Thermoelectric properties of Sn doped BiCuSeO

Abstract

BiCuSeO and Bi1-xSnxCuSeO (x=0.02, 0.04, 0.06, 0.08) were prepared by a two-step solid state synthesis. The phase purity and the crystal structure were investigated by the X-Ray Diffraction (XRD) and confirmed by Energy Dispersive Spectroscopy (EDS). The volatilization of Bi and Bi2O3 lead to off-stoichiometry of the main phase and the formation of CuSe2 secondary phase in the undoped sample. SnO2 secondary phases were found in the doped samples. Both the Seebeck coefficient and the electrical resistivity, measured from the room temperature to 773K linearly increases with the temperature, which indicates that the sample have metallic like behavior. The origin of such a behavior is due to high hole concentration originating from the Bi and the O vacancies. The Sn +4 valence state was confirmed from the X-Ray Photoelectron Spectroscopy (XPS) and from the reduction of lattice parameter ‘a’ with doping. The substitution of Sn+4 in the place of Bi+3 leads to the higher Seebeck coefficient and electrical resistivity in the doped samples. Highest power-factor (∼1mW/m-K2 at 773K), was obtained for the undoped sample and the 4% Sn doped sample (Bi0.96Sn0.04CuSeO). The lowest thermal conductivity was obtained for the undoped sample, from the room temperature to 773K. The presence of thermally-conducting SnO2 secondary phases in the doped samples increases the thermal conductivity in comparison with the undoped sample. The zTs of the doped samples were lower compared to the undoped sample, owing to their higher thermal conductivity. The oxygen vacancies as well as the all-length scale phonon scattering, lowers the thermal conductivity of the undoped sample and, as a result, a maximum zT of 1.09 was achieved at 773K.