Thickness-Dependent Superconductivity in a Layered Electride on Silicon.

Layered materials exhibit a plethora of fascinating properties. The challenge is to make the materials into epitaxial films, preferably integrated with mature technological platforms to facilitate their potential applications. Progress in this direction can establish the film thickness as a valuable parameter to control various phenomena, superconductivity in particular. Here, a synthetic route to epitaxial films of SrAlSi, a layered superconducting electride, on silicon is designed. A set of films ranging in thickness is synthesized employing a silicene-based template. Their structure and superconductivity are explored by a combination of techniques. Two regimes of TC dependence on the film thickness are identified, the coherence length being the crossover parameter. The results can be extended to syntheses of other honeycomb-lattice ternary compounds on Si or Ge exhibiting superconducting, magnetic, and other properties.

Intrinsic exchange bias state in silicene and germanene materials EuX2.

2D magnets have recently emerged as a host for unconventional phases and related phenomena. The prominence of 2D magnetism stems from its high amenability to external stimuli and structural variations. The low dimensionality facilitates competition between magnetic orders which may give rise to exchange bias, in particular in magnetic heterostructures. Here, we propose a strategy for the search of exchange bias state in 2D individual compounds. We track the evolution of magnetic orders driven by the number of monolayers in a system exhibiting antiferromagnetism in the multilayer and ferromagnetism in the monolayer limit. The material, EuSi2, has the structure of multilayer silicene intercalated by Eu. A strong intrinsic exchange bias effect accompanies the dimensional crossover. Comparison with silicene-based GdSi2 and germanene-based EuGe2 suggests the competition between magnetic orders to be a common property of this class of materials that may be useful in spintronic applications.

Femtosecond optical orientation triggering magnetization precession in epitaxial EuO films.

Light-induced magnetization response unfolding on a temporal scale down to femtoseconds presents a way to convey information via spin manipulation. The advancement of the field requires exploration of new materials implementing various mechanisms for ultrafast magnetization dynamics. Here, pump-probe measurements of EuO-based ferromagnets by a time-resolved two-colour stroboscopic technique are reported. Epitaxial films of the pristine semiconductor and metallic Gd-doped EuO demonstrate photo-induced magnetization precession. Comparative experimental studies of both systems are carried out varying temperature, magnetic field, and polarization light helicity of the pump beam, followed by numerical estimates. The study establishes optical spin orientation by the electronic transition 4f75d0 → 4f65d1 as a mechanism triggering collective magnetization precession in these materials. The results suggest applications of EuO-based systems in optoelectronics and spintronics.

Synthesis and HRTEM Investigation of EuRbFe4As4 Superconductor.

In the stoichiometric iron-based superconductor EuRbFe4As4, superconductivity coexists with a long-range magnetic ordering in Eu layers. Using high-resolution transmission electron microscopy (HRTEM), we observed an atomic structure of as-grown EuRbFe4As4 crystals. HRTEM shows that crystals have two-dimensional intrinsic nanoinclusions established to be the RbFe2As2 (122) phase with a volume fraction of ~5.6%. In contrast with the CaKFe4As4 compound, similar inclusions are not superconducting down to 2 K, and no second magnetization peak was observed in the magnetization measurements at low temperature with B ‖ ab. We show that the non-superconducting 122 phase nanoinclusions could act as 2D pinning centers.

Exchange Bias State at the Crossover to 2D Ferromagnetism.

The inherent malleability of 2D magnetism provides access to unconventional quantum phases, in particular those with coexisting magnetic orders. Incidentally, in a number of materials, the magnetic state in the bulk undergoes a fundamental change when the system is pushed to the monolayer limit. Therefore, a competition of magnetic states can be expected in the crossover region. Here, an exchange bias state is observed at the crossover from 3D antiferromagnetism to 2D ferromagnetism driven by the number of monolayers in the metalloxene GdSi2. The material constitutes a stack of alternating monolayers of Gd and silicene, the Si analogue of graphene. The exchange bias manifests itself as a shift of the hysteresis loop signifying coupling of magnetic systems, as evidenced by magnetization studies. Two features distinguish the phenomenon: (i) it is intrinsic, i.e. it is detected in an individual compound; (ii) the exchange bias field, 1.5 kOe, is unusually high, which is conducive to applications. The results suggest magnetic derivatives of 2D-Xenes to be prospective materials for ultracompact spintronics.

Layer-controlled evolution of electron state in the silicene intercalation compound SrSi2.

Silicene, a Si-based analogue of graphene, holds a high promise for electronics because of its exceptional properties but a high chemical reactivity makes it a very challenging material to work with. The silicene lattice can be stabilized by active metals to form stoichiometric compounds MSi2. Being candidate topological semimetals, these materials provide an opportunity to probe layer dependence of unconventional electronic structures. It is demonstrated here that in the silicene compound SrSi2, the number of monolayers controls the electronic state. A series of films ranging from bulk-like multilayers down to a single monolayer have been synthesized on silicon and characterized with a combination of techniques - from electron and X-ray diffraction to high-resolution electron microscopy. Transport measurements reveal evolution of the chiral anomaly in bulk SrSi2 to weak localization in ultrathin films down to 3 monolayers followed by 3D and 2D strong localization in 2 and 1 monolayers, respectively. The results outline the range of stability of the chiral state, important for practical applications, and shed light on the localization phenomena in the limit of a few monolayers.

Challenges for Pulsed Laser Deposition of FeSe Thin Films.

Anti-PbO-type FeSe shows an advantageous dependence of its superconducting properties with mechanical strain, which could be utilized as future sensor functionality. Although superconducting FeSe thin films can be grown by various methods, ultrathin films needed in potential sensor applications were only achieved on a few occasions. In pulsed laser deposition, the main challenges can be attributed to such factors as controlling film stoichiometry (i.e., volatile elements during the growth), nucleation, and bonding to the substrate (i.e., film/substrate interface control) and preventing the deterioration of superconducting properties (i.e., by surface oxidization). In the present study, we address various technical issues in thin film growth of FeSe by pulsed laser deposition, which pose constraints in engineering and reduce the application potential for FeSe thin films in sensor devices. The results indicate the need for sophisticated engineering protocols that include interface control and surface protection from chemical deterioration. This work provides important actual limitations for pulsed laser deposition (PLD) of FeSe thin films with the thicknesses below 30 nm.

Chemical Composition Control at the Substrate Interface as the Key for FeSe Thin-Film Growth.

The strong fascination exerted by the binary compound of FeSe demands reliable engineering protocols and more effective approaches toward inducing superconductivity in FeSe thin films. Our study addresses the peculiarities in pulsed laser deposition that determine FeSe thin-film growth and focuses on the film/substrate interface, which has only been considered hypothetically in the past literature. The FeSe/MgO interface has been assumed (1) to be clean and (2) to obey lattice-matching epitaxy. Our studies reveal that both assumptions are misleading and demonstrate the tendency for domain-matching epitaxial growth, which accompanies the problem of chemical heterogeneity. We propose that homogenization of the film/substrate interface by an Fe buffer can improve the control of stoichiometry and nanostrain in a way that favors superconductivity even in ultrathin FeSe films. We will also show that on a chemically homogenized FeSe/Fe interface, the control of film texture with preparation conditions is still possible.

High Carrier Mobility in a Layered Antiferromagnet Integrated with Silicon.

Coupling various functional properties in one material is always a challenge, more so if the material should be nanostructured for practical applications. Magnetism and high carrier mobility are key components for spintronic applications but rather difficult to bundle together. Here, we establish EuAl2Si2 as a layered antiferromagnet supporting high carrier mobility. Its topotactic synthesis via a sacrificial two-dimensional template results in epitaxial nanoscale films on silicon. Their outstanding structural quality and atomically sharp interfaces are demonstrated by diffraction and microscopy techniques. EuAl2Si2 films exhibit extreme magnetoresistance and a carrier mobility of above 10,000 cm2 V-1 s-1. The marriage of these properties and magnetism makes EuAl2Si2 a promising spintronic material. Importantly, the seamless integration of EuAl2Si2 with silicon technology is particularly appealing for applications.

Two-Dimensional Magnets beyond the Monolayer Limit.

Intrinsic two-dimensional (2D) magnetism has been demonstrated in various materials scaled down to a single monolayer. However, the question is whether 2D magnetism extends beyond the monolayer limit, to chemical species formed by sparse but regular 2D arrays of magnetic atoms. Here we show that sub-monolayer superstructures of Eu atoms self-assembled on the silicon surface exhibit strong magnetic signals. Robust easy-plane magnetism is discovered in both one- and two-dimensionally ordered structures with Eu coverage of half monolayer and above. The emergence of 2D magnetism manifests itself by a strong dependence of the effective transition temperature on weak magnetic fields. The results constitute a versatile platform for miniaturization of 2D magnetic systems and seed an expandable class of atomically thin magnets for applications in information technologies.

Microstructure and superconducting properties of high-rate PLD-derived GdBa2Cu3O7-δ coated conductors with BaSnO3 and BaZrO3 pinning centers.

The microstructure of GdBa2Cu3O7-δ based on superconducting tapes with BaSnO3 and BaZrO3 artificial pinning centers formed by high-rate pulse laser deposition in SuperOx Japan was studied by scanning/transmission electron microscopy. The artificial pinning centers have adopted columnar morphology with average diameter of about 8 nm (BaSnO3-doped sample) and 6.5 nm (BaZrO3-doped sample) and density of 500 µm-2 for the both samples. The average length of the BaSnO3 nanocolumns is about two times higher than the BaZrO3 nanocolumns. The angular dependences of critical current in magnetic field up to 1 Tesla at 77 and 65 K have been obtained. The critical current and its anisotropy depend on artificial pinning centers presence and their type. The angular dependence of resistivity in the field up to 9 Tesla was also studied and discussed.

Controlling the phase transition in nanocrystalline ferroelectric thin films via cation ratio.

Traditionally, the ferroelectric Curie temperature can be manipulated by chemical substitution, e.g., in Ba1-xSrxTiO3 as one of the archetypical representatives. Here, we show a novel approach to tune the ferroelectric phase transition applicable for nanostructured thin films. We demonstrate this effect in nano-grained BaTiO3 films. Based on an enhanced metastable cation solubility with Ba/Ti-ratios of 0.8 to 1.06, a significant shift of the phase transition temperature is discovered. The transition temperature increases linearly from 212 K to 350 K with increasing Ba/Ti ratio. For all Ba/Ti ratios, a completely diffused phase transition is present resulting in a negligible temperature sensitivity of the dielectric constant. Schottky defects are identified as the driving force behind the off-stoichiometry and the shift of the phase transition temperature as they locally induce lattice strain. Complementary temperature dependent Raman experiments reveal the presence of the hexagonal polymorph in addition to the perovskite phase in all cases. Interestingly, the hexagonal BaTiO3 influences the structural transformation on the Ba-rich side, while on the Ti-rich side no changes for the hexagonal polymorph at the ferroelectric transition temperature are observed. This concerted structural change of both polymorphs on the Ba-rich side causes a broad phase transition region spanning over a wide range up to 420 K including the transition temperature of 350 K obtained from dielectric measurements. These findings are promising for fine adjustment of the phase transition temperature and low temperature coefficient of permittivity.

Interface-Induced Anomalous Hall Conductivity in a Confined Metal.

The mature silicon technological platform is actively explored for spintronic applications. Metal silicides are an integral part of the Si technology used as interconnects, gate electrodes, and diffusion barriers; their epitaxial integration with Si results in premier contacts. Recent studies highlight the exceptional role of electronic discontinuities at interfaces in the spin-dependent transport properties. Here, we report a new type of Hall conductivity driven by sharp interfaces of Eu silicide, an antiferromagnetic metal, sandwiched between two insulators - Si and SiO x. Quasi-ballistic transport probes spin-orbit coupling at the interfaces, in particular, charge-spin interconversion. Transverse magnetic field results in anomalous Hall effect signals of an unusual line shape. The interplay between opposite-sign signals from the two interfaces allows efficient control over the magnitude and sign of the overall effect. Selective engineering of interfaces singles out a particular spin signal. The two-channel nature of the effect and its high tunability offer new functional possibilities for future spintronic devices.

Evidence of extended cation solubility in atomic layer deposited nanocrystalline BaTiO3 thin films and its strong impact on the electrical properties.

Thin films of ≈50 nm thickness with Ba/Ti-ratios ranging from 0.8 to 1.06 were prepared by depositing alternating layers of Ba(OH)2 and TiO2. Annealing at 750 °C promoted the solid-solid transformation into polycrystalline BaTiO3 films containing a mixture of the perovskite and the hexagonal polymorphs with average crystallite sizes smaller than 14 nm and without impurity phases. This, together with an increase of the cubic lattice parameters for Ba-rich films, suggests an extended metastable solubility range for the perovskite-phase in these nanocrystalline thin films on both sides of the stoichiometric composition. Mapping of the cation distribution utilizing energy-filtered transmission electron microscopy corroborates defect accommodation within the BaTiO3 grains. While the cation off-stoichiometry in thermodynamic equilibrium is negligible for BaTiO3, the metastable extended solubility range in the thin films can be directly correlated to the low annealing temperature and nanocrystalline nature. The leakage current behavior can be explained by the formation of Schottky defects for nonstoichiometric films, and the cation ratio has a distinct impact on the dielectric properties: while excess-BaO has a marginal detrimental effect on the permittivity, the dielectric constant declines rapidly by more than 50% towards the Ti-rich side. The present findings highlight the importance of compositional control for the synthesis of nanocrystalline BaTiO3 thin films, in particular for low annealing and/or deposition temperatures. Our synthesis approach using alternating layers of Ba(OH)2 and TiO2 provides a route to precisely control the cation stoichiometry.

High-Temperature Magnetism in Graphene Induced by Proximity to EuO.

Addition of magnetism to spectacular properties of graphene may lead to novel topological states and design of spin logic devices enjoying low power consumption. A significant progress is made in defect-induced magnetism in graphene-selective elimination of p z orbitals (by vacancies or adatoms) at triangular sublattices tailors graphene magnetism. Proximity to a magnetic insulator is a less invasive way, which is being actively explored now. Integration of graphene with the ferromagnetic semiconductor EuO has much to offer, especially in terms of proximity-induced spin-orbit interactions. Here, we synthesize films of EuO on graphene using reactive molecular beam epitaxy. Their quality is attested by electron and X-ray diffraction, cross-sectional electron microscopy, and Raman and magnetization measurements. Studies of electron transport reveal a magnetic transition at TC* ≈ 220 K, well above the Curie temperature 69 K of EuO. Up to TC*, the dependence R xy( B) is strongly nonlinear, suggesting the presence of the anomalous Hall effect. The role of synthesis conditions is highlighted by studies of an overdoped structure. The results justify the use of the EuO/graphene system in spintronics.

Emerging two-dimensional ferromagnetism in silicene materials.

The appeal of ultra-compact spintronics drives intense research on magnetism in low-dimensional materials. Recent years have witnessed remarkable progress in engineering two-dimensional (2D) magnetism via defects, edges, adatoms, and magnetic proximity. However, intrinsic 2D ferromagnetism remained elusive until recent discovery of out-of-plane magneto-optical response in Cr-based layers, stimulating the search for 2D magnets with tunable and diverse properties. Here we employ a bottom-up approach to produce layered structures of silicene (a Si counterpart of graphene) functionalized by rare-earth atoms, ranging from the bulk down to one monolayer. We track the evolution from the antiferromagnetism of the bulk to intrinsic 2D in-plane ferromagnetism of ultrathin layers, with its characteristic dependence of the transition temperature on low magnetic fields. The emerging ferromagnetism manifests itself in the electron transport. The discovery of a class of robust 2D magnets, compatible with the mature Si technology, is instrumental for engineering new devices and understanding spin phenomena.

Fine structure of metal-insulator transition in EuO resolved by doping engineering.

Metal-insulator transitions (MITs) offer new functionalities for nanoelectronics. However, ongoing attempts to control the resistivity by external stimuli are hindered by strong coupling of spin, charge, orbital and lattice degrees of freedom. This difficulty presents a quest for materials which exhibit MIT caused by a single degree of freedom. In the archetypal ferromagnetic semiconductor EuO, magnetic orders dominate the MIT. Here we report a new approach to take doping under control in this material on the nanoscale: formation of oxygen vacancies is strongly suppressed to exhibit the highest MIT resistivity jump and magnetoresistance among thin films. The nature of the MIT is revealed in Gd doped films. The critical doping is determined to be more than an order of magnitude lower than in all previous studies. In lightly doped films, a remarkable thermal hysteresis in resistivity is discovered. It extends over 100 K in the paramagnetic phase reaching 3 orders of magnitude. In the warming mode, the MIT is shown to be a two-step process. The resistivity patterns are consistent with an active role of magnetic polarons-formation of a narrow band and its thermal destruction. High-temperature magnetic polaron effects include large negative magnetoresistance and ferromagnetic droplets revealed by x-ray magnetic circular dichroism. Our findings have wide-range implications for the understanding of strongly correlated oxides and establish fundamental benchmarks to guide theoretical models of the MIT.

Formation of BiFeO3 from a Binary Oxide Superlattice Grown by Atomic Layer Deposition.

We report on the growth of polycrystalline BiFeO3 thin films on SiO2 /Si(001) and Pt(111) substrates by atomic layer deposition using the precursors ferrocene, triphenyl-bismuth, and ozone. By growing alternating layers of Fe2 O3 and Bi2 O3 , we employ a superlattice approach and demonstrate an efficient control of the cation stoichiometry. The superlattice decay and the resulting formation of polycrystalline BiFeO3 films are studied by in situ X-ray diffraction, in situ X-ray photoelectron spectroscopy, and transmission electron microscopy. No intermediate ternary phases are formed and BiFeO3 crystallization is initiated in the Bi2 O3 layers at 450 °C following the diffusion-driven intermixing of the cations. Our study of the BiFeO3 formation provides an insight into the complex interplay between microstructural evolution, grain growth, and bismuth oxide evaporation, with implications for optimization of ferroelectric properties.

Europium Silicide - a Prospective Material for Contacts with Silicon.

Metal-silicon junctions are crucial to the operation of semiconductor devices: aggressive scaling demands low-resistive metallic terminals to replace high-doped silicon in transistors. It suggests an efficient charge injection through a low Schottky barrier between a metal and Si. Tremendous efforts invested into engineering metal-silicon junctions reveal the major role of chemical bonding at the interface: premier contacts entail epitaxial integration of metal silicides with Si. Here we present epitaxially grown EuSi2/Si junction characterized by RHEED, XRD, transmission electron microscopy, magnetization and transport measurements. Structural perfection leads to superb conductivity and a record-low Schottky barrier with n-Si while an antiferromagnetic phase invites spin-related applications. This development opens brand-new opportunities in electronics.

Atomic-Scale Engineering of Abrupt Interface for Direct Spin Contact of Ferromagnetic Semiconductor with Silicon.

Control and manipulation of the spin of conduction electrons in industrial semiconductors such as silicon are suggested as an operating principle for a new generation of spintronic devices. Coherent injection of spin-polarized carriers into Si is a key to this novel technology. It is contingent on our ability to engineer flawless interfaces of Si with a spin injector to prevent spin-flip scattering. The unique properties of the ferromagnetic semiconductor EuO make it a prospective spin injector into silicon. Recent advances in the epitaxial integration of EuO with Si bring the manufacturing of a direct spin contact within reach. Here we employ transmission electron microscopy to study the interface EuO/Si with atomic-scale resolution. We report techniques for interface control on a submonolayer scale through surface reconstruction. Thus we prevent formation of alien phases and imperfections detrimental to spin injection. This development opens a new avenue for semiconductor spintronics.