Experimental setup combining in situ hard X-ray photoelectron spectroscopy and real-time surface X-ray diffraction for characterizing atomic and electronic structure evolution during complex oxide heterostructure growth.

We describe the next-generation system for in situ characterization of a complex oxide thin film and heterostructure growth by pulsed laser deposition (PLD) using synchrotron hard X-rays. The system consists of a PLD chamber mounted on a diffractometer allowing both real-time surface X-ray diffraction (SXRD) and in situ hard X-ray photoelectron spectroscopy (HAXPES). HAXPES is performed in the incident X-ray energy range from 4 to 12 keV using a Scienta EW4000 electron energy analyzer mounted on the PLD chamber fixed parallel with the surface normal. In addition to the standard application mode of HAXPES for disentangling surface from bulk properties, the increased penetration depth of high energy photoelectrons is used for investigation of the electronic structure changes through thin films grown deliberately as variable thickness capping layers. Such heterostructures represent model systems for investigating a variety of critical thickness and dead layer phenomena observed at complex oxide interfaces. In this new mode of operation, in situ HAXPES is used to determine the electronic structure associated with unique structural features identified by real-time SXRD during thin film growth. The system is configured for using both laboratory excitation sources off-line and on-line operation at beamline 33-ID-D at the Advanced Photon Source. We illustrate the performance of the system by preliminary scattering and spectroscopic data on oxygen vacancy ordering induced perovskite-to-brownmillerite reversible phase transformation in La2/3Sr1/3MnO3 films capped with oxygen deficient SrTiO3-δ (100) layers of varying thickness.

Deformation twinning and grain partitioning in a hexagonal close-packed magnesium alloy.

Pervasive deformation twinning in magnesium greatly affects its strength and formability. The local stress fields associated with twinning play a key role on deformation behavior and fracture but are extremely difficult to characterize experimentally. In this study, we perform synchrotron experiments with differential-aperture X-ray microscopy to measure the 3D stress fields in the vicinity of a twin with a spatial resolution of 0.5 micrometer. The measured local stress field aids to identify the sequence of events involved with twinning. We find that the selected grain deforms elastically before twinning, and the twin formation splits the grain into two non-interacting domains. Under further straining one domain of the grain continued to deform elastically, whereas the other domain deforms plastically by prismatic slip. This heterogeneous deformation behavior may be mediated by the surrounding medium and it is likely to lead to asymmetric twin growth.

Boundary migration in a 3D deformed microstructure inside an opaque sample.

How boundaries surrounding recrystallization grains migrate through the 3D network of dislocation boundaries in deformed crystalline materials is unknown and critical for the resulting recrystallized crystalline materials. Using X-ray Laue diffraction microscopy, we show for the first time the migration pattern of a typical recrystallization boundary through a well-characterized deformation matrix. The data provide a unique possibility to investigate effects of both boundary misorientation and plane normal on the migration, information which cannot be accessed with any other techniques. The results show that neither of these two parameters can explain the observed migration behavior. Instead we suggest that the subdivision of the deformed microstructure ahead of the boundary plays the dominant role. The present experimental observations challenge the assumptions of existing recrystallization theories, and set the stage for determination of mobilities of recrystallization boundaries.

Dynamic Scaling and Island Growth Kinetics in Pulsed Laser Deposition of SrTiO_{3}.

We use real-time diffuse surface x-ray diffraction to probe the evolution of island size distributions and its effects on surface smoothing in pulsed laser deposition (PLD) of SrTiO_{3}. We show that the island size evolution obeys dynamic scaling and two distinct regimes of island growth kinetics. Our data show that PLD film growth can persist without roughening despite thermally driven Ostwald ripening, the main mechanism for surface smoothing, being shut down. The absence of roughening is concomitant with decreasing island density, contradicting the prevailing view that increasing island density is the key to surface smoothing in PLD. We also report a previously unobserved crossover from diffusion-limited to attachment-limited island growth that reveals the influence of nonequilibrium atomic level surface transport processes on the growth modes in PLD. We show by direct measurements that attachment-limited island growth is the dominant process in PLD that creates step flowlike behavior or quasistep flow as PLD "self-organizes" local step flow on a length scale consistent with the substrate temperature and PLD parameters.

Interfacial bonding and structure of Bi2Te3 topological insulator films on Si(111) determined by surface x-ray scattering.

Interfacial topological states are a key element of interest for topological insulator thin films, and their properties can depend sensitively on the atomic bonding configuration. We employ in situ nonresonant and resonant surface x-ray scattering to study the interfacial and internal structure of a prototypical topological film system: Bi2Te3 grown on Si(111). The results reveal a Te-dominated buffer layer, a large interfacial spacing, and a slightly relaxed and partially strained bottom quintuple layer of an otherwise properly stacked bulklike Bi2Te3 film. The presence of the buffer layer indicates a nontrivial process of interface formation and a mechanism for electronic decoupling between the topological film and the Si(111) substrate.

Symmetry relationship and strain-induced transitions between insulating M1 and M2 and metallic R phases of vanadium dioxide.

The ability to synthesize VO2 in the form of single-crystalline nanobeams and nano- and microcrystals uncovered a number of previously unknown aspects of the metal-insulator transition (MIT) in this oxide. In particular, several reports demonstrated that the MIT can proceed through competition between two monoclinic (insulating) phases M1 and M2 and the tetragonal (metallic) R phase under influence of strain. The nature of such phase behavior has been not identified. Here we show that the competition between M1 and M2 phases is purely lattice-symmetry-driven. Within the framework of the Ginzburg-Landau formalism, both M phases correspond to different directions of the same four-component structural order parameter, and as a consequence, the M2 phase can appear under a small perturbation of the M1 structure such as doping or stress. We analyze the strain-controlled phase diagram of VO2 in the vicinity of the R-M2-M1 triple point using the Ginzburg-Landau formalism and identify and experimentally verify the pathways for strain-control of the transition. These insights open the door toward more systematic approaches to synthesis of VO2 nanostructures in desired phase states and to use of external fields in the control of the VO2 phase states. Additionally, we report observation of the triclinic T phase at the heterophase domain boundaries in strained quasi-two-dimensional VO2 nanoplatelets, and theoretically predict phases that have not been previously observed.

Nonresonant inelastic x-ray scattering and energy-resolved Wannier function investigation of d-d excitations in NiO and CoO.

Nonresonant inelastic x-ray scattering measurements on NiO and CoO show that strong dipole-forbidden d-d excitations appear within the Mott gap at large wave vectors. These dominant excitations are highly anisotropic, and have [001] nodal directions for NiO. Theoretical analyses based on a novel, energy-resolved Wannier function (within the local density approximation+Hubbard U) show that the anisotropy reflects the local exciton wave functions and local point-group symmetry. The sensitivity to weak symmetry breaking in particle-hole wave functions suggests a wide application to strongly correlated systems.

Nonequilibrium interlayer transport in pulsed laser deposition.

We use time-resolved surface x-ray diffraction measurements with microsecond range resolution to study the growth kinetics of pulsed laser deposited . Time-dependent surface coverages corresponding to single laser shots were determined directly from crystal truncation rod intensity transients. Analysis of surface coverage evolution shows that extremely fast nonequilibrium interlayer transport, which occurs concurrently with the arrival of the laser plume, dominates the deposition process. A much smaller fraction of material, which is governed by the dwell time between successive laser shots, is transferred by slow, thermally driven interlayer transport processes.

Polychromatic X-ray microdiffraction studies of mesoscale structure and dynamics.

Polychromatic X-ray microdiffraction is an emerging tool for studying mesoscale structure and dynamics. Crystalline phase, orientation (texture), elastic and plastic strain can be nondestructively mapped in three dimensions with good spatial and angular resolution. Local crystallographic orientation can be determined to approximately 0.01 degree and elastic strain tensor elements can be measured with a resolution of approximately 10(-4) or better. Complete strain tensor information can be obtained by augmenting polychromatic microdiffraction with a monochromatic measurement of one Laue-reflection energy. With differential-aperture depth profiling, volumes tens to hundreds of micrometers below the surface are accessible so that three-dimensional distributions of crystalline morphology including grain boundaries, triple points, second phases and inclusions can all be mapped. Volume elements below 0.25 microm3 are routinely resolved so that the grain boundary structure of most materials can be characterized. Here the theory, instrumentation and application of polychromatic microdiffraction are described.

Differential-aperture X-ray structural microscopy: a submicron-resolution three-dimensional probe of local microstructure and strain.

A recently developed differential-aperture X-ray microscopy (DAXM) technique provides local structure and crystallographic orientation with submicron spatial resolution in three-dimensions; it further provides angular precision of approximately 0.01 degrees and local elastic strain with an accuracy of approximately 1.0 x 10(-4) using microbeams from high brilliance third generation synchrotron X-ray sources. DAXM is a powerful tool for inter- and intra-granular studies of lattice distortions and lattice rotations on mesoscopic length scales of tenths of microns to hundreds of microns that are largely above the range of traditional electron microscopy probes. Nondestructive, point-to-point, spatially resolved measurements of local lattice orientations in bulk materials provide direct information on geometrically necessary dislocation density distributions through measurements of the lattice curvature in plastically deformed materials. This paper reviews the DAXM measurement technique and discusses recent demonstrations of DAXM capabilities for measurements of microtexture, local elastic strain, and plastic deformation microstructure.

Three-dimensional X-ray structural microscopy with submicrometre resolution.

Advanced materials and processing techniques are based largely on the generation and control of non-homogeneous microstructures, such as precipitates and grain boundaries. X-ray tomography can provide three-dimensional density and chemical distributions of such structures with submicrometre resolution; structural methods exist that give submicrometre resolution in two dimensions; and techniques are available for obtaining grain-centroid positions and grain-average strains in three dimensions. But non-destructive point-to-point three-dimensional structural probes have not hitherto been available for investigations at the critical mesoscopic length scales (tenths to hundreds of micrometres). As a result, investigations of three-dimensional mesoscale phenomena--such as grain growth, deformation, crumpling and strain-gradient effects--rely increasingly on computation and modelling without direct experimental input. Here we describe a three-dimensional X-ray microscopy technique that uses polychromatic synchrotron X-ray microbeams to probe local crystal structure, orientation and strain tensors with submicrometre spatial resolution. We demonstrate the utility of this approach with micrometre-resolution three-dimensional measurements of grain orientations and sizes in polycrystalline aluminium, and with micrometre depth-resolved measurements of elastic strain tensors in cylindrically bent silicon. This technique is applicable to single-crystal, polycrystalline, composite and functionally graded materials.