Knowledge of the explicit mechanisms of charge transport is preeminent for a fundamental understanding of the metal-to-insulator transition in ABO
-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 SmNiO
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.
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.
Intermolecular hydrogen bonds impede long-range (anti-)ferroelectric order of water. We confine H
O molecules in nanosized cages formed by ions of a dielectric crystal. Arranging them in channels at ...a distance of ~5 Å with an interchannel separation of ~10 Å prevents the formation of hydrogen networks while electric dipole-dipole interactions remain effective. Here, we present measurements of the temperature-dependent dielectric permittivity, pyrocurrent, electric polarization and specific heat that indicate an order-disorder ferroelectric phase transition at T
≈ 3 K in the water dipolar lattice. Ab initio molecular dynamics and classical Monte Carlo simulations reveal that at low temperatures the water molecules form ferroelectric domains in the ab-plane that order antiferroelectrically along the channel direction. This way we achieve the long-standing goal of arranging water molecules in polar order. This is not only of high relevance in various natural systems but might open an avenue towards future applications in biocompatible nanoelectronics.
Water is characterized by large molecular electric dipole moments and strong interactions between molecules; however, hydrogen bonds screen the dipole-dipole coupling and suppress the ferroelectric ...order. The situation changes drastically when water is confined: in this case ordering of the molecular dipoles has been predicted, but never unambiguously detected experimentally. In the present study we place separate H
O molecules in the structural channels of a beryl single crystal so that they are located far enough to prevent hydrogen bonding, but close enough to keep the dipole-dipole interaction, resulting in incipient ferroelectricity in the water molecular subsystem. We observe a ferroelectric soft mode that causes Curie-Weiss behaviour of the static permittivity, which saturates below 10 K due to quantum fluctuations. The ferroelectricity of water molecules may play a key role in the functioning of biological systems and find applications in fuel and memory cells, light emitters and other nanoscale electronic devices.
Polarized Raman, IR, and time-domain THz spectroscopy of orthorhombic lead zirconate single crystals have yielded a comprehensive picture of temperature-dependent quasiharmonic frequencies of its ...low-frequency phonon modes. It is argued that these modes primarily involve vibrations of Pb ions and librations of oxygen octahedra. Their relation to phonon modes of the parent cubic phase is proposed. Counts of the observed IR and Raman active modes belonging to distinct irreducible representations agree quite well with group-theory predictions. Analysis of the results yields insight into the phase transition mechanism, involving a soft ferroelectric branch coupled by a trilinear term to another two oxygen octahedra tilt modes.
The electrical conductivity of epitaxial BaTiO3 films was studied by small-signal impedance spectroscopy at temperatures of 10–720 K using Pt-BaTiO3−SrRuO3 capacitors. The ∼150-nm-thick BaTiO3 films ...possessed different lattice strains and degrees of oxygen deficiency. A crossover between the low-temperature hopping of small polarons and the high-temperature semiconductor- to metal-type behavior was demonstrated in all films. It was suggested that the small electron polarons originate from self-trapping at Ti in the stoichiometric tensile-strained film and from trapping at Ti next to the oxygen vacancy in the oxygen-deficient films. The conduction-band transport was ascribed to the thermally activated release of the trapped electrons. It was pointed out that the electronic release can mimic the motion of oxygen vacancies, which are actually immobile.
Dielectric spectra of SrTiO
3
and SrTiO
3
:Mn single crystals have been studied in the frequency range of 10‒3000 cm
–1
and in the temperature range of 5–297 K using time-domain terahertz ...spectroscopy and Fourier-transform infrared spectroscopy. A comparative analysis of the experimental results made it possible to detect a significant broadening of the absorption lines corresponding to the Slater and Last phonon modes, while the parameters of the Axe mode when replacing Ti with Mn (2 at %) stay invariant. This effect is associated with an enhance in structural disorder in the cation subsystem (B-sublattice) of the SrTiO
3
crystal. It has been established that doping with Mn ions reduces the antiferrodistortive phase transition temperature by about 20 K, but hardly affects the character of the temperature dependence of the parameters of a ferroelectric soft mode at temperatures of about 60–297 K. It has been found that an additional excitation with the frequency below the frequency of the ferroelectric soft mode should be taken into account for an appropriate model description of the dispersion of the permittivity of SrTiO
3
:Mn in the terahertz frequency range. The results obtained in this work indicate that dielectric relaxation in the SrTiO
3
:Mn crystal is due to thermally activated hops of Mn atoms between displaced (noncentral) crystallographic sites; i.e., the mechanism of radiofrequency relaxation in SrTiO
3
:Mn is hopping rather than polaronic, which is also actively discussed in the literature.
We have fabricated new perovskite multiferroic PbFe Sb O3 with a high degree (up to 0.9) of chemical ordering and unexpectedly high-temperature magnetic relaxor properties, which can barely be ...described within concepts of conventional spin glass physics. Notably, we found that the field-temperature phase diagram of this material, in the extremely wide temperature interval, contains the de Almeida-Thouless-type critical line, which has been the subject of long debates regarding its possible experimental realization. We explain our findings by the creation, at high temperatures of not less than 250 K, of giant superspins (SSs), owing, curiously enough, to the antiferromagnetic superexchange interaction. We show that these SSs are capable of strong high-temperature magnetic relaxation in the relaxor phase, down to about 150 K, where they transform into a SS glass phase. On further cooling, the material experiences another striking transition, this time, into an ordinary (single-spin) antiferromagnetic phase. We comprehensively analyze the above complex physical picture in terms of three complimentary theoretical approaches. Namely, the ab initio calculations elucidate the microscopic mechanism of giant SS formation, the high-temperature expansion accounts for the morphology of these clusters, and the random field approach provides the description of disorder-related characteristics.
PAH concentration and distribution has been examined in surface sediments samples from the Kara Sea, Russia. The study includes 13 samples from the South-eastern Kara Sea shelf, one sample from the ...south-western part of the sea, 4 samples from the Baydaratskaya Bay, 5 samples from the Gulf of Ob and 4 samples from the Yenisei Bay, collected in August–September 1993–1994. Cluster analysis and principal component analysis (PCA) were used to identify common patterns and possible sources of PAHs. The total PAH concentration (sum of two- to six-ring aromatic hydrocarbons) in the Kara Sea sediments was generally lower than in the Barents Sea sediments and comparable to the levels in the Pechora and White seas. Two- and three-ring aromatic hydrocarbons predominated in Kara Sea sediments, which indicate a relatively stronger petrogenic origin than that in the adjacent seas. The highest total PAH concentrations within the Kara Sea were found in sediments from the Yenisei Bay and in the South-western part of the Kara Sea in the Eastern Novaya Zemlya Trough. The PAHs of the Yenisei Bay sediments were dominated by perylene and PAHs of petrogenic origin, but had also a strong indication of PAHs of pyrogenic origin. The dominating PAH group in the South-western part of the Kara Sea were four- to six-ring aromatic hydrocarbons, indicating pyrogenic origin. Perylene levels were high in all the Kara Sea samples, and highest levels were found in areas of strong terrigenous influence. The most probable source is decaying peat products being transported to the Kara Sea by both large and small rivers.
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