Local environments and transport properties of heavily doped strontium barium niobates Sr0.5Ba0.5Nb2O6

Undoped as well as K-doped (40%), Y-doped (40%), Zr-doped (10%), and Mo-doped (12.5%) strontium barium niobate Sr0.5Ba0.5Nb2O6 (SBN50) materials have been investigated to explore the effect of heavy doping on the structural and functional properties (thermo-power, thermal and electrical conductivities) both in the as prepared (oxidized) and reduced states. For all materials, the EXAFS spectra at the Nb - K edge can be consistently analyzed with the same model of six shells around the Nb sites. Doping mostly gives a simple size effect on the structural parameters, but doping on the Nb sites weakens the Nb-O bond regardless of dopant size and charge. Shell sizes and Debye-Waller factors are almost unaffected by temperature and oxidation state, and the disorder is of static nature. The functional effects of heavy doping do not agree with a simple model of hole or electron injection by aliovalent substitutions on a large band gap semiconductor. With respect to the undoped samples, doping with Mo depresses the thermal conductivity by ~ 30%, Y doping enhances the electrical conductivity by an order of magnitude, while Zr doping increases the Seebeck coefficient by a factor of 2-3. Globally, the ZT efficiency factor of the K-, Y-, and Zr-doped samples is enhanced at least by one order of magnitude with respect to the undoped or Mo-doped materials.