Metastability effects in strained and stressed SrTiO3 films

The sequence of ground states for SrTiO3 film subjected to epitaxial strain as well as to mechanical stress along the [001] and [110] axes is calculated from first principles within the density functional theory. Under the fixed-strain boundary conditions, an increase in the lattice parameter of a substrate results in the $I4cm \to I4/mcm \to Ima2 \to Cm \to Fmm2 \to Ima2$(II) sequence of ground states. Under the fixed-stress boundary conditions, the phase sequence is different and depends on how the stress is applied. It is revealed that the simultaneous presence of competing ferroelectric and antiferrodistortive instabilities in SrTiO3 gives rise to the appearance of metastable phases, whose number increases dramatically under the fixed-stress conditions. In the metastable phases, the octahedral rotation patterns are shown to differ substantially from those in the ground state. It is suggested that in systems with competing instabilities, each polar phase has its optimal octahedral rotation pattern which stabilizes this phase and creates a potential barrier preventing this phase to be transformed into other structures.Comment: 14 pages, 5 figures, 1 table plus 12 tables of supplemental materia

On the nature of change in Ni oxidation state in BaTiO3-SrTiO3 system

XAFS studies of Ni-doped Ba$_{1-x}$Sr$_x$TiO$_3$ solid solution reveal that the Ni oxidation state changes from 4 in SrTiO$_3$ to 2.5 in BaTiO$_3$ when varying $x$. This change is accompanied by a noticeable change in the interatomic Ni-O distances in the first shell. The first-principles calculations show that nickel creates an impurity band in the forbidden band gap of BaTiO$_3$ and SrTiO$_3$, which explains the appearance of intense absorption of Ni-doped samples in the visible region. The analysis of the electronic structure of doped crystals and calculations of the oxygen vacancy formation energy in them show that different oxidation states of Ni in SrTiO$_3$ and BaTiO$_3$ can be explained by different formation energies of the oxygen vacancies in these compounds.Comment: 5 pages, 2 figures, 1 tabl

An experimental and theoretical study of Ni impurity centers in Ba0.8_{0.8}Sr0.2_{0.2}TiO3_3

The local environment and the charge state of a nickel impurity in cubic Ba$_{0.8}$Sr$_{0.2}$TiO$_3$ are studied by XAFS spectroscopy. According to the XANES data, the mean Ni charge state is $\sim$2.5+. An analysis of the EXAFS spectra and their comparison with the results of first-principle calculations of the defect geometry suggest that Ni$^{2+}$ ions are in a high-spin state at the $B$ sites of the perovskite structure and the difference of the Ni$^{2+}$ and Ti$^{4+}$ charges is mainly compensated by distant oxygen vacancies. In addition, a considerable amount of nickel in the sample is in a second phase BaNiO$_{3-\delta}$. The measurements of the lattice parameter show a decrease in the unit cell volume upon doping, which can indicate the existence of a small amount of Ni$^{4+}$ ions at the $B$ sites.Comment: 8 pages, 3 figures, 3 table

First-principles study of ferroelectricity and pressure-induced phase transitions in HgTiO3_3

Ground-state structure is found and pressure-induced phase transitions up to 210 kbar are studied in mercury titanate from first principles within the density functional theory. It is established that the $R3c$ structure experimentally observed in HgTiO$_3$ is metastable at ambient pressure. With increasing the hydrostatic pressure, the ground-state structure changes following the $R{\bar 3} \to R3c \to Pbnm$ sequence. It is shown that the appearance of ferroelectricity in HgTiO$_3$ at $P = 0$ is associated with an unstable phonon mode. Optical and elastic properties of different phases of mercury titanate are calculated. The quasiparticle band gap calculated in the \emph{GW} approximation ($E_g = 2.43$ eV) agrees with experimental data better than the value obtained in the LDA approximation (1.49 eV). Analysis of the thermodynamic stability explains why the synthesis of mercury titanate is possible only at high pressures.Comment: 8 pages, 4 figures, 5 tables; to appear in Phase Transition