Non-Monotonic Sequence Control Maximizes Spin Transport in Conjugated Polymers at Room-Temperature.

Guo, Ankang; Zhu, Mingliang; Zhao, Han; Ren, Zebin; Cao, Yanyan; Shao, Zhihao; Li, Yifan; Xiong, Zihan et al. · Adv Mater · 2025

basic_science · Level V

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Abstract

Organic semiconductors have long spin lifetimes supporting non-tunneling spin transport at room temperature, providing a window to control spin transport and enable charge-spin co-processing. Programmable diversity in backbones and side chains expands the design space for tuning structure-transport relationships, yet links between structure and spin transport remain less explored than for charge transport. Focusing on repeat-unit sequence effects on spin transport, a nonmonotonic dependence where intermediate sequence order optimizes π-π packing by balancing long-range coherence and chain flexibility, maximizing spin-transport efficiency is revealed. The three-component regioregular copolymer tightens π-π spacing to 3.48 Å and extends coherence, yielding mobility 0.43 cm<sup>2</sup> V<sup>-1</sup> s<sup>-1</sup> and an on/off ratio near 6 × 10<sup>6</sup>. Stronger cohesion in a bicomponent alternating species flattens the backbone yet widens d<sub>π</sub> and shortens coherence; frontier levels and dihedral angles support this microstructural origin of lower mobility. Electron paramagnetic resonance gives a T1 of 101 ns for the alternating copolymer; spin valves show >8% room-temperature non-tunneling magnetoresistance ratio, ≈200% above bicomponent alternating species. This non-monotonic design rule provides a synthesis strategy to extend spin lifetimes and spin diffusion length, thereby advancing conjugated polymers for applications in logic, memory, sensing, and wearable systems.