Laser sintering as a thermal post treatment method for dispenser printed p- and n-type bismuth telluride based thermoelectric paste materials was investigated. A high-power fiber laser (600 W, 1064 nm) was used in combination with a scanning system to achieve high processing speed. A Design of Experiment (DoE) approach was used to identify the most relevant processing parameters. Printed layers were laser treated with different process parameters and the achieved sheet resistance, electrical conductivity, and Seebeck coefficient are compared to tube furnace processed reference specimen. For p-type material, electrical conductivity of 22 S/cm was achieved, compared to 15 S/cm in tube furnace process. For n-type material, conductivity achieved by laser process was much lower (7 S/cm) compared to 88 S/cm in furnace process. Also, Seebeck coefficient decreases during laser processing (40–70 µV/K and −110 µV/K) compared to the oven process (251 µV/K and −142 µV/K) for p- and n-type material. DoE did not yet deliver a set of optimum processing parameters, but supports doubts about the applicability of area specific laser energy density as a single parameter to optimize laser sintering process.
Polynickeltetrathiooxalate (poly[Ni-tto]) is an n-type semiconducting polymer having outstanding thermoelectric characteristics and exhibiting high stability under ambient conditions. However, its insolubility limits its use in organic electronics. This work is devoted to the production of a printable paste based on a poly[Ni-tto]/PVDF composite by thoroughly grinding the powder in a ball mill. The resulting paste has high homogeneity and is characterized by rheological properties that are well suited to the printing process. High-precision dispenser printing allows one to apply both narrow lines and films of poly[Ni-tto]-composite with a high degree of smoothness. The resulting films have slightly better thermoelectric properties compared to the original polymer powder. A flexible, fully organic double-leg thermoelectric generator with six thermocouples was printed by dispense printing using the poly[Ni-tto]-composite paste as n-type material and a commercial PEDOT-PSS paste as p-type material. A temperature gradient of 100 K produces a power output of about 20 nW.