The dependence of the electrical conductivity and thermoelectric power on the mean grain size in 16% Bi2Se3–84% Bi2Te3 (as n‐type) and 75% Sb2Te3–25% Bi2Te3 (as p‐type) solid solutions is analysed. In p‐type materials, the main process by sintering is the reduction of the contact resistance between grains. In n‐type materials, the changes in carrier concentrations are due to the specific surface of grains.

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The dependence of the thermoelectric figure of merit Z on grain size in sintered 16% Bi2Se3‐84% Bi2Te3 and 75% Sb2Te3‐25% Bi2Te3 solid solutions is analysed. In n‐type materials, due to the carrier density dependence on the specific surface, the maximum moves towards large grain sizes when doping increases. In p‐type materials, the changes of Z with grain size are smaller than in n‐type materials.

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