Hak-Sung Lee

First-principles study on migration mechanism in SrTiO3

The atomistic behavior of migration in SrTiO3 was investigated by first-principles nudged elastic band calculations. Calculated migration energies for Sr and oxygen are consistent with experimental values. In contrast, the calculated energy for Ti with a simple Ti-vacancy mechanism is far larger than the experimental value. In examining different Ti-migration mechanisms, the Ti-migration energy is found to decrease and become comparable to the Sr-migration energy by introducing a Sr vacancy. This Sr-vacancy-mediated Ti migration, which is consistent with the experimentally proposed mechanism by Gomann et al. [Phys. Chem. Chem. Phys. 6, 3639 (2004)], is confirmed theoretically by the present calculations.

Assessment of Strain-Generated Oxygen Vacancies Using SrTiO3 Bicrystals

Atomic-scale defects strongly influence the electrical and optical properties of materials, and their impact can be more pronounced in localized dimensions. Here, we directly demonstrate that strain triggers the formation of oxygen vacancies in complex oxides by examining the tilt boundary of SrTiO3 bicrystals. Through transmission electron microscopy and electron energy loss spectroscopy, we identify strains along the tilt boundary and oxygen vacancies in the strain-imposed regions between dislocation cores. First-principles calculations support that strains, irrespective of their type or sign, lower the formation energy of oxygen vacancies, thereby enhancing vacancy formation. Finally, current-voltage measurements confirm that such oxygen vacancies at the strained boundary result in a decrease of the nonlinearity of the I-V curve as well as the resistivity. Our results strongly indicate that oxygen vacancies are preferentially formed and are segregated at the regions where strains accumulate, such as heterogeneous interfaces and grain boundaries.

Quantifying stoichiometry-induced variations in structure and energy of a SrTiO3 symmetric Σ13 {510}/ grain boundary

Grain boundaries (GBs) in complex oxides such as perovskites have been shown to readily accommodate nonstoichiometry changing the electrostatic potential at the boundary plane and effectively controlling material properties such as capacitance, magnetoresistance and superconductivity. Understanding and quantifying exactly how variations in atomic scale nonstoichiometry at the boundary plane extend to the practical mesoscale operating length of the system is therefore critical for improving the overall properties. Bicrystals of SrTiO3 were fabricated to provide the model GB model structures that are analysed in this paper. We show that statistical analysis of aberration-corrected scanning transmission electron microscope images acquired from a large area of GB is an effective routine to understanding the variation in boundary structure that occurs to accommodate nonstoichiometry. In the case of the SrTiO3 22.6° ∑13 (510)/[100] GB analysed here, the symmetric atomic structures observed from a micron-long GB can be categorized as two different competing structural arrangements, with and without a rigid-body translation along the boundary plane. How this quantified experimental approach can provide direct insights into the GB energetics is further confirmed from the first principles density functional theory, and the effect of nonstoichiometry in determining the GB energies is quantified.

The effect of vacancies on the annular dark field image contrast of grain boundaries: A SrTiO3 case study

The analysis of grain boundary structure in high resolution electron microscopy is often hindered by contrast variation within the grain boundary region which is not explained by simple models of the grain boundary structure. Recent work suggests that structural disorder along the beam direction and the presence of vacancies contribute significantly to this effect. One might expect a significant reduction in contrast in a Z-contrast image of a grain boundary would imply that vacancies present must result from the absence of heavier elements. Using a [001](210) Σ5 grain boundary in SrTiO(3) as a test case and first principles structure relaxation to calculate stable defect structures, we show that the reduction in the intensity from fully occupied Sr columns due to the structural distortion resulting from a nearby O vacancy can be as great as that due to introducing a Sr vacancy in the column itself. The effect on energy dispersive X-ray spectroscopy signals is also considered, but found to be smaller than that on Z-contrast images.

Amphoteric doping of praseodymium Pr3+ in SrTiO3 grain boundaries

Charge compensation in rare-earth Praseodymium (Pr3+) doped SrTiO3 plays an important role in determining the overall photoluminescence properties of the system. Here, the Pr3+ doping behavior in SrTiO3 grain boundaries (GBs) is analyzed using aberration corrected scanning transmission electron microscopy. The presence of Pr3+ induces structural variations and changes the statistical prevalence of the GB structures. In contrast to the assumption that Pr3+ substitutes on the Sr site in the bulk, Pr3+ is found to substitute on both Sr and Ti sites inside the GBs, with the highest concentration at the Ti sites. This amphoteric doping behavior in the boundary plane is further confirmed by first principles theoretical calculations.

Disordered ferroelectricity in the PbTiO3/SrTiO3 superlattice thin film

The PbTiO3/SrTiO3 superlattice thin films with a low volume fraction of PbTiO3 have not attracted much interest because they are thought to exhibit only a paraelectric state. In this study, we focus on a superlattice thin film with thin PbTiO3 (PTO) and thick SrTiO3 (STO) layers, wherein the hidden ferroelectricity in the thin PbTiO3 layer is revealed. Atomic scale imaging analysis and electron energy loss spectroscopy reveal the existence of a disordered ferroelectric polarization state without innate tetragonal distortion in the (6PTO/15STO)5 superlattice. The piezoelectric force microscopy analysis confirms that this disordered ferroelectricity can enhance piezoelectric response.

First principles calculation of thermal expansion coefficients of pure and Cr doped α-alumina crystals

We have performed theoretical analysis of thermal expansion behavior of alumina crystals under finite temperature based on first principles phonon state calculations. Liner thermal expansion coefficients of a pure α-alumina crystal have been evaluated based on quasi-harmonic approximation including crystalline anisotropy. The Cr doping effect on the alumina crystal has also been examined and found that the doping can cause a noticeable change on the thermal expansion coefficient. The present results demonstrate that the first principles theoretical approach can be helpful for reproducing or predicting thermal expansion behaviors including dopant effects, which may pave a way for possible control of thermal expansion of materials by doping or alloying.