A fast and simple bottom-up methodology is reported to allow, thanks to a spontaneous phenomenon, the grafting of various materials on polymer substrates. In 60 seconds, the inert surface of polystyrene material is converted into a functional platform onto which organic molecules and metal particles can be anchored. A polystyrene (PS) matrix is blended with a small amount of a diblock copolymer additive engineered to both segregate at the material surface and be able to involve chemical reaction. Indeed, poly(penta fluorostyrene) (PSF) contains surface active fluorine atoms and the nucleophuge para-fluorine atom that allow nucleophilic substitution with thiols. Films of blend of PS matrix and PS-b-PSF additive are submitted to a microwave annealing to accelerate the spontaneous surface segregation of fluorine low surface energy atoms. XPS was performed to find that the optimal annealing condition was a treatment at 30 W during 60 seconds. With this procedure, a blend of 5 w% in additive can lead to a surface composed of 13 at% of fluorine atoms corresponding to 55 w% of diblock. The pentafluorostyrene units decorating the surface were used as anchors to immobilize gold nanoparticles via the para-fluoro-thiol click reaction.

Herein, we report the selective surface functionalization of nano-domains obtained by the self-assembly of a polystyrene-block-poly(vinyl benzyl azide). Click chemistry was used to bind functional gold nanoparticles and poly(N-isopropylacrylamide).

Herein, a novel strategy to overcome the influence of π−π stacking on the rodcoil copolymer organization of is reported. A diblock copolymer poly(3-hexylthiophene)-blockpoly(ethylene glycol methylether methacrylate) P3HT-b-PEGMA was synthesized by a Huisgen cyclo-addition, so-called "Click chemistry", combining the P3HT and PEGMA blocks synthesized by Atom Transfer Radical Polymerization (ATRP) and Kumada Catalyst Transfer Polymerization (KCTP), respectively. Using a dip-coating process, the original film organization of the diblock copolymer was controlled by the crystallization of the P3HT block via π−π stacking. The morphology of the P3HT-b-PEGMA films was influenced by the incorporation of gold nanoparticles GNPs coated by Poly(EthyleneGlycol) ligands. Indeed, the crystalline structuration of the P3HT sequence was counterbalanced by the addition in the film of gold nanoparticles finely localized within the copolymer PEGMA matrix. Transmission Electron Microscopy (TEM) and ToF-SIMS analysis validated the GNPs homogeneous localization into the compatible PEGMA phase. Differential Scanning Calorimetry (DSC) showed the rod block crystallization disruption. A morphological transition of the self-assembly is observed by Atomic Force Microscopy (AFM) from P3HT fibrils into out of plane cylinders-like driven by the nanophase segregation.