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.

Three-dimensional high-resolution quantitative microscopy of extended crystals.

Hard X-ray lens-less microscopy raises hopes for a non-invasive quantitative imaging, capable of achieving the extreme resolving power demands of nanoscience. However, a limit imposed by the partial coherence of third generation synchrotron sources restricts the sample size to the micrometer range. Recently, X-ray ptychography has been demonstrated as a solution for arbitrarily extending the field of view without degrading the resolution. Here we show that ptychography, applied in the Bragg geometry, opens new perspectives for crystalline imaging. The spatial dependence of the three-dimensional Bragg peak intensity is mapped and the entire data subsequently inverted with a Bragg-adapted phase retrieval ptychographical algorithm. We report on the image obtained from an extended crystalline sample, nanostructured from a silicon-on-insulator substrate. The possibility to retrieve, without transverse size restriction, the highly resolved three-dimensional density and displacement field will allow for the unprecedented investigation of a wide variety of crystalline materials, ranging from life science to microelectronics.

Coherent x-ray wavefront reconstruction of a partially illuminated Fresnel zone plate.

A detailed characterization of the coherent x-ray wavefront produced by a partially illuminated Fresnel zone plate is presented. We show, by numerical and experimental approaches, how the beam size and the focal depth are strongly influenced by the illumination conditions, while the phase of the focal spot remains constant. These results confirm that the partial illumination can be used for coherent diffraction experiments. Finally, we demonstrate the possibility of reconstructing the complex-valued illumination function by simple measurement of the far field intensity in the specific case of partial illumination.

Nanoscale structures and dynamics of a boundary liquid layer.

Our long term scientific interest is the understanding of the interface properties of flowing liquids on a microscopic level. Various mechanisms have been introduced to explain the origin of slip at a solid-liquid interface like the formation of a thin depletion layer or a molecular ordering of the liquid near the interface. Reflectometry (using x-rays or neutrons) is a powerful technique to probe structures in this surface region. However, to date much less attention has been paid to the dynamical properties. In the first part of this paper we show that a different ordering of water exists next to a hydrophobic substrate in comparison to a hydrophilic interface. Furthermore, we find that shear has no effect on the depletion layer on hydrophobic substrates, while no depletion layer exists for hydrophilic surfaces. The second part of the paper addresses the dynamical properties of the boundary layer, and we present a new method which enables the observation of the diffusion dynamics of polymers next to a solid substrate. As a proof of concept, the dynamics of micelles next to the interface has been explored using grazing incidence neutron spin-echo spectroscopy. We were able to verify that investigation of the dynamics of the sample is feasible with this grazing incidence technique and we present data taken near the critical angle of total reflection. It appears that the diffusive motion of micelles at the hydrophobic (repulsive) interface is faster than at a hydrophilic interface or in the bulk. Furthermore, neutron spin-echo spectroscopy was extended to a first evaluation of the Doppler shift which occurs under flow.

Three-dimensional diffraction mapping by tuning the X-ray energy.

Three-dimensional reciprocal-space maps of a single SiGe island around the Si(004) Bragg peak are recorded using an energy-tuning technique with a microfocused X-ray beam with compound refractive lenses as focusing optics. The map is in agreement with simulated data as well as with a map recorded by an ordinary rocking-curve scan. The energy-tuning approach circumvents both the comparatively large sphere of confusion of diffractometers compared with nanostructures and vibrations induced by motors. Thus, this method offers new possibilities for novel combinations of three-dimensional micro- and nano-focused X-ray diffraction with complex in situ sample environments such as scanning probe microscopes.

Three-dimensional x-ray Fourier transform holography: the Bragg case.

A novel approach to determine the structure of nanoscale crystals in three dimensions is proposed by the use of coherent x-ray Fourier transform holography in Bragg geometry. The full internal description is directly obtained by a single Fourier transform of the 3D intensity hologram. Together with the morphology, Bragg geometry gives access to the 3D displacement field within the crystal. This result opens great possibilities for the investigation of strain fields inside nanocrystals in a simple way.

X-ray diffraction as a local probe tool.

For the structural characterization of nanoscale objects, X-ray diffraction is widely used as a technique complementing local probe analysis methods such as scanning electron microscopy and transmission electron microscopy. Details on strain distributions, chemical composition, or size and shape of nanostructures are addressed. X-ray diffraction traditionally obtains very good statistically averaged properties over large ensembles-provided this averaging is meaningful for ensembles with sufficiently small dispersion of properties. In many cases, however, it is desirable to combine different analysis techniques on exactly the same nano-object, for example, to gain a more detailed insight into the interdependence of properties. X-ray beams focused to diameters in the sub-micron range, which are available at third-generation synchrotron sources, allow for such X-ray diffraction studies of individual nano-objects.

Structural and magnetic properties of an InGaAs/Fe3Si superlattice in cylindrical geometry.

The structure and magnetic properties of an InGaAs/Fe(3)Si superlattice in a cylindrical geometry are investigated by electron microscopy techniques, x-ray diffraction and magnetometry. To form a radial superlattice, a pseudomorphic InGaAs/Fe(3)Si bilayer has been released from its substrate self-forming into rolled-up microtubes. Oxide-free interfaces as well as areas of crystalline bonding are observed and an overall lattice mismatch between succeeding layers is determined. The cylindrical symmetry of the final radial superlattice shows a significant effect on the magnetization behavior of the rolled-up layers.

Ion-induced nanopatterns on semiconductor surfaces investigated by grazing incidence x-ray scattering techniques.

In this review we cover and describe the application of grazing incidence x-ray scattering techniques to study and characterize nanopattern formation on semiconductor surfaces by ion beam erosion under various conditions. It is demonstrated that x-rays under grazing incidence are especially well suited to characterize (sub)surface structures on the nanoscale with high spatial and statistical accuracy. The corresponding theory and data evaluation is described in the distorted wave Born approximation. Both ex situ and in situ studies are presented, performed with the use of a specially designed sputtering chamber which allows us to follow the temporal evolution of the nanostructure formation. Corresponding results show a general stabilization of the ordering wavelength and the extension of the ordering as a function of the ion energy and fluence as predicted by theory. The in situ measurements are especially suited to study the early stages of pattern formation, which in some cases reveal a transition from dot to ripple formation. For the case of medium energy ions crystalline ripples are formed buried under a semi-amorphous thick layer with a ripple structure at the surface being conformal with the crystalline/amorphous interface. Here, the x-ray techniques are especially advantageous since they are non-destructive and bulk-sensitive by their very nature. In addition, the GI x-ray techniques described in this review are a unique tool to study the evolving strain, a topic which remains to be explored both experimentally and theoretically.

X-ray structure analysis of free-standing lipid membranes facilitated by micromachined apertures.

Silicon and Teflon substrates have been structured by wet etching and a focused ion beam (FIB) to obtain very defined, clean apertures. Planar, free-standing lipid membranes (black lipid membranes (BLM)) with enhanced long-term stability have been prepared on these apertures by the methods of Montal and Müller(1,2) as well as Müller and Rudin.(3) The stability and geometric control enables the use of X-ray analysis of free-standing single bilayers. With the presented setup, simultaneous structural and electrophysiological measurements will become feasible.

Early stage of ripple formation on Ge(001) surfaces under near-normal ion beam sputtering.

We present a study of the early stage of ripple formation on Ge(001) surfaces irradiated by a 1 keV Xe(+) ion beam at room temperature and near-normal incidence. A combination of a grazing incidence x-ray scattering technique and atomic force microscopy allowed us to observe a variation of the symmetry of the surface nanopattern upon increase of the ion fluence. The isotropic dot pattern formed during the first minutes of sputtering evolves into an anisotropic ripple pattern for longer sputtering time. These results provide a new basis for further steps in the theoretical description of the morphology evolution during ion beam sputtering.

X-ray pushing of a mechanical microswing.

We report here for the first time the combination of x-ray synchrotron light and a micro-electro-mechanical system (MEMS). We show how it is possible to modulate in real time a MEMS mass distribution to induce a nanometric and tunable mechanical oscillation. The quantitative experimental demonstration we present here uses periodic thermal dilatation of a Ge microcrystal attached to a Si microlever, induced by controlled absorption of an intensity modulated x-ray microbeam. The mechanism proposed can be envisaged either for the detection of small heat flux or for the actuation of a mechanical system.

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.

Local structure of a rolled-up single crystal: an X-ray microdiffraction study of individual semiconductor nanotubes.

Crystals with cylindrical symmetry, not existing in nature, are mimicked by the roll-up of single-crystalline and highly strained semiconductor bilayers. Exploiting this, the local structure of such individual rolled-up nanotubes is locally probed and quantified nondestructively by x-ray microbeam diffraction. A comparison to simulations, based on the minimization of the elastic energy, allows us to determine layer thicknesses and lattice parameter distributions within the strongly curved bilayers.

Ordered micro/mesoporous composite prepared as thin films.

A new synthesis method for preparation of thin films and powders consisting of zeolite beta nanocrystals embedded in ordered mesoporous silica matrix is described. The final structures possessing bimodal porosity, i.e., high degree of mesophase order and spatially defined microporous zeolite nanocrystals are obtained via simultaneous solvent evaporation of preformed silica/surfactant/ethanol/nanosized zeolite beta assemblies. The films were characterized with grazing-incident diffraction (GID), nitrogen sorption based on gravimetric measurements with quartz crystal microbalance (QCM) devices, and transmission electron microscopy (TEM). It is shown that the incorporation of beta nanocrystals in the mesoporous silica matrix and the mesophase order itself can be controlled through the variation of the fractional amounts of the zeolite nanoparticles and silica/surfactant solutions. The HR-TEM measurements showed that the nanosized Beta microporous crystals are separated and at the same time connected through an ordered mesostructured matrix.

SARS E protein in phospholipid bilayers: an anomalous X-ray reflectivity study.

We report on an anomalous X-ray reflectivity study to locate a labelled residue of a membrane protein with respect to the lipid bilayer. From such experiments, important constraints on the protein or peptide conformation can be derived. Specifically, our aim is to localize an iodine-labelled phenylalanine in the SARS E protein, incorporated in DMPC phospholipid bilayers, which are deposited in the form of thick multilamellar stacks on silicon surfaces. Here, we discuss the experimental aspects and the difficulties associated with the Fourier synthesis analysis that gives the electron density profile of the membranes.

A focusing crystal analyser for the rejection of inelastic X-ray scattering.

A focusing crystal analyser has been constructed that allows the rejection of inelastic X-ray scattering during diffuse scattering measurements close to an absorption edge. A Johann geometry was obtained by cylindrical bending of perfect silicon and germanium crystals. The choice of reflection, the effect of bending and the contribution of the source size are discussed in relation to the energy resolution. Measurements at the As K-edge (11.867 keV) and at the Cs K-edge (35.985 keV) are presented to demonstrate that the focusing analyser can be used over a wide energy range. A direct comparison with a flat perfect crystal with comparable energy resolution shows a gain in intensity by a factor of 50.

Direct determination of strain and composition profiles in SiGe islands by anomalous x-Ray diffraction at high momentum transfer.

Anomalous x-ray scattering is employed for quantitative measurements of the Ge composition profile in islands on Si(001). The anomalous effect in SiGe is enhanced exploiting the dependence of the complex atomic form factors on the momentum transfer. Comparing the intensity ratios for x-ray energies below and close to the K edge of Ge at various Bragg reflections in the grazing incidence diffraction setup, the sensitivity for the Ge profile is considerably enhanced. The method is demonstrated for SiGe dome-shaped islands grown on Si(001). It is found that the composition inside the island changes rather abruptly, whereas the lattice parameter relaxes continuously.

Pure silica BETA colloidal zeolite assembled in thin films.

Pure silica nanoscale zeolite BETA with monomodal particle size distribution was synthesized from a colloidal precursor solution and successfully applied for the preparation of hydrophobic ultrathin films on silicon wafers via spin coating.

X-ray diffraction from rectangular slits.

It is shown that for micrometre-sized beams the X-ray diffraction from slits is a source of strong parasitic background, even for slits of high quality. In order to illustrate this effect, the coherent diffraction from rectangular slits has been studied in detail. A large number of interference fringes with strong visibility have been observed using a single set of slits made of polished cylinders. For very small apertures, asymmetrical slits generate asymmetrical patterns. This pattern is calculated from the theory of electromagnetic field propagation and compared with experiment in the far-field regime. The use of guard slits to remove Fraunhofer diffraction from the beam-defining slits is treated theoretically. Numerical simulations yield the optimum aperture of the guard slits with respect to the distance to the primary slits. Diffraction theory is shown to be essential to understand how to reduce the background-to-signal ratio in high-resolution experiments.