Resonant States in the Electronic Structure of the High Performance Thermoelectrics AgPbmSbTe2+m: The Role of Ag-Sb Microstructures

Abstract

Ab initio electronic structure calculations based on gradient corrected density-functional theory were performed on a class of novel quaternary compounds $\mathrm{A}\mathrm{g}{\mathrm{P}\mathrm{b}}_m\mathrm{S}\mathrm{b}{\mathrm{T}\mathrm{e}}_{2+m}$, which were found to be excellent high temperature thermoelctrics with a large figure of merit $ZT\sim 2.2$ at 800 K. We find that resonant states appear near the top of the valence and bottom of the conduction bands of bulk PbTe when Ag and Sb replace Pb. These states can be understood in terms of modified Te-Ag(Sb) bonds. The electronic structure near the gap depends sensitively on the microstructural arrangements of Ag-Sb atoms, suggesting that large $ZT$ values may originate from the nature of these ordering arrangements.