Rare-earth Iron Research Articles

Rare-Earth Iron Garnet Superlattices with Sub-unit Cell Composition Modulation.

Oxide superlattices reveal a rich array of emergent properties derived from the composition modulation and the resulting lattice distortion, charge transfer, and symmetry reduction that occur at the interfaces between the layers. The great majority of studies have focused on perovskite oxide superlattices, revealing, for example, the appearance of an interfacial 2D electron gas, magnetic moment, or improper ferroelectric polarization that is not present in the parent phases. Garnets possess greater structural complexity than perovskites: the cubic garnet unit cell contains 160 atoms with the cations distributed between three different coordination sites, and garnets exhibit a wide range of useful properties, including ferrimagnetism and ion transport. However, there have been few reports of the synthesis or properties of garnet superlattices, with layer thicknesses approaching the unit cell dimension of 1.2 nm. Here, we describe superlattices made from Bi and rare earth (RE = Tm, Tb, Eu, Lu) iron garnets (IGs) grown by pulsed laser deposition. Atom probe tomography and transmission electron microscopy reveal the composition modulation without dislocations and layer thicknesses as low as 0.45 nm, less than half a unit cell. TmIG/TbIG superlattices exhibit perpendicular magnetic anisotropy that is qualitatively different from the in-plane anisotropy of the solid solution, and BiIG/LuIG superlattices exhibit ferromagnetic resonance linewidth characteristics of the end-members rather than the solid solution. Garnet superlattices provide a playground for exploring interface physics within the vast parameter space of cation coordination and substitution.

Synthesis of nanosized phases with a garnet structure using supercritical СО2 fluid

A method was developed for the production of nanosized complex oxides and oxysulfides. The first stage uses supercritical СО2 fluid (SAS – supercritical antisolvent method). This approach makes it possible to obtain precursor-free complex oxides in a narrow nanoscale range. Nanosized rare-earth iron garnets with the general formula R3Fe5O12, where R is a rare earth element, were obtained and studied by physicochemical methods. The resulting samples have a size of less than 100 nm, exhibit ferromagnetic ordering, and can be used as soft magnetic materials. The multi-stage method for the preparation of complex oxysulfides was not previously demonstrated anywhere in the literature. The method involves three stages. At the first stage, a nanosized X-ray amorphous solid solution of the original salts is obtained using the SAS method. Then a nanosized X-ray amorphous component – the oxide phase – is obtained by annealing in a furnace. After this, the resulting oxide phase is mixed with the disulfide of a transition element (Nb, Mo), and high-temperature annealing is performed in an evacuated quartz ampoule. As a result, compact and nanosized phases of the composition Eu3Fe5-3/2xMox□1/2xO12-2xS2x and Eu3Fe5-3/2xNbx□1/2xO12-2xS2x, where x = 0.15, were obtained for the first time. The introduction of the sulfide component, namely NbS2, into the garnet structure increases its magnetic parameters by the factor of 1.5.

Pinning of domain walls in epitaxial garnet film patterned by surface arrays of ferromagnetic metal particles

Rare-earth iron garnet epitaxial films famous for their unique magnetic, microwave and optical properties consistently attract high interest. Domain structure of both bulk and interfaces of garnet films is closely connected with their magnetic properties and magnetization dynamics. In this work, we investigate the magnetic behaviour and domain structure of an epitaxial bismuth-substituted lutetium iron garnet film with a regular array of planar submicron particles made of Co film or Co/Pt multilayer on its surface. Optical polarization microscopy and magnetic force microscopy techniques used for the characterization of these composite structures confirm the mutual influence of the garnet and metal nanostructured layers on each other. On the one hand, dense ordered metal particles provide the pinning of the surface magnetic domains of the garnet film, which further affects the organization of the bulk stripe domains. On the other hand, we observed that the domain structure in the metallic pattern is governed by the domain structure of the garnet placed beneath it.

Development of novel Gd-Fe/Ti composites with tunable thermal expansion property

Abstract Titanium alloys are considered one of the most promising materials. However, their poor thermal expansion property remains a major obstacle to their widespread application. In this study, we explored an innovative design strategy to tune the thermal expansion properties of titanium alloy. Specifically, we used rare earth iron intermetallic compounds (Gd-Fe IMCs) with low coefficient of thermal expansion (CTE) as expansion inhibitors to prepare composites with the required thermal expansion properties via in situ reaction. The morphology and size of Gd-Fe IMCs can be effectively controlled by electromagnetic and ultrasonic fields, resulting in a dense distribution of micro/nano-structured Gd-Fe IMCs and strong interfacial bonding of the composites. This alloy has an excellent CTE of 6.8 × 10−6/K and a high ultimate tensile strength of 921 MPa. The improvement in the physical properties (especially in thermal expansion properties) of titanium alloy can be attributed to the synergistic effect between Gd-Fe IMCs and Ti matrix. This design strategy can also be extended to other titanium alloys as a reference for designing low thermal expansion titanium alloys.

Spin magnetotransport in rare-earth iron garnet (REIG)/Pt: Effects of modulated bulk and REIG/Pt interfaces

The intrinsic magnetization compensation behaviors of rare-earth iron garnets (REIGs) make the material promising for applications in ultrafast spin storage devices. REIG/heavy metal heterostructures such as TbIG/Pt often display two sign crossovers of anomalous Hall effect resistance with varying temperatures. One of these crossovers is attributed to the magnetization compensation of REIG, and the other to the competition between the magnetic proximity effect and the spin Hall effect. Here, we design trilayer REIG heterostructures based on two rare-earth species (Tb and Eu). We modulate the layer stacking of the TbIG/EuIG/TbIG sandwich with a fixed total thickness and explore the contributions of REIG bulk and REIG/Pt interfaces on these two crossover points. As TbIG gradually moves away from Pt, the compensation temperature shows some fluctuations. However, when TbIG is entirely out of contact with Pt, the second crossover point undergoes a change that shows REIG/Pt interface dependency. The results highlight the dominance of REIG bulk on the compensation behavior and the interface sensitivity of the second crossover point. This study provides a reference for designing controllable spintronics devices, such as magnon valve applications.

Enhancing terahertz magneto-optical effects in wafer-scale RIG single crystal thick films with anti-reflective coatings for improved transmittance

Wafer-scale rare-earth iron garnet (RIG) single crystal thick films were fabricated on 3-in. gadolinium gallium garnet (GGG) substrates using liquid phase epitaxy. The terahertz transmittance of the RIG crystals improved after removing the GGG substrate by polishing. The time-domain spectra at Terahertz (THz) frequencies indicate the existence of a magneto-optical effect in RIG samples. The results indicate that the RIG samples exhibit a high refractive index of ∼4.50 within the 0.1–1.0 THz frequency range, a transmittance of around 40%, and an absorption rate of only 10–50 cm−1. The Faraday rotation angles of the thick single-crystal films of the RIG samples were measured using a THz-TDS system. The RIG has a thickness of ∼330 μm. The Faraday rotation angles of RIG crystals at THz frequencies can reach up to 16° when an external magnetic field of 0.18 T is applied. The Verdet constants of the RIG sample were calculated to be ∼120°/mm/T. To improve the transmittance of the RIG sample, epoxy resin and polymethylpentene (TPX) were used as anti-reflective films. The transmittance of the RIG sample increased by ∼5% for the 80 μm thick epoxy and about 10% for the 320 μm thick TPX. Therefore, this RIG single crystal thick film can achieve a low loss, a high transmittance, and a strong magneto-optical effect in the terahertz region with the cooperation of a reflection-reducing film. It is expected to have wide applications in terahertz magnetic polarization conversion, non-reciprocal phase shifters, and isolators.

A Novel Electrochemical Process for Recovery of Rare Earth Elements and Iron from Neodymium–Iron–Boron Based Magnets

A Novel Electrochemical Process for Recovery of Rare Earth Elements and Iron from Neodymium–Iron–Boron Based Magnets

Recent progress in research and development of rare-earth free iron nitride permanent magnet

The high cost of rare earth materials, unstable supply and high demand remain big problems to solve for permanent magnet industries. Thus α″-Fe16N2 has been picked up as one of the most promising rare earth-free magnet candidates because of its use of environmental-friendly raw materials, confirmed giant saturation magnetic flux density (2.9 T), and reasonably high magnetic anisotropy constant (1.8 MJ/m3). Also, α”-Fe16N2 metastable with film form exhibits high tetragonality (c/a=1.1) by interstitial introduction of N atoms, leading to a high magnetocrystalline anisotropy constant (Ku = 1.0 MJ/m3). but synthesis of bulk form has lower properties than thin film (<230 nm) because of magnetic interaction, experimentally low anisotropy, and low density. In this paper, we review the synthetic methods of metastable α”-Fe16N2 with powder and bulk form and discuss the approaches to enhance magnetocrystalline anisotropy of α”-Fe16N2.

Atomic order of rare earth ions in a complex oxide: a path to magnetotaxial anisotropy

Complex oxides offer rich magnetic and electronic behavior intimately tied to the composition and arrangement of cations within the structure. Rare earth iron garnet films exhibit an anisotropy along the growth direction which has long been theorized to originate from the ordering of different cations on the same crystallographic site. Here, we directly demonstrate the three-dimensional ordering of rare earth ions in pulsed laser deposited (EuxTm1-x)3Fe5O12 garnet thin films using both atomically-resolved elemental mapping to visualize cation ordering and X-ray diffraction to detect the resulting order superlattice reflection. We quantify the resulting ordering-induced ‘magnetotaxial’ anisotropy as a function of Eu:Tm ratio using transport measurements, showing an overwhelmingly dominant contribution from magnetotaxial anisotropy that reaches 30 kJ m−3 for garnets with x = 0.5. Control of cation ordering on inequivalent sites provides a strategy to control matter on the atomic level and to engineer the magnetic properties of complex oxides.

Effect of the interaction of Fe- and Ce-contents on the structure and magnetic properties of M-type strontium ferrites

Sr1-xCexFe12O19 and Sr1-xCexFe12-yO19-δ (x = 0–0.2, y = 0–2) powders were synthesized by sol-gel auto-combustion method, and the effect on the structure and magnetic properties of changes in doping concentration and iron content has been investigated. XRD results confirmed the formation of M phase and impurities of CeO2 and Fe2O3. The SEM results show that cerium doping leads to a decrease in grain size. For Sr1-xCexFe12O19, the saturation magnetization increases to 77.73 emu/g first and then decreases with the increase of cerium doping. More importantly, our study also found that as the Ce doping concentration and iron content change, the interaction between the two changes differently. This interaction will have different effects on the occupancy of iron ions at spin-up and spin-down sites, ultimately leading to a significant characteristic change in magnetic properties. For Sr1-xCexFe12-yO19-δ, with the iron content decreases, the magnetic properties continue to decrease at x = 0.03, increase first and then decrease at x = 0.1, and keep improving at x = 0.2. It is of reference significance to change the magnetic properties of strontium ferrites by adjusting the relationship between rare earth doping concentration and iron content.

Enhancing temperature stability of Ce: RIG films Faraday rotation through magnetic sublattice control

Cerium doped rare-earth iron garnet (Ce: RIG) film is a promising candidate for magneto-optical devices in laser systems with giant Faraday effect; nevertheless, devices fail nonreciprocally with increasing temperature due to a negative Faraday rotation angle temperature coefficient. To mitigate this effect, the relationship between the magnetic moments of three distinct magnetic sublattices and the temperature coefficients of the Faraday rotation angle was investigated. Cerium doped holmium iron garnet (Ce: HoIG) film, where magnetic Ho3+ occupied the dodecahedrons, exhibited an enhanced Faraday rotation angle retention at a temperature of 400 K. However, the nonmagnetic ion doping in tetrahedral and octahedral sites yielded a negligible effect. The mechanism behind this occurrence is attributed to the magnetic compensation effect, which results in a small magnetic moment temperature coefficient within the range of 300–400 K. The study not only offers strategies for designing Ce: RIG components with reduced temperature coefficient, but also presents the development of a Ce: HoIG film exhibiting promising stability in Faraday rotation angle as a function of temperature.

Electrodeposited NiFeCo + Tb and Dy for enhanced magnetostrictive properties and soft magnetism

Magnetostrictive thin films have numerous applications in communications, sensors, and microelectronic devices. Such devices usually require magnetostrictive thin films with large magnetostriction and soft magnetic properties. Nickel-Iron-Cobalt (NiFeCo) alloys have excellent soft magnetic properties and can be easily fabricated as thin films. However, their main drawback for these sensing applications is that they have very low magnetostriction. On the other hand, Iron-Rare Earth (RE) alloys such as Fe-Tb-Dy or Fe-Ga have large magnetostriction at the cost of some soft magnetic properties. Moreover, their magnetostrictive properties are degraded when reduced to thin films as opposed to bulk materials due to structural imperfections and oxidation of the REs. In this paper, we report the development of NiFeCo thin films with incorporated rare earth elements prepared via electrodeposition. Electrochemical cells were prepared using Ni, Fe, and Co sulfate salts. Tb and Dy sulfates were added to the electrochemical cell in order of increasing concentration. Electrodeposition was then carried out under galvanostatic control for each RE concentration in the bath. The produced films were analyzed for composition, crystallinity, and magnetic properties to draw out trends based on the initial concentrations of rare earth salts in the bath. The produced thin films retained soft magnetic properties while exhibiting giant magnetostriction of up to ∼370 ppm depending on the type and amount of incorporated REs within the film. The combination of soft magnetism and giant magnetostriction makes these NiFeCo thin films with added Tb and Dy excellent candidates for developing resonant frequency sensing devices.

Developing abundant rare-earth iron perovskite electrodes for high-performance and low-cost solid oxide fuel cells

The swift advancement of the solid oxide fuel cell (SOFC) sector necessitates a harmony between electrode performance and commercialization cost. The economic value of elements is frequently linked to their abundance in the Earth's crust. Here, we develop abundant rare-earth iron perovskite electrodes of Ln0.6Sr0.4FeO3-δ (Ln= La, Pr, and Nd) with high abundant rare-earth metals and preferred iron metal for SOFCs. All three symmetric electrode materials display a cubic perovskite phase and excellent chemical compatibility with Gd0.2Ce0.8O2-δ electrolyte. All three electrodes possess exceptional surface oxygen exchange ability. At 800°C, single cells with La0.6Sr0.4FeO3-δ, Pr0.6Sr0.4FeO3-δ, and Nd0.6Sr0.4FeO3-δ symmetric electrodes attained excellent open circuit voltages of 1.108, 1.101, and 1.097 V, respectively, as well as peak powers of 213.52, 281.12, and 254.58 mW cm-2. The results suggest that overall performance of abundant rare-earth iron perovskite electrodes has a favorable impact on the extensive expansion of SOFCs, presenting significant potential for practical applications.

Electrical Structure between the Main and Eastern Deposits of the Bayan Obo Mine: Results from Time-Domain CSEM Methods

Bayan Obo is a well-known polymetallic deposit containing significant quantities of rare earth elements, niobium, thorium, and iron. However, the epoch in which mineralization occurred and the mineralization process are still debated due to the complex nature of its mineralization and geological evolution. Inadequate geophysical exploration has further contributed to this lack of clarity surrounding critical issues, such as the deep link between the main orebody and the eastern orebody, the form and distribution of the extensive dolomite, and the geologic structures in the area. Therefore, we implemented the time-domain controlled-source electromagnetic method (CSEM) to acquire electrical structures at depths down to 2.5 km between the Main and Eastern mines. According to the inverted resistivity structure, in conjunction with existing geological and drilling data, we classified the main lithologies and faults based on their resistivity characteristics. Overall, the mineralized carbonatite reflects high to moderately high resistivity. The mineralized carbonatite dips overall from north to south, with a maximum extension depth not exceeding 1.5 km, and its range of occurrence is controlled by nearly east–west-striking faults distributed along the bounding line between the roof and floor rocks. The Main and Eastern mines are connected at depth, but the morphology and position of the ore bodies have significantly changed due to multiple phases of tectonic activity. The electrical structure does not reveal any obvious syncline structures, further refuting the traditional view that the Bayan syncline controls ore formation.

Magnetic Phase Transition-Induced Modulation of Ferroelectric Properties in Hexagonal RFeO3 (R = Tb and Ho).

Hexagonal rare-earth iron oxides (h-RFeO3) exhibit spontaneous magnetization and room-temperature ferroelectricity simultaneously. However, achieving a large magnetoelectric coupling necessitates further exploration. Herein, we report the impact of the magnetic phase transition on the ferroelectric properties of epitaxial h-RFeO3 (R = Tb and Ho) films prepared by pulsed laser deposition. The metastable h-RFeO3 phase is successfully stabilized with high crystallinity and low leakage current due to the ITO buffer layer, making it possible to investigate the ferroelectric properties. The h-TbFeO3 film exhibits a magnetic-field-induced transition from antiferromagnetic (AFM) to weak ferromagnetic (wFM) phases below 30 K, while also exhibiting ferroelectricity at 300 K. The dielectric constants change with the magnetic phase transition, demonstrating hysteresis in the magnetocapacitance. In contrast, the h-HoFeO3 film exhibits antiferroelectric-like behavior and an AFM-wFM phase transition. Notably, the h-HoFeO3 film shows a rapid increase in the remnant polarization during the AFM-wFM phase transition accompanied by an increase in the ferroelectric component. Considering the strong connection between the antiferroelectric behavior in the h-RFeO3 system and the ferroelectric domain wall motion, this considerable modification of ferroelectric properties during the magnetic phase transition is probably due to the faster movement of the ferroelectric domain walls in the wFM phase induced by the clamping effect. Our findings indicate the effectiveness of magnetic phase transitions in enhancing the magnetoelectric coupling, particularly when utilizing domain wall clamping properties.

Thermally generated magnonic spin currents in a polycrystalline gadolinium iron garnet thin film with perpendicular magnetic anisotropy

Rare-earth iron garnets (REIGs) are the benchmark systems for magnonics, including the longitudinal spin Seebeck effect (LSSE). While most research has focused on single-crystalline REIGs on complimentary garnet substrates, moving to more, cost-effective complementary metal-oxide semiconductor (CMOS)-compatible substrates is important to integrate REIG thin films with existing technology. In this regard, we grow a 130 nm-thick polycrystalline gadolinium iron garnet (GdIG) film on the Si/SiO2 substrate and investigate the temperature-dependent LSSE. Interestingly, the polycrystalline GdIG film exhibits perpendicular magnetic anisotropy (PMA) at room temperature which is induced by tensile in-plane (IP)-strain originating from the thermal-expansion mismatch between the GdIG film and the substrate during rapid thermal annealing. Further, a spin-reorientation transition from the out-of-plane IP direction below TS = 180 K is observed. Additionally, the film reveals a magnetic compensation temperature, TComp, of ≈240 K. The LSSE voltage not only demonstrates a sign-inversion around TComp, but also shows noticeable changes around TS. As compared to a single-crystalline GdIG film, the lower LSSE voltage for the polycrystalline GdIG is attributed to the higher effective magnetic anisotropy and enhanced magnon scattering at the grain boundaries. Our study not only paves the way for the cost-effective growth of CMOS-compatible REIG-based systems with PMA for magnonic memory and information processing applications, but also highlights the fact that the spincaloritronic and spin-insulatronic properties of the polycrystalline REIGs follow those of their single-crystalline counterparts with reduced spin-to-charge conversion efficiency through LSSE which can be tuned further by controlling the average gran size and interface engineering.

Magnon spin current from a non-collinear magnetic phase in a compensated rare earth ferrimagnet

The rare earth iron garnets have been commonly treated like ferromagnets due to the strong exchange coupling between the Fe3+ sublattices. However, the exchange coupling between the rare earth (RE) and transition metal (TM) in the RE-TM compounds is relatively weak and cannot hold the magnetic moments rigidly in a collinear state upon effective anisotropy energy. In this work, we show that a non-collinear magnetic phase is readily presented for a rare earth ferrimagnetic insulator, gadolinium iron garnet (GdIG), when a small magnetic field (H) is applied in the hard axis. We excite magnons from both the collinear and non-collinear magnetic configuration in GdIG via the spin Seebeck effect and detect these magnons in the adjacent normal metal. The comparison between the collinear and non-collinear magnetic configurations reveals a comparable magnon compensating temperature (TMM) for both cases. Moreover, as temperature decreases, the in-plane component of the magnon from the non-collinear case enhances and becomes comparable with that of the collinear case at TMM, representing the dominant role Gd3+ 4f spin plays at low T. Our study shows a wide magnetic tunability in the compensated ferrimagnetic insulator, which offers a myriad of opportunities for magnonic applications.

Temperature Evolution of Magnon Propagation Length in Tm3Fe5O12 Thin Films: Roles of Magnetic Anisotropy and Gilbert Damping.

The magnon propagation length, ⟨ξ⟩, of a ferro-/ferrimagnet (FM) is one of the key factors that controls the generation and propagation of thermally driven magnonic spin current in FM/heavy metal (HM) bilayer based spincaloritronic devices. For the development of a complete physical picture of thermally driven magnon transport in FM/HM bilayers over a wide temperature range, it is of utmost importance to understand the respective roles of temperature-dependent Gilbert damping (α) and effective magnetic anisotropy (Keff) in controlling the temperature evolution of ⟨ξ⟩. Here, we report a comprehensive investigation of the temperature-dependent longitudinal spin Seebeck effect (LSSE), radio frequency transverse susceptibility, and broad-band ferromagnetic resonance measurements on Tm3Fe5O12 (TmIG)/Pt bilayers grown on different substrates. We observe a significant drop in the LSSE voltage below 200 K independent of TmIG film thickness and substrate choice. This is attributed to the noticeable increases in effective magnetic anisotropy field, HKeff (∝Keff) and α that occur within the same temperature range. From the TmIG thickness dependence of the LSSE voltage, we determined the temperature dependence of ⟨ξ⟩ and highlighted its correlation with the temperature-dependent HKeff and α in TmIG/Pt bilayers, which will be beneficial for the development of rare-earth iron garnet based efficient spincaloritronic nanodevices.

High temperature magneto-dielectric response and dielectric relaxations in PrIG

A high temperature MD effect has been observed in Pr3Fe5O12 (PrIG) which is a new member of rare earth iron garnets (RIG) family. Research indicates that this material has two dielectric relaxations in the temperature range from 370 K to 565 K and a dielectric anomaly around 580 K. The first dielectric relaxation is attributed to the conduction for the similar activation energy with conduction. The other dielectric relaxation in the higher temperature range originated from the inhomogeneous structure. And, the coupling between the ferrimagnetic phase transition and the dielectric response was observed at 1 kHz 0.35 T 580K.

A new Ni/Bi Co-doping rare earth iron garnet crystal with high transmittance, low temperature and wavelength coefficients

Bi-doped rare earth iron garnet (Bi:RIG) crystal is an ideal magneto-optical material for optical isolators in the near-infrared band, which has been widely used in optical communication applications. In this paper, centimeter-sized and good-quality Ni2+-doped Bi:RIG crystals were successfully grown by top-seeded solution growth (TSSG). The transmittance reaches 72.6% at 1550 nm, which is higher than commercial Bi:TbIG crystal and close to the theoretical values of RIG crystals. Doping Ni can not only greatly improve the transmittance, magnetic, and magneto-optical properties, but also decrease the Faraday rotation temperature (FTC) and wavelength coefficients (FWC) of the Bi:RIG crystal. The FTC and FWC of (Bi0.37Ho1.18Eu0.83Gd0.62)(Fe4.20Ni0.25Ga0.55)O12 crystal reduced to − 6.3 × 10−4 K−1 and 8.0 × 10−4 nm−1, which are about 30% and 80% of commercial Bi:TbIG crystal, respectively. (Bi0.37Ho1.18Eu0.83Gd0.62)(Fe4.20Ni0.25Ga0.55)O12 exhibits potential for utilization in new high-performance, wideband magneto-optical isolators, and is expected to find application in the field of wavelength division multiplexing fiber communication.