Heusler Alloys Research Articles

Investigation of phase stability and martensitic transformation of all-d-metal Heusler alloys Fe2VIr and Fe2TaIr in high pressure: A first-principles study

First-principles calculations are used to investigate the phase stability and martensitic transformation of two new all-d-metal Heusler alloys Fe2VIr and Fe2TaIr at 0–50 GPa. The difference in phase stability between Fe2VIr and Fe2TaIr is due to the effect of d-d orbital hybridisation between different atoms and the appearance of triply degenerate in the pressure-induced phonon optical modes. The softening behaviour of the transverse phonon mode along the high symmetry point X is responsible for the martensitic transformation of Fe2TaIr. We also observed the softening of the shear elastic constant C′ = (C11-C12)/2. Strong Fe-Fe magnetic coupling, softening of transverse acoustic phonon modes and anomalous softening of C′ awaken the martensitic transformation. Low-frequency phonon hybridisation of the heavy elements Ta and Ir is the driving force behind the softening. A surprising phenomenon is found during tetragonal deformation of the structure of Fe2TaIr at 45 GPa, whereby the structure break through the energy barrier of the leap and produced a tetragonal martensitic phase with a much lower energy. It may imply that pressure-induced Fe2TaIr produced a premartensitic phase. This work presents a detailed analysis of the anomalous softening behaviour of Fe2TaIr and the mechanism of the pressure-induced martensitic transformation. A new idea is proposed for an in-depth study of the martensitic phase transition precursor reaction.

Strategic Design and Mechanistic Understanding of Vacancy-Filling Heusler Thermoelectric Semiconductors.

Doping narrow-gap semiconductors is a well-established approach for designing efficient thermoelectric materials. Semiconducting half-Heusler (HH) and full-Heusler (FH) compounds have garnered significant interest within the thermoelectric field, yet the number of exceptional candidates remains relatively small. It is recently shown that the vacancy-filling approach is a viable strategy for expanding the Heusler family. Here, a range of near-semiconducting Heuslers, TiFexCuySb, creating a composition continuum that adheres to the Slater-Pauling electron counting rule are theoretically designed and experimentally synthesized. The stochastic and incomplete occupation of vacancy sites within these materials imparts continuously changing electrical conductivities, ranging from a good semiconductor with low carrier concentration in the endpoint TiFe0.67Cu0.33Sb to a heavily doped p-type semiconductor with a stoichiometry of TiFe1.00Cu0.20Sb. The optimal thermoelectric performance is experimentally observed in the intermediate compound TiFe0.80Cu0.28Sb, achieving a peak figure of merit of 0.87 at 923 K. These findings demonstrate that vacancy-filling Heusler compounds offer substantial opportunities for developing advanced thermoelectric materials.

Investigation on the structural, elastic, electronic, thermodynamic, and vibrational properties of the full heusler Sc2XAl (X =Cd and Zn): An ab initio study

The structural, mechanical, electronic, thermodynamic, and phonon characteristics of Sc2CdAl and Sc2ZnAl in L21 phase were the main focuses on this investigation. The density of states (DOS) and electronic band spectra signify the metallic behavior of the L21 phase of both materials. The impact of atomic arrangement with respect to the Wyckoff sites on the mechanical stability were additionally studied. The elastic constants of Sc2CdAl and Sc2ZnAl alloys indicated that these alloys convened Born mechanical stability criteria. Using the density functional perturbation theory's first-principle linear response method, complete phonon spectra have been acquired. Moreover, the quasi-harmonic approximation, specific heat capacity at constant volume, the internal free energy, entropy, and vibrational free energy variations of Sc2CdAl and Sc2ZnAl as full Heusler alloys have been utilized in examination the change over the temperature between 0 and 800 K. Both alloys might find application in real industrial applications.

The magnetic and half-metallic properties of the d0-quaternary Heusler alloys KYBX(Y=Ca or Sr, X=S or Se) in ab-initio approach

The magnetic and half-metallic properties of the d0-quaternary Heusler alloys KYBX(Y=Ca or Sr, X=S or Se) in ab-initio approach

First-principles Study on Structural and Electronic Properties: The Li Based of Full-Hesulter Alloys LiGa2Ir

Abstract: Due to their excellent electronic properties, full-Heusler compounds have become one of the most interesting families of alloys in superconductivity. More recently, computational methods have been actively employed to support the rapid discovery of new complete Heusler alloys by identifying stable compositions with desired properties. Therefore, we investigated the stability, structure, and electronic properties of the lithium-based Heusler compound LiGa2Ir using first-principles calculations. We explored the effects of exchange-correlation, namely Perdew-Burke-Ernzerhof (PBE), PBE+U, and Tran-Blaha modified Becke-Johnson potentials, as well as the effect of heavy metal spin-orbit coupling on these Heusler compounds. The results show that LiGa2Ir is energetically stable, and the obtained lattice parameter value (a = 6.0927 Å) agrees with the experimental results. LiGa2Ir exhibits metallic behavior under all three exchange-correlation estimates. A much stronger spin-orbit coupling effect is observed for electronic states with energies below the Fermi level EF, especially in the Tran-Blaha modified Becke-Johnson approximation. Significant spin-orbit coupling effects are evident from the total and partial density of states figures, especially in the energy range from -4.5 eV to -2 eV. The contributions from Ir-d and Ga-p orbitals are the largest, while the contribution from the Li atom is small. Our findings will benefit future theoretical and practical work on lithium-based full-Heusler alloys. Keywords: Full-Heusler, DFT, Spin-orbit coupling, Electronic properties, Density of states.

The second-order magnetic transformation and magnetocaloric effect in all-d-metal Heusler ribbon Ni35Co15Mn34Ti16

The new all-d-metal Heusler alloys with good mechanical properties are candidates for magnetocaloric materials compared other famous refrigeration materials. In this work, Ni35Co15Mn34Ti16 ribbon with a second-order magnetic transformation was investigated for magnetoclaoric effect. It crystalizes pure B2 structure at room temperature and undergoes a SOMT at Curie temperature in austenite (TCA = 358 K) between paramagnetic and ferromagnetic phase. A large saturation magnetization (MS) at 5 K is 166 emu/g. The maximum values of magnetic entropy change (−ΔSM) and the temperature-averaged entropy change TEC(10 K) reach 1.62(3.42) J kg−1 K−1 and 1.64 (3.44) J kg−1 K−1 with magnetic field change (ΔH) of 20(50) kOe, respectively, which are comparable to most of other all-d-metal Heusler alloys.

Accurate prediction of magnetocaloric effect in NiMn-based Heusler alloys by prioritizing phase transitions through explainable machine learning

Accurate prediction of magnetocaloric effect in NiMn-based Heusler alloys by prioritizing phase transitions through explainable machine learning

Data-driven design of high-curie temperature full-heusler alloys for spintronic applications

In this study, we employ density functional theory (DFT) and subgroup discovery (SGD) to explore the structural and magnetic properties of full cubic Heusler compounds, with a particular emphasis on their Curie temperatures (Tc) and magnetic stability. Our comprehensive examination of 2903 structures across both L21 and Xa phases identifies configurations that exhibit both structural stability and superior magnetic properties. Notable among these, compounds such as Co2MnSi, Co2CrGe, and Cr2VGe exhibit remarkable magnetic stability, maintaining their ferromagnetic properties well above room temperature. Co2MnSi displays a substantial magnetic moment of 5.00 μB and maintains its ferromagnetic properties up to a Curie temperature of 937 K, underscoring its suitability for high-temperature applications. Similarly, Co2CrGe, with a magnetic moment of 4.00 μB, transitions to a paramagnetic state at a higher temperature of 952 K, demonstrating enhanced thermal durability. Moreover, Cr2VGe, notable for its robust magnetic moment of 2.81 μB, retains its ferromagnetic characteristics until an exceptional 2412 K, making it extremely valuable for thermally intensive environments. These findings underscore the potential of these materials in developing durable and efficient spintronic devices that operate under extreme thermal conditions. By mapping the interplay between electronic structure and magnetic properties, our study provides a predictive framework for optimizing the performance of spintronic materials.

First-principles calculations and experimental studies on Cr2MnAl Heusler alloy nanoparticles for spintronics applications

In depth understanding of the magnetic, structural and electrical properties of Heusler alloys are crucial to achieve potential applications in spin-based device. Wherein, we report the synthesis of Cr2MnAl Heusler alloy nanoparticles (NPs) via co-precipitation method and also demonstrated their transport properties. Interestingly X-ray analysis confirms the cubic phase of the synthesized Heusler alloy NPs and transmission electron microscopy (TEM) analysis reveals that the Cr2MnAl as particle size of 10 ± 2 nm. Moreover, this particle size has adverse effect on symmetry of Cr2MnAl Heusler alloy due to their higher surface to volume ratio that significantly changes their magnetic and electrical properties. These NPs exhibit soft ferromagnetic properties with a Curie temperature (Tc) of 25 K. Besides, resistivity measurements indicate the semiconducting nature and also we report the observation of anomalous Hall effect. In addition, we support our experimental results by studying the electronic and magnetic properties of alloy using first principle calculations. This density functional theory reveals that Cr2MnAl has half metallic characteristics with high spin polarization. In light of above, this material can be used as intermediate layer to decouple the two ferromagnetic layers which acts as spin-polarized carriers in spin-based device.

Unconventionally Large Exchange Bias and Cluster Spin Glass State in Mn2(Ni,Sn) Heusler Alloys Melt Spun Ribbons

Unconventionally Large Exchange Bias and Cluster Spin Glass State in Mn₂(Ni,Sn) Heusler Alloys Melt Spun Ribbons

Micromagnetic study of exchange bias effect in sub-micron dots of Co2MnSi interfaced with uncompensated IrMn

Owing to its crucial role in spintronics devices, the exchange bias (EB) phenomenon has been extensively investigated in various ferromagnet (FM) and antiferromagnet (AFM) bilayers since its discovery in Co/CoO core–shell nanoparticles. In this study, we present the emergence of negative EB for the first time in the Co2MnSi Heusler alloy interfacing with an uncompensated AFM, exhibiting analogous anisotropy to the IrMn. Due to the high pinning and IrMn anisotropy values, EB is stronger here. Investigation into the influence of ferromagnetic layer thickness (tFM) on exchange bias reveals an inverse relationship, while coercivity displays a non-monotonic increase. The analysis of spin canting angles suggests the presence of a maximum canting angle in the Co2MnSi layer close to the interface. We thoroughly analyze the spin configurations at the interface as well as away from it in the Co2MnSi (25 nm)/IrMn (5 nm) bilayer to better understand the mechanism of magnetization reversal. Interestingly, our findings unveiled distinct spin behaviors for the first and second reversals. In cases of small AFM thicknesses (tAFM), the exchange field is proportionate to the tAFM, contrasting with large tAFM, where it scales as 1/tAFM. Notably, coercivity demonstrates an increasing behavior across all tAFM variations. The angular dependence of the Heusler alloy revealed a four-fold symmetry indicative of cubic anisotropy and a two-fold symmetry representative of uniaxial anisotropy. The angular dependency study of exchange bias indicated similar clockwise (CW) and counterclockwise (CCW) rotations, with cos (θ) unidirectional dependence. However, loop shifting revealed that the lower pinning ability at 0° was due to a low Meiklejohn-Bean parameter (R) value. Additionally, through the manipulation of the R-parameter, we can tune the magnitude of the coercive field and EB. All these results are crucial for the utilization of the Co2MnSi/IrMn heterostructures for various applications in spintronics-based devices.

Vacancy formation modulating the local atomic environment for remarkable Multi-functional Magnetic properties in Ni–Co–Mn–In alloy

Defect (mainly vacancy) engineering has shown its potential for modulating the functional behavior of magnetic materials. In this work, dense Ni vacancies are introduced in Ni45Mn36.5In13.5Co5 alloy and the effect of these vacancies on the magnetic properties is both theoretically and experimentally clarified. In detail, Ni vacancy with the lowest formation energy is introduced by high energy electron irradiation, which shortens the distance between adjacent Mn atoms to strengthen the interaction between them and increase the corresponding magnetic moments, leading to the dTm/dH increase from −2.89 to 6.28 KT−1. As a result, a breakthrough in the magnetocaloric performance is correspondingly achieved, i.e., the entropy change (ΔSM) increases up to an ultra-high value of 48.15 J/(kg·K), much higher than all other reported values. Moreover, the reversible magnetostrain is also improved from 80 to 200 ppm. In summary, this work provides strong guidance for optimizing the magnetic performance of Ni–Mn based Heusler alloys via vacancy modulation.

Temperature-dependent lattice dynamics study on phase stability, martensitic transformation mechanism, and vibrational entropy properties of B2-type Ni–Mn–Ti Heusler alloy

The all-d-metal Ni–Mn–Ti Heusler alloy with its good mechanical properties and colossal caloric effects has attracted significant attention for mechanocaloric refrigeration. However, the phase stability of the B2-type disordered structure at finite temperatures and the physical origin of large phase transformation entropy change in theoretical calculation remain unclear. In view of thermal and strongly anharmonic effects, we combined the first-principles and temperature dependent effective potential calculations to systematically study the phase stability, martensitic transformation mechanism, and vibrational entropy properties of B2 partial disordered structures for Ni8Mn5Ti3 and Ni8Mn6Ti2. Our results showed the austenitic structures of Ni8Mn5Ti3 and Ni8Mn6Ti2 both exhibit antiferromagnetic interaction behaviors at targeted temperatures, resolving the contradiction between previous calculations and experiments. By the analysis of phonon dispersion relations and Helmholtz free energies at low and high temperatures, we provided a deeper explanation for the underlying mechanism of martensitic transformation. Meanwhile, the phase transformation temperatures and vibrational entropy changes were accurately predicted compared with the experiment results. Specifically, we demonstrated that the large vibrational entropy change of Ni–Mn–Ti material originates from the contributions of both the tetragonal distortion ratio and volume change, which provides important theoretical guidance and has great practical significance for designing the solid-state material with large vibrational entropy change in the application of solid-state refrigeration.

First-principles study on electronic and mechanical properties of Ru2XAl (X = Mn, Zr, Ti, Hf) alloys

The magnetic properties of Heusler alloys have been a hot research topic. However, the current understanding of the properties of Ru-based Heusler alloys is still very limited. The magnetic, electronic, and mechanical properties of four Ru-based Heusler alloys, Ru2XAl (X = Mn, Zr, Ti, and Hf) were calculated by the first-principles. This article studied the basic mechanical parameters of four types of Heusler alloys, such as bulk elastic modulus, Cauchy pressure, Pugh’s ratio, shear modulus, Kleinman parameter, Young’s modulus, Poisson’s ratio, and elastic constant. The calculated results of the elastic constant prove that all four alloys are mechanically stable. Ru2MnAl alloy exhibits brittleness, while the other three alloys exhibit excellent ductility based on Poisson’s ratio and Pugh’s ratio. The Kleinman parameter of the four alloys are all greater than 0.5, indicating that they have stronger stability in the tensile state. In addition, the spin magnetic moment of Ru2MnAl alloy is 2.113 μB, which is consistent with the SP rule and other theoretical calculations.

Unraveling the negative charge-to-spin conversion in the Heusler alloy Co2FeSi

Recent discoveries of Heusler alloy achieve a strong advantage of the chemically disordered sample in the charge-to-spin conversion and attracted interests for spintronics applications. Here, we observe the negative charge-to-spin conversion in single magnetic layer of Co2FeSi/MgO and prove generations of σy and σx by spin-torque ferromagnetic resonance (ST-FMR). We also report that the change in charge-to-spin conversion efficiency could be controlled by chemical disordering. Furthermore, the thickness dependents of Co2FeSi demonstrated bulk effect is responsible for the generation of spin current. This study contributes to understanding the mechanisms of spin current generation from magnetic full Heusler alloy and also paves the way for the applications of magnetic memory and nonvolatile spin logic technologies.

Exploring microstructure and caloric effects in gas-atomized Ni–Mn–Sn–Co precursor for additive manufacturing

Recently, additive manufacturing (AM) of intrinsically brittle Ni–Mn–X alloys, in which obtaining high-quality powders is imperative, has received widespread attention. Here, a batch weight of about 34 kg Ni–Mn–Sn–Co powder was prepared using industrial gas atomization equipment. To explore the sinterability of the gas-atomized powder and provide a direct comparison in caloric effects for binder-based AM techniques, we sintered Ni–Mn–Sn–Co alloy powder samples at 1173–1273 K for 2–24 h by using a powder metallurgy process with air cooling. The sintered powder samples had a relative density of about 60.3–80.1 %, and 5M martensite and L21–ordered austenite were found to coexist at room temperature. For all sintered samples, martensitic transformation temperature width of about 11–17 K and hysteresis of about 21–23 K were obtained, and strong magneto-structural coupling was observed. The magnetocaloric and elastocaloric effects of the sample sintered at 1273 K for 2 h were examined. A magnetic entropy change of about 23.0 J kg−1·K−1 and an adiabatic temperature change (ΔTad) of −0.97 K were achieved for magnetic fields of 5.0 and 1.25 T, respectively. Furthermore, a ΔTad of −4.71 K was achieved upon unloading a compressive stress of 350 MPa. These competitive caloric effects in the gas-atomized powder lay the foundation for the AM of Ni–Mn–Sn–Co alloys with complex structures. This study provides a reference for the reliable manufacturing of composition-sensitive Ni–Mn–X Heusler alloys.

Computational Exploration of Pd-Based Heusler alloys for permanent Magnets: Density Functional Theory and High-Throughput methods

In this work, we have explored the potential of a relatively new class of Pd-based Heusler alloys as permanent magnets. Our approach began with a high-throughput study using the Automatic Flow (AFLOW) electronic structure database to identify Pd₂YZ-type Heusler systems with tetragonal symmetry and high magnetization. For the alloys that passed our initial selection filters, we performed a detailed investigation of their magnetic properties using density functional theory (DFT) calculations. These calculations included assessments of magnetocrystalline anisotropy energy (EMCA) and exchange interactions. The selected candidates, which met all our criteria, were then subjected to Monte Carlo simulations to analyze the temperature dependence of their magnetization and determine their Curie temperatures (TC). Our results indicate that Pd₂FeNi and Pd₂FePt are promising candidates for permanent magnets. Pd₂FeNi exhibited an EMCA of 2.4 MJ/m3 and a TC of 504 K, while Pd₂FePt showed an EMCA of 4.11 MJ/m3 and a TC of 463 K. Both Curie temperatures are significantly above room temperature by more than 160 K, demonstrating the alloys’ potential for high-temperature applications and their overall suitability as efficient, rare earth-free permanent magnets.

Ab initio analysis of structural, electronic, magnetic, thermodynamic, and elastic properties of Half Heusler alloys ZMnAs (Z = Be, Mg) for spintronics applications

In this study, the structural, electronic, magnetic, thermodynamic, and elastic attributes of ZMnAs (Z = Be, Mg) have been investigated. These Half-Heusler alloys exhibit stability in the ferromagnetic state (FM), as demonstrated by optimization-related energy release. The half-metallicity (HM) of these compounds is examined through the band structures and density of states (DOS). In addition, the crystal field and exchange energies are reported to confirm the control of electron spin. Additionally, the double exchange process and exchange constants were premeditated. In this case, ferromagnetism (FM) is caused by the quantum exchange of electrons, as evidenced by the negative pd exchange energy and the exchange constants, rather than being a result of clustering effects. The quasi-harmonic Debye model, included within the Gibbs code, was utilized to calculate the thermodynamic properties. These two compounds are mechanically stable and show ductile nature confirmed by the value of Poisson's ratio (v), Pugh's ratio (B/G), and Cauchy pressure (CP), which demonstrates the ability to withstand substantial plastic deformation before fracturing. Based on our calculations, the half-metallic (HM) nature, thermodynamic, ferromagnetic, ductile, and high inherent magnetic moment have been evaluated. These alloys are crucial in the advancement of spintronics and renewable energy systems.

First-principles study of the martensitic transformation in pressure of the all-d-metal Heusler alloy Fe2NbIr

The martensitic transformation of the new all-d-metal Heusler alloy Fe2NbIr is investigated using first-principles. The structure undergoes softening and hardening under pressure, which corresponds to the two phases of the martensitic phase transformation, i.e. C′ softening of the austenite and C′ hardening of the pre-martensite phase, implying that the pressure may induces to produce a cubic pre-martensite phase. An exciting phenomenon is found in the tetragonal deformation of the pre-martensite phase, where the pre-martensite phase overcome the energy barrier of the jump to produce a tetragonal martensite phase with a much lower energy. It explains the presence of a pre-martensite phase in shape memory alloys, i.e., it provides a conduit for the phase change. This work presents an analysis of the anomalous softening behaviour of Fe2NbIr and the mechanism of the pressure-induced martensitic transformation, and provides a new idea for study of the precursor effect of martensitic phase transformation.

Ni50Mn37.5Sn12.5 Heusler Alloy: Influence of Co Addition on the Structure, Martensitic Transition, and Magnetic Properties

The impact of Co-addition (x = 0, 2, 4, and 6 at. %) in the as-cast and annealed Ni50Mn37.5Sn12.5 Heusler alloy at 900 °C for 24 h on the microstructure, magnetic properties, and the martensitic transition was studied using X-ray diffraction (XRD), scanning electron microscopy, vibrating sample magnetometry, and differential scanning calorimetry. The crystal structure of as-cast samples consists of a 14M modulated martensite structure, a face-centered (FCC) γ phase, and a face-centered tetragonal (FCT) MnNi-type phase L10. The as-cast samples show a dendritic microstructure with different contrasts and non-uniform distribution. The annealed samples exhibit dual 14M and γ phases for the Co0 and Co2, but 14M + γ + MnNi for the Co4 and Co6. The appearance of the martensitic transformation in the annealed Co0 and Co2 samples can be due to the disappearance of the dendritic microstructure. The characteristic temperatures (martensite start, Ms; martensite finish, Mf; austenite start, As; and austenite finish, Af) decrease with Co addition. A ferromagnetic-like order exists at a lower temperature of 1.8 K for the as-cast and annealed samples and decreases at 300 K. The annealing increases the fraction of the AFM contributions at 300 K. The exchange bias values of the Co0, An-Co2, and An-Co6 are 146.7 Oe, 24 O2, and 32.6 Oe, respectively, at 300 K.