Thermoelectric Properties of Cu2S Doped with P, As, Sb and Bi—Theoretical and Experimental Studies

The aim of this work was to investigate the possibility of doping copper sulfide Cu₂S with selected fifth-group elements, potentially having a positive effect on the thermoelectric properties of the resulting materials. For the selected model structures, theoretical calculations and an analysis of the electronic structure and changes in the enthalpy of formation due to doping were performed using the WIEN2k package employing the Full-Potential Linearized Augmented Plane Wave (FP-LAPW) method within density functional theory (DFT) formalism. Polycrystalline materials with the nominal composition of Cu₃₂S₁₅X₁ (<i>X</i> = P, As, Sb, Bi) were synthesized in quartz ampoules, then sintered using the spark plasma sintering (SPS) technique and "SPS melting" method. The chemical and phase compositions of the obtained sinters were studied by X-Ray diffraction (XRD) and scanning electron microscopy (SEM). Additionally, investigations of thermoelectric properties, i.e., electrical conductivity, Seebeck coefficient and thermal conductivity in the temperature range 300-920 K, were performed. The results of this study indicate that only phosphorus is successfully incorporated into the Cu₂S structure.