Engineering topics

May, Andrew F.

Publications and source records attributed to May, Andrew F..

18 records

DOE OSTI2024

Anisotropic magnetism of polymorphic ErAl 3

ErAl 3 can form in either a trigonal (α) or cubic (β) polymorph and this paper investigates the physical properties of these polymorphs through characterizations of single crystals grown in an aluminum flux. Here, we demonstrate that polymorph selection can be achieved based on the nominal composition of the crystal growth. Magnetic measurements confirm that both β-ErAl 3 and α-ErAl 3 order antiferromagnetically at low temperatures. β-ErAl 3 undergoes antiferromagnetic ordering at a Néel temperature T N = 5.1 K, and the transition is suppressed continually with applied field. α-ErAl 3 displays more complex behavior, with successive magnetic transitions at T N = 5.7 K and T 2 = 4.6 K for zero field, where heat capacity and dilatometry measurements evidence that these transitions are second and first order, respectively. Under magnetic field, strong anisotropy is revealed in α-ErAl 3 , with several steplike metamagnetic transitions observed below T 2 for H ∥ c. These transitions produce sequential magnetization plateaus near one-half of the apparent saturation magnetization. The electrical resistivity of α-ErAl 3 is strongly coupled to its magnetism. At T = 2 K, we observe a positive magnetoresistance reaching 60%, with distinct anomalies at the metamagnetic transitions. The results are summarized in H-T phase diagrams that demonstrate complex magnetic behavior for α-ErAl 3 , suggesting an important role of competing interactions in this metallic system that possesses characteristics of Ising physics.

36 MATERIALS SCIENCE↗

DOE OSTI2024

MnRhBi 3 : A Cleavable Antiferromagnetic Metal

Cleavable metallic antiferromagnets may be of use for low-dissipation spintronic devices; however, few are currently known. Here, in this study, we present orthorhombic MnRhBi 3 as one such compound and present a thorough study of its physical properties. Exfoliation is demonstrated experimentally, and the cleavage energy and electronic structure are examined by density functional theory calculations. It is concluded that MnRhBi 3 is a van der Waals-layered material that cleaves easily between neighboring Bi layers and that the Bi atoms have lone pairs extending into the van der Waals gaps. A series of four phase transitions are observed below room temperature, and neutron diffraction shows that at least two of the transitions involve the formation of antiferromagnetic order. Anomalous thermal expansion points to a crystallographic phase transition and/or strong magnetoelastic coupling. This work reveals a complex phase evolution in MnRhBi 3 and establishes this cleavable antiferromagnetic metal as an interesting material for studying the interplay of structure, magnetism, and transport in the bulk and ultrathin limits, as well as the role of lone pair electrons in interface chemistry and proximity effects in van der Waals heterostructures.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Spin dynamics of the centrosymmetric skyrmion material GdRu 2 Si 2

Magnetic skyrmion crystals are traditionally associated with non-centrosymmetric crystal structures; however, it has been demonstrated that skyrmion crystals can be stabilized by competing interactions in centrosymmetric crystals. To understand and optimize the physical responses associated with topologically nontrivial skyrmion textures, it is important to quantify their magnetic interactions by comparing theoretical predictions with spectroscopy data. Here, we present neutron diffraction and spectroscopy data on the centrosymmetric skyrmion material GdRu 2 Si 2 and show that the key spectroscopic features can be explained by magnetic interactions calculated using density functional theory. We further show that the recently proposed 2-q “topological spin stripe” structure yields better agreement with our data than a 1-q helical structure and identify how the magnetic structure evolves with temperature.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Real-space visualization of atomic displacements in a long-wavelength charge density wave using cryogenic 4D-STEM

EuA⁢l 4 , a known skyrmion magnet, represents a class of materials that show complex electronic behaviors involving long-wavelength charge density wave (CDW). Here we realize direct real-space imaging of the concomitant periodic lattice distortion (PLD) with picometer precision in EuA⁢l 4 . Simultaneous imaging of microstructure, polarization, and interatomic distance is made possible using cryogenic four-dimensional scanning transmitting electron microscopy (cryo-4DSTEM). With this approach, we determined that the PLD in EuA⁢l 4 incorporates two out-of-phase atomic displacement modes on the Eu and Al sublattices. The PLD introduces periodic local symmetry fluctuations from the average symmetry of the bulk EuA⁢l 4 crystal. This critical local structural insight helps understanding of charge-spin-lattice couplings behind the intertwined quantum order in EuA⁢l 4 . Furthermore, our results also demonstrate cryo-4DSTEM as an indispensable approach for probing CDW and related quantum materials at low temperatures.

Ni, Haoyang↗

DOE OSTI2024

Nanometric modulations of the magnetic structure of the element Nd

The rare earth neodymium arguably exhibits the most complex magnetic ordering and series of magnetic phase transitions of the elements. Here we report the results of small-angle neutron scattering (SANS) measurements as a function of temperature and applied magnetic field to study magnetic correlations on nanometer length scales in Nd. We support these results with additional neutron diffraction, thermodynamic and synchrotron x-ray measurements. The SANS measurements reveal the presence of modulation vectors characterizing the ordered spin configuration which exhibit changes in magnitude and direction that are phase dependent. Between 5.9 and 7.6 K an additional modulation vector is observed with magnitude Q = 0.12 Å -1 . This scattering appears to originate from order of the Nd layers which contain a center of inversion. Tracking this modulation vector as a function of magnetic field indicates a phase boundary at ≈1 T. The modulation vectors observed in this study establish the presence of nanometer length scale spin textures which are likely stabilized by frustrated Ruderman–Kittel–Kasuya–Yosida (RKKY) interactions.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Spin-dependent electron transfer in electrochemically transparent van der Waals heterostructures for oxygen evolution reaction

Spin selective catalysis is an emerging approach for improving the thermodynamics and kinetics of reactions. The role of electron spins has been scarcely studied in catalytic reactions. One exception is the oxygen evolution reaction (OER) where strongly correlated metals and oxides are used as catalysts. In OER, spin alignment facilitates the transition of singlet state of the reactant to the triplet state of O 2 . However, the influence of strong correlations on spin exchange mechanism and spin selective thermodynamics of most catalytic reactions remain unclear. Here we decouple the strongly correlated catalyst from the electrolyte to study spin exchange in two-dimensional (2D) magnetic iron germanium telluride (FGT) heterostructure. We demonstrate that transmission of spin and electrochemical information between the catalyst and the reactant can occur through quantum exchange interaction despite the catalyst of FGT being completely encapsulated by graphene or hexagonal boron nitride (hBN). The strong correlations in FGT that lead to enhanced spin exchange in OER are observed in graphene or hBN layers with thicknesses of up to 6 nm. We demonstrate that spin alignment in FGT leads to a lowering of thermodynamic barrier for adsorption of hydroxide ion and electron transfer to the catalyst. This results in up to fivefold enhancement in OER performance and improved kinetics. Our results provide clear evidence that transmission of both quantum mechanical and electrochemical information through quantum spin exchange interaction in FGT leads to an enhancement in catalytic performance.

2D materials↗

DOE OSTI2024

Crystal growth and evolution of magnetism in the EuCuP-EuCuAs solid solution

The hexagonal EuMX (M = Cu, Ag, Au; X = P, As, Sb, Bi) compounds host interesting electronic and magnetic properties, with seemingly intertwined topology and transport properties. One key feature of such behavior is the nature of the ordered magnetic structure. In EuCuAs, a topological Hall effect is caused by a conical spin structure that emerges when a field is applied within the easy-plane (H ⊥ c) of the helical ground state that exists below the Neel temperature of T N = 14 K. On the other hand, EuCuP is an easy-axis ferromagnet with a Curie temperature T C near 31 K. Here, in this study, we investigate the evolution of the magnetic properties in EuCuAs 1-x P x single crystals with 0.16 ≤ x ≤ 0.75. Crystals grown by cooling slowly in a Sn flux possessed macroscale inhomogeneity of As/P, particularly for arsenic-rich crystals. However, growth in a Sn flux via an isothermal dwell at 600 °C produced crystals that were homogeneous within the resolution of the probes utilized to investigate these crystals. The unit cell volumes, Curie-Weiss temperatures, and magnetic transitions trend linearly with composition and the magnetic anisotropy is reduced in the alloys. The magnetization data of crystals with x = 0.16 and 0.24 indicate an easy-plane antiferromagnetic ground state while ferromagneticlike behavior is observed for crystals with x ≥ 0.41. The temperature-dependent magnetization data possess multiple transitions for compositions near EuCuAs 0.75 P 0.25 , revealing a competition of ground states in this arsenic-rich region of the phase diagram. Neutron diffraction data for EuCuP are also presented as a follow up to previous results that revealed a two-step transition at T C ; the observed data were consistent with ferromagnetic order at T = 5K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Intricate Magnetic Landscape in Antiferromagnetic Kagome Metal TbTi 3 Bi 4 and Interplay with Ln 2– x Ti 6+ x Bi 9 (Ln: Tb···Lu) Shurikagome Metals

Here we present the discovery and characterization of the kagome metal TbTi 3 Bi 4 in tandem with a new series of compounds, the Ln 2–x Ti 6+x Bi 9 (Ln: Tb–Lu) shurikagome metals. We previously reported on the growth of the LnTi 3 Bi 4 (Ln: La–Gd 3+ , Eu 2+ , Yb 2+ ) family, a chemically diverse and exfoliable series of kagome metals with complex and highly anisotropic magnetism. However, unlike the La–Gd analogs, TbTi 3 Bi 4 cannot be synthesized by our previous methodology due to phase competition with crystals of Ln 2–x Ti 6+x Bi 9 (x ~ 1.7–1.2). Here we discuss the phase competition between the LnTi 3 Bi 4 and Ln 2–x Ti 6+x Bi 9 families, helping to frame the difficulty in synthesizing LnTi 3 Bi 4 compounds with small Ln species and providing a strategy to circumvent the formation of Ln 2–x Ti 6+x Bi 9 . Detailed characterization of the magnetic and electronic transport properties on single crystals of TbTi 3 Bi 4 reveals a highly complex landscape of magnetic phases arising from an antiferromagnetic ground state. A series of metamagnetic transitions creates at least 5 unique magnetic phase pockets, including a 1/3 and 2/3 magnetization plateau. Further, the system exhibits an intimate connection between the magnetism and magnetotransport, exhibiting sharp switching from positive (+40%) to negative magnetoresistance (–50%). Like the LnTi 3 Bi 4 kagome metals, the Ln 2–x Ti 6+x Bi 9 family exhibits quasi-2D networks of titanium and chains of rare earth. Finally, we present the structures and some basic magnetic properties of the Ln 2–x Ti 6+x Bi 9 family alongside our characterization of the newly discovered TbTi 3 Bi 4 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Efficient Optical Control of Magnon Dynamics in van der Waals Ferromagnets

Optical control of magnons in two-dimensional (2D) materials promises new functionalities for spintronics and magnonics in atomically thin devices. Here, we report control of magnon dynamics, using laser polarization, in a ferromagnetic van der Waals (vdW) material, Fe 3.6 Co 1.4 GeTe 2 . The magnon amplitude, frequency, and lifetime are controlled and monitored by time-resolved pump-probe spectroscopy. We show substantial (over 25%) and continuous modulation of magnon dynamics as a function of incident laser polarization. Our results suggest that the modification of the effective demagnetization field and magnetic anisotropy by the pump laser pulses with different polarizations is due to anisotropic optical absorption. This implies that pump laser pulses modify the local spin environment, which enables the launch of magnons with tunable dynamics. Our first-principles calculations confirm the anisotropic optical absorption of different crystal orientations. Our findings suggest a new route for the development of opto-spintronic or opto-magnonic devices.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Revisiting spin ice physics in the ferromagnetic Ising pyrochlore Pr 2 Sn 2 O 7

Pyrochlore materials are characterized by their hallmark network of corner-sharing rare-earth tetrahedra, which can produce a wide array of complex magnetic ground states. Ferromagnetic Ising pyrochlores often obey the “two-in-two-out” spin ice rules, which can lead to a highly degenerate spin structure. Large moment systems, such as Ho 2 Ti 2 O 7 and Dy 2 Ti 2 O 7 , tend to host a classical spin ice state with low-temperature spin freezing and emergent magnetic monopoles. Systems with smaller effective moments, such as Pr 3+ -based pyrochlores, have been proposed as excellent candidates for hosting a “quantum spin ice” characterized by entanglement and a slew of exotic quasiparticle excitations. However, experimental evidence for a quantum spin ice state has remained elusive. Here, in this work, we show that the low-temperature magnetic properties of Pr 2 Sn 2 O 7 satisfy several important criteria for continued consideration as a quantum spin ice. We find that Pr 2 Sn 2 O 7 exhibits two distinct spin-correlation time scales of τ ≥ 10 –4 and ~10 –10 s in the spin ice regime. Our comprehensive bulk characterization and neutron scattering measurements enable us to map out the magnetic field-temperature phase diagram, producing results consistent with expectations for a ferromagnetic Ising pyrochlore. We identify key hallmarks of spin ice physics and show that the application of small magnetic fields (μ 0 H c ~0.5 T) suppresses the spin ice state and induces a field-polarized, ordered spin-ice phase. Together, our work clarifies the current state of Pr 2 Sn 2 O 7 and encourages future studies aimed at exploring the potential for a quantum spin ice ground state in this system.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Quantum magnetism in the frustrated square lattice oxyhalides YbBi 2 IO 4 and YbBi 2 ClO 4

Square-lattice systems offer a direct route for realizing two-dimensional (2D) quantum magnetism with frustration induced by competing interactions. In this work, the square lattice materials YbBi 2 IO 4 and YbBi 2 ClO 4 were investigated using a combination of magnetization and specific-heat measurements on polycrystalline samples. Specific-heat measurements provide evidence for long-range magnetic order below $T$ N = 0.21 K (0.25 K) for YbBi 2 IO 4 (YbBi 2 ClO 4 ). On the other hand, a rather broad maximum is found in the temperature-dependent magnetic susceptibility, located at $T$ max = 0.33 K (0.38 K) in YbBi 2 IO 4 (YbBi 2 ClO 4 ), consistent with the quasi-2D magnetism expected for the large separation between the magnetic layers. Estimation of the magnetic entropy supports the expected Kramers' doublet ground state for Yb 3+ and the observed paramagnetic behavior is consistent with a well-isolated doublet. Roughly two-thirds of the entropy is consumed above $T$ N , due to a combination of the quasi-2D behavior and magnetic frustration. The impact of frustration is examined from the viewpoint of a simplified $J$ 1 -$J$ 2 square lattice model, which is frustrated for antiferromagnetic interactions. Specifically, a high-temperature series expansion analysis of the temperature-dependent specific-heat and magnetization data yields $J$ 2 /$J$ 1 = 0.30 (=0.23) for YbBi 2 IO 4 (YbBi 2 ClO 4 ). In conclusion, this simplified analysis suggests strong frustration that should promote significant quantum fluctuations in these compounds, and thus motivates future work on the static and dynamic magnetic properties of these materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Two-dimensional heavy fermions in the van der Waals metal CeSiI

Heavy-fermion metals are prototype systems for observing emergent quantum phases driven by electronic interactions. A long-standing aspiration is the dimensional reduction of these materials to exert control over their quantum phases, which remains a significant challenge because traditional intermetallic heavy-fermion compounds have three-dimensional atomic and electronic structures. Here we report comprehensive thermodynamic and spectroscopic evidence of an antiferromagnetically ordered heavy-fermion ground state in CeSiI, an intermetallic comprising two-dimensional (2D) metallic sheets held together by weak interlayer van der Waals (vdW) interactions. Owing to its vdW nature, CeSiI has a quasi-2D electronic structure, and we can control its physical dimension through exfoliation. The emergence of coherent hybridization of f and conduction electrons at low temperature is supported by the temperature evolution of angle-resolved photoemission and scanning tunnelling spectra near the Fermi level and by heat capacity measurements. Electrical transport measurements on few-layer fakes reveal heavy-fermion behaviour and magnetic order down to the ultra-thin regime. Importantly, our work establishes CeSiI and related materials as a unique platform for studying dimensionally confined heavy fermions in bulk crystals and employing 2D device fabrication techniques and vdW heterostructures to manipulate the interplay between Kondo screening, magnetic order and proximity effects.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Stacking disorder and thermal transport properties of α-RuCl 3

α-RuCl 3 , a well-known candidate material for Kitaev quantum spin liquid, is prone to stacking disorder due to the weak van der Waals bonding between the honeycomb layers. After a decade of intensive experimental and theoretical studies, the detailed correlation between stacking degree of freedom, structure transition, magnetic, and thermal transport properties remains unresolved. In this work, we reveal the effects of a small amount of stacking disorder inherent even in high quality α-RuCl 3 crystals. This small amount of stacking disorder results in the variation of the magnetic ordering temperature, and it suppresses the structure transition and thermal conductivity. Crystals with a minimal amount of stacking disorder have a T N > 7.4 K and exhibit a well-defined structure transition around 140 K upon cooling. For those with more stacking faults and a T N below 7 K, the structure transition occurs well below 140 K upon cooling and is incomplete, manifested by the diffuse streaks and the coexistence of both high-temperature and low-temperature phases down to the lowest measurement temperature. Both types of crystals exhibit oscillatory field-dependent thermal conductivity and a plateaulike feature in thermal Hall resistivity in the field-induced quantum spin liquid state. However, α-RuCl 3 crystals with a minimal amount of stacking disorder have a higher thermal conductivity that pushes the thermal Hall conductivity to be closer to the half-integer quantized value. Importantly, these findings demonstrate a strong correlation between layer stacking, structure transition, magnetic, and thermal transport properties, underscoring the importance of interlayer coupling in α-RuCl3 despite the weak van der Waals bonding.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Evolution of Highly Anisotropic Magnetism in the Titanium-Based Kagome Metals LnTi 3 Bi 4 (Ln: La···Gd 3+ , Eu 2+ , Yb 2+ )

Here, we present a family of titanium-based kagome metals of the form LnTi 3 Bi 4 (Ln: La···Gd 3+ , Eu 2+ , Yb 2+ ). Four previously unreported compounds are presented: YbTi 3 Bi 4 , GdTi 3 Bi 4 , NdTi 3 Bi 4 , and PrTi 3 Bi 4 . Single-crystal growth methods are provided alongside detailed magnetic and thermodynamic measurements across the entire series. The LnTi 3 Bi 4 family of compounds are orthorhombic (Fmmm), layered compounds that exhibit slightly distorted titanium-based kagome nets interwoven with zigzag lanthanide-based (Ln) chains. Crystals are easily exfoliated parallel to the kagome sheets, and angular resolved photoemission (ARPES) measurements highlight the intricacy of the electronic structure in these compounds. Density functional theory (DFT) and ARPES studies find Dirac points near the Fermi level, consistent with the kagome-derived band structure. The magnetic properties and the associated anisotropy emerge from the quasi-1D zigzag chains of Ln and impart a wide array of magnetic ground states ranging from anisotropic ferromagnetism to complex antiferromagnetism with a cascade of metamagnetic transitions. In conclusion, the combination of the kagome-based electronic structure and highly anisotropic Ln-based magnetism on an exfoliatable platform cements the LnTi 3 Bi 4 family as an interesting addition to the ever-expanding suite of kagome metals.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Sample-dependent and sample-independent thermal transport properties of α – RuCl 3

In this study, we investigated the thermal transport properties of two α–RuCl 3 crystals with different degrees of stacking disorder to understand the origin of the previously reported oscillatory feature in the field dependence of thermal conductivity. Crystal I shows only one magnetic order around 13 K, which is near the highest T N for α–RuCl 3 with stacking faults. Crystal II has less stacking disorder, with a dominant heat capacity at 7.6 K along with weak anomalies at 10 and 13 K. In the temperature and field dependence of thermal conductivity, no obvious anomaly was observed to be associated with the magnetic order around 13 K for either crystal or around 10 K for crystal II. Crystal II showed clear oscillations in the field dependence of thermal conductivity, while crystal I did not. For crystal I, an L-shaped region in the temperature-field space was observed where thermal Hall conductivity κ xy /T is within ±20% of the half quantized thermal Hall conductivity κ HQ /T, while for crystal II, κ xy /T reaches κ HQ /T only in the high field and high temperature regime with no indication of a plateau at κ HQ /T. Our thermal conductivity data suggest the oscillatory features are inherent to the zigzag ordered phase with T N near 7 K. Our planar thermal Hall effect measurements suggest the sensitivity of this phenomena to stacking disorder. Overall, our results highlight the importance of understanding and controlling crystallographic disorder for obtaining and interpreting intrinsic thermal transport properties in α–RuCl 3 .

36 MATERIALS SCIENCE↗

DOE OSTI2023

Nonthermal Bonding Origin of a Novel Photoexcited Lattice Instability in SnSe

Lattice dynamics measurements are often crucial tools for understanding how materials transform between different structures. Here, we report time-resolved x-ray scattering-based measurements of the nonequilibrium lattice dynamics in SnSe, a monochalcogenide reported to host a novel photoinduced lattice instability. By fitting interatomic force models to the fluence dependent excited-state dispersion, we determine the nonthermal origin of the lattice instability to be dominated by changes of interatomic interactions along a bilayer-connecting bond, rather than of an intralayer bonding network that is of primary importance to the lattice instability in thermal equilibrium.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Exchange Bias Between van der Waals Materials: Tilted Magnetic States and Field-Free Spin–Orbit-Torque Switching

Magnetic van der Waals heterostructures provide a unique platform to study magnetism and spintronics device concepts in the 2D limit. Here, studies of exchange bias from the van der Waals antiferromagnet CrSBr acting on the van der Waals ferromagnet Fe3GeTe2 (FGT) are reported. Additionally, the orientation of the exchange bias is along the in-plane easy axis of CrSBr, perpendicular to the out-of-plane anisotropy of the FGT, inducing a strongly tilted magnetic configuration in the FGT. Furthermore, the in-plane exchange bias provides sufficient symmetry breaking to allow deterministic spin–orbit torque switching of the FGT in CrSBr/FGT/Pt samples at zero applied magnetic field. A minimum thickness of the CrSBr of >10 nm is needed to provide a non-zero exchange bias at 30 K.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Electronic and Thermal Properties of the Cation Substitution-Derived Quaternary Chalcogenide CuInSnSe 4

Quaternary chalcogenides continue to be of interest for a variety of technological applications, with physical properties stemming from their structural complexity and stoichiometric variation. In certain structure types, partial vacancies on specific lattice positions present an opportunity to investigate electrical and thermal properties in light of these lattice defects. In this work, we investigated the structural, thermal, and electronic properties of CuInSnSe 4 , a material that belongs to a relatively unexplored class of quaternary chalcogenides with a defect adamantine crystal structure. First-principles calculations together with experimental measurements revealed a chalcopyrite-like structure with inherent vacancies and characteristic s–p and p–d orbital hybridizations in the electronic structure of the material. Cation disorder and lattice anharmonicity result in very low thermal conductivity with values significantly lower than those for related compositions. In conclusion, this work reveals the fundamental physical properties of a previously uninvestigated quaternary chalcogenide and may aid investigations of similar as well as other quaternary chalcogenide compositions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗