A Dy-based single ion magnet in a SrLaGaO4 matrix: enhanced parameters in an expanded crystal lattice.

Dy3+ doped SrLaGaO4 exhibits unusually slow relaxation of magnetization determined by two widely separated excited Kramers doublets with a second remagnetization energy barrier of 223 cm-1. This value considerably exceeds that for analogous Ca(Y,Dy)AlO4 in spite of the apparently enlarged Dy3+ coordination sphere.

An ultra-high-entropy rare earth orthoferrite (UHE REO): solution combustion synthesis, structural features and ferrimagnetic behavior.

A novel ultra-high-entropy rare earth orthoferrite (UHE REO) of Sc1/16Y1/16La1/16Ce1/16Pr1/16Nd1/16Sm1/16Eu1/16Gd1/16Tb1/16Dy1/16Ho1/16Er1/16Tm1/16Yb1/16Lu1/16FeO3 nominal composition was successfully synthesized for the first time through a simple and efficient solution combustion approach. PXRD, Raman, and 57Fe Mössbauer spectroscopy confirmed the high chemical and phase purity of the synthesized UHE REO (hereafter denoted as ΣREFeO3), which belonged to the Pnma space group, typical of the perovskite-like rare earth orthoferrites. Despite the fact that the main X-ray reflections, vibration modes, and spectral Mössbauer components unambiguously indicate the single-phase nature of the sample, the results of SEM and TEM make it possible to establish the presence of a main (about 50 nm) and a minor ultrafine (about 10 nm) fraction of ΣREFeO3 nanoparticles. The bimodal size distribution of nanoparticles was also reflected in the magnetic behavior of this substance: the presence of several sextet components in the Mössbauer spectra, the hard single-domain magnetic nature of the main fraction of 50 nm UHE REO nanoparticles, and the superparamagnetic state of the minor fraction of 10 nm UHE REO nanoparticles. Thus, the unusual features of nanostructured ΣREFeO3 can potentially be used for the creation of new generations of transformers, magnetic memory systems, magnetic screens, radio devices, etc.

Dy3+ single ion magnet in the extended inorganic solid Ca(Y,Dy)AlO4.

The first instance of a rare-earth single-ion magnet in a robust extended solid has been found, which possesses a crystal structure different from apatite. The compound exhibits slow relaxation of magnetization in a zero field revealing simultaneously two energy barriers for magnetization reversal.

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.

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.

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.

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.

All-Inorganic Single-Ion Magnets in Ceramic Matrices.

All-inorganic single-ion magnets representing paramagnetic ions incorporated in a crystalline diamagnetic matrix are reviewed. Key results and advantages of this approach in comparison with the common strategy based on molecular metal-organic complexes are considered, and some unsolved problems and future perspectives are discussed.

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.

TbO+ in a calcium apatite matrix featuring a triple trigger-type relaxation of magnetization.

Tb for Ca substituted hydroxyapatite ceramic samples with composition Ca10-xTbx(PO4)6(OH1-x/2-δ)2, where x = 0.1, 0.5, were synthesized by solid-state reaction at 1300 °C in air, and their crystal structure, vibrational spectra, luminescence, and magnetic properties were studied. Implanting Tb3+ into the calcium apatite crystal lattice results in formation of an effective TbO+ ion which displays a short terbium-oxygen bond of 2.15 Å and a stretching vibration at 534 cm-1. The Tb3+ electronic structure has been revealed by analyzing the luminescence spectra and dc/ac magnetization data. Accordingly, the ground state represents a pseudo doublet with MJ = ±6 and the first exited level is by 112 cm-1 higher in energy. The ion exhibits field induced magnetic bistability with the magnetization reversing over the first exited state. Three paths of magnetization relaxation with field-temperature controlled switching between the paths have been identified.

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.

Slow Spin Relaxation in Dioxocobaltate(II) Anions Embedded in the Lattice of Calcium Hydroxyapatite.

Pure-phase cobalt-doped calcium hydroxyapatite ceramic samples with composition Ca10(PO4)6[(CoO2)x(OH)1-2x]2, where x = 0-0.2, were synthesized by high-temperature solid-state reaction, and their crystal structures, vibrational spectra, and magnetic properties were studied. Co atoms are found to enter into the apatite trigonal channel formally substituting H atoms and forming bent dioxocobaltate(II) anions. The anion exhibits single-molecule-magnet (SMM) behavior: slow relaxation of magnetization below 8 K under a nonzero magnetic field with an energy barrier of 63 cm-1. The barrier value does not depend on the concentration of Co ions, virtually coincides with the zero-field-splitting energy as determined from direct-current magnetization, and is very close to the value obtained earlier for cobalt-doped strontium hydroxyapatite. Moreover, the vibration frequencies of the dioxocobaltate(II) anion are found to be the same in calcium and strontium apatite matrixes. The very weak dependence of the SMM parameters on the matrix nature in combination with good chemical and thermal stabilities of the compounds provides wide opportunities to exploit the intrinsic properties of such a SMM-like anion.

"Isolated" DyO+ Embedded in a Ceramic Apatite Matrix Featuring Single-Molecule Magnet Behavior with a High Energy Barrier for Magnetization Relaxation.

Meeting the challenges of Moore's Law, predicting ambitious miniaturization rates of integrated circuits, requires to go beyond the traditional top-down approaches, and to employ synthetic chemistry methods, to use bottom-up techniques. During the recent decades, it has been shown that open-shell coordination compounds may exhibit intramolecular spontaneous magnetization, thus offering promising prospects for storage and processing of digital information. Against this background we regarded it rewarding to implement similar magnetic centers into a ceramic material, which would provide better long-term mechanical and chemical durability. Here we present new robust inorganic compounds containing separate DyO+ ions in an apatite matrix, which behave like single-molecule magnets. The materials exhibit a blocking temperature of 11 K and an energy barrier for spin reversal of a thousand inverse centimeters which is among the highest values ever achieved.

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).

Cobalt-Based Single-Ion Magnets on an Apatite Lattice: Toward Patterned Arrays for Magnetic Memories.

Single-ion magnets (SIMs) that can maintain magnetization direction on an individual transition metal atom represent the smallest atomic-scale units for future magnetic data storage devices and molecular electronics. Here we present a robust extended inorganic solid hosting efficient SIM centers, as an alternative to molecular SIM crystals. We show that unique dioxocobaltate(II) ions, confined in the channels of strontium hydroxyapatite, exhibit classical SIM features with a large energy barrier for magnetization reversal (Ueff) of 51-59 cm-1. The samples have been tuned such that a magnetization hysteresis opens below 8 K and Ueff increases by a factor of 4 and can be further enhanced to the highest values among 3d metal complexes of 275 cm-1 when Ba is substituted for Sr. The SIM properties are preserved without any tendency toward spin ordering up to a high Co concentration. At a maximal Co content, a hypothetical regular hexagonal grid of SIMs with a 1 nm interspacing on the (001) crystal facet would allow a maximal magnetic recording density of 105 Gb/cm2.

ß-Ag3 RuO4, a Ruthenate(V) Featuring Spin Tetramers on a Two-Dimensional Trigonal Lattice.

Open-shell solids exhibit a plethora of intriguing physical phenomena that arise from a complex interplay of charge, spin, orbital, and spin-state degrees of freedom. Comprehending these phenomena is an indispensable prerequisite for developing improved functional materials. This type of understanding can be achieved, on the one hand, by experimental and theoretical investigations into known systems, or by synthesizing new solids displaying unprecedented structural and/or electronic features. ß-Ag3 RuO4 may serve as such a model system because it possesses a remarkable anionic structure, consisting of tetrameric polyoxoanions (Ru4 O16 )(12-) , and is an embedded fragment of a 2D trigonal MO2 lattice. The notorious frustration of antiferromagnetic (AF) exchange couplings on such lattices is thus lifted, and instead strong AF occurs within the oligomeric anion, where only one exchange path remains frustrated among the relevant six. The strong magnetic anisotropy of the [Ru4 O16 ](12-) ion, and the effectively orbital nature of its net magnetic moment, implies that this anion may reveal the properties of a single-molecule magnet if well-diluted in a diamagnetic matrix.

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.

Rich diversity of single-ion magnet features in the linear OCu(III)O(-) ion confined in the hexagonal channels of alkaline-earth phosphate apatites.

Following our recent discovery of slow spin relaxation in the unique [OCu(III)O](-) anion located in the apatite-type pigment A10(PO4)6(CuxOH1-x-y)2, where A = Sr, we present the magnetic behavior of this anion for the cases of A = Ca and Ba, which provides evidence for a cation field impact on the properties of a single-ion magnet molecular anion.