ABSTRACT
The development of the new generation of non-volatile high-density ferroelectric memory requires the utilization of ultrathin ferroelectric films. The most promising candidates are polycrystalline-doped HfO2 films because of their perfect compatibility with silicon technology and excellent ferroelectric properties. However, the remanent polarization of HfO2 films is known to degrade when their thickness is reduced to a few nanometers. One of the reasons for this phenomenon is the wake-up effect, which is more pronounced in the thinner the film. For the ultrathin HfO2 films, it can be so long-lasting that degradation occurs even before the wake-up procedure is completed. In this work, an approach to suppress the wake-up in ultrathin Hf0.5Zr0.5O2 films is elucidated. By engineering internal built-in fields in an as-prepared structure, a stable ferroelectricity without a wake-up effect is induced in 4.5 nm thick Hf0.5Zr0.5O2 film. By analysis of the functional characteristics of ferroelectric structures with a different pattern of internal built-in fields and their comparison with the results of in situ piezoresponse force microscopy and synchrotron X-ray micro-diffraction, the important role of built-in fields in ferroelectricity of ultrathin Hf0.5Zr0.5O2 films as well as the origin of stable ferroelectric properties is revealed.
ABSTRACT
La-, Nd- and La/Nd-based polysubstituted high-entropy oxides (HEOs) were produced by solid-state reactions. Composition of the B-site was fixed for all samples (Cr0.2Mn0.2Fe0.2Co0.2Ni0.2) with varying of A-site cation (La, Nd and La0.5Nd0.5). Nominal chemical composition of the HEOs correlates well with initial calculated stoichiometry. All produced samples are single phase with perovskite-like structure. Average particle size is critically dependent on chemical composition. Minimal average particle size (~400 nm) was observed for the La-based sample and maximal average particle size (5.8 µm) was observed for the Nd-based sample. The values of the configurational entropy of mixing for each sample were calculated. Electrical properties were investigated in the wide range of temperatures (150-450 K) and frequencies (10-1-107 Hz). Results are discussed in terms of the variable range hopping and the small polaron hopping mechanisms. Magnetic properties were analyzed from the temperature and field dependences of the specific magnetization. The frustrated state of the spin subsystem was observed, and it can be a result of the increasing entropy state. From the Zero-Field-Cooling and Field-Cooling regimes (ZFC-FC) curves, we determine the average and Smax maximum size of a ferromagnetic nanocluster in a paramagnetic matrix. The average size of a ferromagnetic cluster is ~100 nm (La-CMFCNO) and ~60 nm (LN-CMFCNO). The Smax maximum size is ~210 nm (La-CMFCNO) and ~205 nm (LN-CMFCNO). For Nd-CMFCNO, spin glass state (ferromagnetic cluster lower than 30 nm) was observed due to f-d exchange at low temperatures.
ABSTRACT
Three high-entropy Sm(Eu,Gd)Cr0.2Mn0.2Fe0.2Co0.2Ni0.2O3 perovskite solid solutions were synthesized using the usual ceramic technology. The XRD investigation at room temperature established a single-phase perovskite product. The Rietveld refinement with the FullProf computer program in the frame of the orthorhombic Pnma (No 62) space group was realized. Along with a decrease in the V unit cell volume from ~224.33 Å3 for the Sm-based sample down to ~221.52 Å3 for the Gd-based sample, an opposite tendency was observed for the unit cell parameters as the ordinal number of the rare-earth cation increased. The average grain size was in the range of 5-8 µm. Field magnetization was measured up to 30 kOe at 50 K and 300 K. The law of approach to saturation was used to determine the Ms spontaneous magnetization that nonlinearly increased from ~1.89 emu/g (Sm) up to ~17.49 emu/g (Gd) and from ~0.59 emu/g (Sm) up to ~3.16 emu/g (Gd) at 50 K and 300 K, respectively. The Mr residual magnetization and Hc coercive force were also determined, while the SQR loop squareness, k magnetic crystallographic anisotropy coefficient, and Ha anisotropy field were calculated. Temperature magnetization was measured in a field of 30 kOe. ZFC and FC magnetization curves were fixed in a field of 100 Oe. It was discovered that the Tmo magnetic ordering temperature downward-curve decreased from ~137.98 K (Sm) down to ~133.99 K (Gd). The spin glass state with ferromagnetic nanoinclusions for all the samples was observed. The
ABSTRACT
Bi nanocrystalline films were formed from perchlorate electrolyte (PE) on Cu substrate via electrochemical deposition with different duration and current densities. The microstructural, morphological properties, and elemental composition were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM), and energy-dispersive X-ray microanalysis (EDX). The optimal range of current densities for Bi electrodeposition in PE using polarization measurements was demonstrated. For the first time, it was shown and explained why, with a deposition duration of 1 s, co-deposition of Pb and Bi occurs. The correlation between synthesis conditions and chemical composition and microstructure for Bi films was discussed. The analysis of the microstructure evolution revealed the changing mechanism of the films' growth from pillar-like (for Pb-rich phase) to layered granular form (for Bi) with deposition duration rising. This abnormal behavior is explained by the appearance of a strong Bi growth texture and coalescence effects. The investigations of porosity showed that Bi films have a closely-packed microstructure. The main stages and the growth mechanism of Bi films in the galvanostatic regime in PE with a deposition duration of 1-30 s are proposed.
ABSTRACT
Nanostructured NiFe film was obtained on silicon with a thin gold sublayer via pulsed electrodeposition and annealed at a temperature from 100 to 400 °C in order to study the effect of heat treatment on the surface microstructure and mechanical properties. High-resolution atomic force microscopy made it possible to trace stepwise evolving microstructure under the influence of heat treatment. It was found that NiFe film grains undergo coalescence twice-at ~100 and ~300 °C-in the process of a gradual increase in grain size. The mechanical properties of the Au/NiFe nanostructured system have been investigated by nanoindentation at two various indentation depths, 10 and 50 nm. The results showed the opposite effect of heat treatment on the mechanical properties in the near-surface layer and in the material volume. Surface homogenization in combination with oxidation activation leads to abnormal strengthening and hardening-up of the near-surface layer. At the same time, a nonlinear decrease in hardness and Young's modulus with increasing temperature of heat treatment characterizes the internal volume of nanostructured NiFe. An explanation of this phenomenon was found in the complex effect of changing the ratio of grain volume/grain boundaries and increasing the concentration of thermally activated diffuse gold atoms from the sublayer to the NiFe film.
ABSTRACT
The possibility of the formation of high entropy single-phase perovskites using solid-state sintering was investigated. The BaO-SrO-CaO-MgO-PbO-TiO2, BaO-SrO-CaO-MgO-PbO-Fe2O3 and Na2O-K2O-CaO-La2O3-Ce2O3-TiO2 oxide systems were investigated. The optimal synthesis temperature is found between 1150 and 1400 °C, at which the microcrystalline single phase with perovskite structure was produced. The morphology, chemical composition, crystal parameters and dielectric properties were studied and compared with that of pure BaTiO3. According to the EDX data, the single-phase product has a formula of Na0.30K0.07Ca0.24La0.18Ce0.21TiO3 and a cubic structure.
ABSTRACT
Crystalline high-entropy single-phase products with a magnetoplumbite structure with grains in the µm range were obtained using solid-state sintering. The synthesis temperature was up to 1400 °C. The morphology, chemical composition, crystal structure, magnetic, and electrodynamic properties were studied and compared with pure barium hexaferrite BaFe12O19 matrix. The polysubstituted high-entropy single-phase product contains five doping elements at a high concentration level. According to the EDX data, the new compound has a formula of Ba(Fe6Ga1.25In1.17Ti1.21Cr1.22Co1.15)O19. The calculated cell parameter values were a = 5.9253(5) Å, c = 23.5257(22) Å, and V = 715.32(9) ų. The increase in the unit cell for the substituted sample was expected due to the different ionic radius of Ti/In/Ga/Cr/Co compared with Fe3+. The electrodynamic measurements were performed. The dielectric and magnetic permeabilities were stable in the frequency range from 2 to 12 GHz. In this frequency range, the dielectric and magnetic losses were -0.2/0.2. Due to these electrodynamic parameters, this material can be used in the design of microwave strip devices.
ABSTRACT
Barium hexaferrite powder samples with grains in the µm-range were obtained from solid-state sintering, and crystals with sizes up to 5 mm grown from PbO, Na2CO3, and BaB2O4 fluxes, respectively. Carbonate and borate fluxes provide the largest and structurally best crystals at significantly lower growth temperatures of 1533 K compared to flux-free synthesis (1623 K). The maximum synthesis temperature can be further reduced by the application of PbO-containing fluxes (down to 1223 K upon use of 80 at % PbO), however, Pb-substituted crystals Ba1-xPbxFe12O19 with Pb contents in the range of 0.23(2) ≤ x ≤ 0.80(2) form, depending on growth temperature and flux PbO content. The degree of Pb-substitution has only a minor influence on unit cell and magnetic parameters, although the values for Curie temperature, saturation magnetization, as well as the coercivity of these samples are significantly reduced in comparison with those from samples obtained from the other fluxes. Due to the lowest level of impurities, the samples from carbonate flux show superior quality compared to materials obtained using other methods.
ABSTRACT
The coexistence of three valence states of Mn ions, namely, +2, +3, and +4, in substituted magnetoplumbite-type BaFe12-xMnxO19 was observed by soft X-ray absorption spectroscopy at the Mn-L2,3 edge. We infer that the occurrence of multiple valence states of Mn situated in the pristine purely iron(III) compound BaFe12O19 is made possible by the fact that the charge disproportionation of Mn3+ into Mn2+ and Mn4+ requires less energy than that of Fe3+ into Fe2+ and Fe4+, related to the smaller effective Coulomb interaction of Mn3+ (d4) compared to Fe3+ (d5). The different chemical environments determine the location of the differently charged ions: with Mn3+ occupying positions with (distorted) octahedral local symmetry, Mn4+ ions prefer octahedrally coordinated sites in order to optimize their covalent bonding. Larger and more ionic bonded Mn2+ ions with a spherical charge distribution accumulate at tetrahedrally coordinated sites. Simulations of the experimental Mn-L2,3 XAS spectra of two different samples with x = 1.5 and x = 1.7 led to Mn2+:Mn3+:Mn4+ atomic ratios of 0.16:0.51:0.33 and 0.19:0.57:0.24.
