Self-Nanostructuring in SrTiO₃: A Novel Strategy for Enhancement of Thermoelectric Response in Oxides

Nanostructuring is recognized as an efficient route for enhancing thermoelectric response. Here, we report a new synthesis strategy for nanostructuring oxide ceramics and demonstrate its effectiveness on an important n-type thermoelectric SrTiO₃. Ceramics of Sr_0.9La_0.1TiO₃ with additions of B₂O₃ were synthesized by the mixed oxide route. Samples were sintered in air followed by annealing in a reducing atmosphere. Crystallographic data from X-ray and electron diffraction showed Pm3 m cubic symmetry for all the samples. High-resolution transmission electron microscopy (HRTEM) showed the formation of a core-shell type structure within the grains for the annealed ceramics. The cores contain nanosize features comprising pairs of nanosize voids and particles; the feature sizes depend on annealing time. Atomic-resolution, high-angle annular-dark-field imaging and electron energy loss spectroscopy in the scanning transmission electron microscopy (STEM-HAADF-EELS) showed the particles to be rich in Ti and the areas around the voids to contain high concentrations of Ti³⁺. Additionally, dislocations were observed, with significantly higher densities in the shell areas. The observed dislocations are combined (100) and (110) edge dislocations. The major impact of the core-shell type microstructures, with nanosize inclusions, is the reduction of the thermal conductivity. Sr_0.9La_0.1TiO₃ ceramics containing grain boundary shells of size ≈ 1 μm and inclusions in the core of 60-80 nm exhibit a peak power factor of 1600 μW/m·K² at 540 K; at 1000 K, they exhibit a low thermal conductivity (2.75 W/m·K) and a power factor of 1050 μW/m·K² leading to a high of ZT of 0.39 ± 0.03. This is the highest ZT reported so far for Sr_0.9La_0.1TiO₃ based-compositions. This nanostructuring strategy should be readily applicable to other functional oxides.