Exploring the Origin of Contact Destruction in Tetradymite-Like-Based Thermoelectric Elements

Polycrystalline thermoelectric elements of n-type Bi2(Te0.95Se0.05)3 and p-type (Bi0.25Sb0.75)2Te3 were fabricated by modified Bridgman technique, followed by electrospark cutting. A thermoelectric micromodule, consisting of 12 legs with an Ni anti-diffusion barrier and high-temperature SnSb solder between them, was assembled. To investigate thermoelements under conditions close to operating ones, the micromodule was annealed at 443 K for 1000 h. It was revealed that after annealing for more than 40 h, the near-contact zone of the n-type legs degraded, leading to a complete break of the micromodule junctions. Our results revealed that during annealing, the SnSb solder flowed into the unprotected side surface of the legs, and contacted with the cleavage planes along which tin can diffuse into the thermoelement volume. In contrast, the p-type legs were not affected by the contact with the solder. Different impacts of the solder on n- and p-type legs were explained in the framework of density functional theory (DFT) calculations. Substitution, diffusion and thermodynamic stability calculations showed that Bi to Sn substitution is energetically more beneficial than Sb to Sn substitution. Additionally, it was calculated that for the Bi2Te3 + Sn system, it is more beneficial to form a TeSn and Bi phase, while an Sb2Te3 + Sn system is thermodynamically stable.