This work presents a comprehensive study of the fabrication and optimization of electrodeposited p‐ and n‐type thermoelectric films. The films are deposited on Au and stainless steel substrates over a wide range of deposition potentials. The influence of the preparative parameters such as the composition of the electrolyte bath and the deposition potential are investigated. Furthermore, the p‐doped (BixSb1‐x)2Te3 and the n‐doped Bi2(TexSe1‐x)3 films are annealed for a period of about 1 h under helium and under tellurium atmosphere at 250 °C for 60h. Annealing in He already leads to significant improvements in the thermoelectric performance. Furthermore, due to the equilibrium conditions during the process, annealing in Te atmosphere leads to a strongly improved film composition, charge carrier density and mobility. The Seebeck coefficients increase to values up to +182 μV K−1 for p‐doped and–130 μV K−1 for n‐doped materials at room temperature. The power factors also exhibit improvements with 1320 μW m−1 K−2 and 820 μW m−1 K−2 for p‐doped and n‐doped films, respectively. Additionally, in‐situ XRD measurements performed during annealing of the films up to 600K under He atmosphere show stepwise improvements of the crystal structure leading to the improvements in thermoelectric parameters. The thermal conductivity is between 1.2 W m−1 K−1 and 1.0 W m−1 K−1.

A systematic optimization of p-type Sb 2 Te 3 thermoelectric films made by potentiostatic electrodeposition on Au and stainless steel substrates is presented. The influence of the preparative parameters of deposition voltage, concentration, and the deposition method are investigated in a nitric acid solution. As a postdeposition step, the influence of annealing the films is investigated. The use of a potential-controlled millisecond-pulsed deposition method could improve both the morphology and the composition of the films. The samples are characterized in terms of composition, crystallinity, Seebeck coefficient, and electrical resistivity. Pulsed-deposited films exhibit Seebeck coefficients of up to 160 μV K −1 and an electrical conductivity of 280 S cm −1 at room temperature, resulting in power factors of about 700 μW m −1 K −2 . After annealing, power factors of maximum 852 μW m −1 K −2 are achieved. Although the annealing of DC-deposited films significantly increased the power factor, they do not reach the values of the pulseddeposited films in the preannealing state. Structural analysis is performed with X-ray diffraction and shows the crystalline structure of Sb 2 Te 3 films. The performance is tuned by annealing of deposited films up to 300 °C under He atmosphere while performing in-situ X-ray diffraction and resistivity measurements. The chemical analysis of the films is performed by inductively coupled plasma optical emission spectroscopy (ICP-OES) as well as scanning electron microscope energy dispersive X-ray analysis (SEM-EDX).