Due to the rising need for clean energy, thermoelectricity has raised as a potential alternative to reduce dependence on fossil fuels. Specifically, thermoelectric devices based on polymers could offer an efficient path for near-room temperature energy harvesters. Thus, control over thermoelectric properties of conducting polymers is crucial and, herein, the structural, electrical and thermoelectric properties of poly(3,4-ethylenedioxythiophene) (PEDOT) thin films doped with p-toluenesulfonate (Tos) molecules were investigated with regards to thin film processing. PEDOT:Tos thin films were prepared by in-situ polymerization of (3,4-ethylenedioxythiophene) monomers in presence of iron(III) p-toluenesulfonate with different co-solvents in order to tune the film structure. While the Seebeck coefficient remained constant, a large improvement in the electrical conductivity was observed for thin films processed with high boiling point additives. The increase of electrical conductivity was found to be solely in-plane mobility-driven. Probing the thin film structure by Grazing Incidence Wide Angle X-ray Scattering has shown that this behavior is dictated by the structural properties of the PEDOT:Tos films; specifically by the thin film crystallinity combined to the preferential edge-on orientation of the PEDOT crystallites. Consequentially enhancement of the power factor from 25 to 78.5 μW/mK2 has been readily obtained for PEDOT:Tos thin films following this methodology.
Tl9BiTe6, a substitution variant of Tl5Te3, is one of the leading midtemperature thermoelectrics and is postulated to exceed ZT = 1 above 450 K when prepared by zone-melting and reach ZT = 0.86 at 560 K after hot-pressing. We have prepared the isostructural series Tl9Sb1–x Te6, Tl9–x Sb1+x Te6, Tl9Bi1–x Te6, and Tl9–x Bi1+x Te6, with x ranging from 0 to 0.05, from the elements in the stoichiometric ratios and determined their thermoelectric properties after hot-pressing. In theory, these tellurides are narrow-gap semiconductors when x = 0, with all elements in common oxidation states, according to (Tl+)9(Sb/Bi)3+(Te2–)6. The as-prepared samples of this 9-1-6 stoichiometry, however, exhibit relatively high electrical conductivity, which decreases with increasing temperature, indicative of the presence of extrinsic charge carriers. The Seebeck coefficient is generally above +100 μV K–1. Decreasing the Sb and Bi content increases the hole carrier concentration and thus increases the electrical conductivity while decreasing the Seebeck coefficient. The best feature of these thermoelectrics is their low thermal conductivity, which is consistently well below 0.7 W m–1 K–1. In combination with reasonable electrical conductivity and a high Seebeck coefficient, high ZT values in excess of 1 can also be achieved via simple hot-pressing after experimental optimization of the carrier concentration via introducing deficiencies on the Bi site. Moreover, the variants with Sb instead of Bi exhibit similar thermoelectric performance, a result of the combination of a better electrical performance and higher thermal conductivity.
Various compounds in the (SnTe)x(Bi2Te3)y series are explored by a number of techniques including diffractometry and physical property measurements. Through variation in the x and y integers, one is able to obtain a series of ternary compounds: SnBi2Te4, SnBi4Te7, SnBi6Te10, and Sn2Bi2Te5 each show complex layering motifs similar to that of Bi2Te3. These compounds' increased complexity makes them of interest with respect to thermoelectric studies. The ZT values for cold‐pressed annealed pellets are at room temperature 0.33 for SnBi2Te4, 0.27 for SnBi4Te7, and 0.15 for SnBi6Te10.
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