Influence of increasing D/A ratio on geometric and electronic properties of D–A-type copolymers

A series of D-A-type copolymers was designed and studied systematically for the purpose of gaining a deeper understanding of how the D/A ratio may influence the geometric and electronic properties when it varies from 2:1 to 6:1 by using DFT method. The results show that it has a significant effect on the bond length alternation, band gap, bandwidth and effective mass of carriers of the designed D-A-type copolymers. But its influence on the geometric and electronic properties shows something very different in degree when it increases from 2:1 to 4:1 and then increases further from 4:1 to 6:1. It is found that the effects of increasing D/A ratio on geometric and electronic properties are much stronger when the D/A ratio increases from 2:1 to 4:1 than when it further increases from 4:1 to 6:1. The theoretical results show that the polymers with a D/A ratio of 2:1 have much smaller effective mass of carriers and much wider bandwidth compared to those polymers with the D/A ratio of 4:1 and 6:1. Therefore, the designed D-A-type copolymers with a D/A ratio of 2:1 may actually be the better candidates for intrinsic conduction materials.