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As the advantageous properties of nanoparticles (NPs) often emerge only when appropriate coupling and exchange phenomena between the NPs can take place, the control of the inter-particle distance, regular ordering, and location of the nanoparticles onto solid supports is a critical issue. A robust method to control the spatial organization of NPs onto solid supports, based on the use of self-assembling di-block copolymers (BCPs) as structure-guiding material, is reported. Two different polystyrene-b-poly(methyl methacrylate) (PSb- PMMA) BCPs, characterized by a different PS volume fraction, were used as matrices for the fabrication of nanocomposite thin films with cylindrical and lamellar morphologies controlled at the nanoscale. Selective inclusion of surface functionalized gold (Au) and zinc oxide (ZnO) NPs of appropriate size in the PS nanodomains was achieved from dispersions of the BCPs and NPs in a common solvent. The orientation of the BCPs cylinder and lamellar nanodomains in spin-coated thin films was controlled by solvent and thermal annealing protocols, coupled with techniques of surface neutralization. [ABSTRACT FROM AUTHOR]

This work reports experimental findings about the evolution of lateral ordering of lamellar microdomains in symmetric PS-b-PMMA thin films on featureless substrates. Phase separation and microdomain evolution are explored in a rather wide range of temperatures (190–340 °C) using a rapid thermal processing (RTP) system. The maximum processing temperature that enables the ordering of block copolymers without introducing any significant degradation of macromolecules is identified. The reported results clearly indicate that the range of accessible temperatures in the processing of these self-assembling materials is mainly limited by the thermal instability of the grafted random copolymer layer, which starts to degrade at T > 300 °C, inducing detachment of the block copolymer thin film. For T ⩽ 290 °C, clear dependence of correlation length (ξ) values on temperature is observed. The highest level of lateral order achievable in the current system in a quasi-equilibrium condition was obtained at the upper processing temperature limit after an annealing time as short as 60 s. [ABSTRACT FROM AUTHOR]

Hydroxyl-terminated P(S-r-MMA) random copolymers (RCPs) with molecular weights (Mn) from 1700 to 69000 and a styrene unit fraction of approximately 61% were grafted onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder-forming PS-b-PMMA block copolymer (BCP) thin films. When the thickness (H) of the grafted layer is greater than 5-6 nm, a perpendicular orientation is always observed because of the efficient decoupling of the BCP film from the polar SiO2 surface. Conversely, if H is less than 5 nm, the critical thickness of the grafted layer, which allows the neutralization of the substrate and promotion of the perpendicular orientation of the nanodomains in the BCP film, is found to depend on the Mn of the RCP. In particular, when Mn = 1700, a 2.0 nm thick grafted layer is sufficient to promote the perpendicular orientation of the PMMA cylinders in the PS-b-PMMA BCP film. A proximity shielding mechanism of the BCP molecules from the polar substrate surface, driven by chain stretching of the grafted RCP molecules, is proposed.