A detailed spectroscopic and structural characterization of ultrathin cobalt oxide films grown by O-assisted molecular beam epitaxy on a-Al2O3(0001) single crystals is reported. The experimental results show that the cobalt oxide films become progressively more disordered with increasing thickness, starting from the early stages of deposition. Low energy electron diffraction patterns suggest that the unit cell remains similar to that of a-Al2O3(0001) up to a thickness of 17 A, while at larger thicknesses a pattern identified with that of Co3O4(111) becomes visible. X-ray photoelectron spectroscopy reveals sudden changes in the shape of the Co 2p lines from 3.4 to 17 A cobalt oxide thickness, indicating the transition from an interfacial cobalt oxide layer towards [111]-oriented Co3O4. In particular, the absence of characteristic satellite peaks in the Co 2p lines indicates the formation of a trivalent, octahedrally coordinated, interfacial cobalt oxide layer during the early stages of growth, identified as the Co2O3 corundum phase.
We developed the self-assembly of epitaxial submicrometer-sized face-centered-cubic (fcc) Co(111) dots using pulsed laser deposition. The dots display atomically-fl at facets, from which the ratios of surface and interface energies for fcc Co are deduced. Zero- field magnetic structures are investigated with magnetic force and lorentz microscopies, revealing vortex-based flux-closure patterns. A good agreement is found with micromagnetic simulations.
The direct liquid injection chemical vapor deposition (DLI-CVD) technique has been used for the growth of cobalt ferrite (CFO) films on (100)-oriented MgAl$_2$O$_4$ (MAO) substrates. Smooth and highly epitaxial cobalt ferrite thin films, with the epitaxial relationship $\mathrm{MAO} (100)\:[001] \parallel \mathrm{CFO} (100)\:[001]$, are obtained under optimized deposition conditions. The films exhibit bulk-like structural and magnetic properties with an out-of-plane lattice constant of $8.370\;\mathrmÅ$ and a saturation magnetization of $420\;\mathrm{kA/m}$ at room temperature. The Raman spect…
The ability to manipulate oxygen anion defects rather than metal cations in complex oxides can facilitate creating new functionalities critical for emerging energy and device technologies. However, the difficulty in activating oxygen at reduced temperatures hinders the deliberate control of important defects, oxygen vacancies. Here, strontium cobaltite (SrCoOx) is used to demonstrate that epitaxial strain is a powerful tool for manipulating the oxygen vacancy concentration even under highly oxidizing environments and at annealing temperatures as low as 300 C. By applying a small biaxial tensil…
Graphene is attractive for spintronics due to its long spin life time and high mobility. So far only thick and polycrystalline slabs have been used as ferromagnetic electrodes. We report the growth of flat, epitaxial ultrathin Co films on graphene. These display perpendicular magnetic anisotropy in the thickness range 0.5-1nm, which is confirmed by theory. PMA, epitaxy and ultrathin thickness bring new perspectives for graphene-based spintronic devices such as the zero-field control of an arbitrary magnetization direction, band matching between electrodes and graphene, and interface effects su…
We report direct experimental evidence of room temperature spin filtering in magnetic tunnel junctions (MTJs) containing CoFe2O4 tunnel barriers via tunneling magnetoresistance (TMR) measurements. Pt(111)/CoFe2O4(111)/gamma-Al2O3(111)/Co(0001) fully epitaxial MTJs were grown in order to obtain a high quality system, capable of functioning at room temperature. Spin polarized transport measurements reveal significant TMR values of -18% at 2 K and -3% at 290 K. In addition, the TMR ratio follows a unique bias voltage dependence that has been theoretically predicted to be the signature of spin fil…
Perpendicular magnetic anisotropy (PMA) energy up to $K_{\mathrm{u}}=6.1\pm0.8$ MJ m$^{-3}$ is demonstrated in this study by inducing large lattice-distortion exceeding 3% at room temperature in epitaxially distorted cobalt ferrite Co$ _{x} $Fe$ _{3-x} $O$ _{4} $ (x = 0.72) (001) thin films. Although the thin film materials include no rare-earth elements or noble metals, the observed $ K_{u} $ is larger than that of the neodymium-iron-boron compounds for high-performance permanent magnets. The large PMA is attributed to the significantly enhanced magneto-elastic effects, which are pronounced i…
Remote epitaxial frustration stabilizes a correlated interfacial state
University of Wisconsin-Madison（威斯康星大学麦迪逊分校）；Sandia National Laboratories（桑迪亚国家实验室）；Two-dimensional Crystal Consortium, Materials Research Institute, Pennsylvania State University（宾夕法尼亚州立大学材料研究所二维晶体联盟）；Department of Materials Science and Engineering, Pennsylvania State University（宾夕法尼亚州立大学材料科学与工程系）
Emergent Interfacial Magnetism in Epitaxial RuO$_2$
Zhejiang University（浙江大学）；Westlake University（西湖大学）；Institute of Natural Sciences, Westlake Institute for Advanced Study（西湖高等研究院自然科学院）；Institute for Theoretical Sciences, Westlake Institute for Advanced Study（西湖高等研究院理论科学研究所）；New Cornerstone Science Laboratory, Department of Physics, Westlake University（西湖大学物理学院新基石科学实验室）
We report growth characteristics of epitaxial $β$-Na$_{0.6}$CoO$_{2}$ and $γ$-Na$_{0.7}$CoO$_{2}$ thin films on (001) sapphire substrates grown by pulsed-laser deposition. Reduction of deposition rate could change structure of Na$_{x}$CoO$_{2}$ thin film from $β$-phase with island growth mode to $γ$-phase with layer-by-layer growth mode. The $γ$-Na$_{0.7}$CoO$_{2}$ thin film exhibits spiral surface growth with multiterraced islands and highly crystallized texture compared to that of the $β$-Na$_{0.6}$CoO$_{2}$ thin film. This heterogeneous epitaxial film growth can give opportunity of strain e…
Monolayer epitaxial graphene is an appropriate candidate for a wide variety of electronic and optical applications. One advantage of growing graphene on the Si face of SiC is that it develops as a single crystal, as does the layer underneath, commonly referred to as the interfacial buffer layer. The properties of this supporting layer include a band gap, making it of interest to groups seeking to build devices with on-off capabilities. In this work, using density functional theory, we have calculated the bonding characteristics of the buffer layer to the SiC substrate beneath. These calculatio…
Anatase Ti0.96Co0.04O2 films were grown epitaxially on SrTiO3 (001) substrates by using plused laser deposition with in-situ reflection high-energy electron diffraction. The oxygen partial pressure, PO2, during the growth was systematically varied. As PO2 decreased, the growth behavior was changed from a 2-dimensional layer-by-layer-like growth to a 3-dimensional island-like one, which resulted in an increase in the saturation magnetization. These structural and magnetic changes were explained in terms of the formation of cobalt clusters whose existence was proved by transmission-electron-micr…
In this work, we demonstrate a massive intrinsic exchange bias (3 kOe) in epitaxial CoFe2O4(111) thin films deposited on Al2O3(0001) substrates. This exchange bias is indicative of intrinsic exchange or a ferromagnetic material combined with an antiferromagnet. The analysis of structure, magnetism and electronic states corroborate that there is an interfacial layer CoO between the CoFe2O4(111) thin film and the Al2O3(0001) substrate. The power-law thickness dependence of the intrinsic exchange bias verifies its interfacial origin. This work suggests interfacial engineering can be an effective …
Zero field cooled spontaneous exchange bias (SEB) is observed in epitaxial La0.7Sr0.3MnO3 (LSMO):NiO self-assembled nanocomposite thin films grown on (001) SrTiO3 single crystal substrate by pulsed laser deposition. SEB is displayed by the novel asymmetry in the hysteresis loop of the composite film along with the field cooled conventional exchange bias (CEB) effect. The training effect shows that exchange bias relaxation is disorder mediated. It is revealed from DC magnetization results that such nanocomposite film divulges spin glass like behaviour, which is arising due to competing ferromag…
The effects of growth rate (G_r), deposition temperature (T_d), film thickness (t_F), and substrate induced strain (epsilon) on morphological, crystallographic and magnetic characteristics of equiatomic CoPt epitaxial films synthesized with PLD are investigated. The (001) substrates of MgO, STO and LAO provide different degree of epitaxial strain for growth of the disordered face centered cubic (fcc) and ordered face centered tetragonal (L1_0) phases of CoPt. The films deposited at T_d~600 ^0C on all three substrates are fcc with in-plane magnetization and a narrow hysteresis loop of width~200…
Dzyaloshinskii-Moriya interaction (DMI) manifesting in asymmetric layered ferromagnetic films gives rise to non-colinear spin structures stabilizing magnetization configurations with nontrivial topology. In this work magnetization reversal, domain structure, and strength of DMI are related with the structure of W/Co/Pt multilayers grown by molecular beam epitaxy. Applied growth method enables fabrication of layered systems with higher crystalline quality than commonly applied sputtering techniques. As a result, a high value of D coefficient was determined from the aligned magnetic domain strip…
Cobalt ferrite ultrathin films with inverse spinel structure are among the best candidates for spin-filtering at room temperature. We have fabricated high-quality epitaxial ultrathin CoFe2O4 layers on Ag(001) following a three-step method: an ultrathin metallic CoFe2 alloy was first grown in coherent epitaxy on the substrate, and then treated twice with O2, first at RT and then during annealing. The epitaxial orientation, the surface, interface and film structure were resolved combining LEED, STM, Auger and in situ GIXRD. A slight tetragonal distortion was observed, that should drive the easy …
The epitaxy of MoO2 on c_plane sapphire substrates is examined. A theoretical approach, based on density functional theory calculations of the strain energy, allowed to predict the preferred layer/substrate epitaxial relationships. To test the results of these calculations, MoO2/(001) Al2O3 heterostructures were grown using the chemically_driven isothermal close space vapour transport technique. At the early stages of the growth, two kinds of morphologies were obtained, using the same growth parameters: lying and standing flakes. The composition and morphology, as well as the layer/substrate e…
Facing the ever-growing demand for data storage will most probably require a new paradigm. Nanoscale magnetic skyrmions are anticipated to solve this issue as they are arguably the smallest spin textures in magnetic thin films in nature. We designed cobalt-based multilayered thin films where the cobalt layer is sandwiched between two heavy metals providing additive interfacial Dzyaloshinskii-Moriya interactions, which reach a value close to 2 mJ m-2 in the case of the Ir|Co|Pt asymmetric multilayers. Using a magnetization-sensitive scanning x-ray transmission microscopy technique, we imaged sm…
The interaction of interfacial water with graphitic carbon at the atomic scale is studied as a function of the hydrophobicity of epitaxial graphene. High resolution X-ray reflectivity shows that the graphene-water contact angle is controlled by the average graphene thickness, due to the fraction of the film surface expressed as the epitaxial buffer layer whose contact angle (contact angle θ_c = 73°) is substantially smaller than that of multilayer graphene (θ_c = 93°). Classical and ab initio molecular dynamics simulations show that the reduced contact angle of the buffer layer is due to both …
We investigate the initial growth modes and the role of interfacial electrostatic interactions of EuO epitaxy on MgO(001) by reactive molecular beam epitaxy. A TiO2 interfacial layer is employed to produce high quality epitaxial growth of EuO on MgO(001) with a 45° in plane rotation. For comparison, direct deposition of EuO on MgO, without the TiO2 layer shows a much slower time evolution in producing a single crystal film. Conceptual arguments of electrostatic repulsion of like-ions are introduced to explain the increased EuO quality at the interface with the TiO2 layer. It is shown that ultr…
Stabilizing Magnetic Bubble Domains in Epitaxial 2D Magnet/Topological Insulator Heterostructures through Interfacial Interactions
University of Southern California（南加州大学）；University of South Florida（南佛罗里达大学）；The Ohio State University（俄亥俄州立大学）；Max Planck Institute for Solid State Research（马克斯·普朗克固体研究所）；Helmholtz-Zentrum Berlin für Materialien und Energie（柏林赫尔姆霍兹材料能源中心）
Epitaxial strain energies of epitaxial films and bulk superlattices are studied via first-principles total energy calculations using the local-density approximation. Anharmonic effects due to large lattice mismatch, beyond the reach of the harmonic elasticity theory, are found to be very important in Cu/Au (lattice mismatch 12%), Cu/Ag (12%) and Ni/Au (15%). We find that <001> is the elastically soft direction for biaxial expansion of Cu and Ni, but it is <201> for large biaxial compression of Cu, Ag, and Au. The stability of superlattices is discussed in terms of the coherency strain and inte…
Interfacial Coupling Controls Molecular Epitaxy of HMTP on Graphene/SiC
Masaryk University（马萨里克大学）；Brno University of Technology（布尔诺理工大学）；Charles University（查理大学）；Institute of Physical Engineering, Brno University of Technology（布尔诺理工大学物理工程学院）
The interfacial Dyzaloshinskii-Moria interaction (DMI) helps to stabilize chiral domain walls and magnetic skyrmions, which will facilitate new magnetic memories and spintronics logic devices. The study of interfacial DMI in perpendicularly magnetized structurally asymmetric heavy metal (HM) / ferromagnetic (FM) multilayer systems is of high importance due to the formation of chiral magnetic textures in the presence of DMI. Here, we report the impact of the cobalt oxidation at the cobalt -aluminum oxide interface in Pt/Co/AlOx trilayer structure on the DMI by varying the post-growth annealing …
Epitaxial SrTiO$_3$ (STO) on Si is nowadays the benchmark initial platform for the further addition of functional oxides on Si. Starting the growth of STO on a Sr-passivated Si substrate with 1/2 monolayer (ML) Sr coverage and a (1 $\times$ 2) reconstructed Si surface with rows of Si dimers, the final STO/Sr/Si stack exhibits 1 ML Sr coverage and a (1 $\times$ 1) Si surface without dimer. Using first-principles density functional theory calculations, we investigate how the interface evolves from 1/2 ML to 1 ML Sr coverage, concluding that the latter is indeed most stable and that the reconstru…
Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO3, a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmission electron microscopy complemented by X-ray and optical spectroscopy to study LaCoO3 epitaxial thin films under different strain states. We observed an unconventional strain relaxation behavior re…
AlV$_2$O$_4$ thin films via in-situ interfacial topotaxy
California Institute of Technology（加州理工学院）；Institute for Quantum Information and Matter, California Institute of Technology（加州理工学院量子信息研究所）；Center for High Technology Materials, University of New Mexico（新墨西哥大学高等技术材料中心）
Direct observations using scanning transmission electron microscopy unveil an intriguing interfacial bi-layer that enables epitaxial growth of a strain-free, monoclinic, bronze-phase VO2(B) thin film on a perovskite SrTiO3 (STO) substrate. We observe an ultrathin (2-3 unit cells) interlayer best described as highly strained VO2(B) nanodomains combined with an extra (Ti,V)O2 layer on the TiO2 terminated STO (001) surface. By forming a fully coherent interface with the STO substrate and a semi-coherent interface with the strain-free epitaxial VO2(B) film above, the interfacial bi-layer enables t…
(Li,Al)-co-doped magnesium spinel (Li$_x$Mg$_{1-2x}$Al$_{2+x}$O$_4$) is a solid lithium-ion electrolyte with potential use in all-solid-state lithium-ion batteries. Interfaces with spinel electrodes, such as Li$_y$Mn$_2$O$_4$ and Li$_{4+3z}$Ti$_5$O$_{12}$, may be lattice-matched, with potentially low interfacial resistances. Small lattice parameter differences across a lattice-matched interface are unavoidable, causing residual epitaxial strain. This strain potentially modifies lithium diffusion near the interface, contributing to interfacial resistance. Here we report a density functional the…
It is shown that dilute niobium doping has significant effect on the ferromagnetism and microstructure of dilutely cobalt-doped anatase TiO2 films. Epitaxial films of anatase TiO2 with 3% Co, without and with 1% niobium doping were grown by pulsed-laser deposition at 875 C at different oxygen pressures. For growth at 10^{-5} Torr niobium doping suppresses the ferromagnetism, while it enhances the same in films grown at 10^{-4} Torr. High-resolution Z-contrast Scanning Transmission Electron Microscopy and Electron Energy Loss Spectroscopy show uniform surface segregation of cobalt-rich Ti_{1-x-…
On the basis of first-principles calculations, we report that a novel interfacial atomic structure occurs between graphene and the surface of silicon carbide, destroying the Dirac point of graphene and opening a substantial energy gap there. In the calculated atomic structures, a quasi-periodic $6\times 6$ domain pattern emerges out of a larger commensurate $6\sqrt{3}\times6\sqrt{3}R30^\circ$ periodic interfacial reconstruction, resolving a long standing experimental controversy on the periodicity of the interfacial superstructures. Our theoretical energy spectrum shows a gap and midgap states…
We report experimental and theoretical evidence for the formation of chiral bobbers - an interfacial topological spin texture - in FeGe films grown by molecular beam epitaxy (MBE). After establishing the presence of skyrmions in FeGe/Si(111) thin film samples through Lorentz transmission electron microscopy and topological Hall effect, we perform magnetization measurements that reveal an inverse relationship between film thickness and the slope of the susceptibility (d\c{hi}/dH). We present evidence for the evolution as a function of film thickness, L, from a skyrmion phase for L < LD/2 to a c…
The shape dependence for the technologically important nickel oxide (NiO) nanocrystals on (001) strontium titanate substrates is investigated under the generalized Wulff-Kaichew (GWK) theorem framework. It is found that the shape of the NiO nanocrystals is primarily governed by the existence (or absence) of interfacial strain. Nanocrystals that have a fully pseudomorphic interface with the substrate (i.e. the epitaxial strain is not relaxed) form an embedded smooth ball-crown morphology with {001}, {011}, {111} and high-index {113} exposed facets with a negative Wulff point. On the other hand,…
Epitaxial hcp Cobalt films with pronounced c-axis texture have been prepared by pulsed lased deposition (PLD) either directly onto Al2O3 (0001) single crystal substrates or with an intermediate Ruthenium buffer layer. The crystal structure and epitaxial growth relation was studied by XRD, pole figure measurements and reciprocal space mapping. Detailed VSM analysis shows that the perpendicular anisotropy of these highly textured Co films reaches the magnetocrystalline anisotropy of hcp-Co single crystal material. Films were prepared with thickness t of 20 nm < t < 100 nm to study the crossover …
Interfaces separating ferromagnetic (FM) layers from non-ferromagnetic layers offer unique properties due to spin-orbit coupling and symmetry breaking, yielding effects such as exchange bias, perpendicular magnetic anisotropy, spin-pumping, spin-transfer torques, conversion between charge and spin currents and vice-versa. These interfacial phenomena play crucial roles for magnetic data storage and transfer applications, which require forming FM nano-structures embedded in non-ferromagnetic matrices. Here, we investigate the possiblity of creating such nano-structures by ion-irradiation. We stu…
Control of oxygen stoichiometry in complex oxides via topotactic phase transition is an interesting avenue to not only modifying the physical properties, but utilizing in many energy technologies, such as energy storage and catalysts. However, detailed structural evolution in the close proximity of the topotactic phase transition in multivalent oxides has not been much studied. In this work, we used strontium cobaltites (SrCoOx) epitaxially grown by pulsed laser epitaxy (PLE) as a model system to study the oxidation-driven evolution of the structure, electronic, and magnetic properties. We gre…
The replacement of SiO2 by so-called high-k oxides is one of the major challenges for the semiconductor industry to date. Based on electronic structure calculations and ab-initio molecular dynamics simulations, we are able to provide a consistent picture of the growth process of a class of epitaxial oxides around SrO and SrTiO3. The detailed understanding of the interfacial binding principles has also allowed us to propose a way to engineer the band-offsets between the oxide and the silicon substrate.
A major challenge for future spintronics is to develop suitable spin transport channels with long spin lifetime and propagation length. Graphene can meet these requirements, even at room temperature. On the other side, taking advantage of the fast motion of chiral textures, i.e., Néel-type domain walls and magnetic skyrmions, can satisfy the demands for high-density data storage, low power consumption and high processing speed. We have engineered epitaxial structures where an epitaxial ferromagnetic Co layer is sandwiched between an epitaxial Pt(111) buffer grown in turn onto MgO(111) substrat…
Epitaxial Y3Fe5O12 thin films have been deposited by off-axis sputtering, which exhibit excellent crystalline quality, enabling observation of large spin pumping signals in Pt/Y3Fe5O12 and W/Y3Fe5O12 bilayers driven by cavity ferromagnetic resonance. The inverse spin Hall voltages reach 2.10 mV and -5.26 mV in 5-mm long Pt/Y3Fe5O12 and W/Y3Fe5O12 bilayers, respectively, excited by a radio-frequency magnetic field of 0.3 Oe. From the ferromagnetic resonance linewidth broadening, the interfacial spin mixing conductance of 4.56E14 Ω-1m-2 and 2.30E14 Ω-1m-2 are obtained for Pt/Y3Fe5O12 and W/Y3Fe5…
Control of polarization and polar chiral textures in BiFeO$_3$ by epitaxial strain and interfacial chemistry
Laboratoire Albert Fert, CNRS, Thales, Université Paris–Saclay（阿尔贝·费尔特实验室，法国国家科学研究中心，泰雷兹，巴黎-萨克雷大学）；Department of Materials, ETH Zurich（苏黎世联邦理工学院材料系）；Université Grenoble Alpes, CNRS, Institut Néel（格勒诺布尔阿尔卑斯大学，法国国家科学研究中心，内尔研究所）；Electron Microscopy Center, Empa（电子显微镜中心，瑞士联邦材料科技与测试研究院）
The authors demonstrated that a full-Heusler Co2FeGe (CFG) alloy thin film was epitaxially grown by rapid-thermal-annealing-induced germanidation of an Fe/Co/pseudo-Ge(001)-on-insulator (GOI) multilayer formed on a Si-on-insulator (SOI) substrate. X-ray diffraction (XRD) measurements with the out-of-plane and in-plane configurations revealed that the CFG film was epitaxially grown along the [001] direction with the in-plane epitaxial relation of CFG[100]||GOI[100], although the film slightly contained a texture component. The strong (111) and (200) superlattice diffraction intensities indicate…
We show using scanning tunneling microscopy, spectroscopy, and ab initio calculations that several intercalation structures exist for Na in epitaxial graphene on SiC(0001). Intercalation takes place at room temperature and Na electron-dopes the graphene. It intercalates in-between single-layer graphene and the carbon-rich interfacial layer. It also penetrates beneath the interfacial layer and decouples it to form a second graphene layer. This decoupling is accelerated by annealing and is verified by direct Na deposition onto the interface layer. Our observations show that intercalation in grap…
Magnetic Tunnel Junctions whose basic element consists of two ferromagnetic electrodes separated by an insulating non-magnetic barrier have become intensely studied and used in non-volatile spintronic devices. Since ballistic tunnel of spin-polarized electrons sensitively depends on the chemical composition and the atomic geometry of the lead/barrier interfaces their proper design is a key issue for achieving the required functionality of the devices such as e.g. a high tunnel magneto resistance. An important leap in the development of novel spintronic devices is to replace the insulating barr…
We report on domain pattern transfer from a ferroelectric BaTiO$_{\mathrm{3}}$ substrate with a $(111)$-orientation of the surface to an epitaxial Co film grown on a Pd buffer layer. Spatially modulated interfacial strain transfer from ferroelectric/ferroelastic domains and inverse magnetostriction in the ferromagnetic film induce stripe regions with a modulation of the in-plane uniaxial magnetic anisotropy direction. Using spin-polarized low energy electron microscopy, we observe the formation of two distinct anisotropy configurations between stripe regions. Moreover, through application of a…
Rare earth free alloys are in focus of permanent magnet research since the accessibility of the elements needed for nowadays conventional magnets is limited. Tetragonally strained iron-cobalt (Fe-Co) has attracted large interest as promising candidate due to theoretical calculations. In experiments, however, the applied strain quickly relaxes with increasing film thickness and hampers stabilization of a strong magnetocrystalline anisotropy. In our study we show that already 2 at% of carbon substantially reduce the lattice relaxation leading to the formation of a spontaneously strained phase wi…
Two-Dimensional Altermagnetism in Epitaxial CrSb Ultrathin Films
School of Physics Beihang University（北京航空航天大学物理学院）；Institute of High Energy Physics Chinese Academy of Sciences（中国科学院高能物理研究所）；Singapore University of Technology and Design（新加坡科技设计大学）
