Preparation of Nanoporous Poly(3-hexylthiophene) Films Based on a Template System of Block Copolymers via Ionic Interaction

Abstract

A series of well-defined aniline-chain-end-functionalized regioregular poly(3-hexylthiophene)s (P3HT-NH 2 ) and sulfo-chain-end-functionalized polystyrene (PS-SO 3 H) have been prepared based on quasiliving Grignard metathesis and living anionic polymerization, respectively. Block copolymers via ionic interaction, (P3HT-NH)s, were successfully synthesized, simply by blending P3HT-NH 2 with PS-SO 3 H in toluene. The thermal and optical properties of the block copolymers were investigated by differential scanning calorimetry (DSC) and ultraviolet-visible (UV-vis) spectroscopy. The self-assembly behavior of the (P3HT-NH 3 þ )-b-(PS-SO 3 -) thin film was observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). In addition, grazing incidence X-ray scattering (GIXS) analysis found the microphase separation of P3HT-NH 3 þ and PS-SO 3 domains as well as the packing behavior of P3HT-NH 3 þ segments in block copolymer thin films. By exploiting the pH-sensitive ionic interaction, the PS-SO 3 domains were selectively etched with ethyl acetate/triethylamine, cleaving the ionic interaction between P3HT-NH 3 þ and PS-SO 3 segments, to obtain the target nanoporous P3HT-NH 2 films. The porosity of the films was confirmed by AFM, scanning electron microscopy (SEM) and GIXS analyses.

Block copolymer strategies for solar cell technology

“…For further examples of block copolymer templating in OPVs, the reader is directed elsewhere. [192][193][194][195][196][197][198][199] As discussed earlier, block copolymers have a rich phase diagram enabling a variety of complex structures to be assembled, which primarily depend on the volume fraction of the blocks and their molecular weights. Using the aforementioned well developed design rules it is relatively straightforward to produce lamellar, cylindrical and spherical architectures with pre-programmed domain sizes.…”

Supramolecular Multiblock Polystyrene–Polyisobutylene Copolymers via Ionic Interactions

“…9,12,13,44 In contrast, there has been little investigation of the viscoelastic behavior or the mechanical properties of these types of polymers, which are important if these polymers are to be used in bulk material applications. Another reason for the more limited investigation of these types of systems is the difficulty in synthesis of the telechelic ionomers.…”

Nanoporous poly(3-hexylthiophene) thin films based on “click” prepared degradable diblock copolymers

“…33,35,36 The partial domain collapse was assumed to come from the surface tension force during evaporation of the liquids from the film and was attempted to be reduced by utilizing supercritical CO 2 as solvent in the final treatment of nanoporous film surface. That can be attributed to some partial lateral collapse of the obtained P3HT domains, as has been reported in other nanostructured systems in the literature.…”

“…25 Another strategy also consists on the preparation of donor-acceptor block copolymers containing a P3HT segment as a donor unit and a second block bearing pendent attached acceptor moieties such as fullerene [26][27][28] or perylene. 35,36 After deposition, the removable segment is sacrificed and replaced by an electronically active electron acceptor material in the patterned ordered scaffolds. 31 In order to optimize the nanoscale morphology between the two semiconducting materials, i.e.…”