Roland Kröger

Capillarity Creates Single‐Crystal Calcite Nanowires from Amorphous Calcium Carbonate

Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product.

Investigations of voids in the aragonite platelets of nacre

We studied the structure of the aragonite platelets of Haliotis laevigata nacre, using conventional transmission electron microscopy, Z-contrast, electron tomography, energy-dispersive X-ray analysis and electron energy-loss spectroscopy. We observed faceted voids several nanometers wide within the aragonite platelets. The electron tomography investigations showed that the voids are distributed more or less randomly in the studied specimen and allowed an estimation of the order of magnitude of the width and the volumetric content of the voids. Further investigations of these voids revealed that they contain an increased amount of carbon, which suggests the existence of organic material within the voids.

Enhanced oxidation of nanoparticles through strain-mediated ionic transport

Geometry and confinement effects at the nanoscale can result in substantial modifications to a materials properties with significant consequences in terms of chemical reactivity, biocompatibility and toxicity. Although benefiting applications across a diverse array of environmental and technological settings, the long-term effects of these changes, for example in the reaction of metallic nanoparticles under atmospheric conditions, are not well understood. Here, we use the unprecedented resolution attainable with aberration-corrected scanning transmission electron microscopy to study the oxidation of cuboid Fe nanoparticles. Performing strain analysis at the atomic level, we reveal that strain gradients induced in the confined oxide shell by the nanoparticle geometry enhance the transport of diffusing species, ultimately driving oxide domain formation and the shape evolution of the particle. We conjecture that such a strain-gradient-enhanced mass transport mechanism may prove essential for understanding the reaction of nanoparticles with gases in general, and for providing deeper insight into ionic conductivity in strained nanostructures.

Correlation of the orientation of stacked aragonite platelets in nacre and their connection via mineral bridges

In this work, we studied the correlation of the orientation of stacked aragonite platelets of Haliotis laevigata nacre, using selected area diffraction (SAD) in transmission electron microscopy (TEM). From the position of the center of Laue circle (COLC) within the diffraction patterns the tilt angles of the investigated platelets relatively to a reference platelet (oriented in zone axis) are determined. The strong correlation of the platelets supports the existence of mineral bridges, which connect the stacked platelets and enable a transfer of the platelet orientation during growth. Electron tomography and subsequent reconstruction of the obtained data yield information about the shape of the mineral bridges. The crystalline structure of the material within the mineral bridges was investigated by high resolution TEM (HRTEM).

Confined optical modes in monolithic II-VI pillar microcavities

Monolithic II-VI pillar microcavities made of ZnSSe and MgS∕ZnCdSe supperlattices have been fabricated by molecular-beam epitaxy and focused-ion-beam etching. Discrete optical modes of the pillar microcavities are studied in photoluminescence measurements. The optical modes are identified by means of calculations based on an extended transfer matrix method. Achievable Purcell factors well above 10 can be estimated from the measured quality factors and calculated mode volumes.

Magnesium segregation and the formation of pyramidal defects in p-GaN

Magnesium doping of GaN was found to generate extended defects with a pyramidal shape. Transmission electron micrographs of layers with different doping levels typically showed a defect-free region at the start of doping and a modulation of the defect density in the subsequent film. We developed a rate equation model based on the segregation of Mg to explain the formation process of these defects. The model explains the dependence of the defect-free thickness on the doping level and yields a criterion to avoid the defect formation. Hall measurements show a significant reduction of the free hole concentration for samples grown at doping levels beyond defect formation.

Protein sequences bound to mineral surfaces persist into deep time

Proteins persist longer in the fossil record than DNA, but the longevity, survival mechanisms and substrates remain contested. Here, we demonstrate the role of mineral binding in preserving the protein sequence in ostrich (Struthionidae) eggshell, including from the palaeontological sites of Laetoli (3.8 Ma) and Olduvai Gorge (1.3 Ma) in Tanzania. By tracking protein diagenesis back in time we find consistent patterns of preservation, demonstrating authenticity of the surviving sequences. Molecular dynamics simulations of struthiocalcin-1 and -2, the dominant proteins within the eggshell, reveal that distinct domains bind to the mineral surface. It is the domain with the strongest calculated binding energy to the calcite surface that is selectively preserved. Thermal age calculations demonstrate that the Laetoli and Olduvai peptides are 50 times older than any previously authenticated sequence (equivalent to ~16 Ma at a constant 10°C). DOI: http://dx.doi.org/10.7554/eLife.17092.001

Plasma induced microstructural, compositional, and resistivity changes in ultrathin chemical vapor deposited titanium nitride films

Extremely thin titanium nitride (TiN) barrier layers for Cu based interconnects were deposited using metal organic chemical vapor deposition. The effect of the subsequently performed nitrogen/hydrogen plasma treatment on the microstructure, composition, and electrical properties of these films is studied using conventional and high resolution transmission electron microscopy, Auger electron spectroscopy, and four point probe resistivity measurements. In the studied system the crystallization of the TiN film starts from an amorphous matrix and a polycrystalline morphology is developed upon the H2/N2 plasma treatment. After a short plasma treatment, most of the film is already crystalline and consists of grains of a few nanometers in diameter. Continued plasma treatment leads to grain growth and a significant reduction of contaminants such as oxygen and carbon. The resistivity of the films drops with plasma treatment time, and a correlation between resistivity and oxygen content is found, which suggests tha...

Defect distribution in a-plane GaN on Al2O3

The authors studied the structural and point defect distributions of hydride vapor phase epitaxial GaN film grown in the [11−20] a direction on (1−102) r-plane sapphire with metal-organic vapor phase deposited a-GaN template using transmission electron microscopy, secondary ion mass spectrometry, and positron annihilation spectroscopy. Grown-in extended and point defects show constant behavior as a function of thickness, contrary to the strong nonuniform defect distribution observed in GaN grown along the [0001] direction. The observed differences are explained by orientation-dependent and kinetics related defect incorporation.

An Oligomeric C-RING Nacre Protein Influences Prenucleation Events and Organizes Mineral Nanoparticles

The mollusk shell nacre layer integrates mineral phases with macromolecular components such as intracrystalline proteins. However, the roles performed by intracrystalline proteins in calcium carbonate nucleation and subsequent postnucleation events (e.g., organization of mineral deposits) in the nacre layer are not known. We find that AP7, a nacre intracrystalline C-RING protein, self-assembles to form amorphous protein oligomers and films on mica that further assemble into larger aggregates or phases in the presence of Ca2+. Using solution nuclear magnetic resonance spectroscopy, we determine that the protein assemblies are stabilized by interdomain interactions involving the aggregation-prone T31-N66 C-terminal C-RING domain but are destabilized by the labile nature of the intrinsically disordered D1-T19 AA N-terminal sequence. Thus, the dynamic, amorphous nature of the AP7 assemblies can be traced to the molecular behavior of the N-terminal sequence. Using potentiometric methods, we observe that AP7 protein phases prolong the time interval for prenucleation cluster formation but neither stabilize nor destabilize ACC clusters. Time-resolved flow cell scanning transmission electron microscopy mineralization studies confirm that AP7 protein phases delay the onset of nucleation and assemble and organize mineral nanoparticles into ring-shaped branching clusters in solution. These phenomena are not observed in protein-deficient assays. We conclude that C-RING AP7 protein phases modulate the time period for early events in nucleation and form strategic associations with forming mineral nanoparticles that lead to mineral organization.