Tuning Charge Carrier and Spin Transport Properties via Structural Modification of Polymer Semiconductors

Targeted design of organic semiconductors in organic spintronics is relatively limited. Therefore, four conjugated polymers with analogous structures based on isoindigo (IID) units were designed and synthesized to investigate the structure–property relationships in spin and charge carrier transport. Structural design strategies include introduction of pyridinic nitrogen atoms into IID units to change electronic structures and alteration of different branching points of alkyl chains to adjust the aggregation structure. By fabricating polymer field-effect transistors (PFETs) and organic spin valves (OSVs), all of the polymers exhibited good ambipolar field-effect properties (all of the mobilities exceeding 0.3 cm2 V–1 s–1) and relatively high magnetoresistance (MR) values (maximum up to 25%). Most importantly, it is found that the introduction of pyridinic nitrogen into the IID units can improve MR values of OSVs and electron mobilities of PFETs, whereas the extension of alkyl chain branching points can reduce MR values of the conjugated polymers. This work is the first attempt to thoroughly study the structure–property relationship in the OSVs, combined with molecular design of the conjugated polymers, which provides a guideline for molecular engineering, especially for organic spintronics.