Polysilanes on surfaces

For chain-like polymers on surfaces, the relationship between chain topology and inherent physical properties has long been puzzling due to the lack of proper models and detection systems with ultrahigh sensitivity and high accuracy. Among various chain-like polymers, soluble organopolysilane is one suitable model for elucidating the uniqueness of chain-like polymers on surfaces because of its (1) controllable molecular length, polydispersity, stiffness, and terminal group by an adequate molecular design, a careful synthesis, and a precise purification, and (2) highly luminescent chromophore due to Siσ-Siσ* transition of the Si main chain. This review comprehensively covers the works on (i) molecular imaging with scanning probe microscopy, (ii) tethering on surfaces by a grafting-to approach, (iii) self-assembly, (iv) structural phase transition, (v) orientational phase transition, and (vi) chiroptical switching, memory and amplification in single and double layer films deposited on solid surfaces. This knowledge and understanding may stimulate advanced studies on polymer-based nanoscience, nanotechnology, and nanofabrication as well as in traditional surface chemistry and polymer physics.