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Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being suitable for thermoelectric applications. We measure the thermoelectric properties of various poly( 3,4-ethylenedioxythiophene) samples, and observe a marked increase in the Seebeck coefficient when the electrical conductivity is enhanced through molecular organization. This initiates the transition from a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics.

Thermoelectric generation potentially holds a solution for waste heat recovery issues provided that the availability of inexpensive, biodegradable and highly efficient thermoelectric materials is insured in the near future. Plastic thermoelectrics could successfully comply with the said requirements if the thermoelectric efficiency (ZT) of conducting polymers was higher. However, given the novelty of the subject, at present there are no clear guidelines for ZT optimization in this class of materials. The most important piece of information that is currently missing is the description of a specific electronic makeup that conducting polymers must possess in order to enable good thermoelectric performance. In the present study the thermoelectric properties of poly(3,4-ethylenedioxythiophene) derivatives with two types of counterions, i.e. poly(styrenesulfonate) (PSS) and tosylate (Tos) are evaluated. A striking variation in their thermoelectric performance is attributed to structural and morphological differences between two polymers that manifest itself in dissimilar charge transport mechanism. The superior properties of PEDOT-Tos presumably originate from a high degree of crystallinity and structural order that predetermines the tendency for bipolaron band formation. Unlike polaronic PEDOT-PSS with slowly varying density of localized states (DOS) near the Fermi level (EF), the DOS in PEDOT-Tos is characterized by higher asymmetry and higher charge carrier density at EF (similar to semimetals), which allows for higher thermopower and electrical conductivity. Therefore, we conclude that the polymers with semimetallic electronic makeup are expected to exhibit promising thermoelectric properties with bigger variation in thermopower upon doping.