Theory for anisotropic local ferroelectric switching.

Theoretical modeling of polarization switching around a biased tip contact is important for fundamental understanding and advanced applications of ferroelectrics. Here we propose a simple in-plane two-dimensional model that considers surface charge transport and the associated evolution of the electric field driving domain growth. The model reproduces peculiar domain shapes ranging from round to faceted in KTiOPO4(C2vsymmetry) and LiNbO3(C3vsymmetry). This is done through modulation of dielectric permittivity, which mimics domain wall pinning on the lattice. In contrast to previous works, which attempted to justify domain anisotropy by means of point symmetry invariants, here we illustrate the necessity of taking translational symmetry into account. The results are pertinent to ferroelectric racetrack memories and other applications requiring domain tailoring.

Small-polaron transport in perovskite nickelates.

Knowledge of the explicit mechanisms of charge transport is preeminent for a fundamental understanding of the metal-to-insulator transition in ABO3-type perovskite rare-earth nickelates and for potential applications of these technologically promising materials. Here we suggest that owing to intrinsic Jahn-Teller-driven carrier localization, small-polaron transport is innate in nickelates. We demonstrate experimental evidence for such transport by investigating AC conductivity over a broad range of temperatures and frequencies in epitaxial SmNiO3 films. We reveal the hopping mechanism of conductivity, Holstein-type activation energy for hopping, nonclassical relaxation behavior, and nonclassical consistency between activation and relaxation. By analyzing these observations, we validate small-polaron transport. We anticipate that our findings can lead to precise tailoring of the DC and AC conductivity in nickelates as requested for fruitful employment of these materials. We also believe that further investigations of self-trapped small polarons are essential for a comprehensive understanding of nickelates.

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

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.

Anisotropic chemical expansion due to oxygen vacancies in perovskite films.

In scientifically intriguing and technologically important multifunctional ABO3 perovskite oxides, oxygen vacancies are most common defects. They cause lattice expansion and can alter the key functional properties. Here, it is demonstrated that contrary to weak isotropic expansion in bulk samples, oxygen vacancies produce strong anisotropic strain in epitaxial thin films. This anisotropic chemical strain is explained by preferential orientation of elastic dipoles of the vacancies. Elastic interaction of the dipoles with substrate-imposed misfit strain is suggested to define the dipolar orientation. Such elastic behavior of oxygen vacancies is anticipated to be general for perovskite films and have critical impacts on the film synthesis and response functions.

Mobile and immobile boundaries in ferroelectric films.

The intrinsic mobile interfaces in ferroelectrics-the domain walls can drive and enhance diverse ferroelectric properties, essential for modern applications. Control over the motion of domain walls is of high practical importance. Here we analyse theoretically and show experimentally epitaxial ferroelectric films, where mobile domain walls coexist and interact with immobile growth-induced interfaces-columnar boundaries. Whereas these boundaries do not disturb the long-range crystal order, they affect the behaviour of domain walls in a peculiar selective manner. The columnar boundaries substantially modify the behaviour of non-ferroelastic domains walls, but have negligible impact on the ferroelastic ones. The results suggest that introduction of immobile boundaries into ferroelectric films is a viable method to modify domain structures and dynamic responses at nano-scale that may serve to functionalization of a broader range of ferroelectric films where columnar boundaries naturally appear as a result of the 3D growth.

Control of Mooij correlations at the nanoscale in the disordered metallic Ta-nanoisland FeNi multilayers.

Localisation phenomena in highly disordered metals close to the extreme conditions determined by the Mott-Ioffe-Regel (MIR) limit when the electron mean free path is approximately equal to the interatomic distance is a challenging problem. Here, to shed light on these localisation phenomena, we studied the dc transport and optical conductivity properties of nanoscaled multilayered films composed of disordered metallic Ta and magnetic FeNi nanoisland layers, where ferromagnetic FeNi nanoislands have giant magnetic moments of 10[Formula: see text]-10[Formula: see text] Bohr magnetons ([Formula: see text]). In these multilayered structures, FeNi nanoisland giant magnetic moments are interacting due to the indirect exchange forces acting via the Ta electron subsystem. We discovered that the localisation phenomena in the disordered Ta layer lead to a decrease in the Drude contribution of free charge carriers and the appearance of the low-energy electronic excitations in the 1-2 eV spectral range characteristic of electronic correlations, which may accompany the formation of electronic inhomogeneities. From the consistent results of the dc transport and optical studies we found that with an increase in the FeNi layer thickness across the percolation threshold evolution from the superferromagnetic to ferromagnetic behaviour within the FeNi layer leads to the delocalisation of Ta electrons from the associated localised electronic states. On the contrary, we discovered that when the FeNi layer is discontinuous and represented by randomly distributed superparamagnetic FeNi nanoislands, the Ta layer normalized dc conductivity falls down below the MIR limit by about 60%. The discovered effect leading to the dc conductivity fall below the MIR limit can be associated with non-ergodicity and purely quantum (many-body) localisation phenomena, which need to be challenged further.

In situ anion-doped epitaxial strontium titanate films.

Misfit strains arising from a film-substrate mismatch can induce novel phases and properties in the epitaxial films of perovskite oxides. Here we employ yet another effect, namely, strain-assisted formation of oxygen vacancies. We demonstrate the misfit-promoted presence of oxygen vacancies and related substitutional incorporation of anion dopants in the epitaxial films of archetypal perovskite oxide SrTiO3. Both the oxygen vacancies and hydrogen or nitrogen dopants are introduced in situ during the pulsed-laser deposition of the films using compressive substrates. The films exhibit peculiar chemical expansion and optical properties, which are consistent with substitutional anion doping.

Structure assembly regularities in vapour-deposited gold-fullerene mixture films.

Self-assembly is an attractive phenomenon that, with proper handling, can enable the production of sophisticated hybrid nanostructures with sub-nm-scale precision. The importance of this phenomenon is particularly notable in the fabrication of metal-organic nanomaterials as promising substances for spintronic devices. The exploitation of self-assembly in nanofabrication requires a comprehension of atomic processes creating hybrid nanostructures. Here, we focus on the self-assembly processes in the vapour-deposited Au x C60 mixture films, revealing the exciting quantum plasmon effects. Through a systematic characterization of the Au x C60 films carried out using structure-sensitive techniques, we have established correlations between the film nanostructure and the Au concentration, x. The analysis of these correlations designates the Au intercalation into the C60 lattice and the Au clustering as the basic processes of the nanostructure self-assembly in the mixture films, the efficiency of which strongly depends on x. The evaluation of this dependence for the Au x C60 composite nanostructures formed in a certain composition interval allows us to control the size of the Au clusters and the intercluster spacing by adjusting the Au concentration only. This study represents the self-assembled Au x C60 mixtures as quantum materials with electronic functions tuneable by the Au concentration in the depositing mixture.

Perovskite ferroelectric tuned by thermal strain.

Modern environmental and sustainability issues as well as the growing demand for applications in the life sciences and medicine put special requirements to the chemical composition of many functional materials. To achieve desired performance within these requirements, innovative approaches are needed. In this work, we experimentally demonstrate that thermal strain can effectively tune the crystal structure and versatile properties of relatively thick films of environmentally friendly, biocompatible, and low-cost perovskite ferroelectric barium titanate. The strain arises during post-deposition cooling due to a mismatch between the thermal expansion coefficients of the films and the substrate materials. The strain-induced in-plane polarization enables excellent performance of bottom-to-top barium titanate capacitors akin to that of exemplary lead-containing relaxor ferroelectrics. Our work shows that controlling thermal strain can help tailor response functions in a straightforward manner.

Optical revelation of defects in epitaxial barium titanate films.

Allying epitaxial strain and synthesis conditions allows for the introduction of specific point defects in perovskite oxide films. In ferroelectric films, such defects lead to essential polar and electronic properties, which can enable advanced applications. Here, to elucidate the nature of the defects, optical constants are investigated in the spectral range of 0.7-8.8 eV in epitaxial ferroelectric BaTiO3 films, which are synthesized under different conditions. It is demonstrated that oxygen-vacancy-related defects are responsible for a peculiar transition below the bandgap at ∼2.7-2.9 eV and significant blueshifts of ∼0.3-0.4 eV of the gap and the main interband transitions. These observations suggest that the defects are dipolar complexes comprising titanium cations and oxygen vacancies (Ti3+-VO).

Thermooptical evidence of carrier-stabilized ferroelectricity in ultrathin electrodeless films.

Ferroelectric films may lose polarization as their thicknesses decrease to a few nanometers because of the depolarizing field that opposes the polarization therein. The depolarizing field is minimized when electrons or ions in the electrodes or the surface/interface layers screen the polarization charge or when peculiar domain configuration is formed. Here, we demonstrate ferroelectric phase transitions using thermooptical studies in ∼5-nm-thick epitaxial Pb0.5Sr0.5TiO3 films grown on different insulating substrates. By comparing theoretical modeling and experimental observations, we show that ferroelectricity is stabilized through redistribution of charge carriers (electrons or holes) inside ultrathin films. The related high-density of screening carriers is confined within a few-nanometers-thick layer in the vicinity of the insulator, thus resembling a two-dimensional carrier gas.

Non-thermal air plasma promotes the healing of acute skin wounds in rats.

Non-thermal plasma (NTP) has nonspecific antibacterial effects, and can be applied as an effective tool for the treatment of chronic wounds and other skin pathologies. In this study we analysed the effect of NTP on the healing of the full-thickness acute skin wound model in rats. We utilised a single jet NTP system generating atmospheric pressure air plasma, with ion volume density 5 · 1017 m-3 and gas temperature 30-35 °C. The skin wounds were exposed to three daily plasma treatments for 1 or 2 minutes and were evaluated 3, 7 and 14 days after the wounding by histological and gene expression analysis. NTP treatment significantly enhanced epithelization and wound contraction on day 7 when compared to the untreated wounds. Macrophage infiltration into the wound area was not affected by the NTP treatment. Gene expression analysis did not indicate an increased inflammatory reaction or a disruption of the wound healing process; transient enhancement of inflammatory marker upregulation was found after NTP treatment on day 7. In summary, NTP treatment had improved the healing efficacy of acute skin wounds without noticeable side effects and concomitant activation of pro-inflammatory signalling. The obtained results highlight the favourability of plasma applications for wound therapy in clinics.

Optical Properties of Ferroelectric Epitaxial K0.5Na0.5NbO3 Films in Visible to Ultraviolet Range.

The complex index of refraction in the spectral range of 0.74 to 4.5 eV is studied by variable-angle spectroscopic ellipsometry in ferroelectric K0.5Na0.5NbO3 films. The 20-nm-thick cube-on-cube-type epitaxial films are grown on SrTiO3(001) and DyScO3(011) single-crystal substrates. The films are transparent and exhibit a significant difference between refractive indices Δn = 0.5 at photon energies below 3 eV. The energies of optical transitions are in the range of 3.15-4.30 eV and differ by 0.2-0.3 eV in these films. The observed behavior is discussed in terms of lattice strain and strain-induced ferroelectric polarization in epitaxial perovskite oxide films.

Ferroelectricity in antiferroelectric NaNbO3 crystal.

Sodium niobate (NaNbO3, or NNO) is known to be antiferroelectric at temperatures between 45 and 753 K. Here we show experimentally the presence of the ferroelectric phase at temperatures between 100 and 830 K in the NNO crystals obtained by top-seeded solution growth. The ferroelectric phase and new phase transitions are evidenced using a combination of thermo-optical studies by variable angle spectroscopic ellipsometry, Raman spectroscopy analysis, and photoelectron emission microscopy. The possibility for strain-induced ferroelectricity in NNO is suggested.

Anomalous multi-order Raman scattering in LaMnO3: a signature of quantum lattice effects in a Jahn-Teller crystal.

The multi-order Raman scattering is studied up to fourth order for a detwinned LaMnO3 crystal. Based on a comprehensive data analysis of the polarization-dependent Raman spectra, we show that the anomalous features in the multi-order scattering could be the sidebands on the low-energy mode at about 25 cm(-1). We suggest that this low-energy mode stems from the tunneling transition between the potential energy minima arising near the Jahn-Teller Mn(3+) ion due to the lattice anharmonicity and that the multi-order scattering is activated by this low-energy electronic motion. The sidebands are dominated by the oxygen contribution to the phonon density-of-states, however, there is an admixture of an additional component, which may arise from coupling between the low-energy electronic motion and the vibrational modes.

d0 ferromagnetic interface between nonmagnetic perovskites.

We use computational and experimental methods to study d(0) ferromagnetism at a charge-imbalanced interface between two perovskites. In SrTiO(3)/KTaO(3) superlattice calculations, the charge imbalance introduces holes in the SrTiO(3) layer, inducing a d(0) ferromagnetic half-metallic 2D hole 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 general property of hole-type d(0) perovskite interfaces. Atomically sharp epitaxial d(0) SrTiO(3)/KTaO(3), SrTiO(3)/KNbO(3), and SrTiO(3)/NaNbO(3) interfaces are found to exhibit ferromagnetic hysteresis at room temperature. We suggest that the behavior is due to the high density of states and exchange coupling at the oxygen t(1g) band in comparison with the more studied d band t(2g) symmetry electron gas.

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.

Atmospheric barrier-torch discharge deposited ZnO films: optical properties, doping and grain size effects.

Technology aspects, structure and characteristic properties of the atmospheric barrier torch discharge technique grown nominally pure and Al (0.1-5%) and Mn (0.05-0.5%) doped ZnO nanocrystalline thin films deposited on fused quartz substrates are reported. The set of films with various thicknesses in the range from 70 nm to 1000 nm were prepared for each composition. XRD and AFM analysis show well formed [001] preferably oriented hexagonal high quality films witch could be operatively fabricated in air atmosphere with controlled grain size. All films under study revealed n-type conductivity except some Mn doped films, which revealed p-type. Spectroscopic optical ellipsometry and luminescence spectroscopy studies evidenced luminescence properties typical for well formed ZnO and appreciable influence of Al doping and grain size on the optical absorption edge. Al doping shifts strongly absorption edge to the higher energies. The grain size decreasing (from 100 to 15 nm) leads to distinct diffusing of the absorption edge accompanied by increase of absorption in the near band edge region. For the smallest grains the pronounced Urbach-type absorption tail can be observed manifesting films inhomogeneity development.

Ultrathin SrTiO(3) films: epitaxy and optical properties.

Ultrathin (12-15 nm) SrTiO(3) films are grown by pulsed laser deposition on various single-crystal substrates. The crystal structure, orientation, and strain state of the films are studied by x-ray diffraction. The room-temperature optical properties of the films are experimentally determined using ellipsometric spectroscopy in the 1-6 eV spectral range. Epitaxial films with biaxial in-plane strain are obtained on LaAlO(3), DyScO(3), and KTaO(3) substrates, with the critical thickness for pseudomorphic growth being less than 10 nm. Abrupt strain relaxation has been detected. The optical properties of the films with different microstructure are compared with each other and with those of single-crystal SrTiO(3). Based on the comparison, surface effects are suggested to be dominant in the visible range, while the interband transitions are smeared and suppressed due to small film thickness and the presence of biaxial strain. The energies of gaps can increase due to strain-induced polarization. The absorption edge is affected by all the factors mentioned (surface, thickness, strain, and polarization).

SrTiO(3):Cr nanocrystalline powders: size effects and optical properties.

The crystal structure, optical absorption, and photoluminescence of chromium impurity centers were studied in nanocrystalline SrTiO(3):Cr (0.1 mol%) powders with average particle size within the range 13-100 nm prepared by the Pechini-type polymeric sol-gel method. Only the presence of a cubic perovskite phase of O(h)(1) symmetry was proved for the powders at room temperature, by means of x-ray diffraction. The lattice constant a = 3.910 Å, larger than that of bulk SrTiO(3) crystals (a = 3.905 Å), was found for nanoparticles with the size about 20 nm. The optical absorption edge and the zero-phonon R-line ([Formula: see text]) of luminescence of the octahedral Cr(3+) centers shifted to higher energies with decreasing nanoparticle size. These size effects were regarded as intrinsic to SrTiO(3). An unusual and large temperature shift of the R-line position very similar to the 'dielectric related' one of the bulk crystals was observed for all powders, evidencing their quantum paraelectric behavior. However, the powders with the average particle size about 13 and 20 nm did not reveal completely reproducible behavior of the R-line position at low temperatures. This instability was considered a possible manifestation of a low-temperature phase transition in small enough SrTiO(3) nanoparticles.