The crystal structure and lattice dynamics of quantum paraelectric BaxSr1−xTiO3 (x = 0, 0.01, 0.02) solid solutions are studied using X‐ray diffraction (XRD), Raman and terahertz‐infrared (THz‐IR) ...spectroscopies in a temperature range of 4–300 K. XRD and Raman spectroscopy reveal the cubic‐to‐tetragonal nonpolar structural phase transition at about 100 K. At the same time, Raman spectra manifest the presence of polar modes, TO2 and TO4, normally prohibited in paraelectric phase. Emergence of these modes indicates the appearance of the polar nanoregions in a broad temperature range. The modes become more intensive at low temperatures, and temperature dependence of their intensities on cooling reveals the kink‐like change of the slope from flat to steep, indicating on activation of polar nanoregions. The transmission THz‐IR spectra show that squared frequency of the polar TO1 soft mode, responsible for ferroelectric transition, follows Cochran's behavior at high temperatures. However, at low temperatures, it doesn't vanish at extrapolated Curie temperature but saturates, demonstrating the plateau feature below 20 K. This behavior, coherent with known saturation of the dielectric constant, indicates that transition to ferroelectric phase in BaxSr1−xTiO3 is suppressed by quantum fluctuations and the system stays in quantum paraelectric state at very low temperatures.
Crystal structure and lattice dynamics of quantum paraelectric BaxSr1−xTiO3 are studied at temperatures 4–300 K. Polar nanoclusters appear in a broad temperature range and extend with increasing concentration of Ba ions. Clusters’ activation locally stabilizes the ferroelectric phase and reduces the temperature of structural transition. Quantum fluctuations suppress the ferroelectric state, conserving the paraelectric state at very low temperatures.
We report on the electrodynamic properties of the single crystalline lead-substituted M-type barium hexaferrite, Ba0.3Pb0.7Fe12O19, performed in the broad frequency range including radio-frequency, ...terahertz and sub-terahertz bands, which are particularly important for the development of microelectronic devices. We demonstrate how changing on a molecular level the chemical characteristics (composition, intermolecular interaction, spin-orbital interaction) of lead-substituted M-type hexaferrite influences its radio-frequency and terahertz electrodynamic response. Our results indicate a critical temperature range, 50 K < T < 70 K, where significant changes of the electrodynamic response occur that are interpreted as freezing of dynamical oscillations of bi-pyramidal Fe(2b) ions. In the range 5-300 K, the heat capacity shows no sign of any phase transition and is solely determined by electron and phonon contributions. An anomalous electrodynamic response is detected at 1-2 THz that features a rich set of absorption resonances which are associated with electronic transitions within the fine-structured Fe2+ ground state and are visualized in the spectra due to magnetostriction and electron-phonon interaction. We show that lead substitution of barium in barium hexaferrite, BaFe12O19, leads to the emergence of a pronounced dielectric and magnetic relaxational dynamics at radio-frequencies and that both dynamics have the same characteristic relaxation times, thus evidencing the bi-relaxor-like nature of Ba0.3Pb0.7Fe12O19. We associate the origin of the relaxations as connected with the motion of magnetic domain walls. In order to unveil crucial influence of chemical substitution on electrodynamic characteristics of the compound, we analyze our results on substituted compound in comparison with the data available for pristine barium (BaFe12O19) and pristine lead (PbFe12O19) hexaferrites. The obtained spectroscopic data on the dielectric properties of Ba0.3Pb0.7Fe12O19 provide insight into fundamental phenomena responsible for the absorption mechanisms of the compound and demonstrates that chemical ionic substitution is an effective tool to tune the dielectric properties of the whole family of hexaferrites.
•Discovery of correlated activation energies governing magnetic relaxation and electrical transport in M-type hexaferrites.•Correlation persists with Aluminum substitution.•Magnetic response is ...similar to that of uniaxial antiferromagnets.•Correlation is interpreted as the motion of the charged magnetic domain walls that are screened by free charge carriers.
In this work, we present frequency-dependent magnetic susceptibility and dc electric transport properties of three different compositions of hexaferrite Ba1−xPbxFe12−yAlyO19 single crystals. We found a correlation between the activation energies of the dc electric transport and the ac magnetic susceptibility which persists over the whole studied range of aluminum substitution y = 0–3.3. This result is discussed in the context of charged magnetic domain walls, the pinning of which is determined by charge carriers activated across the transport gap. Our work points toward a general relaxation mechanism in ferrimagnetic semiconductors that directly affects the dynamic magnetic properties via electrical transport.
Double substitution of strontium hexaferrite by calcium and aluminum leads to a tremendous rise of hard magnetic properties, such as coercivity and natural ferromagnetic resonance frequency (NFMR). ...However, the properties are also inextricably linked to the material microstructure (especially, particle size), to the solid solution inhomogeneity as well as aluminum ions distribution among iron sites in crystal structure. In this work, we obtained M-type hexaferrite particles Sr1-x/12Cax/12Fe12-xAlxO19 (x = 4–6) via a facile citrate-nitrate auto-combustion method and studied the influence of the annealing temperature in a broad range on the microstructure, features of crystal structure and hard magnetic properties. At low annealing temperatures (900–1000°С) hexaferrite nanoparticles with 90% of nominal Al content and a wide chemical distribution are formed. Next, with an increase in the annealing temperature the distribution significantly narrows, chemical composition becomes close to the nominal one and particles size transfer firstly to submicron, then to micron range. The aluminum distribution over iron sites is independent distinctly on the annealing temperature. For all the compositions single domain particles with the maximum coercivity values between 22.8 and 36 kOe are obtained at 1200 °C. At 900–1000 °C the samples demonstrate coercivities up to 25 kOe, while above 1300 °C, the crystallites begin to pass into a polydomain state with a reduced coercivity. The hexaferrites with narrow chemical distribution reveal resonance absorption in sub-terahertz band. The highest NFMR frequency of 270 GHz was observed for x = 5.5 sample annealed at 1400 °C.
Display omitted
Intensive development of ultrafast electronics requires materials with high-frequency spin dynamics. In this light, the insulators that possess the magnetization precession phenomenon ...due to magnetic anisotropy are dark horses. On the one hand, modern hard magnetic materials reveal relatively moderate resonance frequencies of the ferromagnetic mode (generally, dozens of GHz), which are lower than the frequencies of the antiferromagnetic resonances; on the other hand, the research in this area is quite scanty, which implies a room for a breakthrough. Here, an example of a hard ferrimagnetic insulator (cobalt ferrite CoFe2O4) was obtained in the form of nanoparticles and bulk ceramics via high-temperature methods. Due to high magnetic anisotropy fields, the samples in a single domain state show broad hysteresis loops. The materials also possess intensive resonance absorption at frequencies higher than 0.20 THz in zero external magnetic fields. For the first time, natural ferromagnetic resonance (NFMR) frequencies higher than 0.30 THz were registered. The ceramic sample demonstrates the highest-known NFMR frequency of 0.35 THz. The model based on the Landau-Lifshitz equation was developed to explain the demonstrated magnetodynamic properties and shed light on those of hard ferrimagnets in general. The practical application of the electron resonances in hard magnetic insulators, including cobalt ferrite, Al-doped M-type hexaferrite, and epsilon iron oxide, is discussed. Our findings reveal that these materials should provide several orders of magnitude more powerful spin pumping at sub-terahertz/terahertz frequencies compared to insulating antiferromagnets, even under unpolarized irradiation and even in the absence of external magnetic fields. This opens new horizons for the development of practical ultrafast electronics.
The crystal structure and lattice dynamics of quantum paraelectric Ba
x
Sr
1−
x
TiO
3
(
x
= 0, 0.01, 0.02) solid solutions are studied using X‐ray diffraction (XRD), Raman and terahertz‐infrared ...(THz‐IR) spectroscopies in a temperature range of 4–300 K. XRD and Raman spectroscopy reveal the cubic‐to‐tetragonal nonpolar structural phase transition at about 100 K. At the same time, Raman spectra manifest the presence of polar modes, TO
2
and TO
4
, normally prohibited in paraelectric phase. Emergence of these modes indicates the appearance of the polar nanoregions in a broad temperature range. The modes become more intensive at low temperatures, and temperature dependence of their intensities on cooling reveals the kink‐like change of the slope from flat to steep, indicating on activation of polar nanoregions. The transmission THz‐IR spectra show that squared frequency of the polar TO
1
soft mode, responsible for ferroelectric transition, follows Cochran's behavior at high temperatures. However, at low temperatures, it doesn't vanish at extrapolated Curie temperature but saturates, demonstrating the plateau feature below 20 K. This behavior, coherent with known saturation of the dielectric constant, indicates that transition to ferroelectric phase in Ba
x
Sr
1−
x
TiO
3
is suppressed by quantum fluctuations and the system stays in quantum paraelectric state at very low temperatures.
In this work we present frequency-dependent magnetic susceptibility and dc electric transport properties of three different compositions of hexaferrite ...Ba\(_{1-x}\)Pb\(_{x}\)Fe\(_{12-y}\)Al\(_{y}\)O\(_{19}\). We find a correlation between activation energies of dc electric transport and ac magnetic susceptibility which persists in the whole researched range of aluminium substitution \(x=0\) to \(3.3\). This result is discussed in the context of charged magnetic domain walls, the pinning of which is determined by charge carriers activated over the transport gap. Our work points toward a general relaxational mechanism in ferrimagnetic semiconductors which directly affects dynamic magnetic properties via electric transport.
Single-domain particles of SrFe8Al4O19 were prepared by thermal treatment at 1473 K of porous products of citrate-nitrate auto-combustion, and the influence of synthesis time on the particle ...morphology and magnetic properties was studied. The procedure allows to obtain SrFe8Al4O19 particles with mean diameters 100 - 460 nm, and their coercivity ranges from 14.5 to 18.4 kOe, while ferromagnetic resonance frequencies vary from 149 to 164 GHz.
Following the game‐changing high‐pressure CO (HiPco) process that established the first facile route toward large‐scale production of single‐walled carbon nanotubes, CO synthesis of cm‐sized graphene ...crystals of ultra‐high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large‐scale monocrystals. Unique features of the Boudouard reaction coupled with CO‐driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene‐catalyst composite production.
Unique features of Boudouard reaction facilitate high‐purity, wafer‐scale single‐crystal graphene on metal catalysts.
PDF
