Accelerating the discovery of novel magnetic materials using machine learning-guided adaptive feedback.

Magnetic materials are essential for energy generation and information devices, and they play an important role in advanced technologies and green energy economies. Currently, the most widely used magnets contain rare earth (RE) elements. An outstanding challenge of notable scientific interest is the discovery and synthesis of novel magnetic materials without RE elements that meet the performance and cost goals for advanced electromagnetic devices. Here, we report our discovery and synthesis of an RE-free magnetic compound, Fe3CoB2, through an efficient feedback framework by integrating machine learning (ML), an adaptive genetic algorithm, first-principles calculations, and experimental synthesis. Magnetic measurements show that Fe3CoB2 exhibits a high magnetic anisotropy (K1 = 1.2 MJ/m3) and saturation magnetic polarization (Js = 1.39 T), which is suitable for RE-free permanent-magnet applications. Our ML-guided approach presents a promising paradigm for efficient materials design and discovery and can also be applied to the search for other functional materials.

Chiral Magnetism and High-Temperature Skyrmions in B20-Ordered Co-Si.

Magnets with chiral crystal structures and helical spin structures have recently attracted much attention as potential spin-electronics materials, but their relatively low magnetic-ordering temperatures are a disadvantage. While cobalt has long been recognized as an element that promotes high-temperature magnetic ordering, most Co-rich alloys are achiral and exhibit collinear rather than helimagnetic order. Crystallographically, the B20-ordered compound CoSi is an exception due to its chiral structure, but it does not exhibit any kind of magnetic order. Here, we use nonequilibrium processing to produce B20-ordered Co_{1+x}Si_{1-x} with a maximum Co solubility of x=0.043. Above a critical excess-Co content (x_{c}=0.028), the alloys are magnetically ordered, and for x=0.043, a critical temperature T_{c}=328 K is obtained, the highest among all B20-type magnets. The crystal structure of the alloy supports spin spirals caused by Dzyaloshinskii-Moriya interactions, and from magnetic measurements we estimate that the spirals have a periodicity of about 17 nm. Our density-functional calculations explain the combination of high magnetic-ordering temperature and short periodicity in terms of a quantum phase transition where excess-cobalt spins are coupled through the host matrix.

Mn5Si3 Nanoparticles: Synthesis and Size-Induced Ferromagnetism.

Mn-based silicides are fascinating due to their exotic spin textures and unique crystal structures, but the low magnetic ordering temperatures and/or small magnetic moments of bulk alloys are major impediments to their use in practical applications. In sharp contrast to bulk Mn5Si3, which is paramagnetic at room temperature and exhibits low-temperature antiferromagnetic ordering, we show ferromagnetic ordering in Mn5Si3 nanoparticles with a high Curie temperature (Tc ≈ 590 K). The Mn5Si3 nanoparticles have an average size of 8.6 nm and also exhibit large saturation magnetic polarizations (Js = 10.1 kG at 300 K and 12.4 kG at 3 K) and appreciable magnetocrystalline anisotropy constants (K1 = 6.2 Mergs/cm(3) at 300 K and at 12.8 Mergs/cm(3) at 3 K). The drastic change of the magnetic ordering and properties in the nanoparticles are attributed to low-dimensional and quantum-confinement effects, evident from first-principle density-functional-theory calculations.

Ultrahigh-density sub-10 nm nanowire array formation via surface-controlled phase separation.

We present simple, self-assembled, and robust fabrication of ultrahigh density cobalt nanowire arrays. The binary Co-Al and Co-Si systems phase-separate during physical vapor deposition, resulting in Co nanowire arrays with average diameter as small as 4.9 nm and nanowire density on the order of 10(16)/m(2). The nanowire diameters were controlled by moderating the surface diffusivity, which affected the lateral diffusion lengths. High resolution transmission electron microscopy reveals that the Co nanowires formed in the face-centered cubic structure. Elemental mapping showed that in both systems the nanowires consisted of Co with undetectable Al or Si and that the matrix consisted of Al with no distinguishable Co in the Co-Al system and a mixture of Si and Co in the Co-Si system. Magnetic measurements clearly indicate anisotropic behavior consistent with shape anisotropy. The dynamics of nanowire growth, simulated using an Ising model, is consistent with the experimental phase and geometry of the nanowires.

Structural and magnetic evolution of bimetallic MnAu clusters driven by asymmetric atomic migration.

The nanoscale structural, compositional, and magnetic properties are examined for annealed MnAu nanoclusters. The MnAu clusters order into the L1(0) structure, and monotonic size-dependences develop for the composition and lattice parameters, which are well reproduced by our density functional theory calculations. Simultaneously, Mn diffusion forms 5 Å nanoshells on larger clusters inducing significant magnetization in an otherwise antiferromagnetic system. The differing atomic mobilities yield new cluster nanostructures that can be employed generally to create novel physical properties.

Accessibility and selective stabilization of the principal spin states of iron by pyridyl versus phenolic ketimines: modulation of the 6A1 ↔ 2T2 ground-state transformation of the [FeN4O2]+ chromophore.

Several potentially tridentate pyridyl and phenolic Schiff bases (apRen and HhapRen, respectively) were derived from the condensation reactions of 2-acetylpyridine (ap) and 2'-hydroxyacetophenone (Hhap), respectively, with N-R-ethylenediamine (RNHCH(2)CH(2)NH(2), Ren; R = H, Me or Et) and complexed in situ with iron(II) or iron(III), as dictated by the nature of the ligand donor set, to generate the six-coordinate iron compounds [Fe(II)(apRen)(2)]X(2) (R = H, Me; X(-) = ClO(4)(-), BPh(4)(-), PF(6)(-)) and [Fe(III)(hapRen)(2)]X (R = Me, Et; X(-) = ClO(4)(-), BPh(4)(-)). Single-crystal X-ray analyses of [Fe(II)(apRen)(2)](ClO(4))(2) (R = H, Me) revealed a pseudo-octahedral geometry about the ferrous ion with the Fe(II)-N bond distances (1.896-2.041 Å) pointing to the (1)A(1) (d(π)(6)) ground state; the existence of this spin state was corroborated by magnetic susceptibility measurements and Mössbauer spectroscopy. In contrast, the X-ray structure of the phenolate complex [Fe(III)(hapMen)(2)]ClO(4), determined at 100 K, demonstrated stabilization of the ferric state; the compression of the coordinate bonds at the metal center is in accord with the (2)T(2) (d(π)(5)) ground state. Magnetic susceptibility measurements along with EPR and Mössbauer spectroscopic techniques have shown that the iron(III) complexes are spin-crossover (SCO) materials. The spin transition within the [Fe(III)N(4)O(2)](+) chromophore was modulated with alkyl substituents to afford two-step and one-step (6)A(1) ↔ (2)T(2) transformations in [Fe(III)(hapMen)(2)]ClO(4) and [Fe(III)(hapEen)(2)]ClO(4), respectively. Previously, none of the X-salRen- and X-sal(2)trien-based ferric spin-crossover compounds exhibited a stepwise transition. The optical spectra of the LS iron(II) and SCO iron(III) complexes display intense d(π) → p(π)* and p(π) → d(π) CT visible absorptions, respectively, which account for the spectacular color differences. All the complexes are redox-active; as expected, the one-electron oxidative process in the divalent compounds occurs at higher redox potentials than does the reverse process in the trivalent compounds. The cyclic voltammograms of the latter compounds reveal irreversible electrochemical generation of the phenoxyl radical. Finally, the H(2)salen-type quadridentate ketimine H(2)hapen complexed with an equivalent amount of iron(III) to afford the µ-oxo-monobridged dinuclear complex [{Fe(III)(hapen)}(2)(µ-O)] exhibiting a distorted square-pyramidal geometry at the metal centers and considerable antiferromagnetic coupling of spins (J ≈ -99 cm(-1)).

Cluster synthesis and direct ordering of rare-earth transition-metal nanomagnets.

Rare-earth transition-metal (R-TM) alloys show superior permanent magnetic properties in the bulk, but the synthesis and application of R-TM nanoparticles remains a challenge due to the requirement of high-temperature annealing above about 800 °C for alloy formation and subsequent crystalline ordering. Here we report a single-step method to produce highly ordered R-TM nanoparticles such as YCo(5) and Y(2)Co(17), without high-temperature thermal annealing by employing a cluster-deposition system and investigate their structural and magnetic properties. The direct ordering is highly desirable to create and assemble R-TM nanoparticle building blocks for future permanent-magnet and other significant applications.

Cluster synthesis of monodisperse rutile-TiO2 nanoparticles and dielectric TiO2-vinylidene fluoride oligomer nanocomposites.

The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO(2) nanoparticles having an average particle size of 14.4 nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO(2)-VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO(2) nanoparticles serve two purposes, namely to prevent the TiO(2) nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO(2)-VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO(2)-VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.

Novel Nd(2)Fe(14)B nanoflakes and nanoparticles for the development of high energy nanocomposite magnets.

High energy ball milling has been shown to be a promising method for large-scale fabrication of rare earth-transition metal nanoparticles. In this work, magnetically hard Nd-Fe-B nanopowders with a coercivity in the range of 1.2-4 kOe have been produced by surfactant-assisted ball milling of nanocrystalline precursor alloys. The nanopowders consisted of Nd(2)Fe(14)B flakes with a thickness below 100 nm and an aspect ratio as high as 10(2)-10(3) and anisotropic square nanoparticles with a size of 11 nm. Both the nanoparticles and nanoflakes showed a strong [001] out-of-plane texture. The nanoparticles showed a spin reorientation temperature which is lower (117 K) than the bulk value (135 K). The successful fabrication of Nd-Fe-B nano-thin flakes and anisotropic nanoparticles provides hope for the development of nanocomposite permanent magnets with an enhanced energy product.

Structure and Magnetism of Co2Ge Nanoparticles.

The structural and magnetic properties of Co2Ge nanoparticles (NPs) prepared by the cluster-beam deposition (CBD) technique have been investigated. As-made particles with an average size of 5.5 nm exhibit a mixture of hexagonal and orthorhombic crystal structures. Thermomagnetic measurements showed that the as-made particles are superparamagnetic at room temperature with a blocking temperature (TB) of 20 K. When the particles are annealed at 823 K for 12 h, their size is increased to 13 nm and they develop a new orthorhombic crystal structure, with a Curie temperature (TC) of 815 K. This is drastically different from bulk, which are ferromagnetic at cryogenic temperatures only. X-ray diffraction (XRD) measurements suggest the formation of a new Co-rich orthorhombic phase (OP) with slightly increased c/a ratio in the annealed particles and this is believed to be the reason for the drastic change in their magnetic properties.

Effect of size confinement on skyrmionic properties of MnSi nanomagnets.

Bulk magnetic materials with the noncentrosymmetric cubic B20 structure are fascinating due to skyrmion spin structures associated with Dzyaloshinskii-Moriya interactions, but the size of skyrmions are generally larger than 50 nm. The control of such spin structures in the 10 nm size ranges is essential to explore them for spintronics, ultra-high-density magnetic recording, and other applications. In this study, we have fabricated MnSi nanoparticles with average sizes of 9.7, 13.1 and 17.7 nm and investigated their structural and magnetic properties. X-ray diffraction and transmission electron microscope studies show that the MnSi nanoparticles crystallize in the cubic B20 structure. Field-dependent dc susceptibility data of the MnSi samples with average particle sizes of 17.7 and 13.1 nm show anomalies in limited field (about 25-400 Oe) and temperature (25 K-43 K) ranges. These features are similar to the signature of the skyrmion-like spin structures observed below the Curie temperature of MnSi. Our results also show that this anomalous behavior is size-dependent and suppressed in the smallest nanoparticles (9.7 nm), and this suppression is interpreted as a confinement effect that leads to a truncation of the skyrmion structure.

Structure and Magnetism of Mn5Ge3 Nanoparticles.

In this work, we investigated the magnetic and structural properties of isolated Mn5Ge3 nanoparticles prepared by the cluster-beam deposition technique. Particles with sizes between 7.2 and 12.6 nm were produced by varying the argon pressure and power in the cluster gun. X-ray diffraction (XRD)and selected area diffraction (SAD) measurements show that the nanoparticles crystallize in the hexagonal Mn5Si3-type crystal structure, which is also the structure of bulk Mn5Ge3. The temperature dependence of the magnetization shows that the as-made particles are ferromagnetic at room temperature and have slightly different Curie temperatures. Hysteresis-loop measurements show that the saturation magnetization of the nanoparticles increases significantly with particle size, varying from 31 kA/m to 172 kA/m when the particle size increases from 7.2 to 12.6 nm. The magnetocrystalline anisotropy constant K at 50 K, determined by fitting the high-field magnetization data to the law of approach to saturation, also increases with particle size, from 0.4 × 105 J/m³ to 2.9 × 105 J/m³ for the respective sizes. This trend is mirrored by the coercivity at 50 K, which increases from 0.04 T to 0.13 T. A possible explanation for the magnetization trend is a radial Ge concentration gradient.

Magnetism of new metastable cobalt-nitride compounds.

The search for new magnetic materials with high magnetization and magnetocrystalline anisotropy is important for a wide range of applications including information and energy processing. There is only a limited number of naturally occurring magnetic compounds that are suitable. This situation stimulates an exploration of new phases that occur far from thermal-equilibrium conditions, but their stabilization is generally inhibited due to high positive formation energies. Here a nanocluster-deposition method has enabled the discovery of a set of new non-equilibrium Co-N intermetallic compounds. The experimental search was assisted by computational methods including adaptive-genetic-algorithm and electronic-structure calculations. Conventional wisdom is that the interstitial or substitutional solubility of N in Co is much lower than that in Fe and that N in Co in equilibrium alloys does not produce materials with significant magnetization and anisotropy. By contrast, our experiments identify new Co-N compounds with favorable magnetic properties including hexagonal Co3N nanoparticles with a high saturation magnetic polarization (Js = 1.28 T or 12.8 kG) and an appreciable uniaxial magnetocrystalline anisotropy (K1 = 1.01 MJ m-3 or 10.1 Mergs per cm3). This research provides a pathway for uncovering new magnetic compounds with computational efficiency beyond the existing materials database, which is significant for future technologies.

Effect of boron doping on nanostructure and magnetism of rapidly quenched Zr2Co11-based alloys.

The role of B on the microstructure and magnetism of Zr16Co82.5-x Mo1.5B x ribbons prepared by arc melting and melt spinning is investigated. Microstructure analysis show that the ribbons consist of a hard-magnetic rhombohedral Zr2Co11 phase and a minor amount of soft-magnetic Co. We show that the addition of B increases the amount of hard-magnetic phase, reduces the amount of soft-magnetic Co and coarsens the grain size from about 35 nm to 110 nm. There is a monotonic increase in the volume of the rhombohedral Zr2Co11 unit cell with increasing B concentration. This is consistent with a previous theoretical prediction that B may occupy a special type of large interstitial sites, called interruption sites. The optimum magnetic properties, obtained for x = 1, are a saturation magnetization of 7.8 kG, a coercivity of 5.4 kOe, and a maximum energy product of 4.1 MGOe.

Magnetic nanostructuring and overcoming Brown's paradox to realize extraordinary high-temperature energy products.

Nanoscience has been one of the outstanding driving forces in technology recently, arguably more so in magnetism than in any other branch of science and technology. Due to nanoscale bit size, a single computer hard disk is now able to store the text of 3,000,000 average-size books, and today's high-performance permanent magnets--found in hybrid cars, wind turbines, and disk drives--are nanostructured to a large degree. The nanostructures ideally are designed from Co- and Fe-rich building blocks without critical rare-earth elements, and often are required to exhibit high coercivity and magnetization at elevated temperatures of typically up to 180 °C for many important permanent-magnet applications. Here we achieve this goal in exchange-coupled hard-soft composite films by effective nanostructuring of high-anisotropy HfCo7 nanoparticles with a high-magnetization Fe65Co35 phase. An analysis based on a model structure shows that the soft-phase addition improves the performance of the hard-magnetic material by mitigating Brown's paradox in magnetism, a substantial reduction of coercivity from the anisotropy field. The nanostructures exhibit a high room-temperature energy product of about 20.3 MGOe (161.5 kJ/m(3)), which is a record for a rare earth- or Pt-free magnetic material and retain values as high as 17.1 MGOe (136.1 kJ/m(3)) at 180°C.

Novel nanostructured rare-earth-free magnetic materials with high energy products.

Novel nanostructured Zr2 Co11 -based magnetic materials are fabricated in a single step process using cluster-deposition method. The composition, atomic ordering, and spin structure are precisely controlled to achieve a substantial magnetic remanence and coercivity, as well as the highest energy product for non-rare-earth and Pt-free permanent-magnet alloys.

Theoretical and experimental characterization of structures of MnAu nanoclusters in the size range of 1-3 nm.

Relative stabilities of MnAu magic-number nanoclusters with 55, 147, 309, and 561 atoms and highly symmetric morphologies (cuboctahedron, icosahedron, onion-like, and core-shell, respectively) are investigated based on density functional theory methods. Through an extensive search, spin arrangements on Mn atoms that give rise to lowest-energy clusters are predicted. The antiferromagnetic spin configurations are found to be the most favorable for all morphologies investigated. The energy rankings among MnAu nanoclusters with the same size and Mn/Au ratio but different morphologies are also determined. The L1(0) structure is found to be increasingly favorable as the size increases from 1.0 to 2.9 nm, consistent with experimental measurements of MnAu nanoparticles in the size range of 1.8-4.6 nm. The decahedron L1(0) morphology is found to be energetically more preferred when the Mn/Au ratio is close to 1:2, whereas the cuboctahedron L1(0) morphology is more preferred when the Mn/Au ratio is close to 1:1. The calculated lattice constants are in excellent agreement with high-resolution TEM measurements for MnAu nanoparticles of similar size. Magnetic states of MnAu nanoclusters are predicted to be stable at room temperature based on estimated Curie or Neél temperature.

Enhancement of the critical current density in FeO-coated MgB(2) thin films at high magnetic fields.

The effect of depositing FeO nanoparticles with a diameter of 10 nm onto the surface of MgB(2) thin films on the critical current density was studied in comparison with the case of uncoated MgB(2) thin films. We calculated the superconducting critical current densities (J(c)) from the magnetization hysteresis (M-H) curves for both sets of samples and found that the J(c) value of FeO-coated films is higher at all fields and temperatures than the J(c) value for uncoated films, and that it decreases to ~10(5) A/cm(2) at B = 1 T and T = 20 K and remains approximately constant at higher fields up to 7 T.

Synthesis of monodisperse TiO2-paraffin core-shell nanoparticles for improved dielectric properties.

Core-shell structures of oxide nanoparticles having a high dielectric constant, and organic shells with large breakdown field are attractive candidates for large electrical energy storage applications. A high growth temperature, however, is required to obtain the dielectric oxide nanoparticles, which affects the process of core-shell formation and also leads to poor control of size, shape, and size-distribution. In this communication, we report a new synthetic process to grow core-shell nanoparticles by means of an experimental method that can be easily adapted to synthesize core-shell structures from a variety of inorganic-organic or inorganic-inorganic materials. Monodisperse and spherical TiO2 nanoparticles were produced at room temperature as a collimated cluster beam in the gas phase using a cluster-deposition source and subsequently coated with uniform paraffin nanoshells using in situ thermal evaporation, prior to deposition on substrates for further characterization and device processing. The paraffin nanoshells prevent the TiO2 nanoparticles from contacting each other and also act as a matrix in which the volume fraction of TiO2 nanoparticles was varied by controlling the thickness of the nanoshells. Parallel-plate capacitors were fabricated using dielectric core-shell nanoparticles having different shell thicknesses. With respect to the bulk paraffin, the effective dielectric constant of TiO2-paraffin core-shell nanoparticles is greatly enhanced with a decrease in the shell thickness. The capacitors show a minimum dielectric dispersion and low dielectric losses in the frequency range of 100 Hz-1 MHz, which are highly desirable for exploiting these core-shell nanoparticles for potential applications.