photoalignment is most efficient when performed just under the clearing point of the liquid crystal, at which the cylindrical nanostructures are reoriented within minutes. These results allow the generation of highly ordered sub‐5 nm patterns in thin films at macroscopic length scales, with control over the orientation in a noncontact fashion. Highly ordered nanopatterns are obtained at sub‐5 nm periodicities by the photoalignment of hybrid oligo(dimethylsiloxane) liquid crystals. By using light, aligned structures can be realized on macroscopic length scales in a noncontact fashion with 3D control over the thin‐film orientation.