X-ray Diffraction Imaging Techniques Research Articles

X-ray diffraction imaging of the diamond anvils based on the microfocus x-ray source with a liquid anode.

This paper presents the results of using laboratory x-ray systems in the study of the crystal structure of anvil made from single-crystal diamond. The system is equipped with an Excillum MetalJet D2 + 70kV high-brightness x-ray source with a liquid GaIn anode. The x-ray diffraction imaging (topography) technique with the use of a high-resolution x-ray Rigaku camera was applied to analyze crystal structure defects. Two-dimensional images were experimentally recorded using 400 and 111 reflections with a resolution of 1.5 and 5μm, respectively. These topograms displayed various defects, such as growth striations and dislocations. Possible applications of the proposed laboratory-based optical scheme for high-pressure physics are discussed and future improvements to the setup are suggested.

A finite difference scheme for integrating the Takagi-Taupin equations on an arbitrary orthogonal grid.

Calculating dynamical diffraction patterns for X-ray diffraction imaging techniques requires numerical integration of the Takagi-Taupin equations. This is usually performed with a simple, second-order finite difference scheme on a sheared computational grid in which two of the axes are aligned with the wavevectors of the incident and scattered beams. This dictates, especially at low scattering angles, an oblique grid of uneven step sizes. Here a finite difference scheme is presented that carries out this integration in slab-shaped samples on an arbitrary orthogonal grid by implicitly utilizing Fourier interpolation. The scheme achieves the expected second-order convergence and a similar error to the traditional approach for similarly dense grids.

Origin of structural degradation in Li-rich layered oxide cathode

Li- and Mn-rich(LMR) cathode materials that utilize both cation and anion redox can yield substantial increases in battery energy density1-3. However, although voltage decay issues cause continuous energy loss and impede commercialization, the prerequisite driving force for this phenomenon remains a mystery3-6 Here, with in situ nanoscale sensitive coherent X-ray diffraction imaging techniques, we reveal that nanostrain and lattice displacement accumulate continuously during operation of the cell. Evidence shows that this effect is the driving force for both structure degradation and oxygen loss, which trigger the well-known rapid voltage decay in LMR cathodes. By carrying out micro- to macro-length characterizations that span atomic structure, the primary particle, multiparticle and electrode levels, we demonstrate that the heterogeneous nature of LMR cathodes inevitably causes pernicious phase displacement/strain, which cannot be eliminated by conventional doping or coating methods. We therefore propose mesostructural design as a strategy to mitigate lattice displacement and inhomogeneous electrochemical/structural evolutions, thereby achieving stable voltage and capacity profiles. These findings highlight the significance of lattice strain/displacement in causing voltage decay and will inspire a wave of efforts to unlock the potential of the broad-scale commercialization of LMR cathode materials.

Deformation field mapping of the X-ray silicon Fresnel Zone Plate

The characterization of the deformations of the circular Fresnel Zone Plate (FZP) by the X-ray diffraction imaging technique is presented in this paper. The research was performed at the ID06 ESRF beamline using the 12.38 keV radiation energy. During the experiment, the contour map of the FZP deformation field was obtained. This map was used in the reconstruction of the surface curvature profile at three points: at the FZP center, 60 μm, and 120 μm below the FZP center. As result, the FZP with 242 zones has a concave profile in its center and a convex profile near the outermost zones. The inflection points close to the 115th zone were observed. This technique can be used not only for the characterization of the conventional binary FZP but also for the Multilayer Laue Lenses and FZP with multilevel, and kinoform profiles.

Limitations of Structural Insight into Ultrafast Melting of Solid Materials with X-ray Diffraction Imaging

In this work, we analyze the application of X-ray diffraction imaging techniques to follow ultrafast structural transitions in solid materials using the example of an X-ray pump–X-ray probe experiment with a single-crystal silicon performed at a Linac Coherent Light Source. Due to the spatially non-uniform profile of the X-ray beam, the diffractive signal recorded in this experiment included contributions from crystal parts experiencing different fluences from the peak fluence down to zero. With our theoretical model, we could identify specific processes contributing to the silicon melting in those crystal regions, i.e., the non-thermal and thermal melting whose occurrences depended on the locally absorbed X-ray doses. We then constructed the total volume-integrated signal by summing up the coherent signal contributions (amplitudes) from the various crystal regions and found that this significantly differed from the signals obtained for a few selected uniform fluence values, including the peak fluence. This shows that the diffraction imaging signal obtained for a structurally damaged material after an impact of a non-uniform X-ray pump pulse cannot be always interpreted as the material’s response to a pulse of a specific (e.g., peak) fluence as it is sometimes believed. This observation has to be taken into account in planning and interpreting future experiments investigating structural changes in materials with X-ray diffraction imaging.

Operando 3D imaging of defects dynamics of twinned-nanocrystal during catalysis

Using operando Bragg coherent x-ray diffraction imaging, we visualised three-dimensionally a single twinned-gold nanocrystal during the CO oxidation reaction. We describe the defect dynamics process occurring under operating conditions and indicate the correlation between the nucleation of highly strained regions at the surface of the nanocrystal and its catalytic activity. Understanding the twinning deformation mechanism sheds light on the creation of active sites, and could well contribute to the understanding of the catalytic behaviour of other catalysts. With the start-up of 4th generation synchrotron sources, we anticipate that coherent hard x-ray diffraction imaging techniques will play a major role in imaging in situ chemical processes.

Optical and vibrational properties of Ni doped ZnSe nanospheres

Ni doped ZnSe nanospheres in presence of PVA have been synthesized via a cost effective and simple solvothermal method. The structural and rnorphological characterization of as undoped and doped samples have been made using X-ray diffraction (XRD) and FESEM imaging techniques and it reveals the formation of Ni doped ZnSe nanospheres with crystallite size 6 nm. The observed red shift in absorption edge of Ni doped ZnSe as compared to undoped sample also indicates the formation of nanospheres. The PL spectra of Ni doped sample shows red shift with enhanced intensity. The molecular vibrations of PVA capped Ni doped ZnSe nanospheres have been studied and four new vibrational modes have been observed and reported.

Spin–phonon interactions in silicon carbide addressed by Gaussian acoustics

Hybrid spin-mechanical systems provide a platform for integrating quantum registers and transducers. Efficient creation and control of such systems require a comprehensive understanding of the individual spin and mechanical components as well as their mutual interactions. Point defects in silicon carbide (SiC) offer long-lived, optically addressable spin registers in a wafer-scale material with low acoustic losses, making them natural candidates for integration with high quality factor mechanical resonators. Here, we show Gaussian focusing of a surface acoustic wave in SiC, characterized by a novel stroboscopic X-ray diffraction imaging technique, which delivers direct, strain amplitude information at nanoscale spatial resolution. Using ab initio calculations, we provide a more complete picture of spin-strain coupling for various defects in SiC with C3v symmetry. This reveals the importance of shear for future device engineering and enhanced spin-mechanical coupling. We demonstrate all-optical detection of acoustic paramagnetic resonance without microwave magnetic fields, relevant to sensing applications. Finally, we show mechanically driven Autler-Townes splittings and magnetically forbidden Rabi oscillations. These results offer a basis for full strain control of three-level spin systems.

Nanoscale Strain Imaging using Coherent X-ray Light Sources

Coherence properties available from the advanced X-ray synchrotrons and X-ray Free Electron Laser sources bring the opportunities to get new information of the dynamics and local structures non-destructively. Here we review recent progress of the coherent X-ray diffraction imaging technique for measuring internal strain distribution of the nanomaterial systems. We introduce the general coherence properties of the sources and show the fundamental principle and technical aspects of the technique. Some examples of the applications are shown for various nanostructures, grains in polycrystalline films, and semiconducting devices even with in situ and operando conditions. We discuss the future development of the technique in terms of the understanding and control of the strains, which are very crucial in nanomaterial design and applications.

Advances in 6d diffraction contrast tomography

The ability to measure 3D orientation fields and to determine grain boundary character plays a key role in understanding many material science processes, including: crack formation and propagation, grain coarsening, and corrosion processes. X-ray diffraction imaging techniques offer the ability to retrieve such information in a non-destructive manner. Among them, Diffraction Contrast Tomography (DCT) is a monochromatic beam, near-field technique, that uses an extended beam and offers fast mapping of 3D sample volumes. It was previously shown that the six-dimensional extension of DCT can be applied to moderately deformed samples (⩽ 5% total strain), made from materials that exhibit low levels of elastic deformation of the unit cell (⩽ 1%). In this article, we improved over the previously proposed 6D-DCT reconstruction method, through the introduction of both a more advanced forward model and reconstruction algorithm. The results obtained with the proposed improvements are compared against the reconstructions previously published in [1], using Electron Backscatter Diffraction (EBSD) measurements as a reference. The result was a noticeably higher quality reconstruction of the grain boundary positions and local orientation fields. The achieved reconstruction quality, together with the low acquisition times, render DCT a valuable tool for the stop-motion study of polycrystalline microstructures, evolving as a function of applied strain or thermal annealing treatments, for selected materials.

Development of Loaded Microspheres for Tamper-Activated Security Features

The ongoing technological fight against counterfeiting demands the development of new anti-counterfeiting strategies based on novel material systems. In this work, we report on a unique material system, employing porous-wall hollow glass microspheres as versatile carriers for functional security materials. To evaluate the feasibility of using these glass microspheres in anti-counterfeiting applications, several deployment configurations and processing routes were developed, whereby microsphere cargo included either (1) precursor functional materials, (2) functional materials, or (3) reactive functional materials. Microspheres were loaded using a wet vacuum technique and subsequently characterized using scanning electron microscopy, energy dispersive x-ray spectroscopy, x-ray diffraction, and spectral imaging techniques.

Coherent X-ray diffraction imaging of nanoengineered polymeric capsules

For the first time, nanoengineered polymeric capsules and their architecture have been studied with coherent X-ray diffraction imaging technique. The use of coherent X-ray diffraction imaging technique allowed us to analyze the samples immersed in a liquid. We report about the significant difference between polymeric capsule architectures under dry and liquid conditions.

Merging single-shot XFEL diffraction data from inorganic nanoparticles: a new approach to size and orientation determination.

X-ray free-electron lasers (XFELs) provide new opportunities for structure determination of biomolecules, viruses and nanomaterials. With unprecedented peak brilliance and ultra-short pulse duration, XFELs can tolerate higher X-ray doses by exploiting the femtosecond-scale exposure time, and can thus go beyond the resolution limits achieved with conventional X-ray diffraction imaging techniques. Using XFELs, it is possible to collect scattering information from single particles at high resolution, however particle heterogeneity and unknown orientations complicate data merging in three-dimensional space. Using the Linac Coherent Light Source (LCLS), synthetic inorganic nanocrystals with a core-shell architecture were used as a model system for proof-of-principle coherent diffractive single-particle imaging experiments. To deal with the heterogeneity of the core-shell particles, new computational methods have been developed to extract the particle size and orientation from the scattering data to assist data merging. The size distribution agrees with that obtained by electron microscopy and the merged data support a model with a core-shell architecture.

Bragg projection ptychography on niobium phase domains

Bragg projection ptychography (BPP) is a coherent x-ray diffraction imaging technique which combines the strengths of scanning microscopy with the phase contrast of x-ray ptychography. Here we apply it for high resolution imaging of the phase-shifted crystalline domains associated with epitaxial growth. The advantages of BPP are that the spatial extent of the sample is arbitrary, it is nondestructive, and it gives potentially diffraction limited spatial resolution. Here we demonstrate the application of BPP for revealing the domain structure caused by epitaxial misfit in a nanostructured metallic thin film. Experimental coherent diffraction data were collected from a niobium thin film, epitaxially grown on a sapphire substrate as the beam was scanned across the sample. The data were analyzed by BPP using a carefully selected combination of refinement procedures. The resulting image shows a close packed array of epitaxial domains, shifted with respect to each other due to misfit between the film and its substrate.

CARNAÚBA: The Coherent X-Ray Nanoprobe Beamline for the Brazilian Synchrotron SIRIUS/LNLS

The CARNAÚBA beamline is the tender-to-hard X-ray (2 – 15 keV) scanning nanoprobe planned for the 4th generation storage ring SIRIUS at the LNLS. CARNAÚBA uses an undulator source with vertical linear polarization in a low-beta straight section and grazing incidence-focusing mirrors to create a nanoprobe at 143 m from the source. The beamline optic is based on KB mirrors and provides high brilliance at an achromatic focal spot down to the diffraction limit diameter of ∼30 nm with a working distance of ∼6 cm. These characteristics are crucial for studying nanometric samples in experiments involving complex stages and environments. The CARNAÚBA beamline aims to perform raster scans using x-ray fluorescence, x-ray absorption spectroscopy, x-ray diffraction and coherent x-ray imaging techniques. Computed tomography will extend these methods to three dimensions.

Mineral chemistry and phase equilibrium constraints on the origin of accretions formed during copper flash smelting

This paper delves into the constraints on the nature, origin and thermal evolution of the accretions formed in the uptake shaft of the flash smelting furnace operated by Atlantic Copper in Huelva, Spain, outlining recommended practices for preventing accretion buildup. The accretions were investigated using quantitative electron probe microanalysis, X-ray diffraction and digital imaging techniques, and the experimental data on mineral composition, crystal chemistry and textural relationships were interpreted in terms of thermodynamic phase equilibrium in the SiO2-Fe-O-S system. The results suggest that two distinct types of accretions were formed by the fractional crystallization of two coexisting immiscible melts, under changing conditions of oxygen partial pressure (pO2). The type I accretion of magnetite + delafossite ± cuprite ± tridymite ± metallic copper crystallized from a fractionating copper-rich melt at pO2 above about 10−5 atm, while the type II accretion of magnetite + fayalite + metallic copper + chalcocite derived from a melt with lower copper concentration when pO2 levels dropped below that critical level. Phase compositions and textures were consistent with a cooling history of both compositionally contrasting liquids from about 1,250 °C, the liquidus temperature of magnetite, to eutectic or near-eutectic temperatures of around 1,100 °C. The maintenance of appropriate temperatures — above the liquidus temperature of magnetite — and oxygen partial pressure levels may be critical for the prevention of accretion buildup.

Nanox: a miniature mechanical stress rig designed for near-field X-ray diffraction imaging techniques

Multi-modal characterization of polycrystalline materials by combined use of three-dimensional (3D) X-ray diffraction and imaging techniques may be considered as the 3D equivalent of surface studies in the electron microscope combining diffraction and other imaging modalities. Since acquisition times at synchrotron sources are nowadays compatible with four-dimensional (time lapse) studies, suitable mechanical testing devices are needed which enable switching between these different imaging modalities over the course of a mechanical test. Here a specifically designed tensile device, fulfilling severe space constraints and permitting to switch between X-ray (holo)tomography, diffraction contrast tomography and topotomography, is presented. As a proof of concept the 3D characterization of an Al-Li alloy multicrystal by means of diffraction contrast tomography is presented, followed by repeated topotomography characterization of one selected grain at increasing levels of deformation. Signatures of slip bands and sudden lattice rotations inside the grain have been shown by means of in situ topography carried out during the load ramps, and diffraction spot peak broadening has been monitored throughout the experiment.

Nondestructive Monitoring of Die Warpage in Encapsulated Chip Packages

We describe an X-ray diffraction imaging technique for nondestructive, in situ measurement of die warpage in encapsulated chip packages at acquisition speeds approaching real time. The results were validated on a series of samples with known inbuilt convex die warpage, and the measurement of wafer bow was compared with the results obtained by optical profilometry. We use the technique to demonstrate the impact of elevated temperature on a commercially sourced micro quad flat nonlead chip package and show that the strain becomes locked in at a temperature between 94 °C and 120 °C. Using synchrotron radiation at the Diamond Light Source, warpage maps for the entire 2.2 mm × 2.4 mm × 150-μm Si die were acquired in 50 s, and individual line scans in times as short as 500 ms.

B-Spline X-Ray Diffraction Imaging — Rapid non-destructive measurement of die warpage in ball grid array packages

Next generation “More than Moore” integrated circuit (IC) technology will rely increasingly on the benefits attributable to advanced packaging (www.itrs.net[1]). In these increasingly heterogeneous systems, the individual semiconductor die is becoming much thinner (25 to 50μm, typically) and multiple dies can be stacked upon each other. It is difficult to assess non-destructively, non-invasively and in situ the stress or warpage of the semiconductor die inside these chip packages and conventional approaches tend to monitor the warpage of the package rather than the die.This paper comprises an account of a relatively new technique, which we call B-Spline X-Ray Diffraction Imaging (B-XRDI) and its application, in this instance, to the non-destructive mapping of Si semiconductor die lattice misorientation inside wire bonded encapsulated Low-profile Fine-pitch Ball Grid Array (LFPGA) packages. B-XRDI is an x-ray diffraction imaging technique which allows the user to reconstruct from a series of section x-ray topographic images a full profile of the warpage of the silicon semiconductor die inside such a chip package. There is no requirement for pre-treatment or pre-processing of the chip package and we show that synchrotron-based B-XRDI mapping of wafer warpage can be achieved with angular tilt resolutions of the order of 50μrad≈0.003° in times as short as 9–180s (worst case X–Y spatial resolution=100μm) for a full 8.7mm×8.7mm semiconductor die inside the fully encapsulated LFBGA packages. We confirm the usefulness of the technique by correlating our data with conventional warpage measurements performed by mechanical and interferometric profilometry and finite element modelling (FEM). We suggest that future developments will lead to real-time, or near real-time, mapping of thermomechanical stresses during chip packaging processes, which can run from bare wafer through to a fully encapsulated chip package.

Characterization of defects in mono-like silicon for photovoltaic applications using X-ray Bragg diffraction imaging.

Rocking curve imaging (projection and section X-ray topography) has been used to study the generation and propagation of defects at the junctions between and above the seed crystals in mono-like silicon ingots. The images of different kinds of defects such as precipitates, dislocations and twins in the integrated intensity, full width at half-maximum and peak position maps resulting from the experiment have been studied. The qualitative and quantitative information that can be extracted from these maps, in particular the contrast of the images of the various defects, is discussed. These defects have a detrimental effect on solar cell efficiency and their detailed investigation allows clues to be obtained in order to improve the growth process. This work shows that synchrotron X-ray diffraction imaging techniques, because of their high angular resolution (<10-4°) and large field of view (several mm2), constitute a powerful tool for investigating the initial stages of growth of directionally solidified mono-like silicon.