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.

Chloroform is a general solvent for poly(3-hexylthiophene) (P3HT) active layers in field-effect transistors. However, its low boiling point and rapid evaporation limit the time for crystallization during the spin-coating process, and field-effect mobilities achieved for P3HT films spin-coated from chloroform are typically on the order of 0.01 cm2/(V s). Here we investigate a range of solvents with higher boiling points. We find that 1,2,4-trichlorobenzene with good solubility and a high boiling point significantly improves the field-effect mobilities up to 0.12 cm2/(V s) with on:off ratios of 106. By controlling the microstructure through the choice of solvent while keeping the molecular weight fixed, we observe a clear correlation between the field-effect mobility and the degree of microcrystalline order as measured by X-ray diffraction, as well as the strength of polaronic relaxation of charge carriers in the accumulation layer as measured by optical spectroscopy of field-induced charge.

Organic field-effect transistors (OFETs) are attracting attention because of their potential application in cheap, large-area, flexible electronic devices, such as bendable displays, complementary circuits, and radio-frequency identification tags (RFID). [1][2][3][4] To this end, polymer semiconductors are particularly well-suited, due to their mechanical flexibility and facile processing. However, OFETs have been hampered by very low charge-carrier mobilities, often less than 0.01 cm 2 V À1 s À1

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported. Crystalline-crystalline/semiconducting-insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself.