Summary: | Electrodeposition is an important method for preparing bismuth telluride (Bi<sub>2</sub>Te<sub>3</sub>)-based thermoelectric (TE) thin films and micro-column arrays. When the concentrations of Bi:Te in electrolytes were 3 mM:4 mM, the TE films satisfied the Bi<sub>2</sub>Te<sub>3</sub> stoichiometry and had no dependence on deposition potential. With increasing over-potential, crystal grains changed from lamellar structures with uniform growth directions to large clusters with staggered dendrites, causing a decrease in the deposition density. Meanwhile, the preferred (110) orientation was diminished. The TE film deposited at −35 mV had an optimum conductivity of 2003.6 S/cm and a power factor of 2015.64 μW/mK<sup>2</sup> at room temperature due to the (110)-preferred orientation. The electrodeposition of TE micro-columns in the template was recently used to fabricate high-power micro-thermoelectric generators (micro-TEG). Here, microporous glass templates were excellent templates for micro-TEG fabrication because of their low thermal conductivity, high insulation, and easy processing. A three-step pulsed-voltage deposition method was used for the fabrication of micro-columns with large aspect ratios, high filling rates, and high density. The resistance of a single TE micro-column with a 60 μm diameter and a 200 μm height was 6.22 Ω. This work laid the foundation for micro-TEG fabrication and improved performance.
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