The constituent phases, electrical conductivity, and Seebeck coefficient of Ca-Si films deposited on (001) Al 2 O 3 substrates by a radio frequency magnetron sputtering method using a Mg disk target with Ca and Si chips are investigated. X-ray diffraction analysis indicates that the films consist of a single phase of CaSi 2 , CaSi or Ca 5 Si 3 that are deposited together with the films consisting of a mixture of CaSi 2 and CaSi. Films with a CaSi 2 or CaSi single phase exhibit a metallic behavior. In contrast, films with a Ca 5 Si 3 single phase show p-type conduction and their Seebeck coefficient reaches 90 lV/K at 400°C.
A method for controlling the conduction-type in Mg2Si films without doping is investigated. Mg2Si films exhibit p-type conduction after a post-heat treatment up to 500 °C in atmospheric He. However, covering the films with Mg ribbon during a subsequent heat treatment at 500 °C converts the conduction to n-type, demonstrating that the heat treatment atmosphere can control the conduction type. Based on the reported first principles calculations suggesting that interstitial Mg and Mg vacancies in Mg2Si are the origins of n-type and p-type conduction, respectively, the post-heat treatment in He induces Mg vacancies due to the evaporation of Mg from the film, resulting in p-type conduction. The subsequent heat treatment when the film is covered with Mg ribbon fills the Mg vacancies and the additional interstitial Mg is incorporated, resulting in n-type conduction. These observations differ from the reported data for heat treatment of stable n-type conduction in non-doped Mg2Si-sintered bodies and may realize a novel control method for the conduction type in Mg2Si films.
Mg2Si thin films were deposited at 320 °C on (001)Al2O3 and (100)CaF2 substrates by radio-frequency magnetron sputtering. Both films showed a preferential (111) out-of-plane orientation with an in-plane random orientation irrespective of post-heat treatment. Mg2Si films on (001)Al2O3 substrates were under in-plane tensile strain, while those on (100)CaF2 substrates were under in-plane compressive strain both before and after heat treatment. Heat-treated films showed p-type conduction up to 500 °C. Their electrical conductivity and Seebeck coefficient were almost independent of the kind of substrate within the limit of the present study, from 0.22% compressive strain to 0.34% tensile strain at room temperature.
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