Diffraction-Based Multiscale Residual Strain Measurements.

Modern analytical tools, from microfocus X-ray diffraction (XRD) to electron microscopy-based microtexture measurements, offer exciting possibilities of diffraction-based multiscale residual strain measurements. The different techniques differ in scale and resolution, but may also yield significantly different strain values. This study, for example, clearly established that high-resolution electron backscattered diffraction (HR-EBSD) and high-resolution transmission Kikuchi diffraction (HR-TKD) [sensitive to changes in interplanar angle (Δθθ)], provide quantitatively higher residual strains than micro-Laue XRD and transmission electron microscope (TEM) based precession electron diffraction (PED) [sensitive to changes in interplanar spacing (Δdd)]. Even after correcting key known factors affecting the accuracy of HR-EBSD strain measurements, a scaling factor of ∼1.57 (between HR-EBSD and micro-Laue) emerged. We have then conducted "virtual" experiments by systematically deforming an ideal lattice by either changing an interplanar angle (α) or a lattice parameter (a). The patterns were kinematically and dynamically simulated, and corresponding strains were measured by HR-EBSD. These strains showed consistently higher values for lattice(s) distorted by α, than those altered by a. The differences in strain measurements were further emphasized by mapping identical location with HR-TKD and TEM-PED. These measurements exhibited different spatial resolution, but when scaled (with ∼1.57) provided similar lattice distortions numerically.

Texture Formation in Polycrystalline Thin Films of All-Inorganic Lead Halide Perovskite.

Controlling grain orientations within polycrystalline all-inorganic halide perovskite solar cells can help increase conversion efficiencies toward their thermodynamic limits; however, the forces governing texture formation are ambiguous. Using synchrotron X-ray diffraction, mesostructure formation within polycrystalline CsPbI2.85 Br0.15 powders as they cool from a high-temperature cubic perovskite (α-phase) is reported. Tetragonal distortions (ß-phase) trigger preferential crystallographic alignment within polycrystalline ensembles, a feature that is suggested here to be coordinated across multiple neighboring grains via interfacial forces that select for certain lattice distortions over others. External anisotropy is then imposed on polycrystalline thin films of orthorhombic (γ-phase) CsPbI3- x Brx perovskite via substrate clamping, revealing two fundamental uniaxial texture formations; i) I-rich films possess orthorhombic-like texture (<100> out-of-plane; <010> and <001> in-plane), while ii) Br-rich films form tetragonal-like texture (<110> out-of-plane; <110> and <001> in-plane). In contrast to relatively uninfluential factors like the choice of substrate, film thickness, and annealing temperature, Br incorporation modifies the γ-CsPbI3- x Brx crystal structure by reducing the orthorhombic lattice distortion (making it more tetragonal-like) and governs the formation of the different, energetically favored textures within polycrystalline thin films.

Biomineralization as a Paradigm of Directional Solidification: A Physical Model for Molluscan Shell Ultrastructural Morphogenesis.

Molluscan shells are a model system to understand the fundamental principles of mineral formation by living organisms. The diversity of unconventional mineral morphologies and 3D mineral-organic architectures that comprise these tissues, in combination with their exceptional mechanical efficiency, offers a unique platform to study the formation-structure-function relationship in a biomineralized system. However, so far, morphogenesis of these ultrastructures is poorly understood. Here, a comprehensive physical model, based on the concept of directional solidification, is developed to describe molluscan shell biomineralization. The capacity of the model to define the forces and thermodynamic constraints that guide the morphogenesis of the entire shell construct-the prismatic and nacreous ultrastructures and their transitions-and govern the evolution of the constituent mineralized assemblies on the ultrastructural and nanostructural levels is demonstrated using the shell of the bivalve Unio pictorum. Thereby, explicit tools for novel bioinspired and biomimetic bottom-up materials design are provided.

Electron imaging with an EBSD detector.

Electron Backscatter Diffraction (EBSD) has proven to be a useful tool for characterizing the crystallographic orientation aspects of microstructures at length scales ranging from tens of nanometers to millimeters in the scanning electron microscope (SEM). With the advent of high-speed digital cameras for EBSD use, it has become practical to use the EBSD detector as an imaging device similar to a backscatter (or forward-scatter) detector. Using the EBSD detector in this manner enables images exhibiting topographic, atomic density and orientation contrast to be obtained at rates similar to slow scanning in the conventional SEM manner. The high-speed acquisition is achieved through extreme binning of the camera-enough to result in a 5 × 5 pixel pattern. At such high binning, the captured patterns are not suitable for indexing. However, no indexing is required for using the detector as an imaging device. Rather, a 5 × 5 array of images is formed by essentially using each pixel in the 5 × 5 pixel pattern as an individual scattered electron detector. The images can also be formed at traditional EBSD scanning rates by recording the image data during a scan or can also be formed through post-processing of patterns recorded at each point in the scan. Such images lend themselves to correlative analysis of image data with the usual orientation data provided by and with chemical data obtained simultaneously via X-Ray Energy Dispersive Spectroscopy (XEDS).

Orientation precision of electron backscatter diffraction measurements near grain boundaries.

Electron backscatter diffraction (EBSD) has become a common technique for measuring crystallographic orientations at spatial resolutions on the order of tens of nanometers and at angular resolutions <0.1°. In a recent search of EBSD papers using Google Scholar™, 60% were found to address some aspect of deformation. Generally, deformation manifests itself in EBSD measurements by small local misorientations. An increase in the local misorientation is often observed near grain boundaries in deformed microstructures. This may be indicative of dislocation pile-up at the boundaries but could also be due to a loss of orientation precision in the EBSD measurements. When the electron beam is positioned at or near a grain boundary, the diffraction volume contains the crystal lattices from the two grains separated by the boundary. Thus, the resulting pattern will contain contributions from both lattices. Such mixed patterns can pose some challenge to the EBSD pattern band detection and indexing algorithms. Through analysis of experimental local misorientation data and simulated pattern mixing, this work shows that some of the rise in local misorientation is an artifact due to the mixed patterns at the boundary but that the rise due to physical phenomena is also observed.

Relating pore structure to activity at the subcrystal level for ZSM-5: an electron backscattering diffraction and fluorescence microscopy study.

The catalytic performance of microporous materials such as zeolites is determined not only by the active sites' molecular architecture, but also by the organization of the surrounding pores with varying diameter, shape, and directionality. These pores control transport of reagents and products and induce shape selectivity. Rather than being ideal single crystals, zeolites often have complex 3-dimensional morphologies, comprising intergrowths and various defect types. Here, the underlying pore architecture of the hexagonal facet of an individual zeolite ZSM-5 crystal is successfully determined by electron beam scattering diffraction and is correlated with the initial reactivity toward the acid-catalyzed oligomerization of furfuryl alcohol using polarized fluorescence microscopy.