Interface control of bulk ferroelectric polarization.

The control of material interfaces at the atomic level has led to novel interfacial properties and functionalities. In particular, the study of polar discontinuities at interfaces between complex oxides lies at the frontier of modern condensed matter research. Here we employ a combination of experimental measurements and theoretical calculations to demonstrate the control of a bulk property, namely ferroelectric polarization, of a heteroepitaxial bilayer by precise atomic-scale interface engineering. More specifically, the control is achieved by exploiting the interfacial valence mismatch to influence the electrostatic potential step across the interface, which manifests itself as the biased-voltage in ferroelectric hysteresis loops and determines the ferroelectric state. A broad study of diverse systems comprising different ferroelectrics and conducting perovskite underlayers extends the generality of this phenomenon.

Controlling tetragonality and crystalline orientation in BaTiO3 nano-layers grown on Si.

A hybrid growth process was developed in order to epitaxially integrate nano-layers of the multi-functional perovskite BaTiO3 onto Si(001) substrates. In particular, we combined molecular beam epitaxy (MBE) with radio-frequency sputtering. Due to its strong influence on the functional properties, the crystalline structure of the layers was thoroughly investigated throughout our study. MBE-grown seed layers are tetragonal and c-axis oriented up to a thickness of 20 nm. A transition into a-axis films is visible for thicker layers. When the seed layer thickness exceeds 6 nm, subsequently sputtered BaTiO3 films are epitaxial. However, their crystalline structure, their orientation with respect to the substrate, and their morphology are strongly dependent on the deposition and post-deposition thermal budget. Consistently with their crystalline symmetry, thin MBE BaTiO3 films are piezo- and ferroelectric with a spontaneous polarization perpendicular to the surface. Also for thick films, the functional response, as determined via piezo-force microscopy, is in good agreement with the structural properties.

Atomic structure of highly strained BiFeO3 thin films.

We determine the atomic structure of the pseudotetragonal T phase and the pseudorhombohedral R phase in highly strained multiferroic BiFeO(3) thin films by using a combination of atomic-resolution scanning transmission electron microscopy and electron energy-loss spectroscopy. The coordination of the Fe atoms and their displacement relative to the O and Bi positions are assessed by direct imaging. These observations allow us to interpret the electronic structure data derived from electron energy-loss spectroscopy and provide evidence for the giant spontaneous polarization in strained BiFeO(3) thin films.

Interface ferromagnetism and orbital reconstruction in BiFeO3-La(0.7)Sr(0.3)MnO3 heterostructures.

We report the formation of a novel ferromagnetic state in the antiferromagnet BiFeO3 at the interface with ferromagnet La(0.7)Sr(0.3)MnO3. Using x-ray magnetic circular dichroism at Mn and Fe L(2,3) edges, we discovered that the development of this ferromagnetic spin structure is strongly associated with the onset of a significant exchange bias. Our results demonstrate that the magnetic state is directly related to an electronic orbital reconstruction at the interface, which is supported by the linearly polarized x-ray absorption measurement at the oxygen K edge.

The ultrathin limit of improper ferroelectricity.

The secondary nature of polarization in improper ferroelectrics promotes functional properties beyond those of conventional ferroelectrics. In technologically relevant ultrathin films, however, the improper ferroelectric behavior remains largely unexplored. Here, we probe the emergence of the coupled improper polarization and primary distortive order parameter in thin films of hexagonal YMnO3. Combining state-of-the-art in situ characterization techniques separately addressing the improper ferroelectric state and its distortive driving force, we reveal a pronounced thickness dependence of the improper polarization, which we show to originate from the strong modification of the primary order at epitaxial interfaces. Nanoscale confinement effects on the primary order parameter reduce the temperature of the phase transition, which we exploit to visualize its order-disorder character with atomic resolution. Our results advance the understanding of the evolution of improper ferroelectricity within the confinement of ultrathin films, which is essential for their successful implementation in nanoscale applications.

Uncovering the psychoactivity of a cannabinoid from liverworts associated with a legal high.

Phytochemical studies on the liverwort Radula genus have previously identified the bibenzyl (-)-cis-perrottetinene (cis-PET), which structurally resembles (-)-Δ9-trans-tetrahydrocannabinol (Δ9-trans-THC) from Cannabis sativa L. Radula preparations are sold as cannabinoid-like legal high on the internet, even though pharmacological data are lacking. Herein, we describe a versatile total synthesis of (-)-cis-PET and its (-)-trans diastereoisomer and demonstrate that both molecules readily penetrate the brain and induce hypothermia, catalepsy, hypolocomotion, and analgesia in a CB1 receptor-dependent manner in mice. The natural product (-)-cis-PET was profiled on major brain receptors, showing a selective cannabinoid pharmacology. This study also uncovers pharmacological differences between Δ9-THC and PET diastereoisomers. Most notably, (-)-cis-PET and (-)-trans-PET significantly reduced basal brain prostaglandin levels associated with Δ9-trans-THC side effects in a CB1 receptor-dependent manner, thus mimicking the action of the endocannabinoid 2-arachidonoyl glycerol. Therefore, the natural product (-)-cis-PET is a psychoactive cannabinoid from bryophytes, illustrating the existence of convergent evolution of bioactive cannabinoids in the plant kingdom. Our findings may have implications for bioprospecting and drug discovery and provide a molecular rationale for the reported effects upon consumption of certain Radula preparations as moderately active legal highs.

Quantitative characterisation of chemical inhomogeneities in Al-Ag using high-resolution Z-contrast STEM.

The incoherent imaging model is applied to interpret high-resolution Z-contrast micrographs. A simple method for a column-by-column resolved characterisation of Ag-rich precipitates in Al-Ag is developed. No information on the detailed imaging process is required. Evaluating the high-angle scattering intensities of Al and Ag by image analysis, the number of Ag atoms contained in individual atomic columns can be determined accurately and moreover, the thickness of the thin foil can be calculated. Multislice simulations confirm the broad validity of the incoherent imaging model for Z-contrast STEM and are used to check the method presented. Finally, the image analysis is applied to experimental Z-contrast images of Guinier-Preston zones in Al-3 at% Ag. The Ag content of the individual atomic columns can be determined with an accuracy better than +/-10%.

Bulk interfaces in a Ni-rich Ni-Au alloy investigated by high-resolution Z-contrast imaging.

Interfaces between Au-rich precipitates and the Ni-rich matrix in a decomposed Ni-10 at.% Au alloy were investigated by low-magnification and high-resolution Z-contrast imaging. During aging at 923 K, the originally single crystalline sample decomposed and recrystallized resulting in a microstructure consisting of subgrains separated by small-angle grain boundaries. These small-angle grain boundaries are decorated by Au-rich precipitates. The interfaces between the Au-rich precipitates and the Ni-rich matrix were characterized with respect to the orientation relationship between precipitates and matrix, misfit dislocations and concentration gradients. Two transformation modes were identified that are involved in the decomposition of bulk Ni-rich Ni-Au alloys. While in the first mode the interface is semi-coherent, in the second mode the interface corresponds to an incoherent twin boundary. It is further shown that strain fields around misfit dislocations can result in systematic errors in the determination of the concentration gradients across interfaces between precipitates and matrix.

Quantitative atomic resolution mapping using high-angle annular dark field scanning transmission electron microscopy.

A model-based method is proposed to relatively quantify the chemical composition of atomic columns using high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) images. The method is based on a quantification of the total intensity of the scattered electrons for the individual atomic columns using statistical parameter estimation theory. In order to apply this theory, a model is required describing the image contrast of the HAADF STEM images. Therefore, a simple, effective incoherent model has been assumed which takes the probe intensity profile into account. The scattered intensities can then be estimated by fitting this model to an experimental HAADF STEM image. These estimates are used as a performance measure to distinguish between different atomic column types and to identify the nature of unknown columns with good accuracy and precision using statistical hypothesis testing. The reliability of the method is supported by means of simulated HAADF STEM images as well as a combination of experimental images and electron energy-loss spectra. It is experimentally shown that statistically meaningful information on the composition of individual columns can be obtained even if the difference in averaged atomic number Z is only 3. Using this method, quantitative mapping at atomic resolution using HAADF STEM images only has become possible without the need of simultaneously recorded electron energy loss spectra.

A strain-driven morphotropic phase boundary in BiFeO3.

Piezoelectric materials, which convert mechanical to electrical energy and vice versa, are typically characterized by the intimate coexistence of two phases across a morphotropic phase boundary. Electrically switching one to the other yields large electromechanical coupling coefficients. Driven by global environmental concerns, there is currently a strong push to discover practical lead-free piezoelectrics for device engineering. Using a combination of epitaxial growth techniques in conjunction with theoretical approaches, we show the formation of a morphotropic phase boundary through epitaxial constraint in lead-free piezoelectric bismuth ferrite (BiFeO3) films. Electric field-dependent studies show that a tetragonal-like phase can be reversibly converted into a rhombohedral-like phase, accompanied by measurable displacements of the surface, making this new lead-free system of interest for probe-based data storage and actuator applications.

Direct imaging of lattice atoms and topological defects in graphene membranes.

We present a transmission electron microscopy investigation of graphene membranes, crystalline foils with a thickness of only 1 atom. By using aberration-correction in combination with a monochromator, 1-A resolution is achieved at an acceleration voltage of only 80 kV. The low voltage is crucial for the stability of these membranes. As a result, every individual carbon atom in the field of view is detected and resolved. We observe a highly crystalline lattice along with occasional point defects. The formation and annealing of Stone-Wales defects is observed in situ. Multiple five- and seven-membered rings appear exclusively in combinations that avoid dislocations and disclinations, in contrast to previous observations on highly curved (tube- or fullerene-like) graphene surfaces.

Detection of single atoms and buried defects in three dimensions by aberration-corrected electron microscope with 0.5-A information limit.

The ability of electron microscopes to analyze all the atoms in individual nanostructures is limited by lens aberrations. However, recent advances in aberration-correcting electron optics have led to greatly enhanced instrument performance and new techniques of electron microscopy. The development of an ultrastable electron microscope with aberration-correcting optics and a monochromated high-brightness source has significantly improved instrument resolution and contrast. In the present work, we report information transfer beyond 50 pm and show images of single gold atoms with a signal-to-noise ratio as large as 10. The instrument's new capabilities were exploited to detect a buried Sigma3 {112} grain boundary and observe the dynamic arrangements of single atoms and atom pairs with sub-angstrom resolution. These results mark an important step toward meeting the challenge of determining the three-dimensional atomic-scale structure of nanomaterials.

Distortion and segregation in a dislocation core region at atomic resolution.

The structure of an isolated, Ga terminated, 30 degree partial dislocation in GaAs:Be is determined by high resolution transmission electron microscopes and focal series reconstruction. The positions of atomic columns in the core region are measured to an accuracy of better than 10 pm. A quantitative comparison of the structure predicted by an ab initio electronic structure total energy calculation to the experiment indicates that theory and experiment agree to within 20 pm. Further analysis shows the deviations between theory and experiment appear to be systematic. Electron energy loss spectroscopy establishes that defects segregate to the core region, thus accounting for the systematic deviations.

[Whipple's disease with normal intestinal histology: rarity or reality?]. / Morbus Whipple mit normaler Dünndarmhistologie: Rarität oder Realität?

Whipple's disease has been diagnosed more frequently in recent years as a consequence of better awareness and of improved diagnostic tools. The number of case reports of Whipple's disease without gastrointestinal symptoms and without histological lesions of the intestinal mucosa is increasing. Therefore, the traditional perception of this disease as well as the methods for its diagnosis need to be revised. We report on 2 patients with Whipple's disease who had systemic inflammatory reactions but neither gastrointestinal symptoms nor an abnormal duodenal histology. Whipple's disease was diagnosed on the basis of extraintestinal tissue histology (lymph node, vertebral body) and by polymerase chain reaction, and was treated successfully with antibiotics. Recommendations for diagnostic procedure in Whipple's disease with both typical and atypical clinical presentation are discussed.