Cécile Hébert

Identifying champion nanostructures for solar water-splitting

Charge transport in nanoparticle-based materials underlies many emerging energy-conversion technologies, yet assessing the impact of nanometre-scale structure on charge transport across micrometre-scale distances remains a challenge. Here we develop an approach for correlating the spatial distribution of crystalline and current-carrying domains in entire nanoparticle aggregates. We apply this approach to nanoparticle-based α-Fe₂O₃ electrodes that are of interest in solar-to-hydrogen energy conversion. In correlating structure and charge transport with nanometre resolution across micrometre-scale distances, we have identified the existence of champion nanoparticle aggregates that are most responsible for the high photoelectrochemical activity of the present electrodes. Indeed, when electrodes are fabricated with a high proportion of these champion nanostructures, the electrodes achieve the highest photocurrent of any metal oxide photoanode for photoelectrochemical water-splitting under 100 mW cm(-2) air mass 1.5 global sunlight.

Silicon Filaments in Silicon Oxide for Next-Generation Photovoltaics

Nanometer wide silicon filaments embedded in an amorphous silicon oxide matrix are grown at low temperatures over a large area. The optical and electrical properties of these mixed-phase nanomaterials can be tuned independently, allowing for advanced light management in high efficiency thin-film silicon solar cells and for band-gap tuning via quantum confinement in third-generation photovoltaics.

Multivariate statistical analysis as a tool for the segmentation of 3D spectral data.

Acquisition of three-dimensional (3D) spectral data is nowadays common using many different microanalytical techniques. In order to proceed to the 3D reconstruction, data processing is necessary not only to deal with noisy acquisitions but also to segment the data in term of chemical composition. In this article, we demonstrate the value of multivariate statistical analysis (MSA) methods for this purpose, allowing fast and reliable results. Using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) coupled with a focused ion beam (FIB), a stack of spectrum images have been acquired on a sample produced by laser welding of a nickel-titanium wire and a stainless steel wire presenting a complex microstructure. These data have been analyzed using principal component analysis (PCA) and factor rotations. PCA allows to significantly improve the overall quality of the data, but produces abstract components. Here it is shown that rotated components can be used without prior knowledge of the sample to help the interpretation of the data, obtaining quickly qualitative mappings representative of elements or compounds found in the material. Such abundance maps can then be used to plot scatter diagrams and interactively identify the different domains in presence by defining clusters of voxels having similar compositions. Identified voxels are advantageously overlaid on secondary electron (SE) images with higher resolution in order to refine the segmentation. The 3D reconstruction can then be performed using available commercial softwares on the basis of the provided segmentation. To asses the quality of the segmentation, the results have been compared to an EDX quantification performed on the same data.

Direct visualization of dispersed lipid bicontinuous cubic phases by cryo-electron tomography

Bulk and dispersed cubic liquid crystalline phases (cubosomes), present in the body and in living cell membranes, are believed to play an essential role in biological phenomena. Moreover, their biocompatibility is attractive for nutrient or drug delivery system applications. Here the three-dimensional organization of dispersed cubic lipid self-assembled phases is fully revealed by cryo-electron tomography and compared with simulated structures. It is demonstrated that the interior is constituted of a perfect bicontinuous cubic phase, while the outside shows interlamellar attachments, which represent a transition state between the liquid crystalline interior phase and the outside vesicular structure. Therefore, compositional gradients within cubosomes are inferred, with a lipid bilayer separating at least one water channel set from the external aqueous phase. This is crucial to understand and enhance controlled release of target molecules and calls for a revision of postulated transport mechanisms from cubosomes to the aqueous phase.

Energy loss magnetic chiral dichroism: A new technique for the study of magnetic properties in the electron microscope (invited)

The similarity between x-ray absorption near edge structure and electron energy loss near edge structure is well known. However, “exporting” x-ray magnetic circular dichroism (XMCD) to the transmission electron microscope (TEM) was considered impossible with present technology since electron probes possessing chirality (i.e., spin polarization) cannot be set up with sufficient intensity. But recently magnetically induced chiral electronic transitions were detected in the TEM. In analogy to XMCD we introduced the term EMCD (energy loss magnetic chiral dichroism). The mechanism builds upon the formal equivalence between the mixed dynamic form factor for inelastic electron scattering and the absorption cross section for x-rays. Experiments on the 3d ferromagnets show effects very similar to XMCD. Calculations based on the WIEN2K package are in good agreement with experiments. The recent improvement in signal strength and spatial resolution allows now to study atom specific spin and orbital moments on a scale...

Optimal aperture sizes and positions for EMCD experiments

The signal-to-noise ratio (SNR) in energy-loss magnetic chiral dichroism (EMCD)--the equivalent of X-ray magnetic circular dichroism (XMCD) in the electron microscope--is optimized with respect to the detector shape, size and position. We show that an important increase in SNR over previous experiments can be obtained when taking much larger detector sizes. We determine the ideal shape of the detector but also show that round apertures are a good compromise if placed in their optimal position. We develop the theory for a simple analytical description of the EMCD experiment and then apply it to dynamical multibeam Bloch wave calculations and to an experimental data set. In all cases it is shown that a significant and welcome improvement of the SNR is possible.

Energy-loss magnetic chiral dichroism (EMCD): Magnetic chiral dichroism in the electron microscope

A new technique called energy-loss magnetic chiral dichroism (EMCD) has recently been developed [P. Schattschneider, et al. Nature 441, 486 (2006)] to measure magnetic circular dichroism in the transmission electron microscope (TEM) with a spatial resolution of 10 nm. This novel technique is the TEM counterpart of x-ray magnetic circular dichroism, which is widely used for the characterization of magnetic materials with synchrotron radiation. In this paper we describe several experimental methods that can be used to measure the EMCD signal [P. Schattschneider, et al. Nature 441, 486 (2006); C. Hebert, et al. Ultramicroscopy 108(3), 277 (2008); B. Warot-Fonrose, et al. Ultramicroscopy 108(5), 393 (2008); L. Calmels, et al. Phys. Rev. B 76, 060409 (2007); P. van Aken, et al. Microsc. Microanal. 13(3), 426 (2007)] and give a review of the recent improvements of this new investigation tool. The dependence of the EMCD on several experimental conditions (such as thickness, relative orientation of beam and sample, collection and convergence angle) is investigated in the transition metals iron, cobalt, and nickel. Different scattering geometries are illustrated; their advantages and disadvantages are detailed, together with current limitations. The next realistic perspectives of this technique consist of measuring atomic specific magnetic moments, using suitable spin and orbital sum rules, [L. Calmels, et al. Phys. Rev. B 76, 060409 (2007); J. Rusz, et al. Phys. Rev. B 76, 060408 (2007)] with a resolution down to 2 to 3 nm.

Spin and valence dependence of iron partitioning in Earth’s deep mantle

Significance We studied high-pressure and high-temperature phase equilibria using state-of-the-art microanalytical techniques to measure iron partitioning and valence in iron-bearing lower-mantle rocks. Our data allow us to reconcile the discrepancies observed in previous reports, and to propose a comprehensive model of the evolution of iron partitioning in the lower mantle. We reveal an intricate interplay between spin and valence states. Our results suggest a mineral physics basis for rheological variations in the deep lower mantle as a process for stabilizing large thermochemical piles and large low-shear-velocity provinces. We performed laser-heated diamond anvil cell experiments combined with state-of-the-art electron microanalysis (focused ion beam and aberration-corrected transmission electron microscopy) to study the distribution and valence of iron in Earth’s lower mantle as a function of depth and composition. Our data reconcile the apparently discrepant existing dataset, by clarifying the effects of spin (high/low) and valence (ferrous/ferric) states on iron partitioning in the deep mantle. In aluminum-bearing compositions relevant to Earth’s mantle, iron concentration in silicates drops above 70 GPa before increasing up to 110 GPa with a minimum at 85 GPa; it then dramatically drops in the postperovskite stability field above 116 GPa. This compositional variation should strengthen the lowermost mantle between 1,800 km depth and 2,000 km depth, and weaken it between 2,000 km depth and the D” layer. The succession of layers could dynamically decouple the mantle above 2,000 km from the lowermost mantle, and provide a rheological basis for the stabilization and nonentrainment of large low-shear-velocity provinces below that depth.

Dynamic structure factors of Cu, Ag, and Au: Comparative study from first principles

We present a comparative theoretical and experimental study of dynamic structure factors (momentum-dependent loss functions) of the noble metals Cu, Ag, and Au in the energy range of 0-60 eV. The emphasis is on theoretical results that are compared with new as well as available experimental data. Dynamic structure factors are calculated within the linear-response formalism of time-dependent density-functional theory, using the full-potential linearized augmented plane-wave method. For the studied energy range, local-field effects are found to be very important for Ag and Au and only marginally relevant for Cu. We present an explanation for this surprising behavior. Loss functions of all three metals possess a complex multipeak structure. We classify the features in the loss function as being related to collective excitations, interband transitions, or mixed modes. The impact of short-range correlations on the dynamic response functions is evaluated by comparing the results of the random-phase approximation to those of the time-dependent local density approximation. Exchange-correlation effects are found to be weak for small momentum transfers, but increasingly important for larger momenta. The calculated structure factors agree well with experiments.

Height-resolved quantification of microstructure and texture in polycrystalline thin films using TEM orientation mapping

A method is presented for the quantitative investigation of microstructure and texture evolution in polycrystalline thin films based on in-plane automated crystal orientation mapping in transmission electron microscopy, from the substrate up. To demonstrate the method we apply it to the example of low pressure metal-organic chemical vapor deposited ZnO layers. First, orientation mapping is applied to standard cross-section and plan-view transmission electron microscopy samples of films, illustrating how plan-view samples both reduce the occurrence of grain overlap that is detrimental to reliable orientation mapping and also improve sampling statistics compared to cross-sections. Motivated by this, orientation mapping has been combined with a double-wedge method for specimen preparation developed by Spiecker et al. (2007) [1], which creates a large area plan-view sample that traverses the film thickness. By measuring >10,000 grains in the film, the resulting data give access to grain size, orientation and misorientation distributions in function of height above the substrate within the film, which are, in turn, the inputs necessary for quantitative assessment of growth models and simulations. The orientation data are directly related to microstructural images, allowing correlation of orientations with in-plane and out-of-plane grain sizes and shapes. The spatial correlation of the entire data set gives insights into previously unnoticed growth mechanisms such as the presence of renucleation or preferred misorientations. Finally, the data set can be used to guide targeted, local studies by other transmission electron microscopy techniques. This is demonstrated by the site-specific application of nano-beam diffraction to validate the presence of coherent [21̄1̄0]/(011̄3) twin boundaries first suggested by the orientation mapping.