Transition from Reconstruction toward Thin Film on the (110) Surface of Strontium Titanate.

The surfaces of metal oxides often are reconstructed with a geometry and composition that is considerably different from a simple termination of the bulk. Such structures can also be viewed as ultrathin films, epitaxed on a substrate. Here, the reconstructions of the SrTiO3 (110) surface are studied combining scanning tunneling microscopy (STM), transmission electron diffraction, and X-ray absorption spectroscopy (XAS), and analyzed with density functional theory calculations. Whereas SrTiO3 (110) invariably terminates with an overlayer of titania, with increasing density its structure switches from n × 1 to 2 × n. At the same time the coordination of the Ti atoms changes from a network of corner-sharing tetrahedra to a double layer of edge-shared octahedra with bridging units of octahedrally coordinated strontium. This transition from the n × 1 to 2 × n reconstructions is a transition from a pseudomorphically stabilized tetrahedral network toward an octahedral titania thin film with stress-relief from octahedral strontia units at the surface.

Transition from Order to Configurational Disorder for Surface Reconstructions on SrTiO_{3}(111).

There is growing interest in ternary oxide surfaces due to their role in areas ranging from substrates for low power electronics to heterogeneous catalysis. Descriptions of these surfaces to date focus on low-temperature explanations where enthalpy dominates, and less on the implications of configurational entropy at high temperatures. We report here the structure of three members of the n×n (2≤n≤4) reconstructions of the strontium titanate (111) surface using a combination of transmission electron diffraction, density functional theory modeling, and scanning tunneling microscopy. The surfaces contain a mixture of the tetrahedral TiO_{4} units found on the (110) surface sitting on top of octahedral TiO_{5}[] (where [] is a vacant octahedral site), and TiO_{6} units in the second layer that are similar to those found on the (001) surface. We find clear evidence of a transition from the ordered enthalpy-dominated 3×3 and 4×4 structures to a configurational entropy-dominated 2×2 structure that is formed at higher temperatures. This changes many aspects of how oxide surfaces should be considered, with significant implications for oxide growth.

c(4 × 2) and related structural units on the SrTiO3(001) surface: scanning tunneling microscopy, density functional theory, and atomic structure.

Density functional theory is used to simulate high-bias, constant-current scanning tunneling micrographs for direct comparison with experimental images. Coupled to previous spectroscopic data, these simulations are used to determine the atomic structure of Ti-rich nanostructures on strontium titanate (001) surfaces. These nanostructures have three consecutive TiO(x) surface layers and exploit the distinctive structural motif of the c(4 × 2) reconstruction as their main building block. A structural model of a characteristic triline defect is also proposed.

Hot STM of nanostructure dynamics on SrTiO(3)(001).

The dynamics of nanostructured surface phases on SrTiO(3)(001) have been analysed using in situ scanning tunnelling microscopy (STM) above 800 degrees C. During high-temperature annealing, the formation, growth and ordering of the nanostructures has been observed. Dilines, with a width of approximately 1 nm, are formed from a TiO(2)-rich intermediary at 800 degrees C. STM during annealing at 825 degrees C has enabled us to follow both the growth and dissolution of dilines. Following extended annealing, trilines with a width of approximately 2 nm and ordered two-dimensional (2D) nano-arrays form from the diline domains. Our observations of diline dissolution implies random nucleation and growth, followed by rearrangement at elevated temperature to form domains.