In this paper, we study the elastic properties of the entropy-stabilized oxide (Mg, Co, Ni, Cu, Zn)O, using experimental and first principles techniques. Our measurements of the indentation modulus on grains with a wide range of crystallographic orientations of the entropy-stabilized oxide revealed a high degree of elastic isotropy at ambient conditions. First principles calculations predict mild elastic anisotropy for the paramagnetic structure, which decreases when the system is considered to be non-magnetic. When the antiferromagnetic state of CoO, CuO and NiO is accounted for in the calculations, a slight increase in the elastic anisotropy is observed, suggesting a coupling between magnetic ordering and the orientation dependent elastic properties. Furthermore, an examination of the local structure reveals that the isotropy is favored through local ionic distortions of Cu and Zn - due to their tendency to form tenorite and wurtzite phases. The relationships between the elastic properties of the multicomponent oxide and those of its constituent binary oxides are reviewed. These insights open up new avenues for controlling isotropy for technological applications through tuning composition and structure in the entropy-stabilized oxide or the high entropy compounds in general.
Nanocrystalline materials are well known for their beneficial mechanical and physical properties. However, it is of utmost importance to stabilize the microstructure at elevated temperatures to broaden the window of application e.g. by pinning grain boundaries through impurities or oxides. CuCo alloys, severe plastically deformed using high-pressure torsion, were used to investigate the evolution of oxides upon annealing. These investigations were performed using electron microscopy, synchrotron high-energy X-ray scattering and atom probe tomography. Monitoring the evolution of oxides by in-si…
Entropy stabilization has garnered significant attention as a new approach to designing novel materials. Much of the work in this area has focused on bulk ceramic processing, leaving entropy-stabilized thin films relatively underexplored. Following an extensive multi-variable investigation of polycrystalline (Mg$_{0.2}$Co$_{0.2}$Ni$_{0.2}$Cu$_{0.2}$Zn$_{0.2}$)O thin films deposited via pulsed laser deposition (PLD), it is shown here that substrate temperature and deposition pressure have strong and repeatable effects on film texture and lattice parameter. Further analysis shows that films depo…
Layered oxides have been intensively studied due to their high designability for various electronic functions. Here we synthesize a new oxide as epitaxial thin film form by pulsed laser deposition. Film characterizations including cross-section and plan-view transmission electron microscopy confirm that the film is composed of twisted stack of triangular-lattice Rh and Bi layers. We foresee that the concept of twisted oxide layers will open up a new route to design further functional layered oxides.
Additive manufacturing represents a revolution due to its unique capabilities for freeform fabrication of near net shapes with strong reduction of waste material and capital cost. These unfair advantages are especially relevant for expensive and energy-demanding manufacturing processes of advanced ceramics such as Yttria-stabilized Zirconia, the state-of-the-art electrolyte in Solid Oxide Fuel Cell applications. In this study, self-supported electrolytes of yttria-stabilized zirconia have been printed by using a stereolithography three-dimensional printer. Printed electrolytes and complete cel…
Probing Elastic Isotropy in Entropy Stabilized Transition Metal Oxides: Experimental Estimation of Single Crystal Elastic Constants from Polycrystalline Materials
Interdiffusion between the yttria stabilized zirconia (YSZ) electrolyte and the gadolinia doped ceria (CGO) barrier layer is one of the major causes to the degradation of solid oxide fuel cells (SOFCs). We present in this work experimental investigations on CGO-YSZ bi-layer electrolyte sintered at 1250 C or 1315 C and element transport as a function of sintering temperature and dwelling time. In order to quantitatively simulate the experimental observations, the CALPHAD-type thermodynamic assessment of the CGO-YSZ system is performed by simplifying the system to a CeO2-ZrO2 quasi-binary system…
Based on first-principles calculation, it has been predicted that the magnetic anisotropy energy (MAE) in Co-doped ZnO (Co:ZnO) depends on electron-filling. Results show that the charge neutral Co:ZnO presents a "easy plane" magnetic state. While modifying the total number of electrons, the easy axis rotates from in-plane to out-of-plane. The alternation of the MAE is considered to be the change of the ground state of Co ion, resulting from the relocating of electrons on Co d-orbitals with electron-filling.
Stabilizing high-valent redox couples and exotic electronic states necessitate an understanding of the stabilization mechanism. In oxides, whether they are being considered for energy storage or computing, highly oxidized oxide-anion species rehybridize to form short covalent bonds and are related to significant local structural distortions. In intercalation oxide electrodes for batteries, while such reorganization partially stabilizes oxygen redox, it also gives rise to substantial hysteresis. In this work, we investigate oxygen redox in layered Na2-XMn3O7, a positive electrode material with …
Highly-ordered and spatially-coherent cobalt slanted columnar thin films were deposited by glancing angle deposition onto silicon substrates, and subsequently oxidized by annealing at 475 $^{\circ}$C. Scanning electron microscopy, Raman scattering, generalized ellipsometry, and density functional theory investigations reveal shape-invariant transformation of the slanted nanocolumns from metallic to transparent metal-oxide core-shell structures with properties characteristic of spinel cobalt oxide. We find passivation of Co-SCTFs yielding CoAl$_2$O$_3$ core-shell structures produced by conforma…
The magnetic order and the spin dynamics in the antiferromagnetic entropy-stabilized oxide (Mg$_{0.2}$Co$_{0.2}$Ni$_{0.2}$Cu$_{0.2}$Zn$_{0.2}$)O (MgO-ESO) have been studied using muon spin relaxation ($μ$SR) and inelastic neutron scattering. We find that antiferromagnetic order develops gradually in the sample volume as it is cooled below 140 K, becoming fully ordered around 100 K. The spin dynamics show a critical slowing down in the vicinity of the transition, and the magnetic order parameter grows continuously in the ordered state. These results indicate that the antiferromagnetic transitio…
Single-crystalline thin film of an iridium dioxide polymorph Ir2O4 has been fabricated by the pulsed laser deposition of LixIr2O4 precursor and the subsequent Li-deintercalation using soft chemistry. Ir2O4 crystallizes in a spinel (AB2O4) without A cations in the tetrahedral site, which is isostructural to lambda-MnO2. Ir ions form a pyrochlore sublattice, which is known to give rise to a strong geometrical frustration. This Ir spinel was found to be a narrow gap insulator, in remarkable contrast to the metallic ground state of rutile-type IrO2. We argue that an interplay of strong spin-orbit …
Voltage control of interfacial magnetism has been greatly highlighted in spintronics research for many years, as it might enable ultra-low power technologies. Among few suggested approaches, magneto-ionic control of magnetism has demonstrated large modulation of magnetic anisotropy. Moreover, the recent demonstration of magneto-ionic devices using hydrogen ions presented relatively fast magnetization toggle switching, tsw ~ 100 ms, at room temperature. However, the operation speed may need to be significantly improved to be used for modern electronic devices. Here, we demonstrate that the spee…
Magnetic insulators with strong perpendicular magnetic anisotropy (PMA) play a key role in exploring pure spin current phenomena and developing ultralow-dissipation spintronic devices, thereby it is highly desirable to develop new material platforms. Here we report epitaxial growth of La2/3Sr1/3MnO3 (LSMO)-SrIrO3 (SIO) composite oxide films (LSMIO) with different crystalline orientations fabricated by sequential two-target ablation process using pulsed laser deposition. The LSMIO films exhibit high crystalline quality with homogeneous mixture of LSMO and SIO at atomic level. Ferrimagnetic and …
The existence of approximately 30 noncentrosymmetric metals (NCSM) suggests a contraindication between crystal structures without inversion symmetry and metallic behavior. Those containing oxygen are especially scarce. Here we propose and demonstrate a design framework to remedy this property disparity and accelerate NCSM-oxide discovery: The primary ingredient relies on the removal of inversion symmetry through displacements of atoms whose electronic degrees of freedom are decoupled from the states at the Fermi level. Density functional theory calculations validate this crystal--chemistry str…
Understanding and controlling the interfacial magnetic properties of ferromagnetic thin films are crucial for spintronic device applications. However, using conventional magnetometry, it is difficult to detect them separately from the bulk properties. Here, by utilizing tunneling anisotropic magnetoresistance in a single-barrier heterostructure composed of La0.6Sr0.4MnO3 (LSMO)/ LaAlO3 (LAO)/ Nb-doped SrTiO3 (001), we reveal the presence of a peculiar strong two-fold magnetic anisotropy (MA) along the [110]c direction at the LSMO/LAO interface, which is not observed in bulk LSMO. This MA shows…
Data-Driven Prediction of NaCl-Type Entropy-Stabilized Oxide Compositions from First-Principles and Supervised Learning
Univ Paris Est Creteil, CNRS, ICMPE（巴黎东克雷泰伊大学，法国国家科学研究中心，分子化学与材料研究所）；Université Paris-Saclay, CNRS, Institut de chimie moléculaire et des matériaux d’Orsay（巴黎萨克雷大学，法国国家科学研究中心，奥赛分子化学与材料研究所）
Here we demonstrate numerically that shape anisotropy in MgO-based spin-torque nano-oscillators consisting of an out-of-plane magnetized free layer and an in-plane polarizer is necessary to stabilize out-of-plane magnetization precession without the need of external magnetic fields. As the in-plane anisotropy is increased, a gradual tilting of the magnetization towards the in-plane easy direction is introduced, favouring zero-field dynamics over static in-plane states. Above a critical value, zero-field dynamics are no longer observed. The optimum ratio of in-plane shape to out-of-plane uniaxi…
For the first time, this study shows that distortion in a crystal structure due to magnetic effect is possible in a lattice with extreme chemical disorder. The multicomponent equimolar transition metal oxide (ME TMO), (Co,Cu,Mg,Ni,Zn)O, which is a high entropy oxide, has been attracting a lot of attention due to its unique application potential in many fields including electrochemical energy storage. In the present investigation, nanocrystalline ME TMO was synthesised by three bottom up methods. The presence of distortion in the rocksalt crystal structure, revealed by X ray diffraction and Ram…
Engineering magnetic anisotropy in two-dimensional systems has enormous scientific and technological implications. The uniaxial anisotropy universally exhibited by two-dimensional magnets has only two stable spin directions, demanding 180 degrees spin switching between states. We demonstrate a novel eightfold anisotropy in magnetic SrRuO3 monolayers by inducing a spin reorientation in (SrRuO3)1/(SrTiO3)N superlattices, in which the magnetic easy axis of Ru spins is transformed from uniaxial <001> direction (N = 1 and 2) to eightfold <111> directions (N = 3, 4 and 5). This eightfold anisotropy …
Unlike widely explored complex oxide heterostructures grown along [001], the study of [111]-oriented heterointerfaces are very limited thus far. One of the main challenges is to overcome the polar discontinuity that hinders the epitaxy of atomically sharp interfaces. Here, by taking the LaCoO3/SrTiO3(111) as a prototype, we show that the reconstruction, which effectively compensates the surface polarity, can stabilize the epitaxy of the heterostructure with polar discontinuity. Reconstructed substrate surface is prepared, while the growth is controlled to form reconstruction on the film surfac…
Signatures of symmetry-stabilized Dirac fermions in correlated oxide CaNbO3 thin films
Oak Ridge National Laboratory（橡树岭国家实验室）；Kyung Hee University（庆熙大学）；Pusan National University（釜山国立大学）；Florida State University（佛罗里达州立大学）；Los Alamos National Laboratory（洛斯阿拉莫斯国家实验室）；Argonne National Laboratory（阿贡国家实验室）；Gachon University（嘉泉大学）
The possible importance of oxide formation for the catalytic activity of transition metals in heterogenous oxidation catalysis has evoked a lively discussion over the recent years. On the more noble transition metals (like Pd, Pt or Ag) the low stability of the common bulk oxides suggests primarily sub-nanometer thin oxide films, so-called surface oxides, as potential candidates that may be stabilized under gas phase conditions representative of technological oxidation catalysis. We address this issue for the Pd(100) model catalyst surface with first-principles kinetic Monte Carlo (kMC) simula…
Understanding the magnetic anisotropy at ferromagnetic metal/oxide interface is a fundamental and intriguing subject. Here we propose an approach to manipulate the strength of perpendicular magnetic anisotropy (PMA) by varying MgO thickness in the MgO/CoFeB/Ta thin films. We identify that the PMA at the MgO/CoFeB interface is tuned by the crystalline structure of bulk MgO layer and decreases dramatically due to the onset of crystalline MgO forming with the increase of MgO thickness. Our work opens an avenue to manipulate the magnetic anisotropy by the modification of the ferromagnetic metal/ox…
Microstrip ferromagnetic resonance and Brillouin scattering are used to provide a comparative determination of the magnetic parameters of thin permalloy layers interfaced with a non-magnetic (Al2O3) or with an antiferromagnetic oxide (NiO). It is shown that the perpendicular anisotropy is monitored by an interfacial surface energy term which is practically independent of the nature of the interface. In the investigated interval of thicknesses (5-25 nm) the saturation magnetisation does not significantly differ from the reported one in bulk permalloy. In-plane uniaxial anisotropy and exchange-b…
The 5d transition-metal oxides have been an intriguing platform to demonstrate efficient charge to spin current conversion due to a unique electronic structure dominated by strong spin-orbit coupling. Here, we report on stacking-order effect of spin-orbit torque (SOT), spin-Hall magnetoresistance, and magnetic anisotropy in bilayer Ni$_{81}$Fe$_{19}$-5d iridium oxide, IrO$_2$. While all the IrO$_2$ and Pt control samples exhibit large dampinglike-SOT generation stemming from the efficient charge to spin current conversion, the magnitude of the SOT is larger in the IrO$_2$ (Pt)-bottom sample th…
Oxidative stress, which is one of the main harmful mechanisms of pathologies including is-chemic stroke, contributes to both neurons and endothelial cell damages, leading to vascular lesions. Although many antioxidants have been tested in preclinical studies, no treatment is currently available for stroke patients. Since cerium oxide nanoparticles (CNPs) exhibit remarkable antioxidant capacities, our objective is to develop an innovative coating to enhance CNPs biocompatibility without disrupting their antioxidant capacities or enhance their toxicity. This study reports the synthesis and chara…
We investigated the in-plane anisotropy on the resistivity and thermopower of Bi2-xPbxSr2Co2Oy single crystals, which have a misfit structure between the hexagonal CoO2 layer and the rock salt Bi2Sr2O4 layer. The resistivity and thermopower show significantly large anisotropy, which exceeds two at maximum. This anisotropy would come from the anisotropic pseudogap formation enhanced by the misfit structure. The thermopower changes with Pb doping to take a maximum at x=0.4. The misfit structure improves the thermoelectric properties through chemical pressure. The power factor is as large as 9 mu…
We present a detailed study of the magnetic behavior of iron-oxide (gamma-Fe2O3 and Fe3O4) nanoparticles constituents of ferrofluids (FF's) with average particle sizes <d> = 2.5 and 10 nm. The particles were dispersed in the frozen liquid carrier (pure FF) and in a frozen lyotropic liquid crystalline matrix in the nematic phase or ferronematic (FN) (ferrolyomesophase). Both FF and FN phases displayed superparamagnetic (SPM) behaviour at room temperature, with blocking temperatures T_B ~ 10 and 100 K for <d> = 2.5 and 10 nm, respectively. Dynamic ac susceptibility measurements showed a thermall…
We report on the study of both perpendicular magnetic anisotropy (PMA) and Dzyaloshinskii-Moriya interaction (DMI) at an oxide/ferromagnetic metal (FM) interface, i.e. BaTiO3 (BTO)/CoFeB. Thanks to the functional properties of the BTO film and the capability to precisely control its growth, we are able to distinguish the dominant role of the oxide termination (TiO2 vs BaO), from the moderate effect of ferroelectric polarization in the BTO film, on the PMA and DMI at the oxide/FM interface. We find that the interfacial magnetic anisotropy energy of the BaO-BTO/CoFeB structure is two times large…
High perpendicular magnetic anisotropy (PMA), a property needed for nanoscale spintronic applications, is rare in oxide conductors. We report the observation of a PMA up to 0.23 MJ/m3 in modestly strained epitaxial NiCo2O4 (NCO) films which are room-temperature ferrimagnetic conductors. Spin-lattice coupling manifested as magnetoelastic effect was found as the origin of the PMA. The in-plane xx-yy states of Co on tetrahedral sites play crucial role in the magnetic anisotropy and spin-lattice coupling with an energy scale of 1 meV/f.u. The elucidation of the microscopic origin paves a way for e…
We report a study on the pressure response of the anisotropy energy of hollow and solid maghemite nanoparticles. The differences between the maghemite samples are understood in terms of size, magnetic anisotropy and shape of the particles. In particular, the differences between hollow and solid samples are due to the different shape of the nanoparticles and by comparing both pressure responses it is possible to conclude that the shell has a larger pressure response when compared to the core.
Towards next-generation spintronics devices, such as computer memories and logic chips, it is necessary to satisfy high thermal stability, low-power consumption and high spin-polarization simultaneously. Here, from first-principles, we investigate thermal stability (both structure and magnetization) and the electric field control of magnetic anisotropy on Co2FeAl (CFA)/MgO. A phase diagram of structural thermal stability of the CFA/MgO interface is illustrated. An interfacial perpendicular-anisotropy, coming from the Fe-O orbital hybridization, provides high magnetic thermal stability and a lo…
Quantum spin liquid on a 3D bipartite lattice of spin trimers stabilized by enhanced effective anisotropy
Jožef Stefan Institute（约瑟夫·斯特凡研究所）；Faculty of Mathematics and Physics, University of Ljubljana（卢布尔雅那大学数学与物理学院）；Institut Laue-Langevin（朗之万研究所）；Laboratoire Léon Brillouin, CEA, CNRS, Université Paris-Saclay（巴黎萨克雷大学CEA-CNRS莱昂·布里渊实验室）；Université Grenoble Alpes（格勒诺布尔阿尔卑斯大学）；Institut Néel, CNRS–UGA（内尔研究所，CNRS-UGA）；Department of Physics, Indian Institute of Technology Tirupati（蒂鲁帕蒂印度理工学院物理系）；Department of Physics and Astronomy and Institute of Applied Physics, Seoul National University（首尔大学天文学与物理学系及应用物理研究所）；Department of Physics, Indian Institute of Technology Madras（马德拉斯印度理工学院物理系）
The prospects of half-metallic ferromagnetism being induced by the incorporation of C atoms into alkaline-earth-metal-oxides are investigated by the first principle calculation. The origin of the ferromagnetism is discussed through the calculation of the electronic structure and exchange coupling constant by using the pseudo-potential-like self-interaction-corrected local spin density method. The Curie temperature ($T_c$) is also predicted by employing the Monte Carlo simulation. It is shown that by taking the electron self-interaction into account, the half-metallic ferromagnetism induced by …
We investigated thermal conductivity of free-standing reduced graphene oxide films subjected to a high-temperature treatment of up to 1000 C. It was found that the high-temperature annealing dramatically increased the in-plane thermal conductivity, K, of the films from 3 W/mK to 61 W/mK at room temperature. The cross-plane thermal conductivity, Kc, revealed an interesting opposite trend of decreasing to a very small value of 0.09 W/mK in the reduced graphene oxide films annealed at 1000 C. The obtained films demonstrated an exceptionally strong anisotropy of the thermal conductivity, K/Kc ~ 67…
We study the transport properties in SrVO3/LaVO3 (SVO/LVO) superlattices deposited on SrTiO3 (STO) substrates. We show that the electronic conduction occurs in the metallic LVO layers with a galvanomagnetism typical of a 2D Fermi surface. In addition, a Kondo-like component appears in both the thermal variation of resistivity and the magnetoresistance. Surprisingly, in this system where the STO interface does not contribute to the measured conduction, the Kondo correction is strongly anisotropic. We show that the growth temperature allows a direct control of this contribution. Finally, the key…
Iron oxide nanoparticles were prepared by sol -gel process. Insitu polymerization of pyrrole monomer in the presence of oxygen in iron oxide ethanol suspension resulted in a iron oxide - polypyrrole nanocomposite. The structure and magnetic properties were investigated for varying pyrrole concentrations. The presence of the gamma - iron oxide phase and polypyrrole were confirmed by XRD and FTIR respectively. Agglomeration was found to be comparatively much reduced for the coated samples, as shown by TEM. AC susceptibility measurements confirmed the superparamagnetic behaviour. Numerical simula…
Nitrogen oxides are textbook class of molecular compounds, with extensive industrial applications. Nitrogen and oxygen are also among the most abundant elements in the universe. We explore the N-O system at 0 K and up to 500 GPa though ab initio evolutionary simulations. Results show that two phase transformations of stable molecular NO2 exist at 7 and 64 GPa, and followed by decomposition of NO2 at 91 GPa. All of the NO+NO3- structures are found to be metastable at T=0 K, so experimentally reported ionic NO+NO3- is either metastable or stabilized by temperature. Upon increasing pressure, N2O5…
In past few decades, Rashba spin-orbit coupling (SOC) has been successfully employed for the emergence of exotic phenomena at the quantum oxide interfaces. In these systems, the combined effect of charge transfer, broken symmetries and SOC yields intriguing interfacial magnetism and transport properties. Here, we provide an insight to control and tune interfacial phenomena in CaMnO3/CaIrO3 based 3d-5d oxide heterostructures by the charge transfer driven Rashba SOC. Anomalous Hall effect in these canted antiferromagnetic heterostructures originates from the intrinsic contribution associated wit…
Artificial perovskite-oxide nanostructures possess intriguing magnetic properties due to their tailorable electron-electron interactions, which are extremely sensitive to the oxygen coordination environment. To date, perovskite-oxide nanodots with sizes below 50 nm have rarely been reported. Furthermore, the oxygen octahedral distortion and its relation to magnetic properties in perovskite oxide nanodots remain unexplored yet. Here, we have studied the magnetic anisotropy in patterned SrRuO3 (SRO) nanodots as small as 30 nm while performing atomic-resolution electron microscopy and spectroscop…
Ultrathin (111)-oriented polar iron oxide films were grown on a Pt(111) single crystal either by the reactive deposition of iron or oxidation of metallic iron monolayers. These films were characterized using low energy electron diffraction, scanning tunneling microscopy and conversion electron Mossbauer spectroscopy. The reactive deposition of Fe led to the island growth of Fe3O4, in which the electronic and magnetic properties of the bulk material were modulated by superparamagnetic size effects for thicknesses below 2 nm, revealing specific surface and interface features. In contrast, the ox…
The cubic antifluorite structure comprises a face-centered cubic sublattice of anions with cations on the tetrahedral sites. The voids in the antifluorite structure that are crucial for superionicity in Li2O might also act as atomic traps. Trapping of guest atoms and small molecules within voids of a host structure leads to the formation of what are known as clathrate compounds. Here we investigate the possibility of trapping helium or larger neon guest atoms under pressure within alkali metal oxide and sulfide structures. We find stable helium and neon-bearing compounds at very low pressures.…
Several challenges in designing an operational Skyrmion racetrack memory are well-known. Among those challenges, a few contradictions can be identified if researchers were to rely only on metallic materials. Hence, expanding the exploration on Skyrmion Physics into oxide materials is essential to bridge the contradicting gap. In this topical review, we first briefly revise the theories and criteria involved in stabilizing and manipulating Skymions, followed by studying the behaviors of dipolar-stabilized magnetic bubbles. Next, we explore the properties of multiferroic Skyrmions with magnetoel…
We report for the first time the magnetic structure of the high entropy oxide $(Mg_{0.2}Co_{0.2}Ni_{0.2}Cu_{0.2}Zn_{0.2})O$ using neutron powder diffraction. This material exhibits a sluggish magnetic transition but possesses a long-range ordered antiferromagnetic ground state, as revealed by DC and AC magnetic susceptibility, elastic and inelastic neutron scattering measurements. The magnetic propagation wavevector is k=(1/2, 1/2, 1/2) based on the cubic structure Fm-3m, and the magnetic structure consists of ferromagnetic sheets in the (111) planes with spins antiparallel between two neighbo…
