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We describe a hybrid pixel array detector (EMPAD - electron microscope pixel array detector) adapted for use in electron microscope applications, especially as a universal detector for scanning transmission electron microscopy. The 128 x 128 pixel detector consists of a 500 um thick silicon diode array bump-bonded pixel-by-pixel to an application-specific integrated circuit (ASIC). The in-pixel circuitry provides a 1,000,000:1 dynamic range within a single frame, allowing the direct electron beam to be imaged while still maintaining single electron sensitivity. A 1.1 kHz framing rate enables rapid data collection and minimizes sample drift distortions while scanning. By capturing the entire unsaturated diffraction pattern in scanning mode, one can simultaneously capture bright field, dark field, and phase contrast information, as well as being able to analyze the full scattering distribution, allowing true center of mass imaging. The scattering is recorded on an absolute scale, so that information such as local sample thickness can be directly determined. This paper describes the detector architecture, data acquisition (DAQ) system, and preliminary results from experiments with 80 to 200 keV electron beams., Comment: 39 pages total, 11 Figures in Microscopy and Microanalysis, 2015

We use angle-resolved photoemission spectroscopy to study the doping evolution of infinite-layer Sr$_{1-x}$La$_{x}$CuO$_{2}$ 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 ${p(2\times2)}$ 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 SrCuO$_2$ grown on nonpolar SrTiO$_3$, highlighting the diverse structural changes that can occur in polar complex oxide thin films.

A major goal of energy research is to use visible light to cleave water directly, without an applied voltage, into hydrogen and oxygen. Since the initial reports of the ultraviolet (UV) activity of TiO2 and SrTiO3 in the 1970s, researchers have pursued a fundamental understanding of the mechanistic and molecular-level phenomena involved in photo-catalysis. Although it requires UV light, after four decades SrTiO3 is still the gold standard for splitting water. It is chemically stable and catalyzes both the hydrogen and the oxygen reactions without applied bias. While ultrahigh vacuum (UHV) surface science techniques have provided useful insights, we still know relatively little about the structure of electrodes in contact with electrolytes under operating conditions. Here, we report the surface structure evolution of a SrTiO3 electrode during water splitting, before and after training with a positive bias. Operando high-energy X-ray reflectivity measurements demonstrate that training the electrode irreversibly reorders the surface. Scanning electrochemical microscopy (SECM) at open circuit correlates this training with a tripling of the activity toward photo-induced water splitting. A novel first-principles joint density-functional theory (JDFT) simulation constrained to the X-ray data via a generalized penalty function identifies an anatase-like structure for the more active, trained surface.

The coupling between strain gradients and polarization, known as flexoelectricity, offers a new mechanism to control the functionality of dielectric materials. However, for the effect to be practically attractive, dynamic control of the strain gradient with magnitudes far exceeding those achievable via mechanical deformation (~10 $m^{-1}$) is needed. Strain-engineered thin films exhibit extraordinary strain gradients of $10^5-10^6 m{-1}$ arising from structural relaxation within a short space range that greatly enhances the steady-state flexoelectric effect. Here we report a giant, optically initiated dynamic enhancement of the strain gradient, also on the order of $10^5 -10^6 m^{-1}$, in ferroelectric BiFeO3 epitaxial thin films via time-dependent coherence analysis of X-ray diffractions. The finding opens the door for dynamic coupling of the flexoelectric effect with light, making optical switching of polarization, and thus application such as direct optical writing of non-volatile ferroelectric memory, possible. A combination of time-resolved X-ray scattering and optical spectroscopy shows that the enhancement of the strain gradient is due to a piezoelectric effect driven by a transient screening electric field, opening the opportunity for new ways of studying flexoelectric effect in strain engineered ferroelectric thin films., Comment: 17 pages, 5 figures in the main text; 13 pages, 6 figures in the supplementary information

We report on the magnetic structure and ordering of hexagonal LuFeO3 films grown by molecular-beam epitaxy (MBE) on YSZ (111) and Al2O3 (0001) substrates. Using a set of complementary probes including neutron diffraction, we find that the system magnetically orders into a ferromagnetically-canted antiferromagnetic state via a single transition between 138-155 K, while a paraelectric to ferroelectric transition occurs above 1000 K. 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.

Complex oxide heterostructures display some of the most chemically abrupt, atomically precise interfaces, which is advantageous when constructing new interface phases with emergent properties by juxtaposing incompatible ground states. One might assume that atomically precise interfaces result from stoichiometric growth, but here we show that the most precise control is obtained for non-stoichiometric growth where differing surface energies can be compensated by surfactant-like effects. For the precise growth of Sr$_{n+1}$Ti$_n$O$_{3n+1}$ Ruddlesden-Popper (RP) phases, stoichiometric deposition leads to the loss of the first RP rock-salt double layer, but growing with a strontium-rich surface layer restores the bulk stoichiometry and ordering of the subsurface RP structure. Our results dramatically expand the materials that can be prepared in epitaxial heterostructures with precise interface control---from just the $n=\infty$ end members (perovskites) to the entire RP family---enabling the exploration of novel quantum phenomena at a richer variety of oxide interfaces., Comment: 9 pages, 5 figures

The structural and electronic recovery pathways of a photoexcited ultrathin 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.

With nearly complete spin polarization, the ferromagnetic semiconductor europium monoxide could enable next-generation spintronic devices by providing efficient ohmic spin injection into silicon. Spin injection is greatly affected by the quality of the interface between the injector and silicon. Here, we use atomic-resolution scanning transmission electron microscopy in conjunction with electron energy loss spectroscopy to directly image and chemically characterize a series of EuO|Si and EuO|YAlO3 interfaces fabricated using different growth conditions. We identify the presence of europium silicides and regions of disorder at the EuO|Si interfaces, imperfections that could significantly reduce spin injection efficiencies via spin-flip scattering.

Controlling the electronic properties of interfaces has enormous scientific and technological implications and has been recently extended from semiconductors to complex oxides which host emergent ground states not present in the parent materials. These oxide interfaces present a fundamentally new opportunity where, instead of conventional bandgap engineering, the electronic and magnetic properties can be optimized by engineering quantum many-body interactions. We utilize an integrated oxide molecular-beam epitaxy and angle-resolved photoemission spectroscopy system to synthesize and investigate the electronic structure of superlattices of the Mott insulator LaMnO3 and the band insulator SrMnO3. By digitally varying the separation between interfaces in (LaMnO3)2n/(SrMnO3)n superlattices with atomic-layer precision, we demonstrate that quantum many-body interactions are enhanced, driving the electronic states from a ferromagnetic polaronic metal to a pseudogapped insulating ground state. This work demonstrates how many-body interactions can be engineered at correlated oxide interfaces, an important prerequisite to exploiting such effects in novel electronics., Comment: 14 pages, 13 figures. For published article, see http://www.nature.com/nmat/journal/v11/n10/full/nmat3405.html

Ultrafast strengthening or quenching of the ferromagnetic order of semiconducting Eu1-xGdxO was achieved by resonant photoexcitation. The modification of the magnetic order is established within 3 ps as revealed by optical second harmonic generation. A theoretical analysis shows that the response is determined by the interplay of chemically and optically generated carriers in a nonequilibrium scenario beyond the three-temperature model. General criteria for the design of spintronics materials with tunable ultrafast spin dynamics are given., Comment: 7 pages, 4 figures

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 ultra-thin films and multilayers.

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 films of Sr1-xLaxCuO2 synthesized by oxide molecular-beam epitaxy. Our results reveal a strong coupling between electrons and (pi,pi) antiferromagnetism that induces a Fermi surface reconstruction which pushes the nodal states below the Fermi level. This removes the hole pocket near (pi/2,pi/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.

Polarized infrared reflectivity spectra of a (110)-oriented TbScO3 single crystal plate were measured down to 10 K. The number of observed polar phonons active along the crystallographic c axis at low temperatures is much higher than predicted by factor-group analysis for the orthorhombic Pbnm space group. Moreover, the lowest frequency phonons active in E||c as well as in E||[1-10] polarized spectra exhibit dramatic softening tending to a lattice instability at low temperatures. The dielectric permittivity at microwave frequencies does not show any ferroelectric-like anomaly, but the dielectric loss exhibits a maximum at 100 K. The origin of the discrepancy between the number of predicted and observed polar phonons as well as the tendency toward lattice instability are discussed. Magnetic measurements reveal an antiferromagnetic phase transition near 3 K., Comment: Phase Transitions, in press

Time-resolved two color pump-probe polarization spectroscopy was performed at room temperature on SrTiO3 films grown directly on Si with film thickness varying from 2 nm to 7.8 nm. The E soft mode with a characteristic frequency of 0.2 THz is impulsively generated and measured in these coherently strained tetragonal phase SrTiO3 thin films. Another over-damped signal observed indicates the possible relaxational hopping of Ti ion between double potential wells. The dependence of the coherent phonon signal on pump and probe laser polarization helps to identify the phonon modes.

We analyze both experimentally (where possible) and theoretically from first-principles the dielectric tensor components and crystal structure of five classes of Pbnm perovskites. All of these materials are believed to be stable on silicon and are therefore promising candidates for high-K dielectrics. We also analyze the structure of these materials with various simple models, decompose the lattice contribution to the dielectric tensor into force constant matrix eigenmode contributions, explore a peculiar correlation between structural and dielectric anisotropies in these compounds and give phonon frequencies and infrared activities of those modes that are infrared-active. We find that CaZrO_3, SrZrO_3, LaHoO_3, and LaYO_3 are among the most promising candidates for high-K dielectrics among the compounds we considered., Comment: 17 pages, 9 figures, 4 tables. Supplementary information: http://link.aps.org/supplemental/10.1103/PhysRevB.82.064101 or http://www.physics.rutgers.edu/~sinisa/highk/supp.pdf

Appropriately designed transition metal oxide heterostructures involving small band gap Mott insulators are argued to support spatially separated electron and hole gasses at equilibrium. Spatial separations and carrier densities favoring the formation of excitonic states are achievable. The excitonic states may exhibit potentially novel properties. Energetic estimates are given, candidate material systems are discussed, and the possibility of large photvoltaic effects is mentioned

Using spectroscopic ellipsometry, the refractive index and absorption versus wavelength of the ferroelectric antiferromagnet Bismuth Ferrite, BiFeO_3 is reported. The material has a direct band-gap at 442 nm wavelength (2.81 eV). Using optical second harmonic generation, the nonlinear optical coefficients were determined to be d_15/d_22 = 0.20 +/- 0.01, d_31/d_22 = 0.35 +/- 0.02, d_33/d_22 = -11.4 +/- 0.20 and |d_22| = 298.4 +/- 6.1 pm/V at a fundamental wavelength of 800 nm., Comment: 4 pages, 3 figures

The frequency-dependent polar dynamics of strained SrTiO3 films grown on DyScO3 are investigated using time-resolved confocal scanning optical microscopy. Microwave frequency electric fields are synchronized with a mode-locked laser and applied in-plane to the sample, while the temporal response is probed optically. Local spectroscopic information is obtained with <1 um spatial resolution over the frequency range 2-4 GHz. Investigation of the SrTiO3/DyScO3 system reveals resonances that are localized both in space and in frequency., Comment: 4 pages, 4 figures