Bragg coherent diffraction imaging of single 20†nm Pt particles at the ID01-EBS beamline of ESRF.

Electronic or catalytic properties can be modified at the nanoscale level. Engineering efficient and specific nanomaterials requires the ability to study their complex structure-property relationships. Here, Bragg coherent diffraction imaging was used to measure the three-dimensional shape and strain of platinum nanoparticles with a diameter smaller than 30 nm, i.e. significantly smaller than any previous study. This was made possible by the realization of the Extremely Brilliant Source of ESRF, The European Synchrotron. This work demonstrates the feasibility of imaging the complex structure of very small particles in three dimensions and paves the way towards the observation of realistic catalytic particles.

3D Imaging of a Dislocation Loop at the Onset of Plasticity in an Indented Nanocrystal.

Structural quality and stability of nanocrystals are fundamental problems that bear important consequences for the performances of small-scale devices. Indeed, at the nanoscale, their functional properties are largely influenced by elastic strain and depend critically on the presence of crystal defects. It is thus of prime importance to be able to monitor, by noninvasive means, the stability of the microstructure of nano-objects against external stimuli such as mechanical load. Here we demonstrate the potential of Bragg coherent diffraction imaging for such measurements, by imaging in 3D the evolution of the microstructure of a nanocrystal exposed to in situ mechanical loading. Not only could we observe the evolution of the internal strain field after successive loadings, but we also evidenced a transient microstructure hosting a stable dislocation loop. The latter is fully characterized from its characteristic displacement field. The mechanical behavior of this small crystal is clearly at odds with what happens in bulk materials where many dislocations interact. Moreover, this original in situ experiment opens interesting possibilities for the investigation of plastic deformation at the nanoscale.

Reactor for nano-focused x-ray diffraction and imaging under catalytic in situ conditions.

A reactor cell for in situ studies of individual catalyst nanoparticles or surfaces by nano-focused (coherent) x-ray diffraction has been developed. Catalytic reactions can be studied in flow mode in a pressure range of 10-2-103 mbar and temperatures up to 900 °C. This instrument bridges the pressure and materials gap at the same time within one experimental setup. It allows us to probe in situ the structure (e.g., shape, size, strain, faceting, composition, and defects) of individual nanoparticles using a nano-focused x-ray beam. Here, the setup was used to observe strain and facet evolution of individual model Pt catalysts during in situ experiments. It can be used for heating other (non-catalytically active) nanoparticles (e.g., nanowires) in inert or reactive gas atmospheres or vacuum as well.

Continuous and Collective Grain Rotation in Nanoscale Thin Films during Silicidation.

Texture evolution is an important issue in materials and nanosciences. Understanding it is fundamental for controlling the final orientation, which in fine controls the desired properties of nanodevices. Here, we reveal the formation of a peculiar texture during the silicidation of nanoscale Pd thin films. We demonstrate that the crystallographic relationship observed between the silicide and the Si(001) substrate, named gyroaxy, evolves continuously and collectively during silicidation. This continuous rotation of the nanosized grains over a wide angular range is proposed to be associated with a diffusional mechanism.

In situ three-dimensional reciprocal-space mapping during mechanical deformation.

Mechanical deformation of a SiGe island epitaxically grown on Si(001) was studied by a specially adapted atomic force microscope and nanofocused X-ray diffraction. The deformation was monitored during in situ mechanical loading by recording three-dimensional reciprocal-space maps around a selected Bragg peak. Scanning the energy of the incident beam instead of rocking the sample allowed the safe and reliable measurement of the reciprocal-space maps without removal of the mechanical load. The crystal truncation rods originating from the island side facets rotate to steeper angles with increasing mechanical load. Simulations of the displacement field and the intensity distribution, based on the finite-element method, reveal that the change in orientation of the side facets of about 25° corresponds to an applied pressure of 2-3 GPa on the island top plane.

A combined In situ grazing incidence small angle X-ray scattering and grazing incidence X-ray diffraction study of the growth of Ge Islands on pit-patterned Si(001) substrates.

The growth of Ge islands on a pit-patterned Si(001) template is investigated in situ, combining grazing incidence diffraction, multiple wavelength anomalous diffraction, and small angle scattering. This allows monitoring in situ the detailed structural and morphological evolutions of the pits, of the wetting-layer and of the nucleated islands on the pit-patterned Si(001) substrate. It is shown that after Si regrowth, the Si substrate displays {107} and {1 1 11} facets. During the very first stages of Ge growth, the preliminary facets of the Si substrate are energetically unfavourable, and the pit facets break up into a rather complex pattern of {10n} and {11m} facets with n > 7 and m > 11. At 5 and 6 ML, intensity rods from {105} and {113}-type facets appear in the GISAXS images revealing the formation of pyramids and domes, respectively. The degree of ordering, the shape, strain and composition of the islands are characterized during the growth process to provide a detailed evolution of their structure and morphology.

Enhanced relaxation and intermixing in Ge islands grown on pit-patterned Si(001) substrates.

We compare elastic relaxation and Si-Ge distribution in epitaxial islands grown on both pit-patterned and flat Si(001) substrates. Anomalous x-ray diffraction yields that nucleation in the pits provides a higher relaxation. Using an innovative, model-free fitting procedure based on self-consistent solutions of the elastic problem, we provide compositional and elastic-energy maps. Islands grown on flat substrates exhibit stronger composition gradients and do not show a monotonic decrease of elastic energy with height. Both phenomena are explained using both thermodynamic and kinetic arguments.

Defect cores investigated by x-ray scattering close to forbidden reflections in silicon.

A new x-ray scattering method is presented making possible the detection of defects and the investigation of the structure of their cores. The method uses diffuse x-ray scattering measured close to a forbidden diffraction peak, in which the intensity scattered from the distorted crystal lattice around the defects is minimized. As a first example of this nondestructive method we demonstrate how the local compression of the extra {111} double planes in extrinsic stacking faults in Si can be probed and quantified using a continuum approach for the simulation of the displacements. The results of the theory developed are found to be in very good agreement with atomistic simulations and experiments.