Integrated ab initio modelling of atomic order and magnetic anisotropy for rare-earth-free magnet design: effects of alloying additions in $\mathrm{L}1_0$ FeNi
Christopher D. Woodgate, Laura H. Lewis, Julie B. Staunton
We describe an integrated modelling approach to accelerate the search for novel, single-phase, multicomponent materials with high magnetocrystalline anisotropy (MCA). For a given system we predict the nature of atomic ordering, its dependence on the magnetic state, and then proceed to describe the consequent MCA, magnetisation, and magnetic critical temperature (Curie temperature). Crucially, within our modelling framework, the same ab initio description of the material's electronic structure determines all aspects. We demonstrate this holistic method by studying the effects of alloying additions in FeNi, examining systems with the general stoichiometries Fe$_4$Ni$_3X$ and Fe$_3$Ni$_4X$, for additives including X= Pt, Pd, Al, and Co. The atomic ordering behaviour predicted on adding these elements, fundamental for determining a material's MCA, is rich and varied. Equiatomic FeNi has been reported to require ferromagnetic order to establish the tetragonal L10 order suited for significant MCA. Our results show that when alloying additions are included in this material, annealing in an applied magnetic field and/or below a material's Curie temperature may also promote tetragonal order, along with an appreciable effect on the predicted hard magnetic properties.
In this work we investigate the potential of tetragonal L1$_0$ ordered FeNi as candidate phase for rare earth free permanent magnets taking into account anisotropy values from recently synthesized, partially ordered FeNi thin films. In particular, we estimate the maximum energy product ($BH$)$_\mathrm{max}$ of L1$_0$-FeNi nanostructures using micromagnetic simulations. The maximum energy product is limited due to the small coercive field of partially ordered L1$_0$-FeNi. Nano-structured magnets consisting of 128 equi-axed, platelet-like and columnar-shaped grains show a theoretical maximum ene…
FeNi L10 (tetrataenite) phase has great perspectives for hard magnetic materials production. In this paper it was synthesized in chemically co-precipitated FeNi nanopowder by means of thermal treating included cycling of oxidation and reduction processes at 320 °C. The presence of FeNi L10 phase in the samples was confirmed by magnetic measurements and DSC analysis.
The ordered L1$_0$ FeNi phase (tetrataenite) is recently considered as a promising candidate for the rare-earth free permanent magnets applications. In this work we calculate several characteristics of the L1$_0$ FeNi, where most of the results come form the fully relativistic full potential FPLO method with the generalized gradient approximation (GGA). A special attention deserves the summary of the magnetocrystalline anisotropy energies (MAE's), the full potential calculations of the anisotropy constant $K_3$, and the combined analysis of the Fermi surface and three-dimensional $\mathbf{k}$-…
We explore an opportunity to induce and control tetragonal distortion in materials. The idea involves formation of a binary alloy from parent compounds having body-centered and face-centered symmetries. The concept is illustrated in the case of FeNi$_{1-x}$Co$_x$ magnetic alloy formed by substitutional doping of the L1$_0$ FeNi magnet with Co. Using electronic structure calculations we demonstrate that the tetragonal strain in this system can be controlled by concentration and it reaches maximum for $x=0.5$. This finding is then applied to create a large magnetocrystalline anisotropy (MAE) in …
The ordered phase of the FeNi system is known to have promising magnetic properties as a rare-earth-free permanent magnet. Understanding the parameter space that controls the order-disorder transformation is important to find growth conditions that stabilize the $L1_0$ phase. Magnetic properties and chemical order-disorder transformation of FeNi are investigated as a function of lattice expansion using first-principles theory. Thermodynamic and magnetic calculations are performed using long-range order parameters, which is used to find the ordering temperature. Negative pressure promotes order…
We investigate the effect of chemical disorder on the magnetic exchange couplings and the Curie temperature ($T_{\text{c}}$) in L1$_0$-ordered FeNi using first-principles-based calculations. We use supercells to model chemical disorder, to account for the specific symmetry-broken local chemical environments around the individual atoms. We find a very strong variation of the most dominant first-nearest neighbor Fe-Fe interaction for different inequivalent Fe-Fe pairs, ranging from around 5 meV to 37 meV, compared to a coupling strength of 27 meV in the ordered state. To estimate the influence o…
Using wide-band (0.5-6.5 eV) spectroscopic ellipsometry we study ultrathin [Bi(0.6-2.5 nm)-FeNi(0.8,1.2 nm)]N multilayer films grown by rf sputtering deposition, where the FeNi layer has a nanoisland structure and its morphology and magnetic properties change with decreasing the nominal layer thickness. From the multilayer model simulations of the ellipsometric angles, Psi(omega) and Delta(omega), the complex (pseudo)dielectric function spectra of the Bi layer were extracted. The obtained results demonstrate that the Bi layer can possess the surface metallic conductivity, which is strongly aff…
By using superconducting quantum interference device (SQUID) magnetometry we investigated anisotropic high-field (H < 7 T) low-temperature (10 K) magnetization response of inhomogeneous nanoisland FeNi films grown by rf sputtering deposition on Sitall (TiO2) glass substrates. In the grown FeNi films, the FeNi layer nominal thickness varied from 0.6 to 2.5 nm, across the percolation transition at the d_c=1.8 nm. We discovered that, beyond conventional spin-magnetism of Fe21Ni79 permalloy, the extracted out-of-plane magnetization response of the nanoisland FeNi films is not saturated in the rang…
We use first-principles-based calculations to investigate the interplay between chemical order and the magnetic properties of $L1_0$ FeNi. In particular, we investigate how deviations from perfect chemical order affect the energy difference between the paramagnetic and ferromagnetic states as well as the important magneto-crystalline anisotropy energy. Our calculations demonstrate a strong effect of the magnetic order on the chemical order-disorder transition temperature, and conversely, a strong enhancement of the magnetic transition temperature by the chemical order. Most interestingly, our …
Exchange-coupled nanocomposites are considered as the most promising materials for production of high-energy performance permanent magnets, which can exceed neodymium ones in terms of energy product. In this work, micromagnetic simulations of L10-FeNi/SmCo5 composites based on the initially anisotropic structure of nanorods array were performed. Texturing effect on magnetic properties was investigated. It was revealed that even 30 % of anisotropy axes misalignment of grains in L10-FeNi phase would lead to only 10 % drop of coercivity. To maximize magnetic properties of the composites, paramete…
We study the magnetic Compton profile (MCP) of the disordered Fe$_{0.5}$Ni$_{0.5}$ and of the ordered FeNi alloys and discuss the interplay between structural disorder and electronic correlations. The Coherent Potential Approximation is employed to model the substitutional disorder within the single-site approximation, while local electronic correlations are captured with the Dynamical Mean Field Theory. Comparison with the experimental data reveals the limitation of local spin-density approximation in low momentum region, where we show that including local but dynamic correlations the experim…
Element-selective techniques are central for the understanding of ultrafast spin dynamics in multi-element materials like magnetic alloys. Recently, though, it turned out that the commonly used technique of transverse magneto-optical Kerr effect (T-MOKE) in the EUV range may have linearity issues including unwanted cross talk between different elemental signals. This problem can be sizeable, which puts recent observations of ultrafast spin transfer from Fe to Ni sites in FeNi alloys into question. In this study, we investigate the Fe-to-Ni spin transfer in a cross-talk-free time-resolved X-ray…
We use first principles calculations to investigate how deviations from perfect chemical order affect the magneto-crystalline anisotropy energy (MAE) in L$1_0$ FeNi. We first analyze the local chemical environment of the Fe atoms in various partially ordered configurations, using the orbital magnetic moment anisotropy (OMA) as proxy for a local contribution to the MAE. We are able to identify a specific nearest neighbor configuration and use this "favorable environment" to successfully design various structures with MAE higher than the perfectly ordered system. However, a systematic analysis o…
Magnetic properties of amorphous Co$_x$Nb$_{100-x}$ alloys produced by mechanical alloying
从元素粉末开始通过机械合金化制备三种非晶Co $_x$ Nb $_{100-x}$合金，Co $_{25}$ Nb $_{75}$、Co $_{57}$ Nb $_{43}$和Co $_{80}$ Nb $_{20}$。用交变梯度磁力仪（AGFM）测定了它们的磁性能，并由磁滞回线得到了它们的剩磁、饱和磁场和矫顽磁场。合金具有相对高的饱和磁场，其随着成分变得富含Co而降低。矫顽力和回复磁化强度在57%at.Co附近达到最佳值，使得{ \em a}-Co $_{57}$ Nb $_{43}$成为三种合金中最硬的磁性材料。进一步添加Co产生软合金。
Magnetic high entropy alloys (HEAs) are a new category of high-performance magnetic materials, with multi-component concentrated compositions and complex multi-phase structures. Although there have been numerous reports of their interesting magnetic properties, there is very limited understanding about the interplay between their hierarchical multi-phase structures and their local magnetic structures. By employing high spatial resolution correlative magnetic, structural and chemical studies, we reveal the influence of a hierarchically decomposed B2 + A2 structure in an AlCo0.5Cr0.5FeNi HEA on …
On the basis of density functional calculations, we report on a comprehensive study of the influences of atomic arrangement and Ni substitution for Al on the ground state structural and magnetic properties for Fe$_2$Ni$_{1+x}$Al$_{1-x}$ Heusler alloys. We discuss systematically the competition between five Heusler-type structures formed by shuffles of Fe and Ni atoms and their thermodynamic stability. All~Ni-rich Fe$_2$Ni$_{1+x}$Al$_{1-x}$ tend to decompose into a dual-phase mixture consisting of Fe$_2$NiAl and~FeNi. The~successive replacement of Ni by Al leads to a change of ground state stru…
Alloying Controlled Tuning of Interfacial Spin Orbit Interaction and Magnetic Damping in Crystalline FeCo Alloys
Technical University of Munich（慕尼黑工业大学）；University of Regensburg（雷根斯堡大学）；Fudan University（复旦大学）；Munich Center for Quantum Science and Technology (MCQST)（慕尼黑量子科学与技术中心）；Center for Quantum Engineering (ZQE)（量子工程中心）
Tailoring of individual single-atom-thick layers in nanolaminated materials offers atomic-level control over material properties. Nonetheless, multielement alloying in individual atomic layers in nanolaminates is largely unexplored. Here, we report a series of inherently nanolaminated V2(A'xSn1-x)C (A'=Fe, Co, Ni and Mn, and combinations thereof, with x=1/3) synthesized by an alloy-guided reaction. The simultaneous occupancy of the four magnetic elements and Sn, the individual single-atom-thick A layers in the compound constitute high-entropy-alloy analogues, two-dimensional in the sense that …
Understanding early stages of low-temperature hydrogen-driven direct co-reduction of Fe-Ni mixed oxide thin films at the near atomic scale
Chair for Materials Discovery and Interfaces, Institute for Materials, Ruhr-Universität Bochum（鲁尔大学材料研究所材料发现与界面讲席）；Max Planck Institute for Sustainable Materials（马克斯·普朗克可持续材料研究所）；Center for Interface Dominated High Performance Materials (ZGH), Ruhr-Universität Bochum（鲁尔大学界面主导高性能材料中心）
The electronic structure, magnetic properties and phase formation of hexagonal ferromagnetic Fe$_{3}$Sn-based alloys have been studied from first principles and by experiment. The pristine Fe$_{3}$Sn compound is known to fulfill all the requirements for a good permanent magnet, except for the magnetocrystalline anisotropy energy (MAE). The latter is large, but planar, i.e. the easy magnetization axis is not along the hexagonal c direction, whereas a good permanent magnet requires the MAE to be uniaxial. Here we consider Fe$_{3}$Sn$_{0.75}$M$_{0.25}$, where M= Si, P, Ga, Ge, As, Se, In, Sb, Te …
Iron and its alloys have made modern civilisation possible, with metallic meteorites providing one of the human's earliest sources of usable iron as well as providing a window into our solar system's billion-year history. Here highest-resolution tools reveal the existence of a previously hidden FeNi nanophase within the extremely slowly cooled metallic meteorite NWA 6259. This new nanophase exists alongside Ni-poor and Ni-rich nanoprecipitates within a matrix of tetrataenite, the uniaxial, chemically ordered form of FeNi. The ferromagnetic nature of the nanoprecipitates combined with the antif…
A series on nanocrystalline Fe100-xCrx alloys prepared by mechanical alloying was investigated with X-ray diffraction (XRD), scanning electron microscopy (SEM) and Mössbauer spectroscopy (MS) techniques. XRD and SEM were used to structurally characterize the samples whereas MS permitted phase analysis as well as determination of the Debye temperature, Theta_D. Concerning the latter, an enhancement relative to bulk Theta_D-values was revealed in the range of ca. 40 < x <50. In a sample of Fe55.5Cr44.5 two phases were detected viz. (1) crystalline and magnetic with Theta_D=572(56) K and (2) amor…
The intrinsic antiferromagnetic (AFM) interlayer coupling in two-dimensional magnetic topological insulator MnBi$_2$Te$_4$ places a restriction on realizing stable quantum anomalous Hall effect (QAHE) [Y. Deng et al., Science 367, 895 (2020)]. Through density functional theory calculations, we demonstrate the possibility of tuning the AFM coupling to the ferromagnetic coupling in MnBi$_2$Te$_4$ films by alloying about 50% V with Mn. As a result, QAHE can be achieved without alternation with the even or odd septuple layers. This provides a practical strategy to get robust QAHE in ultrathin MnBi…
A recent experimental study (Phys. Rev. Appl. 9, 024023, 2018) on paramagnetic CeCo$_3$ finds that Magnesium alloying induces a ferromagnetic transition with intrinsic properties large enough for permanent magnet applications. Here we explain these surprising results \textit{via} a first principles study of the electronic structure and magnetism of Magnesium-alloyed CeCo$_3$. We find the origin of this Magnesium-induced ferromagnetic transition to be Stoner physics - the substantial increase in the Fermi-level density-of-states $N(E_F)$ with Mg alloying. Our calculations suggest that both Ce a…
On the basis of the density functional calculations in combination with the supercell approach, we report on a complete study of the influences of atomic arrangement and Ni substitution for Al on the ground state structural and magnetic properties for Fe$_2$Ni$_{1+x}$Al$_{1-x}$ Heusler alloys. We discuss systematically the competition between five cubic Heusler-type structures formed by shuffles of Fe and Ni atoms to reveal routes for improving the phase stability and magnetic properties, in particular magnetocrystalline anisotropy~(MAE). We predict that in case of Fe$_2$NiAl the ground state …
Using \emph{ab initio} alloy theory formulated within the exact muffin-tin orbitals theory in combination with the coherent potential approximation, we investigate the ideal tensile strength (ITS) in the $[001]$ direction of bcc ferro-/ferrimagnetic (FFM) and paramagnetic (PM) Fe$_{1-x}M_{x}$ ($M=$ Al, V, Cr, Mn, Co, or Ni) random alloys. The ITS of ferromagnetic (FM) Fe is calculated to be $12.6$\,GPa, in agreement with available data, while the PM phase turns out to posses a significantly lower value of $0.7\,$GPa. Alloyed to the FM matrix, we predict that V, Cr, and Co increase the ITS of F…
An attempt was made to tailor the magnetostructural transitions (MSTs) over a wide temperature range under the principle of isostructural alloying. A series of wide Curie-temperature windows (CTWs) with a maximal width of 377 K between 69 and 446 K were established in the Mn1-yCoyNiGe1-xSix system. Throughout the CTWs, the magnetic-field-induced metamagnetic behavior and giant magnetocaloric effects are obtained. The (Mn,Co)Ni(Ge,Si) system shows great potential as multifunctional phase-transition materials that work in a wide range covering liquid-nitrogen and above water-boiling temperatures…
The electronic structure and half-metallic gap of Co$_{2}$MnSi in the presence of crystallographic defects, partial Fe substitution for Mn, and thermal spin fluctuations are studied using the coherent potential approximation and the disordered local moment method. In the presence of 5\% Co or Mn vacancies the Fermi level shifts down to the minority-spin valence-band maximum. In contrast to NiMnSb, both types of Mn antisite defects in Co$_{2}$MnSi are strongly exchange-coupled to the host magnetization, and thermal spin fluctuations do not strongly affect the half-metallic gap. Partial substitu…
Surface alloying is a straightforward route to control and modify the structure and electronic properties of surfaces. Here, We present a systematical study on the structural and electronic properties of three novel rare earth-based intermetallic compounds, namely ReAu2 (Re = Tb, Ho, and Er), on Au(111) via directly depositing rare-earth metals onto the hot Au(111) surface. Scanning tunneling microscopy/spectroscopy measurements reveal the very similar atomic structures and electronic properties, e.g. electronic states, and surface work functions, for all these intermetallic compound systems d…
Electronic structure calculations are used to examine the magnetic properties of Fe$_2$P-based alloys and the mechanisms through which the Curie temperature and magnetocrystalline anisotropy can be optimized for specific applications. It is found that at elevated temperatures the magnetic interaction in pure Fe$_2$P develops a pronounced two-dimensional character due to the suppression of the magnetization in one of the sublattices, but the interlayer coupling is very sensitive to band filling and structural distortions. This feature suggests a natural explanation of the observed sharp enhance…
We investigated the temperature dependence of the magnetic damping in the exchange biased Pt/ Fe50Mn50 /Fe20Ni80 /SiOx multilayers. In samples having a strong exchange bias, we observed a drastic decrease of the magnetic damping of the FeNi with increasing temperature up to the blocking temperature. The results essentially indicate that the non-local enhancement of the magnetic damping can be choked by the adjacent antiferromagnet and its temperature dependent exchange bias. We also pointed out that such a strong temperature dependent damping may be very beneficial for spintronic applications.
High energy density magnets are preferred over induction magnets for many applications, including electric motors used in flying rovers, electric vehicles, and wind turbines. However, several issues related to cost and supply with state-of-the-art rare-earth-based magnet necessities development of high-flux magnets containing low cost, earth-abundant materials. Here, we demonstrate the possibility of tuning magnetization and magnetocrystalline anisotropy of one of the candidate materials, MnBi, by alloying it with foreign elements. By using the density functional theory in the high-throughput …
We present an application of a high-throughput search of new rare-earth free permanent magnets focusing on 3d-5d transition metal compounds. The search involved a part of the ICSD database (international crystallographic structural database), together with tailored search criteria and electronic structure calculations of magnetic properties. Our results suggest that it possible to find candidates for rare-earth free permanent magnets using a data-mining/data-filtering approach. The most promising candidates identified here are Pt$_2$FeNi, Pt$_2$FeCu, and W$_2$FeB$_2$. We suggest these material…
