Self-Assembly of All-Conjugated Poly(3-alkylthiophene) Diblock Copolymer Nanostructures from Mixed Selective Solvents

The use of mixed selective solvents provides an effective means to control self-assembly of the all-conjugated diblock copolymer poly(3-butylthiophene)-<i>b</i>-poly(3-hexylthiophene) (P3BHT) into nanostructured morphologies. The solvent and temperature effects on the self-assembly of P3BHT during cooling and subsequent crystallization were explored for the first time. Depending on the poor/good solvent ratio (<i>i.e.</i>, anisole/chloroform), P3BHT chains experience different kinetic pathways, yielding nanowires at a low anisole/chloroform ratio (≤2:1), and nanorings coexisted with some nanowires at a high anisole/chloroform ratio (≥6:1). The nanowires are formed as a direct consequence of strong interchain π−π stacking, while the formation of nanorings is governed by solvophobic interactions between conjugated blocks and the poor solvent anisole to minimize the unfavorable contacts between the P3BT block (∼50 °C) and later P3HT (below 35 °C) block and anisole.