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We report on the magnetic structure and ordering of hexagonal LuFeO3, films of variable thickness grown by molecular-beam epitaxy on YSZ (111) and Al2O3 (0001) substrates. These crystalline films exhibit long-range structural uniformity dominated by the polar P63cm phase, which is responsible for the paraelectric to ferroelectric transition that occurs above 1000 K. Using bulk magnetometry and neutron diffraction, we find that the system orders into a ferromagnetically canted antiferromagnetic state via a single transition below 155 K regardless of film thickness, which is substantially lower than that previously reported in hexagonal LuFeO3 films. The symmetry of the magnetic structure in the ferroelectric state implies that this material is a strong candidate for linear magnetoelectric coupling and control of the ferromagnetic moment directly by an electric field. [ABSTRACT FROM AUTHOR]

Hard x-ray photoelectron spectroscopy (HAXPES) and variable kinetic energy x-ray photoelectron spectroscopy (VKE-XPS) analyses have been performed on ten-unit-cell-thick LaLa((1-δ)Al(1+δ)O3 films, with La:Al ratios of 1.1, 1.0, and 0.9, deposited on SrTiO3. Only Al-rich films are known to have a conductive interface. VKE-XPS, coupled with maximum entropy analysis, shows significant differences in the compositional depth profile among the Al-rich, La-rich, and stoichiometric films: significant La enrichment at the interface is observed in the La-rich and stoichiometric films, while the Al-rich film shows little to no intermixing. Additionally, the La-rich and stoichiometric films show a high concentration of Al at the surface, which is not observed in the Al-rich film. HAXPES valence band (VB) analysis shows a broadening of the VB for the Al-rich sample relative to the stoichiometric and La-rich samples. This broadening is consistent with an electric field across the Al-rich film. These results are consistent with a defect-driven electronic reconstruction. [ABSTRACT FROM AUTHOR]

The phase diagram of (PbTiO3)m/(BaTiO3)n ferroelectric superlattices was computed using the phase-field approach as a function of layer volume fraction and biaxial strain to tune ferroelectric properties through domain engineering. Two interesting domain structures are found: one with mixed Bloch-Neel-Ising domain wall structures and the other with stabilized monoclinic Mc phases. The polarization of the monoclinic Mc phase is able to rotate from out-of-plane to in-plane or vice versa under an electric field, and thus facilitates the domain reversal of rhombohedral domains. This contributes significantly to both reduced coercive fields and enhanced piezoelectric responses. [ABSTRACT FROM AUTHOR]

We apply ultrafast x-ray diffraction with femtosecond temporal resolution to monitor the lattice dynamics in a thin film of multiferroic BiFeO3BiFeO3 after above-band-gap photoexcitation. The sound-velocity limited evolution of the observed lattice strains indicates a quasi-instantaneous photoinduced stress which decays on a nanosecond time scale. This stress exhibits an inhomogeneous spatial profile evidenced by the broadening of the Bragg peak. These new data require substantial modification of existing models of photogenerated stresses in BiFeO3: the relevant excited charge carriers must remain localized to be consistent with the data. [ABSTRACT FROM AUTHOR]

The structural and electronic recovery pathways of a photoexcited ultrathin vanadium dioxide (VO2) film at nanosecond time scales have been studied using time-resolved x-ray diffraction and transient optical absorption techniques. The recovery pathways from the tetragonal metallic phase to the monoclinic insulating phase are highly dependent on the optical pump fluence. At pump fluences higher than the saturation fluence of 14.7 mJ/cm², we observed a transient structural state with lattice parameter larger than that of the tetragonal phase, which is decoupled from the metal-to-insulator phase transition. Subsequently, the photoexcited VO2 film recovered to the ground state at characteristic times dependent upon the pump fluence as a result of heat transport from the film to the substrate. We present a procedure to measure the time-resolved film temperature by correlating photoexcited and temperature-dependent x-ray diffraction measurements. A thermal transport model that incorporates changes of the thermal parameters across the phase transition reproduces the observed recovery dynamics. The optical excitation and fast recovery of ultrathin VO2 films provides a practical method to reversibly switch between the monoclinic insulating and tetragonal metallic state at nanosecond time scales. [ABSTRACT FROM AUTHOR]

We determined the atomic structures and energies of 109°, 180°, and 71° domain walls in BiFeO3, combining density functional theory+U calculations and aberration-corrected transmission electron microscopy images. We find a substantial Bi sublattice shift and a rather uniform Fe sublattice across the walls. The calculated wall energies (γ) follow the sequence γ109<γ180<γ71 for the 109°, 180°, and 71° walls. We attribute the high 71° wall energy to an opposite tilting rotation of the oxygen octahedra and the low 109° wall energy to the opposite twisting rotation of the oxygen octahedra across the domain walls. [ABSTRACT FROM AUTHOR]

Above-band-gap optical excitation produces interdependent structural and electronic responses in a multiferroic BiFeO3 thin film. Time-resolved synchrotron x-ray diffraction shows that photoexcitation can induce a large out-of-plane strain, with magnitudes on the order of half of one percent following pulsed-laser excitation. The strain relaxes with the same nanosecond time dependence as the interband relaxation of excited charge carriers. The magnitude of the strain and its temporal correlation with excited carriers indicate that an electronic mechanism, rather than thermal effects, is responsible for the lattice expansion. The observed strain is consistent with a piezoelectric distortion resulting from partial screening of the depolarization field by charge carriers, an effect linked to the electronic transport of excited carriers. The nonthermal generation of strain via optical pulses promises to extend the manipulation of ferroelectricity in oxide multiferroics to subnanosecond time scales. [ABSTRACT FROM AUTHOR]

The asymmetry between electron and hole doping remains one of the central issues in high-temperature cuprate superconductivity, but our understanding of the electron-doped cuprates has been hampered by apparent discrepancies between the only two known families: Re2-xCexCuO4 and A1-xLaxCuO2. Here we report in situ angle-resolved photoemission spectroscopy measurements of epitaxially stabilized Sr1-xLaxCuO2 thin films synthesized by oxide molecular-beam epitaxy. Our results reveal a strong coupling between electrons and (π,π) antiferromagnetism that induces a Fermi surface reconstruction which pushes the nodal states below the Fermi level. This removes the hole pocket near (π/2, π/2), realizing nodeless superconductivity without requiring a change in the symmetry of the order parameter and providing a universal understanding of all electron-doped cuprates. [ABSTRACT FROM AUTHOR]

A magnetization-induced rotation in the third-order nonlinear optical response is observed in out-of-plane- magnetized epitaxial EuO films. We discuss the relation of this nonlinear magneto-optical rotation to the linear Faraday rotation. It is allowed in all materials but, in contrast to the linear Faraday rotation, not affected by the reduction of the thickness of the material. Thus the third-order magneto-optical rotation is particularly suitable for probing the magnetization of functional magnetic materials such as ultrathin films and multilayers. [ABSTRACT FROM AUTHOR]

Recent reports have identified new metaphases of VO2 with strain and/or doping, suggesting the structural phase transition and the metal-to-insulator transition might be decoupled. Using epitaxially strained VO2/TiO2 (001) thin films, which display a bulklike abrupt metal-to-insulator transition and rutile to monoclinic transition structural phase transition, we employ x-ray standing waves combined with hard x-ray photoelectron spectroscopy to simultaneously measure the structural and electronic transitions. This x-ray standing waves study elegantly demonstrates the structural and electronic transitions occur concurrently within experimental limits (±1 K). [ABSTRACT FROM AUTHOR]

The carrier effective mass plays a crucial role in modern electronic, optical, and catalytic devices and is fundamentally related to key properties of solids such as the mobility and density of states. Here we demonstrate a method to deterministically engineer the effective mass using spatial confinement in metallic quantum wells of the transition metal oxide IrO2. Using a combination of in situ angle-resolved photoemission spectroscopy measurements in conjunction with precise synthesis by oxide molecular-beam epitaxy, we show that the low-energy electronic subbands in ultrathin films of rutile IrO2 have their effective masses enhanced by up to a factor of 6 with respect to the bulk. The origin of this strikingly large mass enhancement is the confinement-induced quantization of the highly nonparabolic, three-dimensional electronic structure of IrO2 in the ultrathin limit. This mechanism lies in contrast to that observed in other transition metal oxides, in which mass enhancement tends to result from complex electron-electron interactions and is difficult to control. Our results demonstrate a general route towards the deterministic enhancement and engineering of carrier effective masses in spatially confined systems, based on an understanding of the three-dimensional bulk electronic structure. [ABSTRACT FROM AUTHOR]

Continuous developments in nanotechnology require new approaches to materials synthesis that can produce novel functional structures. Here, we show that nanoscale defects, such as nonstoichiometric nanoregions (NSNRs), can act as nano-building blocks for creating complex electrical polarization structures in the prototypical multiferroic BiFeO3. An array of charged NSNRs are produced in BiFeO3 thin films by tuning the substrate temperature during film growth. Atomic-scale scanning transmission electron microscopy imaging reveals exotic polarization rotation patterns around these NSNRs. These polarization patterns resemble hedgehog or vortex topologies and can cause local changes in lattice symmetries leading to mixed-phase structures resembling the morphotropic phase boundary with high piezoelectricity. Phase-field simulations indicate that the observed polarization configurations are mainly induced by charged states at the NSNRs. Engineering defects thus may provide a new route for developing ferroelectric- or multiferroic-based nanodevices. [ABSTRACT FROM AUTHOR]

The characteristics of the cooperative Mott-Peierls metal-insulator transition (MIT) of VO2 can be altered by employing epitaxial strain. While the most commonly used substrate for this purpose is isostructural rutile TiO2, thin films often suffer from interdiffusion of Ti ions near the interface. Exploiting this phenomena, we investigate the nature of interfacial V4+/Ti4+ cation intermixing and its effects on the MIT using scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS), soft x-ray absorption spectroscopy (XAS), and hard x-ray photoelectron spectroscopy (HAXPES), along with supporting density functional theory (DFT) calculations. We find that the reduced orbital occupancy in highly Ti incorporated VO2 is responsible for suppressing the MIT. Interdiffused films are found to be metallic at all measured temperatures, despite a resolute dimerization inferred from x-ray absorption data at lower temperatures. Our results demonstrate that the Mott physics can be suppressed in doped VO2, while a lattice dimerization remains thermodynamically favorable. [ABSTRACT FROM AUTHOR]

We report cryogenic magnetic force microscopy (MFM) studies of a 200-nm-thick hexagonal (h) LuFeO3 film grown by molecular-beam epitaxy on a (111)-oriented yttria-stabilized cubic-zirconia substrate. Labyrinthlike domains ~1.8μm in size were observed after zero-field cooling below the Néel temperature, TN≈147 K, where weak ferromagnetic order (P63cm) with a canted moment of MS≈0.02μB/f.u. exists. At 6 K, MFM images of the magnetization reversal process reveal a typical domain behavior of a pinning-dominated hard magnet. The pinning strength is substantially reduced at elevated temperature. The temperature dependence of the domain contrast demonstrates that our MFM is able to detect the domain contrast of magnets with tiny magnetic moments (~0.002μB/f.u.). An upper limit of the linear magnetoelectric coefficient of h-LuFeO3 (αzz<6ps/m) is estimated by magnetoelectric force microscopy measurements. [ABSTRACT FROM AUTHOR]

In the cuprates, carrier doping of the Mott insulating parent state is necessary to realize superconductivity as well as a number of other exotic states involving charge or spin density waves. Cation substitution is the primary method for doping carriers into these compounds, and is the only known method for electron doping in these materials. Here, we report electron doping without cation substitution in epitaxially stabilized thin films of La2CuO4 grown via molecular-beam epitaxy. We use angle-resolved photoemission spectroscopy to directly measure their electronic structure and conclusively determine that these compounds are electron doped with a carrier concentration of 0.09±0.02 e-/Cu. We propose that intrinsic defects, most likely oxygen vacancies, are the sources of doped electrons in these materials. Our results suggest a new approach to electron doping in the cuprates, one which could lead to a more detailed experimental understanding of their properties. [ABSTRACT FROM AUTHOR]

The confluence of electron correlations and spin-orbit interactions is critical to realizing quantum phases in 5d transition metal oxides. Here, we investigate how the strength of the effective electron correlations evolve across a series of d5 iridates comprised of IrO6 octahedra, ranging from the layered correlated insulator Sr2IrO4, to the three-dimensional perovskite semimetal SrIrO3, to metallic rutile IrO2 in which the octahedra are arranged in a mixed edge and corner sharing network. Through a combination of reactive oxide molecular-beam epitaxy, in situ angle-resolved photoemission spectroscopy, core level photoemission, and density functional theory, we show how the effective electron correlations weaken as a function of increasing connectivity of the IrO6 network and p-d hybridization. Our results demonstrate how structure and connectivity can be used to control the strength of correlations in the iridates. [ABSTRACT FROM AUTHOR]

Ferroelectric vortex domains are of significant interest due to their rich physics and potential applications. Here, we propose the crystallographic, strain, and electric conditions for spontaneous vortex domains and study the influence of oxygen octahedral tilt on vortex wall orientations. Using 109° domain walls in BiFeO3 films as an example, it is demonstrated that vortex domains result from bound charge-density waves, i.e., from alternating positive and negative bound charges. The vortex domains lead to a net curl of the polarization vectors that can be switched by an irrotational electric field. [ABSTRACT FROM AUTHOR]

The key challenge in superconductivity research is to go beyond the historical mode of discovery-driven research. We put forth a new strategy, which is to combine theoretical developments in the weak-coupling renormalization-group approach with the experimental developments in lattice-strain-driven Fermi surface engineering. For concreteness we theoretically investigate how superconducting tendencies will be affected by strain engineering of ruthenates' Fermi surface. We first demonstrate that our approach qualitatively reproduces recent experiments under uniaxial strain. We then note that the order of a few percent strain, readily accessible to epitaxial thin films, can bring the Fermi surface close to van Hove singularity. Using the experimental observation of the change in the Fermi surface under biaxial epitaxial strain and ab initio calculations, we predict Tc for triplet pairing to be maximized by getting close to the van Hove singularities without tuning on to the singularity. [ABSTRACT FROM AUTHOR]

We use angle-resolved photoemission spectroscopy to study the doping evolution of infinite-layer Sr1-xLaxCuO2 thin films grown by molecular-beam epitaxy. At low doping, the material exhibits a dispersive lower Hubbard band typical of the superconducting cuprate parent compounds. As carriers are added to the system, a continuous evolution from charge-transfer insulator to superconductor is observed, with the initial lower Hubbard band pinned well below the Fermi level and the development of a coherent low-energy band with electron doping. This two-component spectral function emphasizes the important role that strong local correlations play even at relatively high doping levels. Electron diffraction probes reveal a p(2×2) surface reconstruction of the material at low doping levels. Using a number of simple assumptions, we develop a model of this reconstruction based on the polar nature of the infinite-layer structure. Finally, we provide evidence for a thickness-controlled transition in ultrathin films of SrCuO2 grown on nonpolar SrTiO3, highlighting the diverse structural changes that can occur in polar complex oxide thin films. [ABSTRACT FROM AUTHOR]

The observation of replica bands by angle-resolved photoemission spectroscopy has ignited interest in the study of electron-phonon coupling at low carrier densities, particularly in monolayer FeSe/SrTiO&#95;{3}, where the appearance of replica bands has motivated theoretical work suggesting that the interfacial coupling of electrons in the FeSe layer to optical phonons in the SrTiO&#95;{3} substrate might contribute to the enhanced superconducting pairing temperature. Alternatively, it has also been recently proposed that such replica bands might instead originate from extrinsic final state losses associated with the photoemission process. Here, we perform a quantitative examination of replica bands in monolayer FeSe/SrTiO&#95;{3}, where we are able to conclusively demonstrate that the replica bands are indeed signatures of intrinsic electron-boson coupling, and not associated with final state effects. A detailed analysis of the energy splittings and relative peak intensities between the higher-order replicas, as well as other self-energy effects, allows us to determine that the interfacial electron-phonon coupling in the system corresponds to a value of λ=0.19±0.02, providing valuable insights into the enhancement of superconductivity in monolayer FeSe/SrTiO&#95;{3}. The methodology employed here can also serve as a new and general approach for making more rigorous and quantitative comparisons to theoretical calculations of electron-phonon interactions and coupling constants.

We construct ferroelectric (LuFeO&#95;{3})&#95;{m}/(LuFe&#95;{2}O&#95;{4}) superlattices with varying index m to study the effect of confinement on topological defects. We observe a thickness-dependent transition from neutral to charged domain walls and the emergence of fractional vortices. In thin LuFeO&#95;{3} layers, the volume fraction of domain walls grows, lowering the symmetry from P6&#95;{3}cm to P3c1 before reaching the nonpolar P6&#95;{3}/mmc state, analogous to the group-subgroup sequence observed at the high-temperature ferroelectric to paraelectric transition. Our study shows how dimensional confinement stabilizes textures beyond those in bulk ferroelectric systems.

Recent reports have identified new metaphases of VO&#95;{2} with strain and/or doping, suggesting the structural phase transition and the metal-to-insulator transition might be decoupled. Using epitaxially strained VO&#95;{2}/TiO&#95;{2} (001) thin films, which display a bulklike abrupt metal-to-insulator transition and rutile to monoclinic transition structural phase transition, we employ x-ray standing waves combined with hard x-ray photoelectron spectroscopy to simultaneously measure the structural and electronic transitions. This x-ray standing waves study elegantly demonstrates the structural and electronic transitions occur concurrently within experimental limits (±1  K).

The carrier effective mass plays a crucial role in modern electronic, optical, and catalytic devices and is fundamentally related to key properties of solids such as the mobility and density of states. Here we demonstrate a method to deterministically engineer the effective mass using spatial confinement in metallic quantum wells of the transition metal oxide IrO&#95;{2}. Using a combination of in situ angle-resolved photoemission spectroscopy measurements in conjunction with precise synthesis by oxide molecular-beam epitaxy, we show that the low-energy electronic subbands in ultrathin films of rutile IrO&#95;{2} have their effective masses enhanced by up to a factor of 6 with respect to the bulk. The origin of this strikingly large mass enhancement is the confinement-induced quantization of the highly nonparabolic, three-dimensional electronic structure of IrO&#95;{2} in the ultrathin limit. This mechanism lies in contrast to that observed in other transition metal oxides, in which mass enhancement tends to result from complex electron-electron interactions and is difficult to control. Our results demonstrate a general route towards the deterministic enhancement and engineering of carrier effective masses in spatially confined systems, based on an understanding of the three-dimensional bulk electronic structure.

Continuous developments in nanotechnology require new approaches to materials synthesis that can produce novel functional structures. Here, we show that nanoscale defects, such as nonstoichiometric nanoregions (NSNRs), can act as nano-building blocks for creating complex electrical polarization structures in the prototypical multiferroic BiFeO&#95;{3}. An array of charged NSNRs are produced in BiFeO&#95;{3} thin films by tuning the substrate temperature during film growth. Atomic-scale scanning transmission electron microscopy imaging reveals exotic polarization rotation patterns around these NSNRs. These polarization patterns resemble hedgehog or vortex topologies and can cause local changes in lattice symmetries leading to mixed-phase structures resembling the morphotropic phase boundary with high piezoelectricity. Phase-field simulations indicate that the observed polarization configurations are mainly induced by charged states at the NSNRs. Engineering defects thus may provide a new route for developing ferroelectric- or multiferroic-based nanodevices.

In the cuprates, carrier doping of the Mott insulating parent state is necessary to realize superconductivity as well as a number of other exotic states involving charge or spin density waves. Cation substitution is the primary method for doping carriers into these compounds, and is the only known method for electron doping in these materials. Here, we report electron doping without cation substitution in epitaxially stabilized thin films of La&#95;{2}CuO&#95;{4} grown via molecular-beam epitaxy. We use angle-resolved photoemission spectroscopy to directly measure their electronic structure and conclusively determine that these compounds are electron doped with a carrier concentration of 0.09±0.02 e^{-}/Cu. We propose that intrinsic defects, most likely oxygen vacancies, are the sources of doped electrons in these materials. Our results suggest a new approach to electron doping in the cuprates, one which could lead to a more detailed experimental understanding of their properties.

We report on the magnetic structure and ordering of hexagonal LuFeO&#95;{3} films of variable thickness grown by molecular-beam epitaxy on YSZ (111) and Al&#95;{2}O&#95;{3} (0001) substrates. These crystalline films exhibit long-range structural uniformity dominated by the polar P6&#95;{3}cm phase, which is responsible for the paraelectric to ferroelectric transition that occurs above 1000 K. Using bulk magnetometry and neutron diffraction, we find that the system orders into a ferromagnetically canted antiferromagnetic state via a single transition below 155 K regardless of film thickness, which is substantially lower than that previously reported in hexagonal LuFeO&#95;{3} films. The symmetry of the magnetic structure in the ferroelectric state implies that this material is a strong candidate for linear magnetoelectric coupling and control of the ferromagnetic moment directly by an electric field.

We apply ultrafast x-ray diffraction with femtosecond temporal resolution to monitor the lattice dynamics in a thin film of multiferroic BiFeO3 after above-band-gap photoexcitation. The sound-velocity limited evolution of the observed lattice strains indicates a quasi-instantaneous photoinduced stress which decays on a nanosecond time scale. This stress exhibits an inhomogeneous spatial profile evidenced by the broadening of the Bragg peak. These new data require substantial modification of existing models of photogenerated stresses in BiFeO3: the relevant excited charge carriers must remain localized to be consistent with the data.

We determined the atomic structures and energies of 109°, 180°, and 71° domain walls in BiFeO3, combining density functional theory+U calculations and aberration-corrected transmission electron microscopy images. We find a substantial Bi sublattice shift and a rather uniform Fe sublattice across the walls. The calculated wall energies (γ) follow the sequence γ109<γ180<γ71 for the 109°, 180°, and 71° walls. We attribute the high 71° wall energy to an opposite tilting rotation of the oxygen octahedra and the low 109° wall energy to the opposite twisting rotation of the oxygen octahedra across the domain walls.

Above-band-gap optical excitation produces interdependent structural and electronic responses in a multiferroic BiFeO(3) thin film. Time-resolved synchrotron x-ray diffraction shows that photoexcitation can induce a large out-of-plane strain, with magnitudes on the order of half of one percent following pulsed-laser excitation. The strain relaxes with the same nanosecond time dependence as the interband relaxation of excited charge carriers. The magnitude of the strain and its temporal correlation with excited carriers indicate that an electronic mechanism, rather than thermal effects, is responsible for the lattice expansion. The observed strain is consistent with a piezoelectric distortion resulting from partial screening of the depolarization field by charge carriers, an effect linked to the electronic transport of excited carriers. The nonthermal generation of strain via optical pulses promises to extend the manipulation of ferroelectricity in oxide multiferroics to subnanosecond time scales.

The asymmetry between electron and hole doping remains one of the central issues in high-temperature cuprate superconductivity, but our understanding of the electron-doped cuprates has been hampered by apparent discrepancies between the only two known families: Re(2-x)Ce(x)CuO4 and A(1-x)La(x)CuO2. Here we report in situ angle-resolved photoemission spectroscopy measurements of epitaxially stabilized Sr(1-x)La(x)CuO2 thin films synthesized by oxide molecular-beam epitaxy. Our results reveal a strong coupling between electrons and (π, π) antiferromagnetism that induces a Fermi surface reconstruction which pushes the nodal states below the Fermi level. This removes the hole pocket near (π/2, π/2), realizing nodeless superconductivity without requiring a change in the symmetry of the order parameter and providing a universal understanding of all electron-doped cuprates.

We have observed a weak anisotropic x-ray magnetic linear dichroism (AXMLD) at the Eu M4,5 edges of ferromagnetic EuO(001), which indicates that the 4f states are not rotationally invariant. A quantitative agreement of the AXMLD is obtained with multiplet calculations where the 4f state is split by an effective cubic crystalline electrostatic field. The results indicate that the standard model of rare earths, where 4f electrons are treated as core states, is not correct and that the 4f orbitals contribute weakly to the magnetic anisotropy.