Raman interrogation of the ferroelectric phase transition in polar metal LiOsO3.

Ferroelectric (FE) distortions in a metallic material were believed to be experimentally inaccessible because itinerant electrons would screen the long-range Coulomb interactions that favor a polar structure. It has been suggested by Anderson and Blount [P. W. Anderson, E. I. Blount, Phys. Rev. Lett. 14, 217-219 (1965)] that a transition from paraelectric phase to FE phase is possible for a metal if, in the paraelectric phase, the electrons at the Fermi level are decoupled from the soft transverse optical phonons, which lead to ferroelectricity. Here, using Raman spectroscopy combined with magnetotransport measurements on a recently discovered FE metal LiOsO3, we demonstrate active interplay of itinerant electrons and the FE order: Itinerant electrons cause strong renormalization of the FE order parameter, leading to a more gradual transition in LiOsO3 than typical insulating FEs. In return, the FE order enhances the anisotropy of charge transport between parallel and perpendicular to the polarization direction. The temperature-dependent evolution of Raman active in-plane 3Eg phonon, which strongly couples to the polar-active out-of-the-plane A2u phonon mode in the high-temperature paraelectric state, exhibits a deviation in Raman shift from the expectation of the pseudospin-phonon model that is widely used to model many insulating FEs. The Curie-Weiss temperature (θ ≈ 97 K) obtained from the optical susceptibility is substantially lower than T s, suggesting a strong suppression of FE fluctuations. Both line width and Fano line shape of 3Eg Raman mode exhibit a strong electron-phonon coupling in the high-temperature paraelectric phase, which disappears in the FE phase, challenging Anderson/Blount's proposal for the formation of FE metals.

Atomic-scale determination of spontaneous magnetic reversal in oxide heterostructures.

Interfaces between transition metal oxides are known to exhibit emerging electronic and magnetic properties. Here we report intriguing magnetic phenomena for La2/3Sr1/3MnO3 films on an SrTiO3 (001) substrate (LSMO/STO), where the interface governs the macroscopic properties of the entire monolithic thin film. The interface is characterized on the atomic level utilizing scanning transmission electron microscopy and electron energy loss spectroscopy (STEM-EELS), and density functional theory (DFT) is employed to elucidate the physics. STEM-EELS reveals mixed interfacial stoichiometry, subtle lattice distortions, and oxidation-state changes. Magnetic measurements combined with DFT calculations demonstrate that a unique form of antiferromagnetic exchange coupling appears at the interface, generating a novel exchange spring-type interaction that results in a remarkable spontaneous magnetic reversal of the entire ferromagnetic film, and an inverted magnetic hysteresis, persisting above room temperature. Formal oxidation states derived from electron spectroscopy data expose the fact that interfacial oxidation states are not consistent with nominal charge counting. The present work demonstrates the necessity of atomically resolved electron microscopy and spectroscopy for interface studies. Theory demonstrates that interfacial nonstoichiometry is an essential ingredient, responsible for the observed physical properties. The DFT-calculated electrostatic potential is flat in both the LSMO and STO sides (no internal electric field) for both Sr-rich and stoichiometric interfaces, while the DFT-calculated charge density reveals no charge transfer/accumulation at the interface, indicating that oxidation-state changes do not necessarily reflect charge transfer and that the concept of polar mismatch is not applicable in metal-insulator polar-nonpolar interfaces.

Observing a previously hidden structural-phase transition onset through heteroepitaxial cap response.

Characterization of the onset of a phase transition is often challenging due to the fluctuations of the correlation length scales of the order parameters. This is especially true for second-order structural-phase transition due to minute changes involved in the relevant lattice constants. A classic example is the cubic-to-tetragonal second-order phase transition in SrTiO3 (STO), which is so subtle that it is still unresolved. Here, we demonstrate an approach to resolve this issue by epitaxially grown rhombohedral La0.7Sr0.3MnO3 (LSMO) thin films on the cubic STO (100) substrate. The shear strain induced nanotwinning waves in the LSMO film are extremely sensitive to the cubic-to-tetragonal structural-phase transitions of the STO substrate. Upon cooling from room temperature, the development of the nanotwinning waves is spatially inhomogeneous. Untwinned, atomically flat domains, ranging in size from 100 to 300 nm, start to appear randomly in the twinned phase between 265 and 175 K. At ∼139 K, the untwinned, atomically flat domains start to grow rapidly into micrometer scale and finally become dominant at ∼108 K. These results indicate that the low-temperature tetragonal precursor phase of STO has already nucleated at 265 K, significantly higher than the critical temperature of STO (∼105 K). Our work paves a pathway to visualize the onset stages of structural-phase transitions that are too subtle to be observed using direct-imaging methods.

Designing antiphase boundaries by atomic control of heterointerfaces.

Extended defects are known to have critical influences in achieving desired material performance. However, the nature of extended defect generation is highly elusive due to the presence of multiple nucleation mechanisms with close energetics. A strategy to design extended defects in a simple and clean way is thus highly desirable to advance the understanding of their role, improve material quality, and serve as a unique playground to discover new phenomena. In this work, we report an approach to create planar extended defects-antiphase boundaries (APB) -with well-defined origins via the combination of advanced growth, atomic-resolved electron microscopy, first-principals calculations, and defect theory. In La2/3Sr1/3MnO3 thin film grown on Sr2RuO4 substrate, APBs in the film naturally nucleate at the step on the substrate/film interface. For a single step, the generated APBs tend to be nearly perpendicular to the interface and propragate toward the film surface. Interestingly, when two steps are close to each other, two corresponding APBs communicate and merge together, forming a unique triangle-shaped defect domain boundary. Such behavior has been ascribed, in general, to the minimization of the surface energy of the APB. Atomic-resolved electron microscopy shows that these APBs have an intriguing antipolar structure phase, thus having the potential as a general recipe to achieve ferroelectric-like domain walls for high-density nonvolatile memory.

Nontrivial Berry phase in magnetic BaMnSb2 semimetal.

The subject of topological materials has attracted immense attention in condensed-matter physics because they host new quantum states of matter containing Dirac, Majorana, or Weyl fermions. Although Majorana fermions can only exist on the surface of topological superconductors, Dirac and Weyl fermions can be realized in both 2D and 3D materials. The latter are semimetals with Dirac/Weyl cones either not tilted (type I) or tilted (type II). Although both Dirac and Weyl fermions have massless nature with the nontrivial Berry phase, the formation of Weyl fermions in 3D semimetals require either time-reversal or inversion symmetry breaking to lift degeneracy at Dirac points. Here we demonstrate experimentally that canted antiferromagnetic BaMnSb2 is a 3D Weyl semimetal with a 2D electronic structure. The Shubnikov-de Hass oscillations of the magnetoresistance give nearly zero effective mass with high mobility and the nontrivial Berry phase. The ordered magnetic arrangement (ferromagnetic ordering in the ab plane and antiferromagnetic ordering along the c axis below 286 K) breaks the time-reversal symmetry, thus offering us an ideal platform to study magnetic Weyl fermions in a centrosymmetric material.

Interface-induced multiferroism by design in complex oxide superlattices.

Interfaces between materials present unique opportunities for the discovery of intriguing quantum phenomena. Here, we explore the possibility that, in the case of superlattices, if one of the layers is made ultrathin, unexpected properties can be induced between the two bracketing interfaces. We pursue this objective by combining advanced growth and characterization techniques with theoretical calculations. Using prototype La2/3Sr1/3MnO3 (LSMO)/BaTiO3 (BTO) superlattices, we observe a structural evolution in the LSMO layers as a function of thickness. Atomic-resolution EM and spectroscopy reveal an unusual polar structure phase in ultrathin LSMO at a critical thickness caused by interfacing with the adjacent BTO layers, which is confirmed by first principles calculations. Most important is the fact that this polar phase is accompanied by reemergent ferromagnetism, making this system a potential candidate for ultrathin ferroelectrics with ferromagnetic ordering. Monte Carlo simulations illustrate the important role of spin-lattice coupling in LSMO. These results open up a conceptually intriguing recipe for developing functional ultrathin materials via interface-induced spin-lattice coupling.

Enhanced Superconducting State in FeSe/SrTiO_{3} by a Dynamic Interfacial Polaron Mechanism.

The observation of substantially enhanced superconductivity of single-layer FeSe films on SrTiO_{3} has stimulated intensive research interest. At present, conclusive experimental data on the corresponding electron-boson interaction is still missing. Here we use inelastic electron scattering spectroscopy and angle resolved photoemission spectroscopy to show that the electrons in these systems are dressed by the strongly polarized lattice distortions of the SrTiO_{3}, and the indispensable nonadiabatic nature of such a coupling leads to the formation of dynamic interfacial polarons. Furthermore, the collective motion of the polarons results in a polaronic plasmon mode, which is unambiguously correlated with the surface phonons of SrTiO_{3} in the presence of the FeSe films. A microscopic model is developed showing that the interfacial polaron-polaron interaction leads to the superconductivity enhancement.

Giant magneto-optical Raman effect in a layered transition metal compound.

We report a dramatic change in the intensity of a Raman mode with applied magnetic field, displaying a gigantic magneto-optical effect. Using the nonmagnetic layered material MoS2 as a prototype system, we demonstrate that the application of a magnetic field perpendicular to the layers produces a dramatic change in intensity for the out-of-plane vibrations of S atoms, but no change for the in-plane breathing mode. The distinct intensity variation between these two modes results from the effect of field-induced broken symmetry on Raman scattering cross-section. A quantitative analysis on the field-dependent integrated Raman intensity provides a unique method to precisely determine optical mobility. Our analysis is symmetry-based and material-independent, and thus the observations should be general and inspire a new branch of inelastic light scattering and magneto-optical applications.

Emerging single-phase state in small manganite nanodisks.

In complex oxides systems such as manganites, electronic phase separation (EPS), a consequence of strong electronic correlations, dictates the exotic electrical and magnetic properties of these materials. A fundamental yet unresolved issue is how EPS responds to spatial confinement; will EPS just scale with size of an object, or will the one of the phases be pinned? Understanding this behavior is critical for future oxides electronics and spintronics because scaling down of the system is unavoidable for these applications. In this work, we use La0.325Pr0.3Ca0.375MnO3 (LPCMO) single crystalline disks to study the effect of spatial confinement on EPS. The EPS state featuring coexistence of ferromagnetic metallic and charge order insulating phases appears to be the low-temperature ground state in bulk, thin films, and large disks, a previously unidentified ground state (i.e., a single ferromagnetic phase state emerges in smaller disks). The critical size is between 500 nm and 800 nm, which is similar to the characteristic length scale of EPS in the LPCMO system. The ability to create a pure ferromagnetic phase in manganite nanodisks is highly desirable for spintronic applications.

Classification of charge density waves based on their nature.

The concept of a charge density wave (CDW) permeates much of condensed matter physics and chemistry. CDWs have their origin rooted in the instability of a one-dimensional system described by Peierls. The extension of this concept to reduced dimensional systems has led to the concept of Fermi surface nesting (FSN), which dictates the wave vector [Formula: see text] of the CDW and the corresponding lattice distortion. The idea is that segments of the Fermi contours are connected by [Formula: see text], resulting in the effective screening of phonons inducing Kohn anomalies in their dispersion at [Formula: see text], driving a lattice restructuring at low temperatures. There is growing theoretical and experimental evidence that this picture fails in many real systems and in fact it is the momentum dependence of the electron-phonon coupling (EPC) matrix element that determines the characteristic of the CDW phase. Based on the published results for the prototypical CDW system 2H-NbSe2, we show how well the [Formula: see text]-dependent EPC matrix element, but not the FSN, can describe the origin of the CDW. We further demonstrate a procedure of combing electronic band and phonon measurements to extract the EPC matrix element, allowing the electronic states involved in the EPC to be identified. Thus, we show that a large EPC does not necessarily induce the CDW phase, with Bi2Sr2CaCu2O8+δ as the example, and the charge-ordered phenomena observed in various cuprates are not driven by FSN or EPC. To experimentally resolve the microscopic picture of EPC will lead to a fundamental change in the way we think about, write about, and classify charge density waves.

Manipulating electronic phase separation in strongly correlated oxides with an ordered array of antidots.

The interesting transport and magnetic properties in manganites depend sensitively on the nucleation and growth of electronic phase-separated domains. By fabricating antidot arrays in La0.325Pr0.3Ca0.375MnO3 (LPCMO) epitaxial thin films, we create ordered arrays of micrometer-sized ferromagnetic metallic (FMM) rings in the LPCMO films that lead to dramatically increased metal-insulator transition temperatures and reduced resistances. The FMM rings emerge from the edges of the antidots where the lattice symmetry is broken. Based on our Monte Carlo simulation, these FMM rings assist the nucleation and growth of FMM phase domains increasing the metal-insulator transition with decreasing temperature or increasing magnetic field. This study points to a way in which electronic phase separation in manganites can be artificially controlled without changing chemical composition or applying external field.

Anomalous Acoustic Plasmon Mode from Topologically Protected States.

Plasmons, the collective excitations of electrons in the bulk or at the surface, play an important role in the properties of materials, and have generated the field of "plasmonics." We report the observation of a highly unusual acoustic plasmon mode on the surface of a three-dimensional topological insulator (TI) Bi_{2}Se_{3}, using momentum resolved inelastic electron scattering. In sharp contrast to ordinary plasmon modes, this mode exhibits almost linear dispersion into the second Brillouin zone and remains prominent with remarkably weak damping not seen in any other systems. This behavior must be associated with the inherent robustness of the electrons in the TI surface state, so that not only the surface Dirac states but also their collective excitations are topologically protected. On the other hand, this mode has much smaller energy dispersion than expected from a continuous media excitation picture, which can be attributed to the strong coupling with surface phonons.

Anomalous surface lattice dynamics in the low-temperature phase of Ba(Fe1-xCox)2As2.

In complex materials, how correlation between charge, spin, and lattice affects the emergent phenomena remains unclear. The newly discovered iron-based high-temperature superconductors and related compounds present to the community a prototype family of materials, where interplay between charge, spin, and lattice degrees of freedom can be explored. With the occurrence of structural, magnetic, and superconducting transitions in the bulk of these materials, creating a surface will change the delicate balance between these phases, resulting in new behavior. A surface lattice dynamics study on (001) Ba(Fe(1-x)Co(x))(2)As(2), through electron energy loss spectroscopy measurements, reveals unusual temperature dependence of both the phonon frequency and line width in the low-temperature orthorhombic phase. The rate of change of phonon frequency with temperature is gigantic, two orders of magnitude larger than in the bulk. This behavior cannot be explained using conventional models of anharmonicity or electron-phonon coupling; instead, it requires that a large surface-spin-charge-lattice coupling be included. Furthermore, the higher surface-phase-transition temperature driven by surface stabilization of the low-temperature orthorhombic phase seems to turn the first-order transition (bulk) into the second-order type, equivalent to what is observed in the bulk by applying a uniaxial pressure. Such equivalence indicates that the surface mirrors the bulk under extreme conditions.

Interplay between superconductivity and magnetism in Fe(1-x)Pd(x)Te.

The attractive/repulsive relationship between superconductivity and magnetic ordering has fascinated the condensed matter physics community for a century. In the early days, magnetic impurities doped into a superconductor were found to quickly suppress superconductivity. Later, a variety of systems, such as cuprates, heavy fermions, and Fe pnictides, showed superconductivity in a narrow region near the border to antiferromagnetism (AFM) as a function of pressure or doping. However, the coexistence of superconductivity and ferromagnetic (FM) or AFM ordering is found in a few compounds [RRh4B4 (R = Nd, Sm, Tm, Er), R'Mo6X8 (R' = Tb, Dy, Er, Ho, and X = S, Se), UMGe (M = Ge, Rh, Co), CeCoIn5, EuFe2(As(1-x)P(x))2, etc.], providing evidence for their compatibility. Here, we present a third situation, where superconductivity coexists with FM and near the border of AFM in Fe(1-x)Pd(x)Te. The doping of Pd for Fe gradually suppresses the first-order AFM ordering at temperature T(N/S), and turns into short-range AFM correlation with a characteristic peak in magnetic susceptibility at T'(N). Superconductivity sets in when T'(N) reaches zero. However, there is a gigantic ferromagnetic dome imposed in the superconducting-AFM (short-range) cross-over regime. Such a system is ideal for studying the interplay between superconductivity and two types of magnetic (FM and AFM) interactions.

Role of antiferromagnetic ordering in the (1×2) surface reconstruction of Ca(Fe(1-x)Co(x))2As2.

Low energy electron diffraction, scanning tunneling microscopy and spectroscopy, and first-principles spin-dependent density functional theory are utilized to investigate the geometric, electronic, and magnetic structures of the stripe-ordered (1×2) surface of Ca(Fe1-xCox)2As2 (x=0, 0.075). The surface is terminated with a 50% Ca layer. Compared to the bulk, the surface Ca layer has a large inward relaxation (∼0.5 Å), and the underneath As-Fe2-As layer displays a significant buckling. First-principles calculations show that the (1×2) phase is stabilized by the bulk antiferromagnetic spin ordering through the spin-charge-lattice coupling. Strikingly, a superconducting gap (∼7 meV at 7.4 K) is observed to spatially coexist with the (1×2) phase (x=0.075 compound). This implies the coexistence of both superconductivity and AFM ordering at the surface.

Strain-induced defect superstructure on the SrTiO3(110) surface.

We report on a combined scanning tunneling microscopy and density functional theory calculation study of the SrTiO(3) (110)-(4 × 1) surface. It is found that antiphase domains are formed along the [11[over ¯]0]-oriented stripes on the surface. The domain boundaries are decorated by defect pairs consisting of Ti(2)O(3) vacancies and Sr adatoms, which relieve the residual stress. The formation energy of and interactions between vacancies result in a defect superstructure. It is suggested that the density and distributions of defects can be tuned by strain engineering, providing a flexible platform for the designed growth of complex oxide materials.

Evidence of Coulomb blockade behavior in a quasi-zero-dimensional quantum well on TiO2 surface.

Line defects on the surface of rutile TiO(2)(110) form in pairs separated by 1.2 nm creating a quantum well. The well is effectively closed by the presence of two charged structures at both ends separated by a distance in the 10-20 nm range. As expected for quantum confinement a long period oscillatory feature of the local density of states is observed and attributed to the formation of discrete quantum states inside the system. It is at first glance surprising that the lowest energy quantum state of the well can be observed at room temperature. The properties of the quantum state cannot be explained in an independent-electron, band-like theory. Instead, electron-electron correlation must be included to give a satisfactory picture of the spatial distribution of the charge density. Theory predicts charging energies of 1.30 eV and 1.14 eV for quantum well lengths of 14 nm and 16 nm, respectively, in good agreement with a classical calculation and the size dependence of the capacitance. This observation opens up the possibility of experimentally imaging the transition from a Coulomb blockade localized in a zero-dimensional system to an independent-particle or band-like behavior in an extended one-dimensional system.

Imaging and manipulation of the competing electronic phases near the Mott metal-insulator transition.

The complex interplay between the electron and lattice degrees of freedom produces multiple nearly degenerate electronic states in correlated electron materials. The competition between these degenerate electronic states largely determines the functionalities of the system, but the invoked mechanism remains in debate. By imaging phase domains with electron microscopy and interrogating individual domains in situ via electron transport spectroscopy in double-layered Sr(3)(Ru(1-x)Mn(x))(2)O(7) (x = 0 and 0.2), we show in real-space that the microscopic phase competition and the Mott-type metal-insulator transition are extremely sensitive to applied mechanical stress. The revealed dynamic phase evolution with applied stress provides the first direct evidence for the important role of strain effect in both phase separation and Mott metal-insulator transition due to strong electron-lattice coupling in correlated systems.

Formation of dislocations via misfit strain across interfaces in epitaxial BaTiO3and SrIrO3heterostructures.

Dislocations often occur in thin films with large misfit strain as a result of strain energy accumulation and can drastically change the film properties. Here the structure and dislocations in oxide heterostructures with large misfit strain are investigated on atomic scale. When grown on SrTiO3(001), the dislocations in both the monolithic BaTiO3thin film and its superlattices with SrIrO3appear above a critical thickness around 6 nm. The edge component of the dislocations is seen in both cases with the Burgers vector ofa⟨100⟩. However, compared to monolithic BaTiO3, the dislocation density is slightly lower in BaTiO3/SrIrO3superlattices. In the superlattice, when considering the SrTiO3lattice constant as the reference, BaTiO3has a larger misfit strain comparing with SrIrO3. It is found that in both cases, the formation of dislocation is only affected by the critical thickness of the film with larger lattice misfit (BaTiO3), regardless of the existence of a strong octahedral tilt/rotation mismatch at BaTiO3/SrIrO3interface. Our findings suggest that it is possible to control the position of dislocations, an important step toward defect engineering.

Direct determination of the electron-phonon coupling matrix element in a correlated system.

High-resolution electron energy loss spectroscopy measurements have been carried out on an optimally doped cuprate Bi(2)Sr(2)CaCu(2)O(8+δ). The momentum-dependent energy and linewidth of an A1 optical phonon were obtained. Based on these data as well as detailed knowledge of the electronic structure, we developed a scheme to determine the electron-phonon coupling (EPC) matrix element related to a specific phonon mode. Such an approach is general and applicable to elucidating the full structure of EPC in a system with anisotropic electronic structure.