Field Ion Emission in an Atom Probe Microscope Triggered by Femtosecond-Pulsed Coherent Extreme Ultraviolet Light.

This paper describes initial experimental results from an extreme ultraviolet (EUV) radiation-pulsed atom probe microscope. Femtosecond-pulsed coherent EUV radiation of 29.6 nm wavelength (41.85 eV photon energy), obtained through high harmonic generation in an Ar-filled hollow capillary waveguide, successfully triggered controlled field ion emission from the apex of amorphous SiO2 specimens. The calculated composition is stoichiometric within the error of the measurement and effectively invariant of the specimen base temperature in the range of 25 K to 150 K. Photon energies available in the EUV band are significantly higher than those currently used in the state-of-the-art near-ultraviolet laser-pulsed atom probe, which enables the possibility of additional ionization and desorption pathways. Pulsed coherent EUV light is a new and potential alternative to near-ultraviolet radiation for atom probe tomography.

Electron Beam-Induced Deposition for Atom Probe Tomography Specimen Capping Layers.

Six precursors were evaluated for use as in situ electron beam-induced deposition capping layers in the preparation of atom probe tomography specimens with a focus on near-surface features where some of the deposition is retained at the specimen apex. Specimens were prepared by deposition of each precursor onto silicon posts and shaped into sub-70-nm radii needles using a focused ion beam. The utility of the depositions was assessed using several criteria including composition and uniformity, evaporation behavior and evaporation fields, and depth of Ga+ ion penetration. Atom probe analyses through depositions of methyl cyclopentadienyl platinum trimethyl, palladium hexafluoroacetylacetonate, and dimethyl-gold-acetylacetonate [Me2Au(acac)] were all found to result in tip fracture at voltages exceeding 3 kV. Examination of the deposition using Me2Au(acac) plus flowing O2 was inconclusive due to evaporation of surface silicon from below the deposition under all analysis conditions. Dicobalt octacarbonyl [Co2(CO)8] and diiron nonacarbonyl [Fe2(CO)9] depositions were found to be effective as in situ capping materials for the silicon specimens. Their very different evaporation fields [36 V/nm for Co2(CO)8 and 21 V/nm for Fe2(CO)9] provide options for achieving reasonably close matching of the evaporation field between the capping material and many materials of interest.

Effect of Diels-Alder Reaction in C60-Tetracene Photovoltaic Devices.

Developing organic photovoltaic materials systems requires a detailed understanding of the heterojunction interface, as it is the foundation for photovoltaic device performance. The bilayer fullerene/acene system is one of the most studied models for testing our understanding of this interface. We demonstrate that the fullerene and acene molecules chemically react at the heterojunction interface, creating a partial monolayer of a Diels-Alder cycloadduct species. Furthermore, we show that the reaction occurs during standard deposition conditions and that thermal annealing increases the concentration of the cycloadduct. The cycloaddition reaction reduces the number of sites available at the interface for charge transfer exciton recombination and decreases the charge transfer state reorganization energy, increasing the open circuit voltage. The submonolayer quantity of the cycloadduct renders it difficult to identify with conventional characterization techniques; we use atom probe tomography to overcome this limitation while also measuring the spatial distribution of each chemical species.

Probing Grain-Boundary Chemistry and Electronic Structure in Proton-Conducting Oxides by Atom Probe Tomography.

A laser-assisted atom-probe-tomographic (LAAPT) method has been developed and applied to measure and characterize the three-dimensional atomic and electronic nanostructure at an yttrium-doped barium zirconate (BaZr0.9Y0.1O3-δ, BZY10) grain boundary. Proton-conducting perovskites, such as BZY10, are attracting intense interest for a variety of energy conversion applications. However, their implementation has been hindered, in part, because of high grain-boundary (GB) resistance that is attributed to a positive GB space-charge layer (SCL). In this study, LAAPT is used to analyze BZY10 GB chemistry in three dimensions with subnanometer resolution. From this analysis, maps of the charge density and electrostatic potential arising at the GBs are derived, revealing for the first time direct chemical evidence that a positive SCL indeed exists at these GBs. These maps reveal new insights on the inhomogeneity of the SCL region and produce an average GB potential barrier of approximately 580 mV, agreeing with previous indirect electrochemical measurements.

Moderate level exposure to magnetic nanodots encased in tunable poly(ethylene glycol) analouge biopolymer shell do not deleteriously affect neurite outgrowth.

Recently, huge interest has been generated in investigating the possible therapeutic use of tunable magnetic nanostructures to overcome the existing challenges to treat central nervous system damage related conditions. However, several issues (e.g., biocompatibility or remote controlled actuation for multi-modal therapeutics) limit the use of conventional magnetic nanoparticles for biomedical applications. To address many of these shortcomings, we have synthesized a monodisperse nanoscale system consisting highly water dispersible magnetic nanodots encased in a remotely tunable polyethylene glycol analouge biopolymer shell. The monodisperse nature of the nanospheres, their response to external magnetic field and volumetric transition near physiological temperatures are very attractive, especially for drug delivery systems where triggered release is necessary. To further analyze the potential for combinatorial therapeutics for central nervous system damage related conditions, we have explored the efficiency of the uptake of nanospheres into pheochromocytoma cell line 12 (PC12) cells and assessed several additional measures of neurite outgrowth. We find that nanospheres were readily incorporated into the cytosolic compartment within 3 hours and did not alter the morphology of cellular processes compared to cells not exposed to nanospheres. Quantification of neurite outgrowth did not reveal any significant differences in neurite initiation or elongation between cells treated with moderate level nanomagnet exposure compared to control cultures under similar conditions. Thus, this study reports an attractive nano-scale system with great potential to deliver therapeutics to precise locations within the nervous system for axonal outgrowth and guidance.

Synthesis of LaWN3 nitride perovskite with polar symmetry.

Oxide materials with the perovskite structure have been used in sensors and actuators for half a century, and halide perovskites transformed photovoltaics research in the past decade. Nitride perovskites have been computationally predicted to be stable, but few have been synthesized, and their properties remain largely unknown. We synthesized and characterized a nitride perovskite lanthanum tungsten nitride (LaWN3) in the form of oxygen-free sputtered thin films, according to spectroscopy, scattering, and microscopy techniques. We report a large piezoelectric response measured with scanning probe microscopy that together with synchrotron diffraction confirm polar symmetry of the perovskite LaWN3. Our LaWN3 synthesis should inspire growth of other predicted nitride perovskites, and measurements of their properties could lead to functional integration with nitride semiconductors for microelectromechanical devices.

An algorithm for correcting systematic energy deficits in the atom probe mass spectra of insulating samples.

Improvements in the mass resolution of a mass spectrometer directly correlate to improvements in peak identification and quantification. Here, we describe a post-processing technique developed to increase the quality of mass spectra of strongly insulating samples in laser-pulsed atom probe microscopy. The technique leverages the self-similarity of atom probe mass spectra collected at different times during an experimental run to correct for electrostatic artifacts that present as systematic energy deficits. We demonstrate the method on fused silica (SiO2) and neodymium-doped ceria (CeO2) samples which highlight the improvements that can be made to the mass spectrum of strongly insulating samples.

Orientation mapping with Kikuchi patterns generated from a focused STEM probe and indexing with commercially available EDAX software.

Relating a crystal's microscopic structure-such as orientation and size-to a material's macroscopic properties is of great importance in materials science. Although most crystal orientation microscopy is performed in the scanning electron microscope (SEM), transmission electron microscopy (TEM)-based methods have a number of benefits, including higher spatial resolution. Current TEM orientation methods have either specific hardware requirements or use software that has limited scope, utility, or availability. In this article, a technique is described for orientation mapping using Kikuchi diffraction patterns generated from a focused STEM probe. One key advantage is that indexing and analysis of the patterns and maps occurs in the robust OIM Analysis software, currently widely used for electron backscatter diffraction (EBSD) and transmission Kikuchi diffraction (TKD) analysis. It was found that with minimal to no image processing and by changing only a few software parameters, reliable indexing of Kikuchi patterns is possible. Three samples, a deformed ß-Titanium (Ti), a medium carbon heat-treated steel, and BaCe0.8Y0.2O3-δ were tested to determine the effectiveness of the approach. In all three measurements the algorithms effectively and reliably determined the phases and the crystal orientations of the features measured. For the two orientation maps produced, less than 5% of the patterns were misindexed including boundary areas where overlapping patterns existed. An angular resolution of 0.15° was achieved while features <25 nm were able to be spatially resolved.

A Three-Dimensional Atom Probe Microscope Incorporating a Wavelength-Tuneable Femtosecond-Pulsed Coherent Extreme Ultraviolet Light Source.

Pulsed coherent extreme ultraviolet (EUV) radiation is a potential alternative to pulsed near-ultraviolet (NUV) wavelengths for atom probe tomography. EUV radiation has the benefit of high absorption within the first few nm of the sample surface for elements across the entire periodic table. In addition, EUV radiation may also offer athermal field ion emission pathways through direct photoionization or core-hole Auger decay processes, which are not possible with the (much lower) photon energies used in conventional NUV laser-pulsed atom probe. We report preliminary results from what we believe to be the world's first EUV radiation-pulsed atom probe microscope. The instrument consists of a femtosecond-pulsed, coherent EUV radiation source interfaced to a local electrode atom probe tomograph by means of a vacuum manifold beamline. EUV photon-assisted field ion emission (of substrate atoms) has been demonstrated on various insulating, semiconducting, and metallic specimens. Select examples are shown.

Self-consistent atom probe tomography reconstructions utilizing electron microscopy.

Atom probe tomography reconstructions provide valuable information on nanometer-scale compositional variations within materials. As such, the spatial accuracy of the reconstructions is of primary importance for the resulting conclusions to be valid. Here, the use of transmission electron microscopy images before and after atom probe analysis to provide additional information and constraints is examined for a number of different materials. In particular, the consistency between the input reconstruction parameters and the output reconstruction is explored. It is demonstrated that it is possible to generate reconstructions in which the input and known values are completely consistent with the output reconstructions. Yet, it is also found that for all of the datasets examined, a particular power law relationship exists such that, if the image compression factor or detection efficiency is not constrained, a series of similarly spatially accurate reconstructions results. However, if one of these values can be independently assessed, then the other is known as well. Means of incorporating these findings and this general methodology into reconstruction protocols are also discussed.

Electron diffraction and imaging for atom probe tomography.

Previous work has shown that pre- and post-experiment quantification of atom probe tomography (APT) specimen geometry using electron microscopy can constrain otherwise unknown parameters, leading to an improvement in data fidelity. To that end, an electron microscopy and diffraction system has been developed for in situ compatibility with modern APT hardware. The system is capable of secondary and backscattered scanning electron imaging, bright field and dark field scanning transmission electron imaging, and scanning transmission electron diffraction. Additionally, the system is also capable of in situ dynamic electron diffraction experiments using laser pulsed heating of the APT specimen.

p-type doping efficiency in CdTe: Influence of second phase formation.

Cadmium telluride (CdTe) high purity, bulk, crystal ingots doped with phosphorus were grown by the vertical Bridgman melt growth technique to understand and improve dopant solubility and activation. Large net carrier densities have been reproducibly obtained from as-grown ingots, indicating successful incorporation of dopants into the lattice. However, net carrier density values are orders of magnitude lower than the solubility of P in CdTe as reported in literature, 1018/cm3 to 1019/cm3 [J. H. Greenberg, J. Cryst. Growth 161, 1-11 (1996) and R. B. Hall and H. H. Woodbury, J. Appl. Phys. 39(12), 5361-5365 (1968)], despite comparable starting charge dopant densities. Growth conditions, such as melt stoichiometry and post growth cooling, are shown to have significant impacts on dopant solubility. This study demonstrates that a significant portion of the dopant becomes incorporated into second phase defects as compounds of cadmium and phosphorous, such as cadmium phosphide, which inhibits dopant incorporation into the lattice and limits maximum attainable net carrier density in bulk crystals. Here, we present an extensive study on the characteristics of these second phase defects in relation to their composition and formation kinetics while providing a pathway to minimize their formation and enhance solubility.

Role of engineered nanocarriers for axon regeneration and guidance: current status and future trends.

There are approximately 1.5 million people who experience traumatic injuries to the brain and 265,000 who experience traumatic injuries to the spinal cord each year in the United States. Currently, there are few effective treatments for central nervous system (CNS) injuries because the CNS is refractory to axonal regeneration and relatively inaccessible to many pharmacological treatments. Smart, remotely tunable, multifunctional micro- and nanocarriers hold promise for delivering treatments to the CNS and targeting specific neurons to enhance axon regeneration and synaptogenesis. Furthermore, assessing the efficacy of treatments could be enhanced by biocompatible nanovectors designed for imaging in vivo. Recent developments in nanoengineering offer promising alternatives for designing biocompatible micro- and nanovectors, including magnetic nanostructures, carbon nanotubes, and quantum dot-based systems for controlled release of therapeutic and diagnostic agents to targeted CNS cells. This review highlights recent achievements in the development of smart nanostructures to overcome the existing challenges for treating CNS injuries.

Alternating Magnetic Field Controlled, Multifunctional Nano-Reservoirs: Intracellular Uptake and Improved Biocompatibility.

Biocompatible magnetic nanoparticles hold great therapeutic potential, but conventional particles can be toxic. Here, we report the synthesis and alternating magnetic field dependent actuation of a remotely controllable, multifunctional nano-scale system and its marked biocompatibility with mammalian cells. Monodisperse, magnetic nanospheres based on thermo-sensitive polymer network poly(ethylene glycol) ethyl ether methacrylate-co-poly(ethylene glycol) methyl ether methacrylate were synthesized using free radical polymerization. Synthesized nanospheres have oscillating magnetic field induced thermo-reversible behavior; exhibiting desirable characteristics comparable to the widely used poly-N-isopropylacrylamide-based systems in shrinkage plus a broader volumetric transition range. Remote heating and model drug release were characterized for different field strengths. Nanospheres containing nanoparticles up to an iron concentration of 6 mM were readily taken up by neuron-like PC12 pheochromocytoma cells and had reduced toxicity compared to other surface modified magnetic nanocarriers. Furthermore, nanosphere exposure did not inhibit the extension of cellular processes (neurite outgrowth) even at high iron concentrations (6 mM), indicating minimal negative effects in cellular systems. Excellent intracellular uptake and enhanced biocompatibility coupled with the lack of deleterious effects on neurite outgrowth and prior Food and Drug Administration (FDA) approval of PEG-based carriers suggest increased therapeutic potential of this system for manipulating axon regeneration following nervous system injury.