Chessboard/Diamond Nanostructures and the <i>A</i>‑site Deficient, Li_{1/2–3<i>x</i>} Nd_1/2+<i>x</i>TiO₃, Defect Perovskite Solid Solution

The crystal chemical origin of nanoscale chessboard/diamond ordering in perovskite-related solid solutions of composition Li_{0.5–3<i>x</i>}Nd_0.5+<i>x</i>TiO₃ (LNT, <i>x</i> ∼ 0.02–0.12) is investigated. Experimental and simulated scanning transmission electron microscopy (STEM) images are found to be consistent with the compositional modulation model proposed by previous authors. However, these earlier models do not satisfactorily explain other features observed in high-resolution STEM and TEM images, such as the two-dimensional {100} lattice fringes with the same periodicity, √2<i>a</i>_p × √2<i>a</i>_p, as the local LNT unit cell viewed along the [001] direction (where <i>a</i>_p is the parent perovskite unit cell parameter). Based on bond valence sum calculations, we propose a new set of crystal structures for LNT in which Li ions are primarily bonded to only two O ions, and order one-dimensionally with √2<i>a</i>_p periodicity. Bright-field STEM image simulations performed for this new model reproduced the experimentally observed √2<i>a</i>_p lattice fringes, thus strongly suggesting that the finer features of the high-resolution (S)­TEM images are the result of Li ion ordering and associated local structural relaxation. In this new model, the LNT chessboard supercell then results from the ordered combinations of two sublattices: the Li ion sublattice and its translational variants on the one hand, and the Nd_0.5TiO₃ sublattice and its oxygen octahedral tilt twin variants on the other. Dielectric measurements indicate the presence of long-lived polar clusters that are easily activated under an applied electric field. This suggests that these clusters consist of spatially correlated Li ions

Bimetallic Ions Codoped Nanocrystals: Doping Mechanism, Defect Formation, and Associated Structural Transition

Ionic codoping offers a powerful approach for modifying material properties by extending the selection of potential dopant ions. However, it has been a major challenge to introduce certain ions that have hitherto proved difficult to use as dopants (called “difficult-dopants”) into crystal structures at high concentrations, especially through wet chemical synthesis. Furthermore, the lack of a fundamental understanding of how codopants are incorporated into host materials, which types of defect structures they form in the equilibrium state, and what roles they play in material performance, has seriously hindered the rational design and development of promising codoped materials. Here we take In³⁺ (difficult-dopants) and Nb⁵⁺ (easy-dopants) codoped anatase TiO₂ nanocrystals as an example and investigate the doping mechanism of these two different types of metal ions, the defect formation, and their associated impacts on high-pressure induced structural transition behaviors. It is experimentally demonstrated that the dual mechanisms of nucleation and diffusion doping are responsible for the synergic incorporation of these two dopants and theoretically evidenced that the defect structures created by the introduced In³⁺, Nb⁵⁺ codopants, their resultant Ti³⁺, and oxygen vacancies are locally composed of both defect clusters and equivalent defect pairs. These formed local defect structures then act as nucleation centers of baddeleyite- and α-PbO₂-like metastable polymorphic phases and induce the abnormal trans-regime structural transition of codoped anatase TiO₂ nanocrystals under high pressure. This work thus suggests an effective strategy to design and synthesize codoped nanocrystals with highly concentrated difficult-dopants. It also unveils the significance of local defect structures on material properties