Charge transfer enhanced magnetic correlations in type-II multiferroic Co3TeO6.

Magnetic structure of the Co ions in monoclinic Co3TeO6 in the antiferroelectric state at 16 K has been determined by neutron powder together with single-crystal diffractions. The indices of the magnetic reflections that appear at the incommensurate positions were determined by diffractions from a single crystal, which allow to uniquely identify the magnetic modulation vector. There are two crystallographically distinct Co layers. Magnetic incommensurability appears in the Co spins in the layers comprising zig-zag chains, with a magnetic modulation vector of (0.357, 0.103, 0.121) at 3 K but changes to (0.4439, 0, 0.137) at 16 K, while the Co ions in the honeycomb webs form a collinear antiferromagnetic structure. Thermal reduction rate of the Co moments in the honeycomb webs was found to be much smaller than those in the zigzag chains. Shifting of large amounts of electronic charge into the Co─O bonds in the honeycomb webs on warming is used to understand the behavior.

Enhanced lattice perfection by low temperature thermal annealing in photoelectric (CH3NH3)PbBr3.

The coupling between the organic CH3NH3+ cations and inorganic perovskite PbBr3- framework in a large single crystal of (CH3NH3)PbBr3 weighting 13 g was studied using neutron diffraction and inelastic neutron scattering. Two lattice incommensurate (ICM) phases were found, one at higher temperatures, marked ICMHT, which appeared between 147 and 135 K. The second one, marked ICMLT, developed below 143 K and remained at 75 K. The transition from the ICMLT to ICMHT phase upon warming gave rise to extremely large lattice shrinking, followed by extremely large lattice expansion of the tetragonal basal plane of the PbBr3 lattice. There was a progressive decrease in the width of the Bragg peaks from the PbBr3 lattice upon warming, which can be described using a critical exponent for each type of Bragg peak to show complete ordering of the atoms into a (CH3NH3)PbBr3 lattice at 194 K. (CH3NH3)PbBr3 exhibits six definitive acoustic-like phonon branches at 75 K. The six branches renormalizes into two at 200 K, with the frequencies of both the transverse and longitudinal modes greatly enhanced. The asymmetric structure of the CH3NH3 ions helps to understand the observed behaviors.

Isotropic Nature of the Metallic Kagome Ferromagnet Fe3Sn2 at High Temperatures.

Anisotropy and competing exchange interactions have emerged as two central ingredients needed for centrosymmetric materials to exhibit topological spin textures. Fe3Sn2 is thought to have these ingredients as well, as it has recently been discovered to host room temperature skyrmionic bubbles with an accompanying topological Hall effect. We present small-angle inelastic neutron scattering measurements that unambiguously show that Fe3Sn2 is an isotropic ferromagnet below TC≈660 K to at least 480 K - the lower temperature threshold of our experimental configuration. Fe3Sn2 is known to have competing magnetic exchange interactions, correlated electron behavior, weak magnetocrystalline anisotropy, and lattice anisotropy; all of these features are thought to play a role in stabilizing skyrmions in centrosymmetric systems. Our results reveal that at elevated temperatures, there is an absence of magnetocrystalline anisotropy and that the system behaves as a typical exchange ferromagnet with a spin stiffness DT=0 K=271±9 meV Å2.

Competing magnetic phases and fluctuation-driven scalar spin chirality in the kagome metal YMn6Sn6.

Identification, understanding, and manipulation of novel magnetic textures are essential for the discovery of new quantum materials for future spin-based electronic devices. In particular, materials that manifest a large response to external stimuli such as a magnetic field are subject to intense investigation. Here, we study the kagome-net magnet YMn6Sn6 by magnetometry, transport, and neutron diffraction measurements combined with first-principles calculations. We identify a number of nontrivial magnetic phases, explain their microscopic nature, and demonstrate that one of them hosts a large topological Hall effect (THE). We propose a previously unidentified fluctuation-driven mechanism, which leads to the THE at elevated temperatures. This interesting physics comes from parametrically frustrated interplanar exchange interactions that trigger strong magnetic fluctuations. Our results pave a path to chiral spin textures, promising for novel spintronics.

Materializing rival ground states in the barlowite family of kagome magnets: quantum spin liquid, spin ordered, and valence bond crystal states.

The spin- 1 2 kagome antiferromagnet is considered an ideal host for a quantum spin liquid (QSL) ground state. We find that when the bonds of the kagome lattice are modulated with a periodic pattern, new quantum ground states emerge. Newly synthesized crystalline barlowite (Cu4(OH)6FBr) and Zn-substituted barlowite demonstrate the delicate interplay between singlet states and spin order on the spin- 1 2 kagome lattice. Comprehensive structural measurements demonstrate that our new variant of barlowite maintains hexagonal symmetry at low temperatures with an arrangement of distorted and undistorted kagome triangles, for which numerical simulations predict a pinwheel valence bond crystal (VBC) state instead of a QSL. The presence of interlayer spins eventually leads to an interesting pinwheel q = 0 magnetic order. Partially Zn-substituted barlowite (Cu3.44Zn0.56(OH)6FBr) has an ideal kagome lattice and shows QSL behavior, indicating a surprising robustness of the QSL against interlayer impurities. The magnetic susceptibility is similar to that of herbertsmithite, even though the Cu2+ impurities are above the percolation threshold for the interlayer lattice and they couple more strongly to the nearest kagome moment. This system is a unique playground displaying QSL, VBC, and spin order, furthering our understanding of these highly competitive quantum states.

Topological Singularity Induced Chiral Kohn Anomaly in a Weyl Semimetal.

The electron-phonon interaction (EPI) is instrumental in a wide variety of phenomena in solid-state physics, such as electrical resistivity in metals, carrier mobility, optical transition, and polaron effects in semiconductors, lifetime of hot carriers, transition temperature in BCS superconductors, and even spin relaxation in diamond nitrogen-vacancy centers for quantum information processing. However, due to the weak EPI strength, most phenomena have focused on electronic properties rather than on phonon properties. One prominent exception is the Kohn anomaly, where phonon softening can emerge when the phonon wave vector nests the Fermi surface of metals. Here we report a new class of Kohn anomaly in a topological Weyl semimetal (WSM), predicted by field-theoretical calculations, and experimentally observed through inelastic x-ray and neutron scattering on WSM tantalum phosphide. Compared to the conventional Kohn anomaly, the Fermi surface in a WSM exhibits multiple topological singularities of Weyl nodes, leading to a distinct nesting condition with chiral selection, a power-law divergence, and non-negligible dynamical effects. Our work brings the concept of the Kohn anomaly into WSMs and sheds light on elucidating the EPI mechanism in emergent topological materials.

Three-dimensional magnetism and the Dzyaloshinskii-Moriya interaction in S = 3/2 kagome staircase Co3V2O8.

Time-of-flight neutron data reveal spin waves in the ferromagnetic ground state of the kagome staircase material Co3V2O8. While previous work has treated this material as quasi-two-dimensional, we find that an inherently three-dimensional description is needed to describe the spin wave spectrum throughout reciprocal space. Moreover, spin wave branches show gaps that point to an unexpectedly large Dzyaloshinskii-Moriya interaction on the nearest-neighbor bond, with D 1 ≥ J 1/2. A better understanding of the Dzyaloshinskii-Moriya interaction in this material should shed light on the multiferroicity of the related Ni3V2O8. At a higher temperature where Co3V2O8 displays an antiferromagnetic spin density wave structure, there are no well-defined spin wave excitations, with most of the spectral weight observed in broad diffuse scattering centered at the (0, 0.5, 0) antiferromagnetic Bragg peak.

Structural, magnetic, and electronic evolution of the spin-ladder system BaFe2S3-x Se x with isoelectronic substitution.

We report experimental studies of a series of BaFe2S3-x Se x (0 ⩽ x ⩽ 3) single crystals and powder specimens using x-ray diffraction, neutron-diffraction, muon-spin-relaxation, and electrical transport measurements. A structural transformation from Cmcm (BaFe2S3) to Pnma (BaFe2Se3) was identified around x = 0.7 - 1. Neutron-diffraction measurements on the samples with x = 0.2, 0.4, and 0.7 reveal that the Néel temperature of the stripe antiferromagnetic order is gradually suppressed from ~120 to 85 K, while the magnitude of the ordered Fe2+ moments shows very little variation. Similarly, the block antiferromagnetic order in BaFe2Se3 remains robust for 1.5 ⩽ x ⩽ 3 with negligible variation in the ordered moment and a slight decrease of the Néel temperature from 250 K (x = 3) to 225 K (x = 1.5). The sample with x = 1 near the Cmcm and Pnma border shows coexisting, two-dimensional, short-range stripe- and block-type antiferromagnetic correlations. The system remains insulating for all x, but the thermal activation gap shows an abrupt increase when traversing the boundary from the Cmcm stripe phase to the Pnma block phase. The results demonstrate that the crystal structure, magnetic order, and electronic properties are strongly coupled in the BaFe2S3-x Se x system.

Long-range magnetic order in hydroxide-layer-doped (Li1-x-y Fe x Mn y OD)FeSe.

The (Li1-x Fe x OH)FeSe superconductor has been suspected of exhibiting long-range magnetic ordering due to Fe substitution in the LiOH layer. However, no direct observation such as magnetic reflection from neutron diffraction has been reported. Here, we use a chemical design strategy to manipulate the doping level of transition metals in the LiOH layer to tune the magnetic properties of the (Li1-x-y Fe x Mn y OD)FeSe system. We find Mn doping exclusively replaces Li in the hydroxide layer resulting in enhanced magnetization in the (Li0.876Fe0.062Mn0.062OD)FeSe superconductor without significantly altering the superconducting behavior as resolved by magnetic susceptibility and electrical/thermal transport measurements. As a result, long-range magnetic ordering was observed below 12 K with neutron diffraction measurements. This work has implications for the design of magnetic superconductors for the fundamental understanding of superconductivity and magnetism in the iron chalcogenide system as well as exploitation as functional materials for next-generation devices.

Correlating magnetic structure and magnetotransport in semimetal thin films of Eu1-x Sm x TiO3.

We report on the evolution of the average and depth-dependent magnetic order in thin-film samples of biaxially stressed and electron-doped EuTiO3 for samples across a doping range < 0.1 to 7.8 × 1020 cm-3. Under an applied in-plane magnetic field, the G-type antiferromagnetic ground state undergoes a continuous spin-flop phase transition into in-plane, field-polarized ferromagnetism. The critical field for ferromagnetism slightly decreases with an increasing number of free carriers, yet the field evolution of the spin-flop transition is qualitatively similar across the doping range. Unexpectedly, we observe interfacial ferromagnetism with saturated Eu2+ moments at the substrate interface at low fields preceding ferromagnetic saturation throughout the bulk of the degenerate semiconductor film. We discuss the implications of these findings for the unusual magnetotransport properties of this compound.

Observation of a C-type short-range antiferromagnetic order in layer spacing expanded FeS.

We report neutron diffraction studies of FeS single crystals obtained from Rb x Fe2-y S2 single crystals via a hydrothermal method. While no 5 × 5 iron vacancy order or block antiferromagnetic order typical of Rb x Fe2-y S2 is found in our samples, we observe C-type short-range antiferromagnetic order with moments pointed along the c axis hosted by a different phase of FeS with an expanded interlayer spacing. The Néel temperature for this magnetic order is determined to be 170 ± 4 K. Our finding of a variant FeS structure hosting this C-type antiferromagnetic order demonstrates that the known FeS phase synthesized in this method is in the vicinity of a magnetically ordered ground state, providing insights into understanding a variety of phenomena observed in FeS and the related FeSe1-x S x iron chalcogenide system.

Sixfold enhancement of superconductivity in a tunable electronic nematic system.

The electronic nematic phase-in which electronic degrees of freedom lower the crystal rotational symmetry-is commonly observed in high-temperature superconductors. However, understanding the role of nematicity and nematic fluctuations in Cooper pairing is often made more complicated by the coexistence of other orders, particularly long-range magnetic order. Here we report the enhancement of superconductivity in a model electronic nematic system that is not magnetic, and show that the enhancement is directly born out of strong nematic fluctuations associated with a quantum phase transition. We present measurements of the resistance as a function of strain in Ba1-x Sr x Ni2As2 to show that strontium substitution promotes an electronically driven nematic order in this system. In addition, the complete suppression of that order to absolute zero temperature leads to an enhancement of the pairing strength, as evidenced by a sixfold increase in the superconducting transition temperature. The direct relation between enhanced pairing and nematic fluctuations in this model system, as well as the interplay with a unidirectional charge-density-wave order comparable to that found in the cuprates, offers a means to investigate the role of nematicity in strengthening superconductivity.

Magnetic order and competition with superconductivity in (Ho-Er)Ni2B2C.

The rare earth magnetic order in pure and doped Ho(1-x)ErxNi2B2C (x = 0, 0.25, 0.50, 0.75, 1) single crystal samples was investigated using magnetization and neutron diffraction measurements. Superconducting quaternary borocarbides, RNi2B2C where R = Ho, Er , are magnetic intermetallic superconductors with the transition temperatures~10 K in which long range magnetic order develops in the same temperature range and competes with superconductivity. Depending on the rare earth composition the coupling between superconductivity and magnetism creates several phases, ranging from a near reentrant superconductor with a mixture of commensurate and incommensurate antiferromagnetism to an incommensurate antiferromagnetic spin modulation with a weak ferromagnetic component. All of these phases coexist with superconductivity. RKKY magnetic interactions are used to describe the magnetic orders in the pure compounds. However, the doping of Er on Ho sites which have two strong magnetic moments with two different easy directions creates new and complicated magnetic modulations with possible local disorder effects. One fascinating effect is the development of an induced magnetic state resembling the pure and doped R2CuO4 cuprate with R = Nd and Pr.

Absence of magnetic ordering in the spin liquid candidate Ca3Cu2GeV2O12.

Typically, quantum spin liquid candidates can be found in materials with a combination of geometrical frustration along with low spin. Due to its spin of S = 1/2 the copper (II) ion is often present in the discussion on spin liquid candidates. The solid state compound Ca3Cu2GeV2O12 is a material that crystallizes in the garnet structure (s.g. #230, Ia-3d), where 3D frustration is known to occur. Heat capacity has shown a lack of magnetic ordering down to 0.35 K, confirmed with low temperature neutron diffraction to 0.07 K. This system displays a Weiss temperature of -0.93(1) K indicating net antiferromagnetic interactions and significant J 1-J 2 competition causing frustration. Using both neutron and x-ray diffraction along with heat capacity and magnetometry, the work presented here shows Ca3Cu2GeV2O12 has potential as a new spin liquid candidate.

Spin correlations of quantum spin liquid and quadrupole-ordered states of Tb2+x Ti2-x O7+y.

Spin correlations of the frustrated pyrochlore oxide Tb2+x Ti2-x O7+y have been investigated by using inelastic neutron scattering on single-crystalline samples (x = -0.007, 0.000, and 0.003), which have the putative quantum-spin-liquid (QSL) or electric-quadrupolar ground states. Spin correlations, which are notably observed in nominally elastic scattering, show short-range correlations around L points [ q = ( 1 2 , 1 2 , 1 2 ) ] , tiny antiferromagnetic Bragg scattering at L and Γ points, and pinch-point-type structures around Γ points. The short-range spin correlations were analyzed using a random-phase approximation (RPA) assuming the paramagnetic state and two-spin interactions among Ising spins. These analyses have shown that the RPA scattering intensity well reproduces the experimental data using temperature- and x-dependent coupling constants of up to tenth-neighbor site pairs. This suggests that no symmetry breaking occurs in the QSL sample and that a quantum treatment beyond the semiclassical RPA approach is required. Implications of the experimental data and the RPA analyses are discussed.

Tunable multiferroic order parameters in Sr1- x Ba x Mn1- y Ti y O3.

Responding to the rapidly increasing demand for efficient energy usage and increased speed and functionality of electronic and spintronic devices, multiferroic oxides have recently emerged as key materials capable of tackling this multifaceted challenge. In this paper, we describe the development of single-site manganese-based multiferroic perovskite materials with modest amounts of nonmagnetic Ti substituted at the magnetic Mn site in Sr1- x Ba x Mn1- y Ti y O3 (SBMTO). Significantly enhanced properties were achieved with ferroelectric-type structural transition temperatures boosted to ∼430K. Ferroelectric distortions with large spontaneous polarization values of ∼30µC/cm2, derived from a point charge model, are similar in magnitude to those of the prototypical nonmagnetic BaTiO3. Temperature dependence of the system's properties was investigated by synchrotron x-ray powder diffraction and neutron powder diffraction at ambient and high pressures. Various relationships were determined between the structural and magnetic properties, Ba and Ti contents, and T N and T C. Most importantly, our results demonstrate the large coupling between the magnetic and ferroelectric order parameters and the wide tunability of this coupling by slight variations of the material's stoichiometry.

Amplitude mode in the planar triangular antiferromagnet Na0.9MnO2.

Amplitude modes arising from symmetry breaking in materials are of broad interest in condensed matter physics. These modes reflect an oscillation in the amplitude of a complex order parameter, yet are typically unstable and decay into oscillations of the order parameter's phase. This renders stable amplitude modes rare, and exotic effects in quantum antiferromagnets have historically provided a realm for their detection. Here we report an alternate route to realizing amplitude modes in magnetic materials by demonstrating that an antiferromagnet on a two-dimensional anisotropic triangular lattice (α-Na0.9MnO2) exhibits a long-lived, coherent oscillation of its staggered magnetization field. Our results show that geometric frustration of Heisenberg spins with uniaxial single-ion anisotropy can renormalize the interactions of a dense two-dimensional network of moments into largely decoupled, one-dimensional chains that manifest a longitudinally polarized-bound state. This bound state is driven by the Ising-like anisotropy inherent to the Mn3+ ions of this compound.

Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials.

Layered sodium transition metal oxides of NaTMO2 (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO2. Here, a novel spontaneous TM layer rippling in the sodium ion battery cathode materials is reported, revealed by in situ X-ray diffraction, Cs-corrected scanning transmission electron microscopy, and density functional theory simulation, where the softening and distortion of FeO6 octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.

Complex magnetic incommensurability and electronic charge transfer through the ferroelectric transition in multiferroic Co3TeO6.

Polarized and unpolarized neutron diffractions have been carried out to investigate the nature of the magnetic structures and transitions in monoclinic Co3TeO6. As the temperature is lowered below 26 K long range order develops, which is fully incommensurate (ICM) in all three crystallographic directions. Below 19.5 K additional commensurate magnetic peaks develop, consistent with the Γ4 irreducible representation, along with a splitting of the ICM peaks along the h direction which indicates that there are two separate sets of magnetic modulation vectors. Below 18 K, this small additional magnetic incommensurability disappears, ferroelectricity develops, an additional commensurate magnetic structure consistent with Γ3 irreducible representation appears, and the k component of the ICM wave vector disappears. Synchrotron x-ray diffraction measurements demonstrate that there is a significant shift of the electronic charge distribution from the Te ions at the crystallographic 8 f sites to the neighboring Co and O ions. These results, together with the unusually small electric polarization, its strong magnetic field dependence, and the negative thermal expansion in all three lattice parameters, suggest this material is an antiferroelectric. Below15 K the k component of the ICM structure reappears, along with second-order ICM Bragg peaks, which polarized neutron data demonstrate are magnetic in origin.

Giant electromechanical coupling of relaxor ferroelectrics controlled by polar nanoregion vibrations.

Relaxor-based ferroelectrics are prized for their giant electromechanical coupling and have revolutionized sensor and ultrasound applications. A long-standing challenge for piezoelectric materials has been to understand how these ultrahigh electromechanical responses occur when the polar atomic displacements underlying the response are partially broken into polar nanoregions (PNRs) in relaxor-based ferroelectrics. Given the complex inhomogeneous nanostructure of these materials, it has generally been assumed that this enhanced response must involve complicated interactions. By using neutron scattering measurements of lattice dynamics and local structure, we show that the vibrational modes of the PNRs enable giant coupling by softening the underlying macrodomain polarization rotations in relaxor-based ferroelectric PMN-xPT {(1 - x)[Pb(Mg1/3Nb2/3)O3] - xPbTiO3} (x = 30%). The mechanism involves the collective motion of the PNRs with transverse acoustic phonons and results in two hybrid modes, one softer and one stiffer than the bare acoustic phonon. The softer mode is the origin of macroscopic shear softening. Furthermore, a PNR mode and a component of the local structure align in an electric field; this further enhances shear softening, revealing a way to tune the ultrahigh piezoelectric response by engineering elastic shear softening.