SearcharxivSearch

arXiv subjects

Robert J. Green

Publications and source records attributed to Robert J. Green.

At least 19 recordsLinked to original sources

Disentangling the contributions of individual cations to magnetic order in a spinel high entropy oxide

High entropy oxides (HEOs) can possess long-range ordered magnetic states despite their extreme chemical disorder. Very little is known about how the different chemical constituents in HEOs contribute to the emergence of these magnetic states. In this work, we leverage element-specific magnetometry attained via x-ray magnetic circular dichroism (XMCD) to understand how magnetic order is driven in two ferrimagnetic spinel-structured HEOs with compositions (Cr,Mn,Fe,Co,Ni)$_3$O$_4$ and (Cr,Mn,Fe,Co,Ni)$_{2.4}$Ga$_{0.6}$O$_4$. We find that while the magnetic transition is simultaneous for all chemical species, the rate at which their magnetic moments grow is strongly cation dependent. This behavior is explained by the varying $\textit{3d}$ crystal field level fillings of the magnetic cations, which in turn determine their ability to participate in the different magnetic exchange pathways available in the spinel structure. Dominant $A$-$B$ sublattice exchange enables some species to harden rapidly ($\textit{e.g.}$ tetrahedral Fe$^{3+}$ and octahedral Ni$^{2+}$) while others exhibit a sluggish transition due to frustration from competing interactions ($\textit{e.g.}$ octahedral Fe$^{3+}$ and Cr$^{3+}$). Non-magnetic substitution suppresses these differences, introducing broken magnetic linkages that relieve frustration. Tailoring the magnetism of HEO spinels therefore requires detailed knowledge of both their site selectivities and their exchange pathways.

cond-mat.mtrl-sci

Direct Fabrication of a Superconducting Two-Dimensional Electron Gas on KTaO3(111) via Mg-Induced Surface Reduction

Two-dimensional electron gases (2DEGs) at the surfaces of KTaO3 have become an exciting platform for exploring strong spin-orbit coupling, Rashba physics, and low-carrier-density superconductivity. Yet, a large fraction of reported KTaO3-based 2DEGs has been realized through chemically complex overlayers that both generate carriers and can obscure the native electronic structure, making spectroscopic access to the underlying 2DEG challenging. Here, we demonstrate a simple and direct method to generate a superconducting 2DEG on KTaO3(111) using Mg-induced surface reduction in molecular-beam epitaxy (MBE). Mg has an extremely low sticking coefficient at elevated temperatures, enabling the formation of an ultrathin (less than 1-2 monolayers) MgO layer that is transparent to soft x-ray photoemission spectroscopy (XPS) and angle-resolved photoemission spectroscopy (ARPES). This allows direct measurement of the surface chemistry and low-energy electronic structure of the pristine reduced surface without the need for a several-nanometer-thick capping layer. XPS shows clear reduction of Ta5+ to lower oxidation states, while ARPES reveals a parabolic Ta 5d conduction band with an approximately 150 meV bandwidth and additional subband features arising from quantum confinement. Transport measurements confirm a superconducting transition below 0.7 K. Together, these results demonstrate a chemically straightforward and controllable pathway for fabricating spectroscopically accessible superconducting 2DEGs on KTaO3(111), and provide a powerful new platform for investigating the mechanisms underlying orientation-dependent superconductivity in KTaO3-based oxide interfaces.

cond-mat.supr-con

Biaxial Strain Control of Helimagnetism via Chemical Expansion in Thin Film SrFeO3

We demonstrate control of helimagnetic order in biaxially strained SrFeO3 thin films using neutron diffraction and resonant soft x-ray scattering. SrFeO3, a negative charge-transfer oxide, exhibits a complex magnetic phase diagram that includes multi-q spin structures. Tensile epitaxial strain produces a pronounced shortening of the helimagnetic ordering length and a tilting of the magnetic ordering vector. We interpret this behavior in terms of chemical expansion: lattice dilation under tensile strain lowers the energetic cost of oxygen vacancies, leading to an expanded unit cell that modifies Fe-O hybridization and enhances superexchange relative to double exchange. These results reveal how epitaxial strain can indirectly tune helimagnetism through defect-driven chemical expansion, highlighting the strong coupling between lattice, chemistry, and magnetic order in transition-metal oxides. Our findings establish chemical expansion as an effective mechanism for engineering complex magnetic textures in oxide thin films, with implications for spintronic, magnonic, and quantum information applications.

cond-mat.mtrl-sci

Emergence of interfacial magnetism in strongly-correlated nickelate-titanate superlattices

Strongly-correlated transition-metal oxides are widely known for their various exotic phenomena. This is exemplified by rare-earth nickelates such as LaNiO$_{3}$, which possess intimate interconnections between their electronic, spin, and lattice degrees of freedom. Their properties can be further enhanced by pairing them in hybrid heterostructures, which can lead to hidden phases and emergent phenomena. An important example is the LaNiO$_{3}$/LaTiO$_{3}$ superlattice, where an interlayer electron transfer has been observed from LaTiO$_{3}$ into LaNiO$_{3}$ leading to a high-spin state. However, macroscopic emergence of magnetic order associated with this high-spin state has so far not been observed. Here, by using muon spin rotation, x-ray absorption, and resonant inelastic x-ray scattering, we present direct evidence of an emergent antiferromagnetic order with high magnon energy and exchange interactions at the LaNiO$_{3}$/LaTiO$_{3}$ interface. As the magnetism is purely interfacial, a single LaNiO$_{3}$/LaTiO$_{3}$ interface can essentially behave as an atomically thin strongly-correlated quasi-two-dimensional antiferromagnet, potentially allowing its technological utilisation in advanced spintronic devices. Furthermore, its strong quasi-two-dimensional magnetic correlations, orbitally-polarized planar ligand holes, and layered superlattice design make its electronic, magnetic, and lattice configurations resemble the precursor states of superconducting cuprates and nickelates, but with an $S \rightarrow 1$ spin state instead.

cond-mat.str-el

Impact of synthesis method on the structure and function of high entropy oxides

The term sample dependence describes the troublesome tendency of nominally equivalent samples to exhibit different physical properties. High entropy oxides (HEOs) are a class of materials where sample dependence has the potential to be particularly profound due to their inherent chemical complexity. In this work, we prepare a spinel HEO of identical nominal composition by five distinct methods, spanning a range of thermodynamic and kinetic conditions: solid state, high pressure, hydrothermal, molten salt, and combustion syntheses. By structurally characterizing these five samples across all length scales with a variety of x-ray methods, we find that while the average structure is unaltered, the samples vary significantly in their local structures and their microstructures. The most profound differences are observed at intermediate length scales, both in terms of crystallite morphology and cation homogeneity. As revealed by x-ray fluorescence microscopy ideal cation homogeneity is achieved only in the case of combustion synthesis. These structural differences in turn significantly alter the observed functional properties, which we demonstrate via characterization of their magnetic response. While ferrimagnetic order is retained across all five samples, the sharpness of the transition, the size of the saturated moment, and the coercivity all show marked variations with synthesis method. We conclude that the chemical flexibility inherent to HEOs is complemented by strong synthesis method dependence, providing another axis along which to optimize these materials for a wide range of applications.

cond-mat.mtrl-sci

Tetragonal BaCoO$_3$: A Co$^{4+}$ Ferromagnetic Mott Insulator with Inverted Spin Crossover

The interplay between crystal electric field splitting of d states and Hund's rule exchange energy in cobalt-based perovskites offers a promising avenue for inducing spin-state transitions. This study reports a new body-centered tetragonal (BCT) phase of BaCoO$_3$ (BCT-BaCoO$_3$), synthesized under high pressure (15 GPa) and high temperature (1200 °C) conditions. BCT-BaCoO$_3$ adopts a double perovskite structure of EuTiO$_3$-type (space group I4/mcm, #140), confirmed by high-resolution scanning transmission electron microscopy. X-ray photoelectron spectroscopy reveals a rare Co$^{4+}$ valence state. Magnetization and X-ray absorption measurements reveal a low-spin to high-spin transition that takes place between 200 and 300 K. While spin crossovers are relatively common among common oxides, the one observed in BCT-BaCoO$_3$ is remarkable in that it proceeds in the opposite direction from conventional spin transitions. BCT-BaCoO$_3$ exhibits a low-spin (S = 1/2) state at high temperatures and transitions to a high-spin (S = 5/2) state at low temperatures. Within the high-spin state, hard ferromagnetic order onsets at T$_C$ = 107 K. Electrical resistivity indicates weak magnetoresistance and insulating behavior. Overall, BCT-BaCoO$_3$ presents an exceptional model for the exploration of spin-state transitions and the study of Co spin states in cobalt-based perovskites.

cond-mat.mtrl-sci

Negative charge transfer energy in correlated compounds

In correlated compounds containing cations in high formal oxidation states (assigned by assuming that anions attain full valence shells), the energy of ligand to cation charge transfer can become small or even negative. This yields compounds with a high degree of covalence and can lead to a self-doping of holes into the ligand states of the valence band. Such compounds are of particular topical interest, as highly studied perovskite oxides containing trivalent nickel or tetravalent iron are negative charge transfer systems, as are nickel-containing lithium ion battery cathode materials. In this report, we review the topic of negative charge transfer energy, with an emphasis on plots and diagrams as analysis tools, in the spirit of the celebrated Tanabe-Sugano diagrams which are the focus of this Special Topics Issue.

cond-mat.str-el

Signatures of polarized chiral spin disproportionation in rare earth nickelates

In rare earth nickelates (RENiO$_3$), electron-lattice coupling drives a concurrent metal-to-insulator and bond disproportionation phase transition whose microscopic origin has long been the subject of active debate. Of several proposed mechanisms, here we test the hypothesis that pairs of self-doped ligand holes spatially condense to provide local spin moments that are antiferromagnetically coupled to Ni spins. These singlet-like states provide a basis for long-range bond and spiral spin order. Using magnetic resonant X-ray scattering on NdNiO$_3$ thin films, we observe the chiral nature of the spin-disproportionated state, with spin spirals propagating along the crystallographic (101)$_\mathrm{ortho}$ direction. These spin spirals are found to preferentially couple to X-ray helicity, establishing the presence of a hitherto-unobserved macroscopic chirality. The presence of this chiral magnetic configuration suggests a potential multiferroic coupling between the noncollinear magnetic arrangement and improper ferroelectric behavior as observed in prior studies on NdNiO$_3$ (101)$_\mathrm{ortho}$ films and RENiO$_3$ single crystals. Experimentally constrained theoretical double-cluster calculations confirm the presence of an energetically stable spin-disproportionated state with Zhang-Rice singlet-like combinations of Ni and ligand moments.

cond-mat.str-el

Mixed-valence state in the dilute-impurity regime of La-substituted SmB$_6$

Homogeneous mixed-valence (MV) behaviour is one of the most intriguing phenomena of $f$-electron systems. Despite extensive efforts, a fundamental aspect which remains unsettled is the determination of the limiting cases for which MV emerges. Here we address this question for SmB$_6$, a prototypical MV system characterized by two nearly-degenerate Sm$^{2+}$ and Sm$^{3+}$ configurations. By combining angle resolved photoemission spectroscopy (ARPES) and x-ray absorption spectroscopy (XAS), we track the evolution of the mean Sm valence, $v_{Sm}$, in the Sm$_x$La$_{1-x}$B$_6$ series. Upon substitution of Sm ions with trivalent La, we observe a linear decrease of valence fluctuations to an almost complete suppression at $x$$\,$=$\,$0.2, with $v_{Sm}$$\,$$\sim$$\,$2; surprisingly, by further reducing $x$, a re-entrant increase of $v_{Sm}$ develops, approaching the value of $v_{imp}$$\,$$\sim$$\,$2.35 in the dilute-impurity limit. Such observation departs from a monotonic evolution of $v_{Sm}$ across the whole series, as well as from the expectation of its convergence to an integer value for $x$$\,$$\rightarrow$$\,$0. Our ARPES and XAS results, complemented by a phenomenological model, demonstrate an unconventional evolution of the MV character in the Sm$_x$La$_{1-x}$B$_6$ series, paving the way to further theoretical and experimental considerations on the concept of MV itself, and its influence on the macroscopic properties of rare-earth compounds in the dilute-to-intermediate impurity regime.

cond-mat.str-el

Temperature-Dependent Dynamic Disproportionation in LiNiO$_2$

Nickelate materials offer diverse functionalities for energy and computing applications. Lithium nickel oxide (LiNiO$_2$) is an archetypal layered nickelate, but the electronic structure of this correlated material is not yet fully understood. Here we investigate the temperature-dependent speciation and spin dynamics of Ni ions in LiNiO$_2$. Our ab initio simulations predict that Ni ions disproportionate into three states, which dynamically interconvert and whose populations vary with temperature. These predictions are verified using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, and resonant inelastic x-ray scattering at the Ni L$_{3,2}$-edge. Charge-transfer multiplet calculations consistent with disproportionation reproduce all experimental features. Together, our experimental and computational results support a model of dynamic disproportionation that explains diverse physical observations of LiNiO$_2$, including magnetometry, thermally activated electronic conduction, diffractometry, core-level spectroscopies, and the stability of ubiquitous antisite defects. This unified understanding of the fundamental material properties of LiNiO$_2$ is important for applications of nickelate materials as battery cathodes, catalysts, and superconductors.

cond-mat.mtrl-sci

A complementary experimental study of epitaxial La0.67Sr0.33MnO3 to identify morphological and chemical disorder

Gaining insight into the characteristics of epitaxial complex oxide films is essential to control the behavior of devices and catalytic processes. It is known that substrate induced strain, doping, and layer growth can affect the electronic and magnetic properties of the film's bulk. In this study, we demonstrate a clear distinction between the bulk and surface of thin films of La0.67Sr0.33MnO3 in terms of chemical composition, electronic disorder, and surface morphology. We employed a combined experimental approach of X-ray based characterization methods and scanning probe microscopy. X-ray diffraction and resonant X-ray reflectivity revealed surface non-stochiometry in the strontium and lanthanum, as well as an accumulation of oxygen vacancies. Scanning tunneling microscopy showed a staggered growth surface morphology accompanied by an electronic phase separation (EPS) related to this non-stochiometry. The EPS is likely responsible for the temperature-dependent resistivity transition and is a cause of a proposed mixed-phase ferromagnetic and paramagnetic state near room temperature in these thin films.

cond-mat.mtrl-sci

Beyond domain alignment: Revealing the effect of intrinsic magnetic order on electrochemical water splitting

To reach a long term viable green hydrogen economy, rational design of active oxygen evolution reaction (OER) catalysts is critical. An important hurdle in this reaction originates from the fact that the reactants are singlet molecules, whereas the oxygen molecule has a triplet ground state with parallel spin alignment, implying that magnetic order in the catalyst is essential. Accordingly, multiple experimentalists reported a positive effect of external magnetic fields on OER activity of ferromagnetic catalysts. However, it remains a challenge to investigate the influence of the intrinsic magnetic order on catalytic activity. Here, we tuned the intrinsic magnetic order of epitaxial La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ thin film model catalysts from ferro- to paramagnetic by changing the temperature in-situ during water electrolysis. Using this strategy, we show that ferromagnetic ordering below the Curie temperature enhances OER activity. Moreover, we show a slight current density enhancement upon application of an external magnetic field and find that the dependence of magnetic field direction correlates with the magnetic anisotropy in the catalyst film. Our work thus suggests that both the intrinsic magnetic order in La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ films and magnetic domain alignment increase their catalytic activity. We observe no long-range magnetic order at the catalytic surface, implying that the OER enhancement is connected to the magnetic order of the bulk catalyst. Combining the effects found with existing literature, we propose a unifying picture for the spin-polarized enhancement in magnetic oxide catalysts.

cond-mat.mtrl-sci

Intermixing-driven surface and bulk ferromagnetism in the quantum anomalous Hall candidate MnBi$_6$Te$_{10}$

The recent realizations of the quantum anomalous Hall effect (QAHE) in MnBi$_2$Te$_4$ and MnBi$_4$Te$_7$ benchmark the (MnBi$_2$Te$_4$)(Bi$_2$Te$_3$)$_n$ family as a promising hotbed for further QAHE improvements. The family owes its potential to its ferromagnetically (FM) ordered MnBi$_2$Te$_4$ septuple layers (SL). However, the QAHE realization is complicated in MnBi$_2$Te$_4$ and MnBi$_4$Te$_7$ due to the substantial antiferromagnetic (AFM) coupling between the SL. An FM state, advantageous for the QAHE, can be stabilized by interlacing the SL with an increasing number $n$ of Bi$_2$Te$_3$ layers. However, the mechanisms driving the FM state and the number of necessary QLs are not understood, and the surface magnetism remains obscure. Here, we demonstrate robust FM properties in MnBi$_6$Te$_{10}$ ($n = 2$) with $T_C \approx 12$ K and establish their origin in the Mn/Bi intermixing phenomenon by a combined experimental and theoretical study. Our measurements reveal a magnetically intact surface with a large magnetic moment, and with FM properties similar to the bulk. Our investigation thus consolidates the MnBi$_6$Te$_{10}$ system as perspective for the QAHE at elevated temperatures.

cond-mat.mtrl-sci

Entropy engineering and tunable magnetic order in the spinel high entropy oxide

Spinel oxides are an ideal setting to explore the interplay between configurational entropy, site selectivity, and magnetism in high entropy oxides. In this work we characterize the magnetic properties of the spinel (Cr,Mn,Fe,Co,Ni)$_3$O$_4$ and study the evolution of its magnetism as a function of non-magnetic gallium substitution. Across the range of compositions studied here, from 0% to 40% Ga, magnetic susceptibility and powder neutron diffraction measurements show that ferrimagnetic order is robust in the spinel HEO. However, we also find that the ferrimagnetic order is highly tunable, with the ordering temperature, saturated and sublattice moments, and magnetic hardness all varying significantly as a function of Ga concentration. Through x-ray absorption and magnetic circular dichroism, we are able to correlate this magnetic tunability with strong site selectivity between the various cations and the tetrahedral and octahedral sites in the spinel structure. In particular, we find that while Ni and Cr are largely unaffected by the substitution with Ga, the occupancies of Mn, Co, and Fe are each significantly redistributed. Ga substitution also requires an overall reduction in the transition metal valence, and this is entirely accommodated by Mn. Finally, we show that while site selectivity has an overall suppressing effect on the configurational entropy, over a certain range of compositions, Ga substitution yields a striking increase in the configurational entropy and may confer additional stabilization. Spinel oxides can be tuned seamlessly from the low-entropy to the high-entropy regime, making this an ideal platform for entropy engineering.

cond-mat.mtrl-sci

Strain induced stabilization of a static Jahn-Teller distortion in the O$^*$-phase of La$_{7/8}$Sr$_{1/8}$MnO$_3$

At room temperature, bulk La$_{7/8}$Sr$_{1/8}$MnO$_3$ is in the dynamic Jahn--Teller O$^*$ phase, but undergoes a transition to a static, magnetically ordered Jahn--Teller phase at lower temperatures. Here we study a $6$ unit cells thin film of this compound grown on SrTiO$_3$, resulting in small compressive strain due to a lattice mismatch of $\lesssim 0.2\%$. We combine X-ray absorption spectroscopy with multiplet ligand field theory to study the local electronic and magnetic properties of Mn in the film. We determine the Mn $d_{3z^2-r^2}$ orbital to be $0.13\;\text{eV}$ lower in energy than the $d_{x^2-y^2}$, which is a disproportionately large splitting given the small degree of compressive strain. We interpret this as resulting from the strain providing a preferential orientation for the MnO$_6$ octahedra, which are strongly susceptible to such a deformation in the vicinity of the phase transition. Hence, they collectively elongate along the $c$ axis into a static Jahn--Teller arrangement. Furthermore, we demonstrate the strongly covalent character of La$_{7/8}$Sr$_{1/8}$MnO$_3$, with a contribution of nearly $50\%$ of the one-ligand-hole configuration $d^{5} \underline{L}^1$ to the ground state wavefunction. Finally, we find the system to be in a high-spin configuration, with the projection of the local magnetic moment on the quantization axis being about $3.7\;μ_{\text{B}}/\text{Mn}$. We show, however, that the system is close to a high-spin--low-spin transition, which might be triggered by crystal field effects.

cond-mat.str-el

Sudden collapse of magnetic order in oxygen deficient nickelate films

Oxygen vacancies play a crucial role in the control of the electronic, magnetic, ionic, and transport properties of functional oxide perovskites. Rare earth nickelates (RENiO$_{3-x}$) have emerged over the years as a rich platform to study the interplay between the lattice, the electronic structure, and ordered magnetism. In this study, we investigate the evolution of the electronic and magnetic structure in thin films of RENiO$_{3-x}$, using a combination of X-ray absorption spectroscopy and imaging, resonant X-ray scattering, and extended multiplet ligand field theory modeling. We find that oxygen vacancies modify the electronic configuration within the Ni-O orbital manifolds, leading to a dramatic evolution of long-range electronic transport pathways despite the absence of nanoscale phase separation. Remarkably, magnetism is robust to substantial levels of carrier doping, and only a moderate weakening of the $(1/4, 1/4, 1/4)_{pc}$ antiferromagnetic order parameter is observed, whereas the magnetic transition temperature is largely unchanged. Only at a certain point long-range magnetism is abruptly erased without an accompanying structural transition. We propose the progressive disruption of the 3D magnetic superexchange pathways upon introduction of point defects as the mechanism behind the sudden collapse of magnetic order in oxygen-deficient nickelates. Our work demonstrates that, unlike most other oxides, ordered magnetism in RENiO$_{3-x}$ is mostly insensitive to carrier doping. The sudden collapse of ordered magnetism upon oxygen removal may provide a new mechanism for solid-state magneto-ionic switching and new applications in antiferromagnetic spintronics.

cond-mat.str-el

Ubiquitous impact of localised impurity states on the exchange coupling mechanism in magnetic topological insulators

Since the discovery of the quantum anomalous Hall effect in the magnetically doped topological insulators (MTI) Cr:(Bi,Sb)$_2$Te$_3$ and V:(Bi,Sb)$_2$Te$_3$, the search for the exchange coupling mechanisms underlying the onset of ferromagnetism has been a central issue, and a variety of different scenarios have been put forward. By combining resonant photoemission, X-ray magnetic dichroism and multiplet ligand field theory, we determine the local electronic and magnetic configurations of V and Cr impurities in (Bi,Sb)$_2$Te$_3$. While strong pd hybridisation is found for both dopant types, their 3d densities of states show pronounced differences. State-of-the-art first-principles calculations show how these impurity states mediate characteristic short-range pd exchange interactions, whose strength sensitively varies with the position of the 3d states relative to the Fermi level. Measurements on films with varying host stoichiometry support this trend. Our results establish the essential role of impurity-state mediated exchange interactions in the magnetism of MTI.

cond-mat.str-el

Itinerancy-dependent non-collinear spin textures in SrFeO3, CaFeO3, and CaFeO3/SrFeO3 heterostructures probed via resonant x-ray scattering

Non-collinear, multi-q spin textures can give rise to exotic, topologically protected spin structures such as skyrmions, but the reason for their formation over simple single-q structures is not well understood. While lattice frustration and the Dzyaloshinskii-Moriya interaction are known to produce non-collinear spin textures, the role of electron itinerancy in multi-q formation is much less studied. Here we investigated the non-collinear, helical spin structures in epitaxial films of the perovskite oxides SrFeO3 and CaFeO3 using magnetotransport and resonant soft x-ray magnetic diffraction. Metallic SrFeO3 exhibits features in its magnetoresistance that are consistent with its recently proposed multi-q structure. Additionally, the magnetic Bragg peak of SrFeO3 measured at the Fe L edge resonance energy asymmetrically broadens with decreasing temperature in its multi-q state. In contrast, insulating CaFeO3 has a symmetric scattering peak with an intensity 10x weaker than SrFeO3. Enhanced magnetic scattering at O K edge prepeak energies demonstrates the role of a negative charge transfer energy and the resulting oxygen ligand holes in the magnetic ordering of these ferrates. By measuring magnetic diffraction of CaFeO3/SrFeO3 superlattices with thick CaFeO3 layers, we find that the CaFeO3 helical ordering is coherent across 1 unit cell-thick SrFeO3 layers but not 6 unit cell-thick layers. We conclude that insulating CaFeO3 supports only a simple single-q helical structure in contrast to metallic SrFeO3 that hosts multi-q structures. Our results provide important insight into the role of electron itinerancy in the formation of multi-q spin structures.

cond-mat.mtrl-sci