Thermoelectric transport properties of polycrystalline titanium diselenide co-intercalated with nickel and titanium using spark plasma sintering

Polycrystalline samples of nickel intercalated (0-5%) TiSe2 were attempted via solid-state reaction in evacuated quartz tubes followed by densification using a spark plasma sintering process. X-ray diffraction data indicated that mixed NiSe2 and TiSe2 phases were present after initial synthesis by solid-state reaction, but a pure TiSe2 phase was present after the spark plasma sintering. While EPMA data reveals the stoichiometry to be near 1:1.8 (Ti:Se) for all samples, comparisons of the measured bulk densities to the theoretical densities suggest that the off stoichiometry is a result of the co-intercalation of both Ni and Ti rather than Se vacancies. Due to the presence of excess Ti (0.085-0.130 per formula) in the van der Waals gap of all the samples, the sensitive electron-hole balance is offset by the additional Ti-3d electrons, leading to an increase in the thermopower (n-type) over pristine, stoichiometric TiSe2. The effects of the co-intercalation of both Ni and Ti in TiSe2 on the structural, thermal, and electrical properties are discussed herein. (C) 2012 Elsevier Inc. All rights reserved.