Identifying and imaging polymer functionality at high spatial resolution with core-loss EELS.

Electron energy loss spectroscopy (EELS) is a proven tool for probing materials chemistry at high spatial resolution. Core-loss EELS fine structure should allow measurement of local polymer chemistry. For organic materials, sensitivity to radiolysis is expected to limit the resolution achievable with EELS: but core-loss EELS has proven difficult at any resolution, yielding inconsistent spectra that compare unfavorably with theoretically analogous x-ray absorption spectra. Many of the previously identified shortcomings should not be limiting factors on modern equipment. This study establishes that EELS can generate identifiable carbon K-edge spectra for a range of common polymer types and chemistry, and demonstrates fine structure features matching prior x-ray absorption spectra. EELS fine structure features broaden intuitively with the instrument's energy resolution, and beam-induced features are readily differentiated by collecting spectra at a series of doses. The results are demonstrated with spectrum images of a model polymer blend, and used to estimate practical pixel sizes that can be used for mapping core-loss EELS as a function of electron dose.

Manipulating acoustic and plasmonic modes in gold nanostars.

In this contribution experimental evidence of plasmonic edge modes and acoustic breathing modes in gold nanostars (AuNSs) is reported. AuNSs are synthesized by a surfactant-free, one-step wet-chemistry method. Optical extinction measurements of AuNSs confirm the presence of localized surface plasmon resonances (LSPRs), while electron energy-loss spectroscopy (EELS) using a scanning transmission electron microscope (STEM) shows the spatial distribution of LSPRs and reveals the presence of acoustic breathing modes. Plasmonic hot-spots generated at the pinnacle of the sharp spikes, due to the optically active dipolar edge mode, allow significant intensity enhancement of local fields and hot-electron injection, and are thus useful for size detection of small protein molecules. The breathing modes observed away from the apices of the nanostars are identified as stimulated dark modes - they have an acoustic nature - and likely originate from the confinement of the surface plasmon by the geometrical boundaries of a nanostructure. The presence of both types of modes is verified by numerical simulations. Both these modes offer the possibility of designing nanoplasmonic antennas based on AuNSs, which can provide information on both mass and polarizability of biomolecules using a two-step molecular detection process.

Heterodimeric Plasmonic Nanogaps for Biosensing.

We report the study of heterodimeric plasmonic nanogaps created between gold nanostar (AuNS) tips and gold nanospheres. The selective binding is realized by properly functionalizing the two nanostructures; in particular, the hot electrons injected at the nanostar tips trigger a regio-specific chemical link with the functionalized nanospheres. AuNSs were synthesized in a simple, one-step, surfactant-free, high-yield wet-chemistry method. The high aspect ratio of the sharp nanostar tip collects and concentrates intense electromagnetic fields in ultrasmall surfaces with small curvature radius. The extremities of these surface tips become plasmonic hot spots, allowing significant intensity enhancement of local fields and hot-electron injection. Electron energy-loss spectroscopy (EELS) was performed to spatially map local plasmonic modes of the nanostar. The presence of different kinds of modes at different position of these nanostars makes them one of the most efficient, unique, and smart plasmonic antennas. These modes are harnessed to mediate the formation of heterodimers (nanostar-nanosphere) through hot-electron-induced chemical modification of the tip. For an AuNS-nanosphere heterodimeric gap, the intensity enhancement factor in the hot-spot region was determined to be 106, which is an order of magnitude greater than the single nanostar tip. The intense local electric field within the nanogap results in ultra-high sensitivity for the presence of bioanalytes captured in that region. In case of a single BSA molecule (66.5 KDa), the sensitivity was evaluated to be about 1940 nm/RIU for a single AuNS, but was 5800 nm/RIU for the AuNS-nanosphere heterodimer. This indicates that this heterodimeric nanostructure can be used as an ultrasensitive plasmonic biosensor to detect single protein molecules or nucleic acid fragments of lower molecular weight with high specificity.

Multimodal Evidence of Mesostructured Calcium Fatty Acid Deposits in Human Hair and Their Role on Hair Properties.

We provide the first conclusive evidence for the presence of exogenous calcium fatty acid deposits, which not only form in-between the cuticle layers in the lipid-rich cell membrane complex, but also grow to dimensions large enough to cause the structure to bulge, thereby impacting the optical and mechanical properties of the hair fiber. The composition and phase of these deposits were probed using a multimodal analytical approach with spatially resolved techniques including synchrotron micro X-ray fluorescence coupled with X-ray scattering, focused ion beam (FIB)-scanning electron microscopy (SEM), scanning transmission electron microscopy, X-ray energy dispersive spectroscopy, and Fourier transform infrared and Raman imaging where the collective analysis is consistent with a meso-phase composed of calcium C16/C18 saturated fatty acids from natural sources such as sebum. X-ray microtomography and serial "slice and view" FIB/SEM both reveal the location and volumetric shape of the deposits.

A Small Spot, Inert Gas, Ion Milling Process as a Complementary Technique to Focused Ion Beam Specimen Preparation.

This paper reports on the substantial improvement of specimen quality by use of a low voltage (0.05 to ~1 keV), small diameter (~1 µm), argon ion beam following initial preparation using conventional broad-beam ion milling or focused ion beam. The specimens show significant reductions in the amorphous layer thickness and implanted artifacts. The targeted ion milling controls the specimen thickness according to the needs of advanced aberration-corrected and/or analytical transmission electron microscopy applications.

Crystallization kinetics of cerium oxide nanoparticles formed by spontaneous, room-temperature hydrolysis of cerium(iv) ammonium nitrate in light and heavy water.

A stable sol of cerium oxide nanoparticles forms spontaneously when cerium(iv) ammonium nitrate (CAN) is dissolved in room-temperature water at mM concentrations. Electron microscopy experiments reveal the formation of highly crystalline cerium oxide particles several nm in diameter and suggest that they are formed from amorphous particles that are similar in size. Under the low pH conditions of the experiments, the nanoparticles form a stable dispersion and show no evidence of aggregation, even many months after synthesis. The absence of particles large enough to scatter light significantly makes it possible to observe the crystallization kinetics through dramatic changes in the UV-visible absorption spectra that occur during solution aging. Measurements show that the cerium oxide nanocrystals are formed roughly an order of magnitude more slowly in D2O than in H2O solution. This large solvent kinetic isotope effect (kH/kD ∼ 10), which is reported here for the first time for the crystallization of a solid metal oxide phase, indicates a rate-determining proton transfer reaction, which is assigned to the conversion of hydroxy to oxo bridges. In D2O solution, the absorption per mole of cerium ions increases by over 400% at 290 nm as the weakly absorbing precursor phase is transformed into nanocrystalline cerium oxide. An isosbestic point is detected at 368 nm, and the absorption spectra can be modeled throughout aging by the sum of spectra of just two interconverting species. Preliminary ultrafast transient absorption experiments confirm that the optical properties of the amorphous precursors differ greatly from those of the final, nanocrystalline phase. Crystallization of CeO2 from CAN in water has much in common with the crystallization of iron oxides from iron(iii) salts, including the importance of non-classical nucleation and growth pathways. It is an outstanding system for studying the poorly understood events that cause molecularly solvated ions to self-assemble into nanocrystals, following hydrolysis. At the same time, the strong susceptibility of CAN to spontaneously form CeO2 nanocrystals under the mildest of reaction conditions indicates that caution is needed when working with this common sacrificial oxidant.

Nature of the interfaces between the constituent phases in the high entropy alloy CoCrCuFeNiAl.

The interfaces between the phase separated regions in the dendritic grains of laser-deposited samples of the high entropy alloy CoCrCuFeNiAl have been studied using aberration-corrected analytical (scanning) transmission electron microscopy ((S)TEM). The compositional variations have been determined using energy dispersive x-ray spectroscopy (EDS) in (S)TEM. It was found that between B2, consisting mainly of Al, Ni, Co, and Fe, and disordered bcc phase, consisting mainly of Cr and Fe, there is a transition region, approximately 1.5 nm in width, over which the chemical composition changes from the B2 to that of the bcc phase. The crystal structure of this interfacial region is also B2, but with very different sublattice occupancy than that of the adjacent B2 compound. The structural aspects of the interface between the ordered B2 phase and the disordered bcc phase have been characterized using high angle annular dark-field (HAADF) imaging in STEM. It has been determined that the interfaces are essentially coherent, with the lattice parameters of the two B2 regions and the disordered bcc phase being more or less the same, the uncertainty arising from possible relaxations from the proximity of the surfaces of the thin foils used in imaging of the microstructures. Direct observations show that there is a planar continuity between all three constituent phases.