Abstract

In the past two decades, conjugated polymers (CPs) have drawn great attention due to their excellent conductivity and charge mobility, rendering them broad applications in organic electronics. Controlling over the morphologies and nanostructures of CPs is very important to improve the performance of CP-based devices, which is still a tremendously difficult task. Conjugated block copolymers (cBCPs), composed of different CP blocks or CP coupled with coiled polymeric blocks, not only maintain the advantages of high conductivity and mobility but also demonstrate features of morphological versatility and tunability. Due to the strong π–π interaction and crystallinity of the conjugated backbones, the self-assembly behaviors of cBCPs are very complicated and largely remain to be explored. In this tutorial review, we first summarize the general synthetic methods for different types of cBCPs. Then, recent studies on the self-assembly behaviors of cBCPs are discussed, with an emphasis on the structural factors that affect the morphologies of cBCPs both in bulk and thin film states. Finally, we briefly provide our outlook on the future research of the self-assembly of cBCPs.

Highlights

  • Conjugated polymers (CPs) have alternating single and double bonds in the polymer backbone, making the polymer chain rigid and conductive

  • Synthesis of “Rod–Rod” Conjugated Block Copolymers Compared to “rod–coil” conjugated block copolymers (cBCPs), the synthesis of “rod–rod” cBCPs is still very challenging, and many reported studies in the literature mainly focus on the poly(3-alkylthiophene) (P3AT) system prepared by Grignard metathesis (GRIM) polymerization (Figure 7a) [60,61,62,63,64,65,66]

  • Summary and Outlook cBCPs have been considered as a novel type of materials with unique chemical structures, excellent electronic properties, and, more importantly, diverse self-assembly behaviors

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Summary

Introduction

Conjugated polymers (CPs) have alternating single and double bonds in the polymer backbone, making the polymer chain rigid and conductive. Optimizing the morphologies of the active CP-containing layer is critical and one of the most time-consuming steps in device fabrication In this context, conjugated block copolymers (cBCPs) have been proposed as an ideal solution to Polymers 2021, 13, 110. CP-containing layer is critical and one of the most time-consuming steps in device fabrication In this context, conjugated block copolymers (cBCPs) have been propose2dof a20s an ideal solution to address this issue, since cBCPs might combine the advantages of high conductivity and mobility of CPs and morphological versatility and tunability of block caodpdorleysms ethrsis(BisCsuPes,)s. Borsali et al [37] This result indicates that cBCPs containing a rigid block have stronger trend to phase separate than the “coil–coil” BCPs. In addition, conjugated polymer backbon3esof 20 have a strong tendency to form crystalline structures, and the melting temperature (Tm) of crystalline blocks may affect the morphology and size of the phase separation. I(nNMP) th[4is1]p. art, we will mainly focus on the synthesis of “rod–coil” and “rod–rod” cBCPs, and a few examples with different topological architecture will be discussed

Synthesis of “Rod–Coil” Conjugated Block Copolymers
Grafting-Onto Approach
In Solution
Factors that Affect the Self-Assembly of cBCPs
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