High Power Factor Nb-Doped TiO2 Thermoelectric Thick Films: Toward Atomic Scale Defect Engineering of Crystallographic Shear Structures

Donor-doped TiO₂-based materials are promising thermoelectrics (TEs) due to their low cost and high stability at elevated temperatures. Herein, high-performance Nb-doped TiO₂ thick films are fabricated by facile and scalable screen-printing techniques. Enhanced TE performance has been achieved by forming high-density crystallographic shear (CS) structures. All films exhibit the same matrix rutile structure but contain different nano-sized defect structures. Typically, in films with low Nb content, high concentrations of oxygen-deficient {121} CS planes are formed, while in films with high Nb content, a high density of twin boundaries are found. Through the use of strongly reducing atmospheres, a novel Al-segregated {210} CS structure is formed in films with higher Nb content. By advanced aberration-corrected scanning transmission electron microscopy techniques, we reveal the nature of the {210} CS structure at the nano-scale. These CS structures contain abundant oxygen vacancies and are believed to enable energy-filtering effects, leading to simultaneous enhancement of both the electrical conductivity and Seebeck coefficients. The optimized films exhibit a maximum power factor of 4.3 × 10^-4 W m^-1 K^-2 at 673 K, the highest value for TiO₂-based TE films at elevated temperatures. Our modulation strategy based on microstructure modification provides a novel route for atomic-level defect engineering which should guide the development of other TE materials.