Polymer functionalized surfaces are important components of various sensors, solar cells and molecular electronic devices. In this context, the use of self-assembled monolayer (SAM) formation and subsequent reactions on the surface have attracted a lot of interest due to its stability, reliability and excellent control over orientation of functional groups. The chemical reactions to be employed on a SAM must ensure an effective functional group conversion while the reaction conditions must be mild enough to retain the structural integrity. This synthetic constraint has no universal solution; specific strategies such as "graft from", "graft to", "graft through" or "direct" immobilization approaches are employed depending on the nature of the substrate, polymer and its area of applications. We have reviewed current developments in the methodology of immobilization of a polymer in the first part of the article. Special emphasis has been given to the merits and demerits of certain methods. Another issue concerns the utility - demonstrated or perceived - of conjugated or non-conjugated macromolecules anchored on a functionally decorated SAM in the areas of material science and biotechnology. In the last part of the review article, we looked at the collective research efforts towards SAM-based polymer devices and identified major pointers of progress (236 references).

A series of castor oil based polyurethane/siloxane cross-linked films were prepared using castor oil, isophorone diisocyanate, and 3-aminopropyl trimethoxysilane by the sol-gel process. Fourier transform infrared (FT-IR) spectra reveal the cross-linking interaction between polyurethane and siloxane moieties, thereby shifting the peak position of characteristic N-H and C═O groups to higher wavenumber. (29)Si (silica) solid state nuclear magnetic resonance spectra were used to prove the formation of siloxane network linkage in the polyurethane system, thereby analyzing the Si environment present in the polyurethane/siloxane cross-linked films. The activation energy values at two stages (Tmax1 and Tmax2) for the degradation of polyurethane films were increased with increasing silane ratio. The calculated activation energy values for the higher silane ratio (1.5) are 136 and 170 kJ/mol at Tmax1 and Tmax2, respectively. From contact angle measurements, we observed that increasing siloxane cross-linking increased the hydrophobicity of the films. The optical transmittance obtained from ultraviolet-visible spectra indicated that the film samples are transparent in the region 300-800 nm. The moisture sorption/desorption isotherm curve shows a characteristic behavior of type III isotherm corresponds to hydrophobic materials. Dynamic mechanical studies show that the increase in storage modulus reveals siloxane cross-linking gives rigidity to the films. Atomic force microscopic images show that the introduction of siloxane changes the surface roughness of the polyurethane films. It is found that the siloxane cross-linking can be used to obtain hydrophobic surface films having good thermal stability and optical transmittance.