Tunable sub-terahertz resonance absorption in high-coercivity magnetodielectric ceramics.

Recently, giant coercivities (20-42 kOe) and sub-terahertz natural ferromagnetic resonance (NFMR) at 100-300 GHz were observed for single-domain M-type hexaferrite particles with high aluminum substitution. Herein, we fabricated dense ceramics of Sr0.67Ca0.33Fe8Al4O19 and, for the first time, investigated their magnetostatic and magnetodynamic properties in the temperature range of 5-300 K. It was shown that dense ceramics maintain their high magnetic hardness (a coercivity of 10-20 kOe) and NFMR frequencies of 140-200 GHz durably in the entire temperature range. Magnetizing the initially non-magnetized ceramics leads to a considerable decrease in the resonance absorption and to almost complete vanishing of the resonance line at 5 kOe. At the same time, an efficient linear frequency tuning by the external magnetic field was observed for the remanent sample. These findings open new horizons for developing industrial terahertz electronics based on dielectric ferrimagnets.

Nanoceramics of metastable ε-Fe2O3: effect of sintering on the magnetic properties and sub-terahertz electron resonance.

In this study, we demonstrate the sintering of metastable ε-Fe2O3 nanoparticles into nanoceramics containing 98 wt% of the epsilon iron oxide phase and with a specific density of 60%. At room temperature, the ceramics retain a giant coercivity of 20 kOe and a sub-terahertz absorption at 190 GHz inherent in the initial nanoparticles. The sintering leads to an increase in the frequencies of the natural ferromagnetic resonance at 200-300 K and larger coercivities at temperatures below 150 K. We propose a simple but working explanation of the low-temperature dynamics of the macroscopic magnetic parameters of the ε-Fe2O3 materials via the transition of the smallest nanoparticles into a superparamagnetic state. The results are confirmed by the temperature dependence of the magnetocrystalline anisotropy constant and micromagnetic modeling. In addition, based on the Landau-Lifshitz formalism, we discuss features of the spin dynamics in ε-Fe2O3 and the possibility of using nanoceramics as sub-terahertz spin-pumping media. Our observations will expand the applicability of ε-Fe2O3 materials and promote their integration into telecommunication devices of the next generation.

Hard ferrite magnetic insulators revealing giant coercivity and sub-terahertz natural ferromagnetic resonance at 5-300 K.

The temperature behavior of the magnetic properties is crucial for the application of magnetic materials. Recently, giant room temperature coercivities (20-36 kOe) and sub-terahertz natural ferromagnetic resonance (NFMR) frequencies (160-250 GHz) were observed for single-domain M-type hexaferrites with high aluminum substitution. Herein, the temperature dependences of the magnetic properties and natural ferromagnetic resonance are studied at 5-300 K for single-domain Sr1-x/12Cax/12Fe12-xAlxO19 (x = 1.5-5.5) particles. It is shown that the samples maintain their magnetic hardness over the whole temperature range. The coercivity and NFMR frequencies have a maximum shifting to the low-temperature region with a rise in aluminum concentration. The highest coercivity of 42 kOe and the maximum NFMR frequency of 297 GHz are observed for x = 5.5 at 180 K.

Correction: High-coercivity hexaferrite ceramics featuring sub-terahertz ferromagnetic resonance.

Correction for 'High-coercivity hexaferrite ceramics featuring sub-terahertz ferromagnetic resonance' by Evgeny A. Gorbachev et al., Mater. Horiz., 2022, 9, 1264-1272, DOI: https://doi.org/10.1039/D1MH01797G.

Pore Ordering in Anodic Aluminum Oxide: Interplay between the Pattern of Pore Nuclei and the Crystallographic Orientation of Aluminum.

Anodization of aluminum with a pre-patterned surface is a promising approach for preparing anodic aluminum oxide (AAO) films with defect-free pore arrangement. Although pronounced effects of crystallographic orientation of Al on the AAO structure have been demonstrated, all current studies on the anodization of pre-patterned aluminum consider the substrate as an isotropic medium and, thus, do not consider the azimuthal orientation of the pattern relative to the basis vectors of the Al unit cell. Here, we investigate the interplay between the azimuthal alignment of the pore nuclei array and the crystallographic orientation of aluminum. Al(100) and Al(111) single-crystal substrates were pre-patterned by a Ga focused ion beam and then anodized under self-ordering conditions. The thickness-dependent degree of pore ordering in AAO was quantified using statistical analysis of scanning electron microscopy images. The observed trends demonstrate that the preferred azimuthal orientation of pore nuclei rows coincides with the <110> directions in the Al unit cell, which is favorable for creating AAO with a high degree of pore ordering. In the case of an unspecified azimuthal orientation of the pore nuclei array, crystallography-affected disorder within the AAO structure occurs with increasing film thickness. Our findings have important implications for preparing defect-free porous films over 100 µm in thickness that are crucial for a variety of AAO applications, e.g., creating metamaterials and 2D/3D photonic crystals.

High-coercivity hexaferrite ceramics featuring sub-terahertz ferromagnetic resonance.

Herein, we demonstrate for the first time compact ferrite ceramics with giant coercivity. The materials are manufactured via sintering single-domain Sr0.67Ca0.33Fe8Al4O19 particles synthesized by a citrate-nitrate auto-combustion method. The obtained ceramics show coercivities up to 22.5 kOe and natural ferromagnetic resonance frequencies (NFMR) in a sub-THz range of 160-282 GHz. At a maximum density of 95%, the sample displays coercivity of 18.5 kOe, which is the highest value among dense ferrite materials reported so far. In addition, we report an unusual blueshift of the NFMR frequency from 160 to 200 GHz, which occurs during material sintering.

Synthesis of Sandwiched Composite Nanomagnets by Epitaxial Growth of Fe3O4 Layers on SrFe10Cr2O19 Nanoplates in High-Boiling Organic Solvent.

Herein, we demonstrate the synthesis of sandwiched composite nanomagnets, which consist of hard magnetic Cr-substituted hexaferrite cores and magnetite outer layers. The hexaferrite plate-like nanoparticles, with average dimensions of 36.3 nm × 5.2 nm, were prepared via a glass crystallization method and were covered by spinel-type iron oxide via thermal decomposition of iron acetylacetonate in a hexadecane solution. The hexaferrite nanoplates act as seeds for the epitaxial growth of the magnetite, which results in uniform continuous outer layers on both sides. The thickness of the layers can be adjusted by controlling the concentration of metal ions. In this way, layers with an average thickness of 3.7 and 4.9 nm were obtained. Due to an atomically smooth interface, the magnetic composites demonstrate the exchange coupling effect, acting as single phases during remagnetization. The developed approach can be applied to any spinel-type material with matching lattice parameters and opens the way to expand the performance of hexaferrite nanomagnets due to a combination of various functional properties.

Sandwiched CoFe2O4/SrFe11.5Al0.5O19/CoFe2O4 nanoparticles with exchange-coupling effect.

Exchange-coupled hard/soft ferrite nanoparticles are prospective to squeeze out a part of expensive magnets based on rare-earth elements. However, the known exchange-coupled composite ferrite nanoparticles often suffer from the lack of a powerful enough hard magnetic core, high defectivity of magnetic phases, and a poor interface between them. Herein, we demonstrate the first efficient synthesis of sandwiched nanomagnets, which exhibit a pronounced exchange-coupling effect. This work is featured by the use of individual highly coercive strontium hexaferrite nanoplates prepared by a borate glass crystallization method as cores for the composite particles. The high crystal quality of the hexaferrite cores as the substrate promotes the epitaxial growth of CoFe2O4 layers on the 001 facets from an organic high-boiling solvent and results in the enhancement of the remanent magnetization and maximum energy product of the composite material. The results of this work open new prospects for the fabrication of multilayer oxide heterostructures with synergetic performance, which expands the applications of exchange-coupled composites.

Glass-Ceramic Synthesis of Cr-Substituted Strontium Hexaferrite Nanoparticles with Enhanced Coercivity.

Magnetically hard ferrites attract considerable interest due to their ability to maintain a high coercivity of nanosized particles and therefore show promising applications as nanomagnets ranging from magnetic recording to biomedicine. Herein, we report an approach to prepare nonsintered single-domain nanoparticles of chromium-substituted hexaferrite via crystallization of glass in the system SrO-Fe2O3-Cr2O3-B2O3. We have observed a formation of plate-like hexaferrite nanoparticles with diameters changing from 20 to 190 nm depending on the annealing temperature. We demonstrated that chromium substitution led to a significant improvement of the coercivity, which varied from 334 to 732 kA m-1 for the smallest and the largest particles, respectively. The results provide a new strategy for producing high-coercivity ferrite nanomagnets.

Spray-Deposited Anisotropic Ferromagnetic Hybrid Polymer Films of PS-b-PMMA and Strontium Hexaferrite Magnetic Nanoplatelets.

Spray deposition is a scalable and cost-effective technique for the fabrication of magnetic hybrid films containing diblock copolymers (DBCs) and magnetic nanoparticles. However, it is challenging to obtain spray-deposited anisotropic magnetic hybrid films without using external magnetic fields. In the present work, spray deposition is applied to prepare perpendicular anisotropic magnetic hybrid films by controlling the orientation of strontium hexaferrite nanoplatelets inside ultra-high-molecular-weight DBC polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films. During spray deposition, the evolution of DBC morphology and the orientation of magnetic nanoplatelets are monitored with in situ grazing-incidence small-angle X-ray scattering (GISAXS). For reference, a pure DBC film without nanoplatelets is deposited with the same conditions. Solvent-controlled magnetic properties of the hybrid film are proven with solvent vapor annealing (SVA) applied to the final deposited magnetic films. Obvious changes in the DBC morphology and nanoplatelet localization are observed during SVA. The superconducting quantum interference device data show that ferromagnetic hybrid polymer films with high coercivity can be achieved via spray deposition. The hybrid films show a perpendicular magnetic anisotropy before SVA, which is strongly weakened after SVA. The spray-deposited hybrid films appear highly promising for potential applications in magnetic data storage and sensors.

Tb-based silicate apatites showing slow magnetization relaxation with identical parameters for the Tb3+ and Dy3+ counter ions.

Tb-diluted and Tb-rich apatite-type silicates with compositions Y7.75Tb0.25Ca2(SiO4)6O2 and Tb8Ca2(SiO4)6O2, respectively, exhibit field induced multiple slow relaxation of magnetization. The former reveals two slow relaxation paths, the latter only one with a longer relaxation time of several seconds. The relaxation features of the Tb-diluted one are comparable with those of analogue compounds, where Tb is replaced by Dy, as well as with those of a Tb-doped calcium phosphate apatite. The relaxation parameters of the Tb-rich compound virtually match those of the Dy-based analogue Dy8Ca2(SiO4)6O2. The latter represents the first instance of independence of magnetization relaxation on the nature of a paramagnetic rare-earth metal ion in single ion magnet like materials.

Multiple slow relaxation of magnetization in Dy3+ confined in the crystal matrix of rare-earth-calcium silicates with the apatite structure.

Apatite-type silicates Y7.75Dy0.25Ca2(SiO4)6O2 and Dy8Ca2(SiO4)6O2 were prepared by high-temperature solid state synthesis. In the crystal lattice, Dy3+ partially substitutes Ca2+, preferably at the 6h Ca2-site, and forms a short bond of 2.2 Å with the intra-channel O2-. The imposed strong ligand field anisotropy provides large magnetic anisotropy, which manifests itself as slow relaxation of magnetization at low temperatures. The magnetic dynamics is characterized by three or two characteristic values of relaxation time, respectively, which may be attributed to a single Dy3+ center. A phenomenological model is proposed which explains this response in terms of single paramagnetic center multiple relaxation.

Dysprosium magnesium silicate apatite featuring field and temperature stable slow magnetization relaxation.

Dy-Mg silicate Dy8Mg2(SiO4)6O2 has been prepared by high-temperature solid state reaction. It has an apatite type structure (P63/m) with the Dy atoms fully occupying the 6h site and being in random distribution with the Mg atoms at the 4f site. The compound reveals dual magnetization relaxation with widely varying contributions from fast (FR) and slow (SR) relaxation paths controlled by field and temperature. The SR path is stabilized by a strong magnetic field, exhibits a weak dependence of relaxation time τ on field and temperature, and sustains large τ of a few seconds up to a temperature of 40 K and under a field of 50 kOe. The analysis of the electronic structure and comparison with the known Dy-doped phosphate apatites suggests that the Orbach and Raman processes are suppressed.

Ca-Al double-substituted strontium hexaferrites with giant coercivity.

We demonstrate that the simultaneous substitution of calcium and aluminum for strontium and iron in strontium hexaferrite results in a significant increase of coercivity up to a record high of 21.3 kOe. We propose that the effect is originated from a crystal structure distortion causing an increase of the magnetocrystalline anisotropy.

A Co-based single-molecule magnet confined in a barium phosphate apatite matrix with a high energy barrier for magnetization relaxation.

An apatite-type barium phosphate with a high content of cobalt ions in the trigonal channels features slow relaxation of magnetization with an energy barrier Ueff of up to 387 cm-1, which is well above the values for all so far known d-metal based single-molecule magnets (SMMs).

Stable colloidal solutions of strontium hexaferrite hard magnetic nanoparticles.

Herein we demonstrate an approach to prepare a colloidal solution of strontium hexaferrite via a glass-ceramic route. The as obtained colloids are stable and resistive to aggregation or sedimentation. They reveal outstanding magnetic and magneto-optical properties because of their platelet-like anisotropic shape and high permanent magnetic moment.

On the origin of near-IR luminescence in Bi-doped materials (II). Subvalent monocation Bi⁺ and cluster Bi5³âº luminescence in AlCl3/ZnCl2/BiCl3 chloride glass.

Broadband NIR photoluminescence (from 1000 to 2500 nm) was observed from partially reduced AlCl3/ZnCl2/BiCl3 glass, containing subvalent bismuth species. The luminescence consists of three bands, assigned to Bi⁺ , Bi24⁺, and Bi5³âº ions. The physical and optical characteristics of these centers and possible contribution to NIR luminescence from bismuth-doped oxide glasses are discussed.

Controlled way to prepare quasi-1D nanostructures with complex chemical composition in porous anodic alumina.

Herein we propose a novel approach to the preparation of quasi-1D nanostructures with various chemical compositions based on infiltration of colloidal solution into the asymmetric anodic alumina membrane. The proposed technique was successfully applied for the preparation of ordered arrays of the magnetically hard anisotropic hexaferrite nanostructures.