Structure of n-Alkyltrichlorosilane Monolayers on Si(100)/SiO2.

The structure of n-alkyltrichlorosilane self-assembled monolayers (SAMs) of alkyl chain lengths n = 12, 14, 18, and 22 formed on the amorphous native oxide of silicon (100) has been investigated via angstrom-resolution surface X-ray scattering techniques, with particular focus on the proliferation of lateral order along the molecules' long axis. Grazing incidence diffraction shows that the monolayer is composed of hexagonally packed crystalline-like domains for n = 14, 18, and 22 with a lateral size of about 60 Å. However, Bragg rod analysis shows that ∼12 of the CH2 units are not included in the crystalline-like domains. We assign this, and the limited lateral crystallites' size, to strain induced by the size mismatch between the optimal chain-chain and headgroup-headgroup spacings. Analysis of X-ray reflectivity profiles for n = 12, 14, and 22 shows that the density profile used to successfully model n = 18 provides an excellent fit where the analysis-derived parameters provide complementary structural information to the grazing incidence results.

In situ investigation of two-step nucleation and growth of CdS nanoparticles from solution.

We report on a combined ultra-fast in situ SAXS and WAXS study along a free-jet providing insight into the evolution of the morphology and crystalline structure of CdS quantum dots in the very early stage of nucleation between 100 µs and 2.5 ms with a time resolution down to 10 µs. Accessing this yet unexplored time regime provides direct evidence of a two-step mechanism via formation of prenucleation clusters followed by nanoparticle nucleation from coalescing precursors. Using ab initio calculations, the latter species is identified as Cd13S4(SH)18 clusters, the stability of which results from a compact surface and inner structure.

Pseudorotational epitaxy of self-assembled octadecyltrichlorosilane monolayers on sapphire (0001).

The structure of octadecyltrichlorosilane self-assembled monolayers (SAMs) on sapphire (0001) was studied by Å-resolution surface-specific x-ray scattering methods. The monolayer was found to consist of three sublayers where the outermost layer corresponds to vertically oriented, closely packed alkyl tails. Laterally, the monolayer is hexagonally packed and exhibits pseudorotational epitaxy to the sapphire, manifested by a broad scattering peak at zero relative azimuthal rotation, with long powderlike tails. The lattice mismatch of ∼ 1%-3% to the sapphire's and the different length scale introduced by the lateral Si-O-Si bonding prohibit positional epitaxy. However, the substrate induces an intriguing increase in the crystalline coherence length of the SAM's powderlike crystallites when rotationally aligned with the sapphire's lattice. The increase correlates well with the rotational dependence of the separation of corresponding substrate-monolayer lattice sites.

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.

Structure of polymer micelles close to the solid interface. A grazing incidence small angle neutron scattering study.

Block copolymers are widely used in industry. For scientific interests their aqueous solutions offer a model system for the investigation of crystallisation as the macromolecules agglomerate for elevated concentrations into micelles, which crystallise when a critical volume fraction is reached. We report on grazing incidence small angle neutron scattering (GISANS) or near surface small angle neutron scattering (NS-SANS) as an experimental tool to investigate the micelle crystallisation close to interfaces with different chemical termination. We find that in general crystallization is suppressed at a repulsive surface and favoured at an attractive one. Furthermore we show that the crystallization close the interface can be controlled by the micelle stability, resulting from the different composition and length of the monomers. The effect of the interface is found more important for a high micelle stability, whereas for a low stability it is shadowed by adsorbed monomers.

Storage of X-ray photons in a crystal resonator

The temporal structure and high brilliance of the X-ray beams produced by third-generation synchrotrons open up new possibilities in time-dependent diffraction and spectroscopy, where timescales down to the sub-nanosecond regime can now be accessed. These beam properties are such that one can envisage the development of the X-ray equivalent of optical components, such as photon delay lines and resonators, that have proved indispensable in a wide range of experiments--for example, pump-probe and multiple-interaction experiments--and (through shaping the temporal structure and repetition rate of the beams) time-dependent measurements in crystallography, physics, biology and chemistry. Optical resonators, such as those used in lasers, are available at wavelengths from the visible to soft X-rays. Equivalent components for hard X-rays have been discussed for more than thirty years, but have yet to be realized. Here we report the storage of hard X-ray photons (energy 15.817 keV) in a crystal resonator formed by two plates of crystalline silicon. The photons are stored for as many as 14 back-and-forth cycles within the resonator, each cycle separated by one nanosecond.