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.Comment: Nano Letters, accepte

Epitaxy of hexagonal ABO3_3 quantum materials

Hexagonal $AB$O$_3$ oxides ($A$, $B$ = cation) are a rich materials class for realizing novel quantum phenomena. Their hexagonal symmetry, oxygen trigonal bipyramid coordination and quasi-two dimensional layering give rise to properties distinct from those of the cubic $AB$O$_3$ perovskites. As bulk materials, most of the focus in this materials class has been on the rare earth manganites, $R$MnO$_3$ ($R$ = rare earth); these materials display coupled ferroelectricity and antiferromagnetic order. In this review, we focus on the thin film manifestations of the hexagonal $AB$O$_3$ oxides. We cover the stability of the hexagonal oxides and substrates which can be used to template the hexagonal structure. We show how the thin film geometry not only allows for further tuning of the bulk-stable manganites but also the realization of metastable hexagonal oxides such as the $R$FeO$_3$ that combine ferroelectricity with weak ferromagnetic order. The thin film geometry is a promising platform to stabilize additional metastable hexagonal oxides to search for predicted high-temperature superconductivity and topological phases in this materials class.Comment: The following article has been accepted by Applied Physics Review

The role of subjectivity in mitigating incentive contracting risks

We examine how subjectivity in performance measurement and reward systems (PMRS) is used to mitigate incentive contracting risks. Drawing on data from 38 interviews with supervisory and subordinate managers in four firms, we provide a more comprehensive explanation of the role of subjectivity in risk mitigation than is evident in the prior literature. We provide empirical evidence of the importance firms place on the use of subjectivity to mitigate the risk of incentive misalignment and employee sorting errors relative to its well-documented role in mitigating employee compensation risk. We find that incentive misalignment arising from unanticipated behavioral responses to performance measures is a particularly important risk, managed through subjective performance assessments. The extent of subjectivity we observe poses a significant risk of errors and bias. We observe that both vertical and horizontal information gathering and review by calibration panels are key strategies to mitigate the downside risk of subjectivity

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

Hetero-epitaxial EuO Interfaces Studied by Analytic Electron Microscopy

With nearly complete spin polarization, the ferromagnetic semiconductor europium monoxide could enable next-generation spintronic devices by providing efficient ohmic spin injection into silicon. Spin injection is greatly affected by the quality of the interface between the injector and silicon. Here, we use atomic-resolution scanning transmission electron microscopy in conjunction with electron energy loss spectroscopy to directly image and chemically characterize a series of EuO|Si and EuO|YAlO3 interfaces fabricated using different growth conditions. We identify the presence of europium silicides and regions of disorder at the EuO|Si interfaces, imperfections that could significantly reduce spin injection efficiencies via spin-flip scattering

High-quality EuO thin films the easy way via topotactic transformation

Epitaxy is widely employed to create highly oriented crystalline films. A less appreciated, butnonetheless powerful means of creating such films is via topotactic transformation, in which achemical reaction transforms a single crystal of one phase into a single crystal of a differentphase, which inherits its orientation from the original crystal. Topotactic reactions may beapplied to epitactic films to substitute, add or remove ions to yield epitactic films of differentphases. Here we exploit a topotactic reduction reaction to provide a non-ultra-high vacuum(UHV) means of growing highly oriented single crystalline thin films of the easily overoxidizedhalf-metallic semiconductor europium monoxide (EuO) with a perfection rivallingthat of the best films of the same material grown by molecular-beam epitaxy or UHV pulsedlaserdeposition. As the technique only requires high-vacuum deposition equipment, it hasthe potential to drastically improve the accessibility of high-quality single crystalline films ofEuO as well as other difficult-to-synthesize compounds