Camelia V. Stan

Amorphous calcium carbonate particles form coral skeletons

Significance Whether coral skeleton crystals grow by attachment of ions from solution or particles from tissue determines (i) corals’ growth rate, (ii) how they survive acidifying oceans, and (iii) the isotopes in the crystals used for reconstructing ancient temperatures. Our data show that two amorphous precursors exist, one hydrated and one dehydrated amorphous calcium carbonate; that these are formed in the tissue as ∼400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally crystallize into aragonite. Since these particles are formed inside tissue, coral skeleton growth may be less susceptible to ocean acidification than previously assumed. Coral bleaching and postmortem dissolution of the skeleton will occur, but a calcification crisis may not. Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene–Eocene Thermal Maximum that occurred 56 Mya.

Influence of Nonuniform Micron-Scale Strain Distributions on the Electrical Reorientation of Magnetic Microstructures in a Composite Multiferroic Heterostructure

Composite multiferroic systems, consisting of a piezoelectric substrate coupled with a ferromagnetic thin film, are of great interest from a technological point of view because they offer a path toward the development of ultralow power magnetoelectric devices. The key aspect of those systems is the possibility to control magnetization via an electric field, relying on the magneto-elastic coupling at the interface between the piezoelectric and the ferromagnetic components. Accordingly, a direct measurement of both the electrically induced magnetic behavior and of the piezo-strain driving such behavior is crucial for better understanding and further developing these materials systems. In this work, we measure and characterize the micron-scale strain and magnetic response, as a function of an applied electric field, in a composite multiferroic system composed of 1 and 2 μm squares of Ni fabricated on a prepoled [Pb(Mg1/3Nb2/3)O3]0.69-[PbTiO3]0.31 (PMN-PT) single crystal substrate by X-ray microdiffraction and X-ray photoemission electron microscopy, respectively. These two complementary measurements of the same area on the sample indicate the presence of a nonuniform strain which strongly influences the reorientation of the magnetic state within identical Ni microstructures along the surface of the sample. Micromagnetic simulations confirm these experimental observations. This study emphasizes the critical importance of surface and interface engineering on the micron-scale in composite multiferroic structures and introduces a robust method to characterize future devices on these length scales.

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH2)2CsPb-halide (FACsPb-) and CH3NH3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

Synchrotron X-ray microdiffraction and fluorescence imaging of mineral and rock samples

In this report, we describe a detailed procedure for acquiring and processingxa0x-ray microfluorescence (μXRF), and Laue and powder microdiffraction two-dimensional (2D) maps at beamline 12.3.2 of the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory. Measurements can be performed on any sample that is less than 10 cm x 10 cm x 5 cm, with a flat exposed surface. The experimental geometry is calibrated using standard materials (elemental standards for XRF, and crystalline samples such as Si, quartz, or Al2O3 for diffraction). Samples are aligned to the focal point of the x-ray microbeam, and raster scans are performed, where each pixel of a map corresponds to one measurement, e.g., one XRF spectrum or one diffraction pattern. The data are then processed using the in-house developed software XMAS, which outputs text files, where each row corresponds to a pixel position. Representative data from moissanite and an olive snail shell are presented to demonstrate data quality, collection, and analysis strategies.

Probing stress states in silicon nanowires during electrochemical lithiation using in situ synchrotron X-ray microdiffraction

Silicon is considered as a promising anode material for the next generation lithium-ion battery due to its high capacity at nanoscale. However, silicon expands up to 300% during lithiation, which induces high stresses and leads to fractures. To design silicon nanostructures that could minimize fracture, it is important to understand and characterize stress states in the silicon nanostructures during lithiation. Synchrotron X-ray microdiffraction has proven to be effective in revealing insights of mechanical stress and other mechanics considerations in small-scale crystalline structures used in many important technological applications, such as microelectronics, nanotechnology and energy systems. In the present study, an in situ synchrotron X-ray microdiffraction experiment was conducted to elucidate the mechanical stress states during the first electrochemical cycle of lithiation in single-crystalline silicon nanowires (SiNWs) in a lithium-ion battery test cell. Morphological changes in the SiNWs at different levels of lithiation were also studied using scanning electron microscope (SEM). It was found from SEM observation, that lithiation commenced predominantly at the top-surface of SiNWs followed by further progression towards the bottom of the SiNWs gradually. The hydrostatic stress of the crystalline core of the SiNWs at different levels of electrochemical lithiation was determined using the in situ synchrotron X-ray microdiffraction technique. We found that the crystalline core of the SiNWs became highly compressive (up to -~325.5 MPa) once lithiation started. This finding helps unravel insights about mechanical stress states in the SiNWs during the electrochemical lithiation, which could potentially pave the path towards the fracture-free design of silicon nanostructure anode materials in the next generation lithium-ion battery.

Polytypism in natural SiC using Laue microdiffraction at ALS 12.3.2

Silicon carbide (SiC, moissanite) is a common industrial material that is rarely found in terrestrial rocks and meteorites. It has been found to adopt over 300 different crystal structures, most of which are polytypic: they consist of alternating layers of Si and C, with only small stacking faults or shears distinguishing them from one another. In nature, only a few polytypes of SiC have been found, primarily a cubic zincblende type (3C-SiC), several hexagonal wurtzite types (4H-SiC and 6H-SiC), and a rhombohedral type (15R-SiC). Our natural silicon carbide sample is from a Miocene tuff (Yizre’el Valley, Israel) related to interplate alkaline basalt volcanism. Three SiC grains with native silicon and metal silicide inclusions were analyzed using Raman spectroscopy and synchrotron Laue X-ray microdiffraction accompanied by mapping at a 5-8 um resolution. SiC is found to crystallize in only the 4H and 6H polytypes. Due to the crystal orientation of the grains, as well as the significant difference in the c-axis length (~10 vs. ~15 um in 4H and 6H respectively), we were able to unambiguously assign polytypes to each diffraction pattern. Each grain contains large areas where one polytype dominates as a single crystal. In some cases, multiple stacking faults and misoriented polycrystalline aggregates of SiC occur at the 4H/6H interface. In other cases we see intercalation of the 4H and 6H crystals throughout the diffracting volume without a significant change in their crystallographic axes orientation, pointing to a possibly incommensurate crystal structure. Stress and strain are also mapped for all three grains, showing a slight (< 2 ppt) compressive strain in the y direction of all three grains, and a tensile strain in the x and z directions. In the SiC-2 grain, a mostly single-crystalline Si inclusion was found, with an exposed surface diameter of ~30 um. We examine residual strain in Si by both Laue X-ray diffraction and Raman spectroscopy, and find results to generally agree between the two measurements.

Applications of Laue diffraction in rock deformation measurements

Material properties are linked to microstructure, e.g. grain size, grain orientation, phase distribution etc. Accurate crystallographic assignment of phases is critical for correctly assessing properties such as stress and strain in geological materials. In particular, α-quartz (P3121 or P3221) single crystals are prone to various types of twinning, which can lead to ambiguity in grain orientation assignment. Dauphine law twins are a common type of α-quartz twin, where domains with the same chirality intergrow but are distinguishable by a 60° rotation about the c axis of the trigonal unit cell. Proper assignment of single crystal orientation is crucial to accurately determining the stress tensor of the crystal, where misindexation can lead to large errors along the ab plane. At the Advanced Light Source beamline 12.3.2, we have developed energy dispersive diffraction (Laue) coupled with elemental identification using x-ray fluorescence (XRF) with 1-2 um beam size. We use this setup to generate 2D grain maps of polished natural quartz boudin samples from the Bastogne region of Belgium, with dimensions ranging from 160 x 100 um and 1 um step size to 4500 x 2600 um and 20 um step size. Macroscopically, these samples consist of alternating psammite (metamorphic fine-grained sandstone rock) and quartz. We determine quartz grain orientation in these samples unambiguously by using a statistical analysis of peak intensity as a function of indexed orientation in reflections with no harmonic overlap. We then calculate the strain tensor of each Laue pattern (~30,000 in the largest map) and find that all grains display elastic shortening perpendicular to the quartz vein walls, irrespective of grain direction. This indicates that boudinage forms through layer-parallel shortening, contrary to previously held beliefs. This study demonstrates how Laue diffraction can act as a fast, definitive and detailed tool in measurements of rock or mineral deformation.