Morphological Ordering of the Organic Layer for High-Performance Hybrid Thermoelectrics

Inorganic–organic hybrids, such as Te-PEDOT:PSS core/shell nanowires, have emerged as a class of promising thermoelectric materials with combined attributes of mechanical flexibility and low cost. However, the poorly understood structure–property relationship calls for further investigation for performance enhancement. Here, through precise treatments of focused electron beam irradiation and thermal annealing on individual Te-PEDOT:PSS nanowires, new, nonchemical mechanisms are introduced to specifically engineer the organic phase, and the measured results provide an unprecedented piece of evidence, confirming the dominant role of organic shell in charge transport. Paired with the Kang–Snyder model and molecular dynamics simulations, this work provides mechanistic insights in terms of heating-enabled morphological ordering of the polymer chains. The measured results show that thermal annealing on the 42 nm nanowire results in a ZT value of 0.78 at 450 K. Through leveraging the interfacial self-assembly of the organic phase to construct a high electrical conductivity domain, this work lays out a clear framework for the development of next-generation soft thermoelectrics.