Origins of enhanced dielectric properties in titania-modified tantalum pentoxide ceramics

Tantalum oxide (Ta2O5)-based materials are of interest for various applications, including dynamic random access memories (DRAMS) and thermal and environmental barrier coatings (TBCs, EBCs). Widespread use, however, has been limited due to practical difficulties in densification of ceramic forms, and a lack of basic understanding of structure-processing-property relationships for Ta2O5-based ceramics. The current research was designed to investigate these relationships and to determine the origins of a previously reported dielectric enhancement for TiO2 -modified Ta2O5.;Rapid and expansive grain growth associated with the L⇒H-Ta 2O5 phase transformation was found to trap residual porosity, so sintering at temperatures below the transformation was required for full densification. A simple and effective solution-coated powder processing route was developed to enable reduced-temperature densification of chemically-homogeneous TiO2-modified H-Ta2O5 ceramics for the first time.;A new crystal structure of H-Ta2O5 based upon extensive polyhedral edge-sharing was verified using high-resolution X-ray diffraction at the Advanced Photon Source. Simulated diffraction patterns matched data collected at up to 1500°C out to 2theta values equivalent to 110° (CuKalpha). In-situ XRD and Raman studies both revealed two distinct phase transformations during cooling from the high-temperature prototypic phase for specimens containing ≤5% TiO2, but only one transformation for specimens containing 8% TiO2, and revealed that the H-Ta2O5 form present at room temperature depended strongly upon TiO2 content.;Dense and homogeneous specimens enabled the first detailed investigation into the electrical properties of TiO2-modified H-Ta2O 5 ceramics. Specimens containing 8% TiO2 exhibited dielectric constant (K) values of ∼280 at 20°C with tan delta values ∼0.01, but undoped specimens had tan delta values of ∼0.10 and DC resistivity values of <1011O·cm. Hyper-Raman spectroscopy revealed that the ionic polarizability (and thus the intrinsic K) of H-Ta 2O5 ceramics was independent of TiO2 content. Cryogenic electrical measurements suggested that the structural K ≈ 70-80, and showed that enhanced K values resulted from localized carriers related to compensation for deviations from the fully-edge-shared 89Ta2O 5-11TiO2 composition.