Dielectric behaviour of nitrogen doped perovskite SrTiO3dNd films

The authors wish to thank T. Kocourek (PLD) and O. Pacherova (XRD). The work was partly supported by the Czech Science Foundation (Grant No. 22-10832S) (MT), the European Structural and Investment Funds and the Ministry of Education, Youth and Sports of the Czech Republic through Programme ‘‘Research, Development and Education’’ (Project No. SOLID21 – CZ.02.1.01/0.0/0.0/16_019/0000760) (MT, AD), and the Czech Academy of Sciences through the program Strategy AV21‘‘Breakthrough technologies for the future – sensing, digitization, artificial intelligence and quantum technologies’’ (MT, MS, AD). The financial support of M-ERA-NET HetCat project is acknowledged by LR and EK. The Institute of Solid State Physics, University of Latvia (Latvia) as the Centre of Excellence has received funding from the European Union’s Horizon 2020 Frame-work Programme H2020-WIDESPREAD01-2016-2017- Teaming Phase2 under grant agreement No. 739508, project CAMART2. The computer resources were provided by the Stuttgart Supercomputing Center (project DEFTD 12939) and Latvian Super cluster (LASC).Technologically important high-permittivity dielectrics are often achieved using cationic engineering of ABO3-type perovskite para(ferro)electrics. Here, we experimentally and theoretically explore the potential of less conventional anionic engineering in ABO3 dielectrics. We demonstrate that in an archetypal representative SrTiO3, nitrogen substitution can occur on two distinct oxygen atomic sites, reduce crystal symmetry, and lead to significant changes in the patterns and frequencies of lattice vibrations. These phonon transformations diminish permittivity, whereas contribution from nitrogen-induced nanoregions can raise it. The effects of nitrogen are found to be especially strong in epitaxial films. We anticipate that the revealed phenomena may be relevant for a broad class of high-permittivity perovskite oxides. --//-- This is an open-access article: M. Tyunina, L.L. Rusevich, M. Savinov, E.A. Kotomin, A. Dejneka. Dielectric behaviour of nitrogen doped perovskite SrTiO3-δNδ films. J. Mater. Chem. C, 2023, 11, pp. 16689–16698. DOI: 10.1039/d3tc03757f published under the CC BY-NC licence.Czech Science Foundation (Grant No. 22-10832S); European Structural and Investment Funds and the Ministry of Education, Youth and Sports of the Czech Republic (Project No. SOLID21 – CZ.02.1.01/0.0/0.0/16_019/0000760); Czech Academy of Sciences through the program Strategy AV21; M-ERA-NET HetCat project; The Institute of Solid State Physics, University of Latvia (Latvia) as the Centre of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017- Teaming Phase2 under grant agreement No. 739508, project CAMART2

d0 Ferromagnetic Interface Between Non-magnetic Perovskites

We use computational and experimental methods to study d0 ferromagnetism at a charge- imbalanced interface between two perovskites. In SrTiO3/KTaO3 superlattice calculations, the charge imbalance introduces holes in the SrTiO3 layer, inducing a d0 ferromagnetic half-metallic 2D electron gas at the interface oxygen 2p orbitals. The charge imbalance overrides doping by vacancies at realistic concentrations. Varying the constituent materials shows ferromagnetism to be a gen- eral property of hole-type d0 perovskite interfaces. Atomically sharp epitaxial d0 SrTiO3/KTaO3, SrTiO3 /KNbO3 and SrTiO3 /NaNbO3 interfaces are found to exhibit ferromagnetic hysteresis at room temperature. We suggest the behavior is due to high density of states and exchange coupling at the oxygen t1g band in comparison with the more studied d band t2g symmetry electron gas.Comment: 5 pages, 5 figure

The electronic properties of SrTiO3-δ with oxygen vacancies or substitutions

The authors would like to thank R. Dittmann for useful discussions, T. Kocourek, O. Pacherova, S. Cichon, V. Vetokhina, and P. Babor for their contributions to sample preparation and characterization. The authors (M.T., A.D.) acknowledge support from the Czech Science Foundation (Grant No. 19-09671S), the European Structural and Investment Funds and the Ministry of Education, Youth and Sports of the Czech Republic through Programme “Research, Development and Education” (Project No. SOLID21 CZ.02.1.01/0.0/0.0/16-019/0000760). This study was partly supported by FLAG-ERA JTC project To2Dox (L.R. and E.K.). Calculations have been performed on the LASC Cluster in the Institute of Solid State Physics (ISSP), University of Latvia, and at the HLRS supercomputer centre, Stuttgart (Project DEFTD). The ISSP has received funding as a Centre of Excellence through the EU Horizon 2020 Programme H2020-WIDESPREAD-01-2016-2017-Teaming-Phase2 (CAMART2, Grant No. 739508).The electronic properties, including bandgap and conductivity, are critical for nearly all applications of multifunctional perovskite oxide ferroelectrics. Here we analysed possibility to induce semiconductor behaviour in these materials, which are basically insulators, by replacement of several percent of oxygen atoms with nitrogen, hydrogen, or vacancies. We explored this approach for one of the best studied members of the large family of ABO3 perovskite ferroelectrics — strontium titanate (SrTiO3). The atomic and electronic structure of defects were theoretically investigated using the large-scale first-principles calculations for both bulk crystal and thin films. The results of calculations were experimentally verified by studies of the optical properties at photon energies from 25 meV to 8.8 eV for in-situ prepared thin films. It was demonstrated that substitutions and vacancies prefer locations at surfaces or phase boundaries over those inside crystallites. At the same time, local states in the bandgap can be produced by vacancies located both inside the crystals and at the surface, but by nitrogen substitution only inside crystals. Wide-bandgap insulator phases were evidenced for all defects. Compared to pure SrTiO3 films, bandgap widening due to defects was theoretically predicted and experimentally detected. © 2021, The Author(s). Published under the CC BY 4.0 license.This article was funded by FLAG-ERA JTC project To2Dox, Czech Science Foundation (Grant no. 19-09671S), Ministry of Education, Youth and Sports of the Czech Republic, programme “Research, Development and Education” (Grant no. SOLID21 CZ.02.1.01/0.0/0.0/16-019/0000760); the ISSP has received funding as a Centre of Excellence through the EU Horizon 2020 Programme H2020-WIDESPREAD-01-2016-2017-Teaming-Phase2 (CAMART2, Grant No. 739508)

Evidence for Strain-Induced Ferroelectric Order in Epitaxial Thin-Film KTaO3

In perovskite-structure epitaxial films, it has been theoretically predicted that the polarization and the coherence of polar order can increase with increasing crystallographic strain. Experimental evidence of strain-induced long-range ferroelectric order has not been obtained thus far, posing the fundamental question of whether or not strain can induce the long-range polar order. Here we demonstrate the existence of strain-induced ferroelectric order in quantum paraelectric KTaO3 by combining experimental investigations of epitaxial KTaO3 films and density-functional-theory calculations. The long-range ferroelectric order does exist under a large enough epitaxial strain. We suggest that a region of short-range polar order might appear between paraelectric and ferroelectric states in the strain-temperature phase diagrams.Peer reviewe

Epitaxial growth of perovskite oxide films facilitated by oxygen vacancies

The authors would like to thank P. Yudin for valuable discussions, N. Nepomniashchaia for VASE studies, and S. Cichon for XPS analysis. The authors acknowledge support from the Czech Science Foundation (Grant No. 19-09671S), the European Structural and Investment Funds and the Ministry of Education, Youth and Sports of the Czech Republic through Programme ‘‘Research, Development and Education’’ (Project No. SOLID21 CZ.02.1.01/0.0/0.0/16-019/0000760), and ERA NET project Sun2Chem (E. K. and L. R.). Calculations have been done on the LASC Cluster in the ISSP UL.Single-crystal epitaxial films of technologically important and scientifically intriguing multifunctional ABO3 perovskite-type metal oxides are essential for advanced applications and understanding of these materials. In such films, a film-substrate misfit strain enables unprecedented crystal phases and unique properties that are not available in their bulk counterparts. However, the prerequisite growth of strained epitaxial films is fundamentally restricted by misfit relaxation. Here we demonstrate that introduction of a small oxygen deficiency concurrently stabilizes epitaxy and increases lattice strain in thin films of archetypal perovskite oxide SrTiO3. By combining experimental and theoretical methods, we found that lattice distortions around oxygen vacancies lead to anisotropic local stresses, which interact with the misfit strain in epitaxial films. Consequently, specific crystallographic alignments of the stresses are energetically favorable and can facilitate epitaxial growth of strained films. Because anisotropic oxygen-vacancy stresses are inherent to perovskite-type and many other oxides, we anticipate that the disclosed phenomenon of epitaxial stabilization by oxygen vacancies is relevant for a very broad range of functional oxides.This work is licensed under CC BY, CC BY-NC licenses.Czech Science Foundation (Grant No. 19-09671S); European Structural and Investment Funds and the Ministry of Education, Youth and Sports of the Czech Republic through Programme ‘‘Research, Development and Education’’ (Project No. SOLID21 CZ.02.1.01/0.0/0.0/16-019/0000760), and ERA NET project Sun2Chem; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART²

Effects of doping and epitaxy on optical behavior of NaNbO3 films

Cube-on-cube epitaxy of perovskite sub-cell of Pr-doped and undoped NaNbO3 is obtained in 130-nm-thick films on top of (La0.18Sr0.82)(Al0.59Ta0.41)O3 (001) substrates. Experimental studies show that the edge of optical absorption red-shifts and some interband transitions change in the films compared to crystals. Bright red luminescence is achieved at room-temperature under ultraviolet excitation in the Pr-doped film. An interband mechanism of luminescence excitation is detected in the film, which is in contrast to the intervalence charge transfer mechanism in the crystal. The results are discussed in terms of epitaxially induced changes of crystal symmetry and ferroelectric polarization in the films. It is suggested that the band structure and interband transitions in NaNbO3and the transition probabilities in the Pr ions can be significantly modified by these changes.Peer reviewe

A Subretinal Cell Delivery Method via Suprachoroidal Access in Minipigs: Safety and Surgical Outcomes

Ophthalmic researc