arXiv subjects

David A. Muller

Publications and source records attributed to David A. Muller.

138 records · Page 8Linked to original sources

arXiv2012

Channeling of a sub-angstrom electron beam in a crystal mapped to two-dimensional molecular orbitals

The propagation of high-energy electrons in crystals is in general a complicated multiple scattering problem. However, along high-symmetry zone axes the problem can be mapped to the time evolution of a two-dimensional (2D) molecular system. Each projected atomic column can be approximated by the potential of a 2D screened hydrogenic atom. When two columns are in close proximity, their bound states overlap and form analogs to molecular orbitals. For sub-angstrom electron beams, excitation of anti-symmetric orbitals can result in the failure of the simple incoherent imaging approximation. As a result, the standard resolution test and the one-to-one correspondence of atomic positions of a crystal imaged along a zone-axis with closely spaced projected columns ("dumbbells") can fail dramatically at finite and realistic sample thicknesses. This is demonstrated experimentally in high angle annular dark field scanning transmission electron microscope (HAADF STEM) images of [211]-oriented Si showing an apparent inter-column spacing of 1.28(+-.09) Angstroms, over 64% larger than the actual 0.78 Angstrom spacing. Furthermore, the apparent spacing can be tuned with sample thickness and probe size to produce a larger, smaller, or even the actual spacing under conditions when the peaks of two adjacent Si columns should not even have been resolved given the electron probe size.

cond-mat.mtrl-sci↗

arXiv2012

Determining On-Axis Crystal Thickness with Quantitative Position-Averaged Incoherent Bright-Field Signal in an Aberration-corrected STEM

An accurate determination of specimen thickness is essential for quantitative analytical electron microscopy. Here we demonstrate that a position-averaged incoherent bright-field signal recorded on an absolute scale can be used to determine the thickness of on-axis crystals with a precision of \pm1.6 nm. This method measures both the crystalline and the non-crystalline parts (surface amorphous layers) of the sample. However, it avoids the systematic error resulting from surface plasmons contributions to the inelastic mean free path thickness estimated by electron energy loss spectroscopy.

cond-mat.mtrl-sci↗

arXiv2011

3-D Tracking and Visualization of Hundreds of Pt-Co Fuel Cell Nanocatalysts During Electrochemical Aging

We present an electron tomography method that allows for the identification of hundreds of electrocatalyst nanoparticles with one-to-one correspondence before and after electrochemical aging. This method allows us to track, in three-dimensions (3-D), the trajectories and morphologies of each Pt-Co nanocatalyst on a fuel cell carbon support. The use of atomic-scale electron energy loss spectroscopic imaging enables the correlation of performance degradation of the catalyst with changes in particle/inter-particle morphologies, particle-support interactions and the near-surface chemical composition. We found that, aging of the catalysts under normal fuel cell operating conditions (potential scans from +0.6 V to +1.0 V for 30,000 cycles) gives rise to coarsening of the nanoparticles, mainly through coalescence, which in turn leads to the loss of performance. The observed coalescence events were found to be the result of nanoparticle migration on the carbon support during potential cycling. This method provides detailed insights into how nanocatalyst degradation occurs in proton exchange membrane fuel cells (PEMFCs), and suggests that minimization of particle movement can potentially slow down the coarsening of the particles, and the corresponding performance degradation.

cond-mat.mtrl-sci↗

arXiv2011

Data Processing For Atomic Resolution EELS

The high beam current and sub-angstrom resolution of aberration-corrected scanning transmission electron microscopes has enabled electron energy loss spectroscopic (EELS) mapping with atomic resolution. These spectral maps are often dose-limited and spatially oversampled, leading to low counts/channel and are thus highly sensitive to errors in background estimation. However, by taking advantage of redundancy in the dataset map one can improve background estimation and increase chemical sensitivity. We consider two such approaches- linear combination of power laws and local background averaging-that reduce background error and improve signal extraction. Principal components analysis (PCA) can also be used to analyze spectrum images, but the poor peak-to-background ratio in EELS can lead to serious artifacts if raw EELS data is PCA filtered. We identify common artifacts and discuss alternative approaches. These algorithms are implemented within the Cornell Spectrum Imager, an open source software package for spectroscopic analysis.

cond-mat.mtrl-sci↗

arXiv2011

Atomic-resolution spectroscopic imaging of ensembles of nanocatalyst particles across the life of a fuel cell

The thousandfold increase in data-collection speed enabled by aberration-corrected optics allows us to overcome an electron microscopy paradox - how to obtain atomic-resolution chemical structure in individual nanoparticles, yet record a statistically significant sample from an inhomogeneous population. This allowed us to map hundreds of Pt-Co nanoparticles to show atomic-scale elemental distributions across different stages of the catalyst aging in a proton-exchange-membrane fuel cell, and relate Pt-shell thickness to treatment, particle size, surface orientation, and ordering.

cond-mat.mtrl-sci↗

arXiv2011

Quantitative chemical mapping at the atomic scale

Atomic-scale mapping of the chemical elements in materials is now possible using aberration-corrected electron microscopes but delocalization and multiple scattering can confound image interpretation. Here we report atomic-resolution measurements with the elastic and inelastic signals acquired on an absolute scale. By including dynamical scattering in both the elastic and inelastic channels we obtain quantitative agreement between theory and experiment. Our results enable a close scrutiny of the inelastic scattering physics and demonstrate the possibility of element-specific atom counting.

cond-mat.mtrl-sci↗

arXiv2011

Brief Communication Arising from a Corrigendum to "Atomic-resolution chemical analysis using a scanning transmission electron microscope"

This manuscript was originally submitted to Nature for consideration as a "Brief Communication" in response to a "Corrigendum" that appeared in 2006 (1) to an earlier paper in Nature. That corrigendum was the subject of a Nature editorial (2) stating that "key data were misrepresented by the authors, both during the review process and in the final published version of the paper" and it claimed to provide an explanation for alterations in their data that had the effect of changing their priority claim from a result no better than previous work by Isaacson and Scheinfein that was 1 Angstrom shy of atomic resolution to what appeared to be atomic resolution. In this manuscript we show that this explanation is physically inconsistent with the evolution of their data. When originally submitted to Nature, the manuscript was peer-reviewed, deemed "carefully and properly argued" and recommended for publication with appropriate responses from the corrigendum authors. Subsequent exchanges with those authors did not reach a satisfactory state and publication did not occur. We now have learnt that an article is likely to appear in Nature concerning the circumstances surrounding the concerns expressed in this initial document and we consider it important and relevant that this document and the supplementary material be made available in the public domain. As to the question of proper attribution of priority, we would suggest instead citing the concurrent work of Batson (3). 1. Browning, N.D., Chisholm, M.F., and Pennycook, S.J. Corrigendum:Atomic-resolution chemical analysis using a scanning transmission electron microscope, Nature 444, 235 (2006). 2. Editorial. Correction or retraction? Nature 444, 123-124 (2006). 3. Batson, P.E. (1993). Simultaneous STEM imaging and electron energy-loss spectroscopy with atomic-column sensitivity. Nature 366, 727-728.

cond-mat.mtrl-sci↗

arXiv2010

Pt-Decorated PdCo@Pd/C Core-Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for Oxygen Reduction Reaction

A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon has been developed using an adsorbate-induced surface segregation effect. The stability and electrocatalytic activity for the oxygen reduction of PdCo@Pd nanoparticles was enhanced by a small amount of Pt, deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale lower cost production and significantly lowers the Pt loading and thus cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have higher methanol-tolerance for the ORR when compared to Pt/C, and are promising cathode catalysts for fuel cell applications.

cond-mat.mtrl-sci↗

arXiv2010

Extended Depth of Field for High Resolution Scanning Transmission Electron Microscopy

Aberration-corrected scanning transmission electron microscopes (STEM) provide sub-angstrom lateral resolution; however, the large convergence angle greatly reduces the depth of field. For microscopes with a small depth of field, information outside of the focal plane quickly becomes blurred and less defined. It may not be possible to image some samples entirely in focus. Extended depth-of-field techniques, however, allow a single image, with all areas in-focus, to be extracted from a series of images focused at a range of depths. In recent years, a variety of algorithmic approaches have been employed for bright field optical microscopy. Here, we demonstrate that some established optical microscopy methods can also be applied to extend the ~6 nm depth of focus of a 100 kV 5th-order aberration-corrected STEM (alpha_max = 33 mrad) to image Pt-Co nanoparticles on a thick vulcanized carbon support. These techniques allow us to automatically obtain a single image with all the particles in focus as well as a complimentary topography map.

cond-mat.mtrl-sci↗

arXiv2010

Imaging Grains and Grain Boundaries in Single-Layer Graphene: An Atomic Patchwork Quilt

The properties of polycrystalline materials are often dominated by the size of their grains and by the atomic structure of their grain boundaries. These effects should be especially pronounced in 2D materials, where even a line defect can divide and disrupt a crystal. These issues take on practical significance in graphene, a hexagonal two-dimensional crystal of carbon atoms; Single-atom-thick graphene sheets can now be produced by chemical vapor deposition on up to meter scales, making their polycrystallinity almost unavoidable. Theoretically, graphene grain boundaries are predicted to have distinct electronic, magnetic, chemical, and mechanical properties which strongly depend on their atomic arrangement. Yet, because of the five-order-of-magnitude size difference between grains and the atoms at grain boundaries, few experiments have fully explored the graphene grain structure. Here, we use a combination of old and new transmission electron microscope techniques to bridge these length scales. Using atomic-resolution imaging, we determine the location and identity of every atom at a grain boundary and find that different grains stitch together predominantly via pentagon-heptagon pairs. We then use diffraction-filtered imaging to rapidly map the location, orientation, and shape of several hundred grains and boundaries, where only a handful have been previously reported. The resulting images reveal an unexpectedly small and intricate patchwork of grains connected by tilt boundaries. By correlating grain imaging with scanned probe measurements, we show that these grain boundaries dramatically weaken the mechanical strength of graphene membranes, but do not measurably alter their electrical properties. These techniques open a new window for studies on the structure, properties, and control of grains and grain boundaries in graphene and other 2D materials.

cond-mat.mtrl-sci↗

arXiv2010

Mapping local optical densities of states in silicon photonic structures with nanoscale electron spectroscopy

Relativistic electrons in a structured medium generate radiative losses such as Cherenkov and transition radiation that act as a virtual light source, coupling to the photonic densities of states. The effect is most pronounced when the imaginary part of the dielectric function is zero, a regime where in a non-retarded treatment no loss or coupling can occur. Maps of the resultant energy losses as a sub-5nm electron probe scans across finite waveguide structures reveal spatial distributions of optical modes in a spectral domain ranging from near-infrared to far ultraviolet.

physics.optics↗

arXiv2005

Why Some Interfaces Cannot be Sharp

A central goal of modern materials physics and nanoscience is control of materials and their interfaces to atomic dimensions. For interfaces between polar and non-polar layers, this goal is thwarted by a polar catastrophe that forces an interfacial reconstruction. In traditional semiconductors this reconstruction is achieved by an atomic disordering and stoichiometry change at the interface, but in multivalent oxides a new option is available: if the electrons can move, the atoms don`t have to. Using atomic-scale electron energy loss spectroscopy we find that there is a fundamental asymmetry between ionically and electronically compensated interfaces, both in interfacial sharpness and carrier density. This suggests a general strategy to design sharp interfaces, remove interfacial screening charges, control the band offset, and hence dramatically improving the performance of oxide devices.

cond-mat.mtrl-sci↗