Ross Harder

Three-dimensional imaging of strain in a single ZnO nanorod

Nanoscale structures can be highly strained because of confinement effects and the strong influence of their external boundaries. This results in dramatically different electronic, magnetic and optical material properties of considerable utility. Third-generation synchrotron-based coherent X-ray diffraction has emerged as a non-destructive tool for three-dimensional (3D) imaging of strain and defects in crystals that are smaller than the coherence volume, typically a few cubic micrometres, of the available beams that have sufficient flux to reveal the materials structure. Until now, measurements have been possible only at a single Bragg point of a given crystal because of the limited ability to maintain alignment; it has therefore been possible to determine only one component of displacement and not the full strain tensor. Here we report key advances in our fabrication and experimental techniques, which have enabled diffraction patterns to be obtained from six Bragg reflections of the same ZnO nanocrystal for the first time. All three Cartesian components of the ion displacement field, and in turn the full nine-component strain tensor, have thereby been imaged in three dimensions.

Ultrafast three-dimensional imaging of lattice dynamics in individual gold nanocrystals.

Distorted Nanoparticle Nanoparticles have found many applications in modern technology; however, the full characterization of individual particles is challenging. One of the most interesting mechanical properties is the particles response to lattice distortion. This property has been probed for ensembles of nanoparticles, but the required averaging may distort the results. Clark et al. (p. 56, published online 23 May; see the Perspective by Hartland and Lo) were able to image the generation and subsequent evolution of coherent acoustic phonons from an individual perturbed gold nanocrystal on the picosecond time scale. An x-ray free-electron laser is used to probe the elastic modes of a gold nanocrystal. [Also see Perspective by Hartland and Lo] Key insights into the behavior of materials can be gained by observing their structure as they undergo lattice distortion. Laser pulses on the femtosecond time scale can be used to induce disorder in a “pump-probe” experiment with the ensuing transients being probed stroboscopically with femtosecond pulses of visible light, x-rays, or electrons. Here we report three-dimensional imaging of the generation and subsequent evolution of coherent acoustic phonons on the picosecond time scale within a single gold nanocrystal by means of an x-ray free-electron laser, providing insights into the physics of this phenomenon. Our results allow comparison and confirmation of predictive models based on continuum elasticity theory and molecular dynamics simulations.

Topological defect dynamics in operando battery nanoparticles

Watching defects during battery cycling Dislocations affect the mechanical properties of a material. Ulvestad et al. studied the influence of dislocations on a nanoparticle undergoing charge and discharge cycles in a lithium ion battery. The defects influenced the way the material expanded and contracted during cycling. In the future, it may be possible to tune the properties of a material through controlled defect engineering. Science, this issue p. 1344 Coherent x-rays image structural transformations in battery nanoparticles during electrochemical operation. Topological defects can markedly alter nanomaterial properties. This presents opportunities for “defect engineering,” where desired functionalities are generated through defect manipulation. However, imaging defects in working devices with nanoscale resolution remains elusive. We report three-dimensional imaging of dislocation dynamics in individual battery cathode nanoparticles under operando conditions using Bragg coherent diffractive imaging. Dislocations are static at room temperature and mobile during charge transport. During the structural phase transformation, the lithium-rich phase nucleates near the dislocation and spreads inhomogeneously. The dislocation field is a local probe of elastic properties, and we find that a region of the material exhibits a negative Poisson’s ratio at high voltage. Operando dislocation imaging thus opens a powerful avenue for facilitating improvement and rational design of nanostructured materials.

High-resolution three-dimensional partially coherent diffraction imaging

The wave properties of light, particularly its coherence, are responsible for interference effects, which can be exploited in powerful imaging applications. Coherent diffractive imaging relies heavily on coherence and has recently experienced rapid growth. Coherent diffractive imaging recovers an object from its diffraction pattern by computational phasing with the potential of wavelength-limited resolution. Diminished coherence results in reconstructions that suffer from artefacts or fail completely. Here we demonstrate ab initio phasing of partially coherent diffraction patterns in three dimensions, while simultaneously determining the coherence properties of the illuminating wavefield. Both the dramatic improvements in image interpretability and the three-dimensional evaluation of the coherence will have broad implications for quantitative imaging of nanostructures and wavefield characterization with X-rays and electrons.

11 nm hard X-ray focus from a large-aperture multilayer Laue lens

The focusing performance of a multilayer Laue lens (MLL) with 43.4 μm aperture, 4 nm finest zone width and 4.2 mm focal length at 12 keV was characterized with X-rays using ptychography method. The reconstructed probe shows a full-width-at-half-maximum (FWHM) peak size of 11.2 nm. The obtained X-ray wavefront shows excellent agreement with the dynamical calculations, exhibiting aberrations less than 0.3 wave period, which ensures the MLL capable of producing a diffraction-limited focus while offering a sufficient working distance. This achievement opens up opportunities of incorporating a variety of in-situ experiments into ultra high-resolution X-ray microscopy studies.

Coherent diffraction imaging of nanoscale strain evolution in a single crystal under high pressure

The evolution of morphology and internal strain under high pressure fundamentally alters the physical property, structural stability, phase transition and deformation mechanism of materials. Until now, only averaged strain distributions have been studied. Bragg coherent X-ray diffraction imaging is highly sensitive to the internal strain distribution of individual crystals but requires coherent illumination, which can be compromised by the complex high-pressure sample environment. Here we report the successful de-convolution of these effects with the recently developed mutual coherent function method to reveal the three-dimensional strain distribution inside a 400 nm gold single crystal during compression within a diamond-anvil cell. The three-dimensional morphology and evolution of the strain under pressures up to 6.4 GPa were obtained with better than 30 nm spatial resolution. In addition to providing a new approach for high-pressure nanotechnology and rheology studies, we draw fundamental conclusions about the origin of the anomalous compressibility of nanocrystals.

Optimization of overlap uniformness for ptychography

We demonstrate the advantages of imaging with ptychography scans that follow a Fermat spiral trajectory. This scan pattern provides a more uniform coverage and a higher overlap ratio with the same number of scan points over the same area than the presently used mesh and concentric [13] patterns. Under realistically imperfect measurement conditions, numerical simulations show that the quality of the reconstructed image is improved significantly with a Fermat spiral compared with a concentric scan pattern. The result is confirmed by the performance enhancement with experimental data, especially under low-overlap conditions. These results suggest that the Fermat spiral pattern increases the quality of the reconstructed image and tolerance to data with imperfections.

Differential stress induced by thiol adsorption on facetted nanocrystals

Polycrystalline gold films coated with thiol-based self-assembled monolayers (SAM) form the basis of a wide range of nanomechanical sensor platforms. The detection of adsorbates with such devices relies on the transmission of mechanical forces, which is mediated by chemically derived stress at the organic-inorganic interface. Here, we show that the structure of a single 300-nm-diameter facetted gold nanocrystal, measured with coherent X-ray diffraction, changes profoundly after the adsorption of one of the simplest SAM-forming organic molecules. On self-assembly of propane thiol, the crystals flat facets contract radially inwards relative to its spherical regions. Finite-element modelling indicates that this geometry change requires large stresses that are comparable to those observed in cantilever measurements. The large magnitude and slow kinetics of the contraction can be explained by an intermixed gold-sulphur layer that has recently been identified crystallographically. Our results illustrate the importance of crystal edges and grain boundaries in interface chemistry and have broad implications for the application of thiol-based SAMs, ranging from nanomechanical sensors to coating technologies.

Analysis of strain and stacking faults in single nanowires using Bragg coherent diffraction imaging

Coherent diffraction imaging (CDI) on Bragg reflections is a promising technique for the study of three-dimensional (3D) composition and strain fields in nanostructures, which can be recovered directly from the coherent diffraction data recorded on single objects. In this paper, we report results obtained for single homogeneous and heterogeneous nanowires with a diameter smaller than 100 nm, for which we used CDI to retrieve information about deformation and faults existing in these wires. We also discuss the influence of stacking faults, which can create artefacts during the reconstruction of the nanowire shape and deformation.

Single Particle Nanomechanics in Operando Batteries via Lensless Strain Mapping

We reveal three-dimensional strain evolution in situ of a single LiNi0.5Mn1.5O4 nanoparticle in a coin cell battery under operando conditions during charge/discharge cycles with coherent X-ray diffractive imaging. We report direct observation of both stripe morphologies and coherency strain at the nanoscale. Our results suggest the critical size for stripe formation is 50 nm. Surprisingly, the single nanoparticle elastic energy landscape, which we map with femtojoule precision, depends on charge versus discharge, indicating hysteresis at the single particle level. This approach opens a powerful new avenue for studying battery nanomechanics, phase transformations, and capacity fade under operando conditions at the single particle level that will enable profound insight into the nanoscale mechanisms that govern electrochemical energy storage systems.