Origin of the 2D Electron Gas at the SrTiO3 Surface.

Bulk SrTiO3 is a well-known band insulator and the most common substrate used in the field of complex oxide heterostructures. Its surface and interface with other oxides, however, have demonstrated a variety of remarkable behaviors distinct from those expected. In this work, using a suite of in situ techniques to monitor both the atomic and electronic structures of the SrTiO3 (001) surface prior to and during growth, the disappearance and re-appearance of a 2D electron gas (2DEG) is observed after the completion of each SrO and TiO2 monolayer, respectively. The 2DEG is identified with the TiO2 double layer present at the initial SrTiO3 surface, which gives rise to a surface potential and mobile electrons due to vacancies within the TiO2-x adlayer. Much like the electronic reconstruction discovered in other systems, two atomic planes are required, here supplied by the double layer. The combined in situ scattering/spectroscopy findings resolve a number of longstanding issues associated with complex oxide interfaces, facilitating the employment of atomic-scale defect engineering in oxide electronics.

Self-healing Growth of LaNiO3 on a Mixed-Terminated Perovskite Surface.

Developing atomic-scale synthesis control is a prerequisite for understanding and engineering the exotic physics inherent to transition-metal oxide heterostructures. Thus, far, however, the number of materials systems explored has been extremely limited, particularly with regard to the crystalline substrate, which is routinely SrTiO3. Here, we investigate the growth of a rare-earth nickelate─LaNiO3─on (LaAlO3)(Sr2AlTaO6) (LSAT) (001) by oxide molecular beam epitaxy (MBE). Whereas the LSAT substrates are smooth, they do not exhibit the single surface termination usually assumed necessary for control over the interface structure. Performing both nonresonant and resonant anomalous in situ synchrotron surface X-ray scattering during MBE growth, we show that reproducible heterostructures can be achieved regardless of both the mixed surface termination and the layer-by-layer deposition sequence. The rearrangement of the layers occurs dynamically during growth, resulting in the fabrication of high-quality LaNiO3/LSAT heterostructures with a sharp and consistent interfacial structure. This is due to the thermodynamics of the deposition window as well as the nature of the chemical species at interfaces─here, the flexible charge state of nickel at the oxide surface. This has important implications regarding the use of a wider variety of substrates for fundamental studies on complex oxide synthesis.

Tunable side-bounce monochromator.

Side-bounce beamlines with fixed-exit angles have been intended to operate with only one selected energy. However, a tunable monochromator in a new geometry is presented here that will make side-bounce beamlines energy tunable. It requires the addition of two more rotations. Analytic solutions for the values of these two rotation angles are provided. The validity of the new concept was checked by ray tracing and two-dimensional searches in the additional angles. Operational details on the new scheme, including the exit offset and steering of the beams, were determined. In addition to tunability, the new monochromator will reduce the loss from the polarization factor at low energies.

Picoscale structural insight into superconductivity of monolayer FeSe/SrTiO3.

Remarkable enhancement of the superconducting transition temperature (T c) has been observed for monolayer (ML) FeSe films grown on SrTiO3 substrates. The atomic-scale structure of the FeSe/SrTiO3 interface is an important determinant of both the magnetic and interfacial electron-phonon interactions and is a key ingredient to understanding its high-T c superconductivity. We resolve the atomic-scale structure of the FeSe/SrTiO3 interface through a complementary analysis of scanning transmission electron microscopy and in situ surface x-ray diffraction. We find that the interface is more strongly bonded for a particular registration, which leads to a coherently strained ML. We also determine structural parameters, such as the distance between ML FeSe and the oxide, Se─Fe─Se bond angles, layer-resolved distances between Fe─Se, and registry of the FeSe lattice relative to the oxide. This picoscale structure determination provides an explicit structural framework and constraint for theoretical approaches addressing the high-T c mechanism in FeSe/SrTiO3.

How heteroepitaxy occurs on strontium titanate.

In traditional models of heteroepitaxy, the substrate serves mainly as a crystalline template for the thin-film lattice, dictating the initial roughness of the film and the degree of coherent strain. Here, performing in situ surface x-ray diffraction during the heteroepitaxial growth of LaTiO3 on SrTiO3 (001), we find that a TiO2 adlayer composed of the ( 13 × 13 ) R33.7° and ( 2 × 2 ) R45.0° reconstructions is a highly active participant in the growth process, continually diffusing to the surface throughout deposition. The effects of the TiO2 adlayer on layer-by-layer growth are investigated using different deposition sequences and anomalous x-ray scattering, both of which permit detailed insight into the dynamic layer rearrangements that take place. Our work challenges commonly held assumptions regarding growth on TiO2-terminated SrTiO3 (001) and demonstrates the critical role of excess TiO2 surface stoichiometry on the initial stages of heteroepitaxial growth on this important perovskite oxide substrate material.

In Situ Strain Tuning of the Dirac Surface States in Bi2Se3 Films.

Elastic strain has the potential for a controlled manipulation of the band gap and spin-polarized Dirac states of topological materials, which can lead to pseudomagnetic field effects, helical flat bands, and topological phase transitions. However, practical realization of these exotic phenomena is challenging and yet to be achieved. Here we show that the Dirac surface states of the topological insulator Bi2Se3 can be reversibly tuned by an externally applied elastic strain. Performing in situ X-ray diffraction and in situ angle-resolved photoemission spectroscopy measurements during tensile testing of epitaxial Bi2Se3 films bonded onto a flexible substrate, we demonstrate elastic strains of up to 2.1% and quantify the resulting changes in the topological surface state. Our study establishes the functional relationship between the lattice and electronic structures of Bi2Se3 and, more generally, demonstrates a new route toward momentum-resolved mapping of strain-induced band structure changes.

Development of a hybrid molecular beam epitaxy deposition system for in situ surface x-ray studies.

A portable metalorganic gas delivery system designed and constructed to interface with an existing molecular beam epitaxy chamber at beamline 33-ID-E of the Advanced Photon Source is described. This system offers the ability to perform in situ X-ray measurements of complex oxide growth via hybrid molecular beam epitaxy. The performance of the hybrid molecular beam epitaxy system while delivering metalorganic source materials is described. The high-energy X-ray scattering capabilities of the hybrid molecular beam epitaxy system are demonstrated both on oxide films grown solely from the metalorganic source and ABO3 oxide perovskites containing elements from both the metalorganic source and a traditional effusion cell.

Layer-by-Layer Epitaxial Growth of Defect-Engineered Strontium Cobaltites.

Control over structure and composition of (ABO3) perovskite oxides offers exciting opportunities since these materials possess unique, tunable properties. Perovskite oxides with cobalt B-site cations are particularly promising, as the range of the cation's stable oxidation states leads to many possible structural frameworks. Here, we report growth of strontium cobalt oxide thin films by molecular beam epitaxy, and conditions necessary to stabilize different defect concentration phases. In situ X-ray scattering is used to monitor structural evolution during growth, while in situ X-ray absorption near-edge spectroscopy is used to probe oxidation state and measure changes to oxygen vacancy concentration as a function of film thickness. Experimental results are compared to kinetically limited thermodynamic predictions, in particular, solute trapping, with semiquantitative agreement. Agreement between observations of dependence of cobaltite phase on oxidation activity and deposition rate, and predictions indicates that a combined experimental/theoretical approach is key to understanding phase behavior in the strontium cobalt oxide system.

Effect of defects on reaction of NiO surface with Pb-contained solution.

In order to understand the role of defects in chemical reactions, we used two types of samples, which are molecular beam epitaxy (MBE) grown NiO(001) film on Mg(001) substrate as the defect free NiO prototype and NiO grown on Ni(110) single crystal as the one with defects. In-situ observations for oxide-liquid interfacial structure and surface morphology were performed for both samples in water and Pb-contained solution using high-resolution X-ray reflectivity and atomic force microscopy. For the MBE grown NiO, no significant changes were detected in the high-resolution X-ray reflectivity data with monotonic increase in roughness. Meanwhile, in the case of native grown NiO on Ni(110), significant changes in both the morphology and atomistic structure at the interface were observed when immersed in water and Pb-contained solution. Our results provide simple and direct experimental evidence of the role of the defects in chemical reaction of oxide surfaces with both water and Pb-contained solution.

In situ surface/interface x-ray diffractometer for oxide molecular beam epitaxy.

In situ studies of oxide molecular beam epitaxy by synchrotron x-ray scattering has been made possible by upgrading an existing UHV/molecular beam epitaxy (MBE) six-circle diffractometer system. For oxide MBE growth, pure ozone delivery to the chamber has been made available, and several new deposition sources have been made available on a new 12 in. CF (ConFlat, a registered trademark of Varian, Inc.) flange. X-ray diffraction has been used as a major probe for film growth and structures for the system. In the original design, electron diffraction was intended for the secondary diagnostics available without the necessity of the x-ray and located at separate positions. Deposition of films was made possible at the two diagnostic positions. And, the aiming of the evaporation sources is fixed to the point between two locations. Ozone can be supplied through two separate nozzles for each location. Also two separate thickness monitors are installed. Additional features of the equipment are also presented together with the data taken during typical oxide film growth to illustrate the depth of information available via in situ x-ray techniques.

Correlating interfacial octahedral rotations with magnetism in (LaMnO3+δ)N/(SrTiO3)N superlattices.

Lattice distortion due to oxygen octahedral rotations have a significant role in mediating the magnetism in oxides, and recently attracts a lot of interests in the study of complex oxides interface. However, the direct experimental evidence for the interrelation between octahedral rotation and magnetism at interface is scarce. Here we demonstrate that interfacial octahedral rotation are closely linked to the strongly modified ferromagnetism in (LaMnO3+δ)N/(SrTiO3)N superlattices. The maximized ferromagnetic moment in the N=6 superlattice is accompanied by a metastable structure (space group Imcm) featuring minimal octahedral rotations (a(-)a(-)c(-), α~4.2°, γ~0.5°). Quenched ferromagnetism for N<4 superlattices is correlated to a substantially enhanced c axis octahedral rotation (a(-)a(-)c(-), α~3.8°, γ~8° for N=2). Monte-Carlo simulation based on double-exchange model qualitatively reproduces the experimental observation, confirming the correlation between octahedral rotation and magnetism. Our study demonstrates that engineering superlattices with controllable interfacial structures can be a feasible new route in realizing functional magnetic materials.

Direct mapping of phonon dispersion relations in copper by momentum-resolved x-ray calorimetry.

We have developed a new method of mapping phonon dispersion relations based on momentum-resolved x-ray calorimetry. X-ray scattering intensities are measured at selected points in reciprocal space with suitably chosen polarization configurations; the thermal part of the scattering intensity is extracted by scanning the temperature of the sample. The intensity variations, governed by the phonon populations, are analyzed to yield the energies of the phonons. This method is applied to copper. With high-order effects under control, the results are in excellent agreement with the known phonon dispersion relations.

Quantum beating patterns observed in the energetics of Pb film nanostructures.

We have studied the nanoscale structural evolution of Pb films grown at 110 K on a Si(111) substrate as they are annealed to increasingly higher temperatures. Surface x-ray diffraction from a synchrotron source is used to observe the morphology evolve from an initial smooth film through various metastable states before reaching a state of local equilibrium, at which point the coverage of different height Pb structures is analyzed and related to the thickness-dependent surface energy. Rich patterns are seen in the resulting energy landscape similar to the beating patterns heard from the interference of two musical notes of similar pitch. The explanation is, however, very simple, as demonstrated by a model calculation based on the confinement of free electrons to a quantum well.

Quantum oscillations in the layer structure of thin metal films.

Understanding the underlying physical principles that determine the internal structure of objects at the atomic scale is critical for the advancement of nanoscale science. We have performed synchrotron x-ray diffraction studies to determine the structural properties of smooth Pb films with varying thicknesses of 6 to 18 monolayers deposited on a Si(111) substrate at 110 K. We observe quasibilayer variations in the atomic interlayer spacings of the films consistent with charge density oscillations due to quantum confinement of conduction electrons and surface-interface interference effects. Quantum oscillations in atomic step height are also deduced.

Alternating layer and island growth of Pb on Si by spontaneous quantum phase separation.

Real-time in situ x-ray studies of continuous Pb deposition on Si(111)-(7x7) at 180 K reveal an unusual growth behavior. A wetting layer forms first to cover the entire surface. Then islands of a fairly uniform height of about five monolayers form on top of the wetting layer and grow to fill the surface. The growth then switches to a layer-by-layer mode upon further deposition. This behavior of alternating layer and island growth can be attributed to spontaneous quantum phase separation based on a first-principles calculation of the system energy.