Block copolymers have been extensively studied over the last few decades because they can self-assemble into well-ordered nanoscale structures. The morphologies of block copolymers in confined geometries, however, are still not fully understood. In this work, the fabrication and morphologies of three-dimensional polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanostructures confined in the nanopores of anodic aluminum oxide (AAO) templates are studied. It is discovered that the block copolymers can wet the nanopores using a novel solvent-annealing-induced nanowetting in templates (SAINT) method. The unique advantage of this method is that the problem of thermal degradation can be avoided. In addition, the morphologies of PS-b-PDMS nanostructures can be controlled by changing the wetting conditions. Different solvents are used as the annealing solvent, including toluene, hexane, and a co-solvent of toluene and hexane. When the block copolymer wets the nanopores in toluene vapors, a perpendicular morphology is observed. When the block copolymer wets the nanopores in co-solvent vapors (toluene/hexane = 3:2), unusual circular and helical morphologies are obtained. These three-dimensional nanostructures can serve as naontemplates for refilling with other functional materials, such as Au, Ag, ZnO, and TiO2 .

The microphase separation of block copolymers in confined geometries has been widely investigated over the last few decades. The controllability and versatility of the confinement-induced morphologies, however, are still difficult to be achieved because of the limited experimental parameters in the process of fabricating the confined nanostructures. In this work, we study the morphology transitions of lamellae-forming polystyrene-block-polydimethylsiloxane (PS-b-PDMS) nanorods confined in the nanopores of anodic aluminum oxide (AAO) templates. The nanorods are formed by solvent-assisted template wetting, and the morphologies are compared to those in the bulk state. By blending PS-b-PDMS with homopolystyrene (hPS), the morphologies of the nanorods can be controlled because of the changes of the effective volume fractions. Special morphology transitions from concentric lamellar morphology, to multihelical morphology, and finally to spherical-like morphology are observed by increasing the weight ratios of hPS. hPS with different molecular weights is also applied to investigate the effect of hPS on the morphologies of the PS-b-PDMS/hPS blend nanostructures. The unusual morphologies are further confirmed by a selective removal process, which also generates nanochannels for possible refilling with functional materials.

Poly­(3-hexylthiophene) (P3HT) films have been usually prepared by spin-coating for the applications of electronic devices such as organic photovoltaic devices (OPV) and organic field-effect transistors (OFETs). The wetting and dewetting behaviors of the swollen P3HT films during the spin-coating processes, however, are still poorly understood. In this work, we investigate the dewetting behaviors of P3HT thin films and the formation of ring structures during the spin-coating process by controlling the spin rates and the solution temperatures. Quantitative studies of the dewetting phenomena are conducted by measuring the sizes of the ring structures of the dewetting patterns. It is observed that the sizes of the ring structures are larger at lower spin rates because of the longer dewetting times allowed during the spin-coating processes. More importantly, the dewetting behaviors of the P3HT films are discovered to be affected by the formation of the P3HT nanowhiskers (nanowires). This work offers a deeper understanding of the dewetting behaviors of swollen P3HT films during the spin-coating processes, which is crucial for the development of P3HT-based optoelectronic devices.

The microphase separation behavior of block copolymers confined in cylindrical nanopores has been extensively investigated. Recently, the solvent-annealing-induced nanowetting in templates (SAINT) method has been demonstrated to be a versatile approach for the infiltration of block copolymers into the nanopores of porous templates. The function of the annealing solvents, however, is still not well understood, especially in the morphology control of the fabricated block copolymer nanostructures. In this work, we elucidate the function of the annealing solvents in the SAINT method using a lamella-forming block copolymer, polystyrene-block-polydimethylsiloxane (PS-b-PDMS), and anodic aluminum oxide (AAO) templates. By changing the composition of the annealing solvents, different morphologies such as the concentric lamellar morphology, the winding cylinder morphology, and the irregular hybrid morphology are observed, mainly caused by the annealing-solvent-induced volume change. The morphology of the block copolymer nanostructures can be further confirmed using an HF solution to remove the PDMS domain selectively.

We study the dewetting behaviors of poly(methyl methacrylate) (PMMA) thin films coated in the cylindrical nanopores of anodic aluminum oxide (AAO) templates by thermal annealing. Self-assembled monolayers (SAMs) of n-octadecyltrichlorosilane (ODTS) are introduced to modify the pore surfaces of the AAO templates to induce the dewetting process. By using scanning electron microscopy (SEM), the dewetting-induced morphology transformation from the PMMA thin films to PMMA nanoparticles with asymmetric shapes can be observed. The sizes of the PMMA nanoparticles can be controlled by the original PMMA solution concentrations. The dewetting phenomena on the modified nanopores are explained by taking into account the excess intermolecular interaction free energy (ΔG). This work opens a new possibility for creating polymer nanoparticles with asymmetric shapes in confined geometries.