Nanoscale assembly processes revealed in the nacroprismatic transition zone of Pinna nobilis mollusc shells

Intricate biomineralization processes in molluscs engineer hierarchical structures with meso-, nano-, and atomic architectures that give the final composite material exceptional mechanical strength and optical iridescence on the macroscale. This multiscale biological assembly inspires new synthetic routes to complex materials. Our investigation of the prism-nacre interface reveals nanoscale details governing the onset of nacre formation using high-resolution scanning transmission electron microscopy. A wedge polishing technique provides unprecedented, large-area specimens required to span the entire interface. Within this region, we find a transition from nanofibrillar aggregation to irregular early-nacre layers, to well-ordered mature nacre suggesting the assembly process is driven by aggregation of nanoparticles (~50-80 nm) within an organic matrix that arrange in fiber-like polycrystalline configurations. The particle number increases successively and, when critical packing is reached, they merge into early-nacre platelets. These results give new insights into nacre formation and particle-accretion mechanisms that may be common to many calcareous biominerals.Comment: 5 Figure

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

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.Comment: Accepted, Microscopy and Microanalysi

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

Breaking the Crowther Limit: Combining Depth-Sectioning and Tilt Tomography for High-Resolution, Wide-Field 3D Reconstructions

To date, high-resolution (< 1 nm) imaging of extended objects in three-dimensions (3D) has not been possible. A restriction known as the Crowther criterion forces a tradeoff between object size and resolution for 3D reconstructions by tomography. Further, the sub-Angstrom resolution of aberration-corrected electron microscopes is accompanied by a greatly diminished depth of field, causing regions of larger specimens (> 6 nm) to appear blurred or missing. Here we demonstrate a three-dimensional imaging method that overcomes both these limits by combining through-focal depth sectioning and traditional tilt-series tomography to reconstruct extended objects, with high-resolution, in all three dimensions. The large convergence angle in aberration corrected instruments now becomes a benefit and not a hindrance to higher quality reconstructions. A through-focal reconstruction over a 390 nm 3D carbon support containing over one hundred dealloyed and nanoporous PtCu catalyst particles revealed with sub-nanometer detail the extensive and connected interior pore structure that is created by the dealloying instability