A. Stierle

Initial corrosion observed on the atomic scale

Corrosion destroys more than three per cent of the worlds GDP. Recently, the electrochemical decomposition of metal alloys has been more productively harnessed to produce porous materials with diverse technological potential. High-resolution insight into structure formation during electrocorrosion is a prerequisite for an atomistic understanding and control of such electrochemical surface processes. Here we report atomic-scale observations of the initial stages of corrosion of a Cu3Au(111) single crystal alloy within a sulphuric acid solution. We monitor, by in situ X-ray diffraction with picometre-scale resolution, the structure and chemical composition of the electrolyte/alloy interface as the material decomposes. We reveal the microscopic structural changes associated with a general passivation phenomenon of which the origin has been hitherto unclear. We observe the formation of a gold-enriched single-crystal layer that is two to three monolayers thick, and has an unexpected inverted (CBA-) stacking sequence. At higher potentials, we find that this protective passivation layer dewets and pure gold islands are formed; such structures form the templates for the growth of nanoporous metals. Our experiments are carried out on a model single-crystal system. However, the insights should equally apply within a crystalline grain of an associated polycrystalline electrode fabricated from many other alloys exhibiting a large difference in the standard potential of their constituents, such as stainless steel (see ref. 5 for example) or alloys used for marine applications, such as CuZn or CuAl.

Shape Changes of Supported Rh Nanoparticles During Oxidation and Reduction Cycles

The microscopic insight into how and why catalytically active nanoparticles change their shape during oxidation and reduction reactions is a pivotal challenge in the fundamental understanding of heterogeneous catalysis. We report an oxygen-induced shape transformation of rhodium nanoparticles on magnesium oxide (001) substrates that is lifted upon carbon monoxide exposure at 600 kelvin. A Wulff analysis of high-resolution in situ x-ray diffraction, combined with transmission electron microscopy, shows that this phenomenon is driven by the formation of a oxygen–rhodium–oxygen surface oxide at the rhodium nanofacets. This experimental access into the behavior of such nanoparticles during a catalytic cycle is useful for the development of improved heterogeneous catalysts.

Tensile testing of ultrathin polycrystalline films: A synchrotron-based technique

The mechanical properties of metallic thin films on the nanoscale acquire increasingly more importance as applications in microelectromechanical systems/NEMS as well as microelectronics have reached this size scale. Here, we present a synchrotron x-ray diffraction technique by which it is possible to characterize the evolution of mechanical stress in a metallic film thinner than 100 nm at measurement times shorter than 60 s per data point. This high data acquisition rate is achieved because no relative motions or tilting of specimen, x-ray source and detector (a large-area charge coupled device camera) are required. The technique comprises an initial “sin2 ψ” measurement to establish the absolute stress values followed by periodic “sin2 φ” measurements during straining to determine stress increments. We describe an experimental setup established at the synchrotron radiation source ANKA (Karlsruhe, Germany) which is specifically suited for monitoring the stress evolution during in situ tensile tests on thi...

Dedicated Max-Planck beamline for the in situ investigation of interfaces and thin films

A dedicated beamline for the Max-Planck-Institut fur Metallforschung was recently taken into operation at the Angstro/mquelle Karlsruhe (ANKA). Here we describe the layout of the beamline optics and the experimental end-station, consisting of a heavy duty multiple circle diffractometer. For both a new design was realized, combining a maximum flexibility in the beam properties [white, pink, (focused) monochromatic, energy range 6–20 keV] with a special diffractometer for heavy sample environments up to 500 kg, that can be run in different geometrical modes. In addition the angular-reciprocal space transformations for the diffractometer in use are derived, which allows an operation of the instrument in the convenient six circle mode. As an example, results from surface x-ray diffraction on a Cu3Au(111) single crystal are presented.

X-ray investigation of subsurface interstitial oxygen at Nb/oxide interfaces

We have investigated the dissolution of a natural oxide layer on a Nb(110) surface upon heating, combining x-ray reflectivity, grazing incidence diffuse scattering, and core-level spectroscopy. The natural oxide reduces after heating to 145°C partially from Nb2O5 to NbO2, and an enrichment in subsurface interstitial oxygen by ∼70% in a depth of 100A is observed. After heating to 300°C, the oxide reduces to NbO and the surplus subsurface oxygen gets dissolved into the bulk. Our approach can be applied for further investigation of the effect of subsurface interstitial oxygen on the performance of niobium rf cavities.

Atmospheric pressure oxidation of Pt(111)

The oxidation of the platinum (111) single crystal surface and the formation of platinum dioxide have been studied by in situ surface x-ray diffraction and x-ray reflectivity. At an oxygen partial pressure of 500 mbar and at temperatures from 520 to 910 K, the experiments disclose the growth of two atomic layers of a bulk-like, strongly distorted α-PtO2. The epitaxial Pt oxide layer is oriented hexagon on hexagon with respect to the Pt(111) surface leading to a (8 × 8) superstructure surface unit cell. In a second set of experiments, a 100 A thick epitaxial Pt(111) film on sapphire was exposed to oxygen. At 670 K and near atmospheric oxygen pressures we find the formation of a several angstrom thick oxide layer. After annealing the sample at 720 K in a vacuum the oxide layer desorbs, recovering the 100 A thick Pt film. Subsequent oxidation at 720 K and reduction cycles lead to a slight increase in surface roughness and the formation of macroscopically visible holes in the Pt film. These results point to a Pt re-dispersion which sets in during chemical reactions at atmospheric pressures.

Reversible shape changes of Pd nanoparticles on MgO(100)

We studied the interaction of oxygen with MgO(100) supported Pd nanoparticles at 10(-5) mbar oxygen pressure and a sample temperature of 570 K. We employed high-resolution X-ray reciprocal space mapping, which allows us to resolve the average particle shape from the quantitative analysis of intensity diffraction rods running perpendicular to corresponding facet surfaces. We identified the oxygen induced formation of nanosized (112) facets which is reversible in a CO atmosphere. Our results give direct evidence for the microscopic evolution of the nanoparticle shape under reactant exposure, which is essential for an atomistic understanding of catalytic reactions on nanoparticles.

A surface x-ray study of the structure and morphology of the oxidized Pd(001) surface

The oxidation of Pd(100) and the formation of PdO was studied in situ using surface x-ray diffraction. A bulklike, epitaxial PdO film is formed at oxygen partial pressures beyond 1 mbar and sample temperatures exceeding 650 K. The main orientation is PdO(001)/Pd(001), based upon bulk reflections from the PdO film. By comparing with measurements from the Pd crystal truncation rods, we estimate an rms surface roughness of 6 A, in good agreement with previous high pressure scanning tunneling microscopy measurements. Finally, we observed the transformation from the (radical5 x radical5) surface oxide to PdO bulk oxide at 675 K and 50 mbar O(2) pressure.

Organically linked iron oxide nanoparticle supercrystals with exceptional isotropic mechanical properties

It is commonly accepted that the combination of the anisotropic shape and nanoscale dimensions of the mineral constituents of natural biological composites underlies their superior mechanical properties when compared to those of their rather weak mineral and organic constituents. Here, we show that the self-assembly of nearly spherical iron oxide nanoparticles in supercrystals linked together by a thermally induced crosslinking reaction of oleic acid molecules leads to a nanocomposite with exceptional bending modulus of 114 GPa, hardness of up to 4 GPa and strength of up to 630 MPa. By using a nanomechanical model, we determined that these exceptional mechanical properties are dominated by the covalent backbone of the linked organic molecules. Because oleic acid has been broadly used as nanoparticle ligand, our crosslinking approach should be applicable to a large variety of nanoparticle systems.

Structural investigation of the dynamics of the NiO(111) surface by GIXS

Abstract The behaviour of the NiO(111) surface has been investigated by grazing incidence X-ray scattering (GIXS). We show on single crystals with an improved crystalline quality that NiO(111) is always p(2×2) reconstructed. After air annealing the structure is close to the predicted octopolar reconstruction; after in situ annealing and oxidation it is very different. The transformation of the surface is continuous with temperature but seems to be only based on two possible atomic configurations.