Electron holography for the study of magnetic nanomaterials

Transmission electron microscopes fitted with field-emission guns (to provide coherent electron waves) can be adapted to record the magnetic fields within and surrounding nanoparticles or metal clusters, for example, the lines of force of a nanoferromagnet encapsulated within a multiwalled carbon nanotube. Whereas most chemists are aware that electron microscopy readily identifies crystallographic symmetries and phases, solves structures, and, in conjunction with electron energy-loss spectroscopy, yields valence states and electronic information of materials, relatively few know that it can also provide important quantitative information, with nanometer-scale spatial resolution, pertaining to such materials' magnetic properties. In this Account, with the aid of representative examples embracing solid-state chemistry, geochemistry, and bio-inorganic phenomena, we illustrate how off-axis electron holography affords deep insight into magnetic phenomena on the nanoscale. Specifically, we describe the unprecedented level of information available regarding the magnetic nature of magnetotactic bacteria, magnetic nanoparticle chains and chiral bracelets, and geochemically relevant phenomena involving exsolution (the un-mixing of two mineral phases, as in the magnetite-ulv?spinel system). It is, for example, possible to reveal vortices and multidomain states that have no net magnetization in minute blocks of magnetite. With the current burgeoning interest and activity in nanoscience and nanotechnology, our Account concludes with examples of some existing enigmas that electron holography, especially when augmented by the related technique of electron tomography, might play an important experimental role in resolving, such as the occurrence of ferromagnetism in nanocrystals of silver within carbon tubes and in clusters of alkali metals incarcerated within zeolites.     

Dopant profiling of focused ion beam milled semiconductors using off-axis electron holography; reducing artifacts,extending detection limits and reducing the effects of gallium implantation

Focused ion beam (FIB) milling is one of the few specimen preparation techniques that can be used to prepare parallel-sided specimens with nm-scale site specificity for examination using off-axis electron holography in the transmission electron microscope (TEM). However, FIB milling results in the implantation of Ga, the formation of amorphous surface layers and the introduction of defects deep into the specimens. Here we show that these effects can be reduced by lowering the operating voltage of the FIB and by annealing the specimens at low temperature. We also show that the electrically inactive thickness is dependent on both the operating voltage and type of ion used during FIB milling.     

Simulation of textured surface topography during a low wear process

Wear experiments were conducted on a block-on ring tester. The stationary block made from cast iron of 50 HRC hardness was ground. The rotated ground ring was made from 42CrMo4 steel of 32 HRC hardness. The rings were modified by a burnishing technique in order to obtain surfaces with oil pockets. Oil pockets of spherical and of drop shape were tested. The correlation and regression analysis of parameters of textured surface topography was carried out. Two sets of surfaces were analysed: after machining and after “zero-wear”. As the result of analysis, minimum number of parameters describing this surface kind was obtained. A simple truncation model of the ring surface change was used. Worn surface topographies, after a low wear, were also modeled in a different way. An idea of the proposed method of surface topography modeling is imposition of random surface of Gaussian ordinate distribution on the base surface (after burnishing). The modeled surfaces were correctly matched to the measured surfaces in 90% of all analysed cases. Basing on the simulation, the local wear values during a low wear process were calculated and compared with experimental ones.     

Quantitative electron holographic tomography for the 3D characterisation of semiconductor device structures

Electron tomography and electron holography experiments have been combined to investigate the 3D electrostatic potential distribution in semiconductor devices. The experimental procedure for the acquisition and data reconstruction of holographic tilt series of silicon p-n junction specimens is described. A quantitative analysis of the experimental results from specimens of two different thicknesses is presented, revealing the 3D electrostatic potential variations arising from the presence of surfaces and damage generated by focused ion beam (FIB) sample preparation. Close to bulk-like properties are measured in the centre of the tomographic reconstruction of the specimen, revealing higher electrically active dopant concentrations compared to the measurements obtained at the specimen surfaces. A comparison of the experimental results from the different thickness specimens has revealed a 'critical' thickness for this specimen preparation method of 350nm that is required for this device structure to retain 'bulk'-like properties in the centre of the membrane.     

Transition metal ion capture using functional mesoporous carbon made with 1,10-phenanthroline

Functional mesoporous carbon has been built using 1,10-phenanthroline as the fundamental building block, resulting in a nanoporous, high surface area sorbent capable of selectively binding transition metal ions. This material had a specific surface area of 870 m²/g, an average pore size of about 30 Å, and contained as much as 8.2 wt% N. Under acidic conditions, where the 1,10-phenanthroline ligand is protonated, this material was found to be an effective anion exchange material for transition metal anions like ${\text{PdCl}}_4^{2-}$ and ${\text{H}}_2{\text{VO}}_4^{1-}$. 1,10-Phenanthroline functionalized mesoporous carbon (“Phen-FMC”) was found to have a high affinity for Cu(II), even down to a pH of 1. At pHs above 5, Phen-FMC was found to bind a variety of transition metal cations (e.g. Co(II), Ni(II), Zn(II), etc.) from filtered ground water, river water and seawater. Phen-FMC displayed rapid sorption kinetics with Co(II) in filtered river water, reaching equilibrium in less than an hour, and easily lowering the [Co(II)] to sub-ppb levels. Phen-FMC was found to be more effective for transition metal ion capture than ion-exchange resin or activated carbon.     

Bulk Synthesis and Surface Patterning of Nanoporous Metals and Alloys from Supraspherical Nanoparticle Aggregates

Supraspheres (SS) composed of hundreds to thousands of metal nanoparticles (NPs) and crosslinked by dithiol linkers are assembled into larger structures, which are subsequently converted into nanoporous metals (NMs). Conversion is achieved by heating which removes organic molecules stabilizing the NPs and allows for NP fusion. Heating of SS solutions leads to NMs of overall macroscopic dimensions; localized radiation using collimated electron beam is used to prepare metallized surface micropatterns. Depending on the composition of supraspherical precursors, nanoporous materials composed of up to three metals can be obtained. Strategies for controlling pore size and nanoscale surface roughness of these materials are discussed.     

Spatial attention deficits in humans: A comparison of superior parietal and temporal-parietal junction lesions.

Although clinical evidence of spatial attention deficits, such as neglect and extinction, is typically associated with lesions of the right temporal-parietal junction, recent evidence has suggested an important role for the superior parietal lobe. Two groups of patients, selected for lesions at the temporal-parietal junction including the superior temporal gyrus (TPJ group), or for lesions involving the parietal but not the superior temporal region (PAR group), performed cued-target detection tasks in 2 experiments. An extinction-like response time pattern was found for the TPJ but not the PAR group. In addition, both groups were able to use expectancy information, in the form of cue predictiveness, suggesting that separate mechanisms mediate exogenous and endogenous processes during attention shifts. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Saccade preparation inhibits reorienting to recently attended locations.

We measured manual reaction time in normal human Ss to confirm that an eccentric visual signal has a biphasic effect on covert attention and eye movements. First, it summons attention and biases a saccade toward the signal; a subsequent inhibition of return then slows responses to signals at that location. A temporal hemifield dominance for inhibition of return was shown; this finding coverges with observations (M. I. Posner et al; see record 1986-22316-001) in neurologic patients to suggest that it is mediated by midbrain pathways. Endogenous orienting of attention, from a central arrow cue, did not activate inhibition of return, whereas endogenous saccade preparation did so as effectively as an exogenous signal, even when no saccade was made. Inhibition of return is activated by midbrain oculomotor pathways and may function as a location "tagging" mechanism to optimize efficiency of visual search. (PsycINFO Database Record (c) 2010 APA, all rights reserved)