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The aim of this study was the preparation of different amorphous silicon-carbon hybrid thin-layer materials according to the liquid phase deposition (LPD) process using single-source precursors. In our study, 2-methyl-2-silyltrisilane (methylisotetrasilane; 2), 1,1,1-trimethyl-2,2-disilyltrisilane (trimethylsilylisotetrasilane; 3), 2-phenyl-2-silyltrisilane (phenylisotetrasilane; 4), and 1,1,2,2,4,4,5,5-octamethyl-3,3,6,6-tetrasilylcyclohexasilane (cyclohexasilane; 5) were utilized as precursor materials and compared with the parent compound 2,2-disilyltrisilane (neopentasilane; 1). Compounds 2-5 were successfully oligomerized at λ = 365 nm with catalytic amounts of the neopentasilane oligomer (NPO). These oligomeric mixtures (NPO and 6-9) were used for the preparation of thin-layer materials. Optimum solution and spin coating conditions were investigated, and amorphous silicon-carbon films were obtained. All thin-layer materials were characterized via UV/vis spectroscopy, light microscopy, spectroscopic ellipsometry, XPS, SEM, and SEM/EDX. Our results show that the carbon content and especially the bandgap can be easily tuned using these single-source precursors via LPD.
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Stoichiometric precipitates owe their fixed composition to an ordered crystal structure. Deviations from that nominal value, however, are encountered at times. Here we investigate composition, structure and diffusion phenomena of ordered precipitates that form during heat treatment in an industrially cast Al-Mg-Sc-Zr alloy system. Experimental investigations based on aberration-corrected scanning transmission electron microscopy and analytical tomography reveal the temporal evolution of precipitate ordering and formation of non-equilibrium structures with unprecedented spatial resolution, supported by thermodynamic calculations and diffusion simulations. This detailed view reveals atomic-scale spinodal decomposition to majorly define the ongoing diffusion process. It is illustrated that even small deviations in composition and ordering can have a considerable impact on a system's evolution, due to the interplay of Gibbs energies, atomic jump activation energies and phase ordering, which may play an important role for multicomponent alloys.
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Vanadium oxide clusters with a mean diameter below 10 nm are investigated by high resolution Scanning Transmission Electron Microscopy (STEM), Electron Energy Loss Spectroscopy (EELS) and UV-vis absorption spectroscopy. The clusters are synthesised by sublimation from bulk vanadium(v) oxide, in combination with a pick-up by superfluid helium droplets. The latter act as reaction chambers which enable cluster growth under fully inert and solvent-free conditions. High-resolution STEM images of deposited vanadium oxide particles allowing for the determination of lattice constants, clearly indicate a dominating presence of V2O5. This finding is further supported by UV-vis absorption spectra of nanoparticles after deposition on fused silica substrates, which indicates that the oxidation state of the material is preserved over the entire process. From the results of the UV-vis measurement, the band gap of the nanosized V2O5 could be determined to be 3.3 eV. The synthesis approach provides a route to clean V2O5 clusters as it does not involve any surfactant or solvents, which is crucial for an unbiased measurement of intrinsic catalyst properties.
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Hybrid core-shell type nanoparticles from gold nanoparticle cores and poly( N-isopropylacrylamide) shells were investigated with regard to their structural plasticity. Reversible addition-fragmentation chain transfer polymerization was used to synthesize well-defined polymers that can be readily anchored onto the gold nanoparticle surface. The polymer shell morphologies were directly visualized in their native solution state at high resolution by cryogenic transmission electron microscopy, and the microscopic results were further corroborated by dynamic light scattering. Different environmental conditions and brush architectures are covered by our experiments, which leads to distinct thermally induced responses. These responses include constrained dewetting of the nanoparticle surface at temperatures above the lower critical solution temperature of poly( N-isopropylacrylamide), leading to surface polymer patches. This effect provides a novel approach toward breaking the symmetry of nanoparticle interactions, and we show first evidence for its impact on the formation of colloidal superstructures.
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The preparation of nanoparticles and their targeted connection with other functional units is one key challenge in developing nanoscale devices. Herein, we report an experimental strategy toward the development of anisotropic nanoparticle architectures. Our approach is based on phase separation of binary mixed polymer brushes on gold nanoparticle surfaces leading to Janus-type structures, as revealed by scanning transmission electron microscopy and electron energy-loss spectroscopy and, additionally, corroborated by computer simulation. We show that such structures can be used for the site-selective functionalization with additional nanosized entities.
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Plasmonic gap modes provide the ultimate confinement of optical fields. Demanding high spatial resolution, the direct imaging of these modes was only recently achieved by electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). However, conventional 2D STEM-EELS is only sensitive to components of the photonic local density of states (LDOS) parallel to the electron trajectory. It is thus insensitive to specific gap modes, a restriction that was lifted with the introduction of tomographic 3D EELS imaging. Here, we show that by 3D EELS tomography the gap mode LDOS of a vertically stacked nanotriangle dimer can be fully imaged. Besides probing the complete mode spectrum, we demonstrate that the tomographic approach allows disentangling the signal contributions from the two nanotriangles that superimpose in a single measurement with a fixed electron trajectory. Generally, vertically coupled nanoparticles enable the tailoring of 3D plasmonic fields, and their full characterization will thus aid the development of complex nanophotonic devices.
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Herein a convenient synthetic method to obtain 2,2,3,3-tetrasilyltetrasilane 3 and 2,2,3,3,4,4-hexasilylpentasilane 4 on a multigram scale is presented. Proton-coupled 29 Siâ NMR spectroscopy and single-crystal X-ray crystallography enabled unequivocal structural assignment. Owing to their unique properties, which are reflected in their nonpyrophoric character on contact with air and their enhanced light absorption above 250â nm, 3 and 4 are valuable precursors for liquid-phase deposition (LPD) and the processing of thin silicon films. Amorphous silicon (a-Si:H) films of excellent quality were deposited starting from 3 and characterized by conductivity measurements, ellipsometry, optical microscopy, and Raman spectroscopy.
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Electron tomography in combination with electron energy-loss spectroscopy (EELS) experiments and simulations was used to unravel the interplay between structure and plasmonic properties of a silver nanocuboid dimer. The precise 3D geometry of the particles fabricated by means of electron beam lithography was reconstructed through electron tomography, and the full three-dimensional information was used as an input for simulations of energy-loss spectra and plasmon resonance maps. Excellent agreement between experiment and theory was found throughout, bringing the comparison between EELS imaging and simulations to a quantitative and correlative level. In addition, interface mode patterns, normally masked by the projection nature of a transmission microscopy investigation, could be unambiguously identified through tomographic reconstruction. This work overcomes the need for geometrical assumptions or symmetry restrictions of the sample in simulations and paves the way for detailed investigations of realistic and complex plasmonic nanostructures.
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The classical implementation for putting quantitative figures on maps to reveal elemental compositions in transmission electron microscopy is by analytical methods like X-ray and energy-loss spectroscopy. Typically, the technique in use often depends on whether lighter or heavier elements are present and-more practically-which calibrations are available or sample-related properties are known. A framework linking electron energy-loss spectroscopy (EELS) and energy-dispersive X-ray (EDX) signals such that absolute volumetric concentrations can be derived without assumptions made a priori about the unknown sample, is largely missing. In order to combine both techniques and harness their respective potentials for a light and heavy element analysis, we have set up a powerful hardware configuration and implemented an experimental approach, which reduces the need for estimates on many parameters needed for quantitative work such as densities, absolute thicknesses, theoretical ionization cross-sections, etc. Calibrations on specimens with known geometry allow the measurement of inelastic mean free paths. As a consequence, mass-thicknesses obtained from the EDX ζ-factor approach can be broken up and quantities like concentrations and partial energy-differential ionization cross-sections become accessible. ζ-factors can then be used for conversion into EELS cross-sections that are hard to determine otherwise, or conversely, connecting EDXS and EELS in a quantitative manner quite effectively.
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For three types of colloidal magnetic nanocrystals, we demonstrate that postsynthetic cation exchange enables tuning of the nanocrystal's magnetic properties and achieving characteristics not obtainable by conventional synthetic routes. While the cation exchange procedure, performed in solution phase approach, was restricted so far to chalcogenide based semiconductor nanocrystals, here ferrite-based nanocrystals were subjected to a Fe(2+) to Co(2+) cation exchange procedure. This allows tracing of the compositional modifications by systematic and detailed magnetic characterization. In homogeneous magnetite nanocrystals and in gold/magnetite core shell nanocrystals the cation exchange increases the coercivity field, the remanence magnetization, as well as the superparamagnetic blocking temperature. For core/shell nanoheterostructures a selective doping of either the shell or predominantly of the core with Co(2+) is demonstrated. By applying the cation exchange to FeO/CoFe(2)O(4) core/shell nanocrystals the Neél temperature of the core material is increased and exchange-bias effects are enhanced so that vertical shifts of the hysteresis loops are obtained which are superior to those in any other system.
Assuntos
Cobalto/química , Compostos Férricos/química , Nanoestruturas/química , Óxidos/química , Cátions/química , Campos Magnéticos , Tamanho da Partícula , Propriedades de Superfície , TemperaturaRESUMO
INTRODUCTION: Pinhole intraocular lenses (IOLs) were developed to improve reading by compensating for loss of accommodative function. The IC-8® Apthera™ is a small-aperture presbyopia-correcting IOL that combines the proven principle of small-aperture optics with an aspheric monofocal lens to deliver a continuous range of vision for patients with cataracts from distance to near vision. Posterior capsule opacification is the most common sequela after cataract surgery. It is effectively treated by laser capsulotomy. However, if the laser beam is incorrectly focused, the IOL can be permanently damaged (pits/shots). METHODS: In this experimental study, yttrium-aluminum-garnet (YAG) pits were purposefully created. Defects were analyzed and compared between the periphery of the ring in the clear area of the hydrophobic acrylic lens and at the carbon black (CB)-polyvinylidene fluoride (PVDF) filtering component (FilterRing™) of the pinhole lens. All defects were made using identical settings/energy levels (2.6 mJ). The damage induced to the IC-8® Apthera™ IOL was examined by low-magnification images, light microscopy, scanning electron microscopy, and micro-computed tomography (micro-CT). RESULTS: YAG defects in the carbon black filter ring were much more severe than those in the clear zone due to the high absorption of the carbon black. Massive defects and destruction of the lens with tearing out of fragments and particles were observed. The missing volume calculated from the micro-CT reconstruction was 0.266 mm3, which is 1.6% of the entire IOL volume, or more than 1000 times the volume damaged in the largest shot in the periphery. CONCLUSION: Based on the results, we highly recommend using the lowest possible energy levels, posterior offset setting, and circular pattern for maximum safety when performing laser capsulotomy with pinhole implants. Care should be taken to avoid creating irreversible iatrogenic defects that may affect overall quality. The safest area for performing capsulotomy seems to be the periphery of the ring segment. Video available for this article.
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The fundamental dependence between process parameters during focused electron beam induced deposition and the chemistry of functional PtC nanostructures have been studied via a multi-technique approach using SEM, (S)TEM, EELS, AFM, and EFM. The study reveals that the highest Pt contents can only be achieved by an ideal balance between potentially dissociating electrons and available precursor molecules on the surface. For precursor regimes apart from this situation, an unwanted increase of carbon is observed which originates from completely different mechanisms: (1) an excess of electrons leads to polymerization of precursor fragments whereas (2) a lack of electrons leads to incompletely dissociated precursor molecules incorporated into the nanostructures. While the former represents an unwanted class of carbon, the latter condition maximizes the volume growth rates and allows for post-growth curing strategies which can strongly increase the functionality. Furthermore, the study gives an explanation of why growing deposits can dynamically change their chemistry and provides a straightforward guide towards more controlled fabrication conditions.
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We theoretically investigate the tomographic reconstruction of the three-dimensional photonic environment of nanoparticles. As input for our reconstruction we use electron energy loss spectroscopy (EELS) maps for different rotation angles. We perform the tomographic reconstruction of surface polariton fields for smooth and rough nanorods and compare the reconstructed and simulated photonic local density of states, which are shown to be in very good agreement. Using these results, we critically examine the potential of our tomography scheme and discuss limitations and directions for future developments.
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Even though hydrogen-metal surface interactions play an important role in energy technologies and metal corrosion, a thorough understanding of these interactions at the nanoscale remains elusive due to obstructive detection limits in instrumentation and the volatility of pure hydrogen. In the present paper we use analytical spectroscopy in TEM to show that hydrogen adsorbs directly at the (0001) surfaces of hexagonal helium bubbles within neutron irradiated beryllium. In addition to hydrogen, we also found Al, Si and Mg at the beryllium-bubble interfaces. The strong attraction of these elements to (0001) surfaces is underlined with ab-initio calculations. In situ TEM heating experiments reveal that hydrogen can desorb from the bubble walls at T ≥ 400 °C if the helium content is reduced by opening the bubbles. Based on our results we suggest the formation of a complex hydride consisting of up to five elements with a remarkably high decomposition temperature. These results therefore promise novel insights into metal-hydrogen interaction behavior and are invaluable for the safety of future fusion power plants.
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The passivity of aluminum is detrimental to its performance as an anode in batteries. Soaking of native oxide-covered aluminum in a chloroaluminate deep eutectic solvent gradually activates the electrode surface, which is reflected in a continuously decreasing open circuit potential. The underlying processes were studied by analyzing the 3 to 7 nm thick layer of native oxide after increasing periods of soaking with secondary neutral mass spectrometry, X-ray photoelectron spectroscopy, and energy-dispersive spectroscopy in a transmission electron microscope. They consistently show permeation of electrolyte species into the layer associated with gradual swelling. After extended periods of soaking at open circuit potentials, local deposits of a range of foreign metals have been found in scanning electron microscopy images of the electrode surface. The pitting corrosion is caused by trace metal ion impurities present in the electrolyte and results in highly nonuniform current density distribution during discharge/charge cycling of battery cells as shown by local deposits of aluminum. The processes during soaking at open circuit potentials have been monitored by electrochemical impedance spectroscopy and could be analyzed by fitting an equivalent circuit model for pitting corrosion.
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Magnetic force microscopy (MFM) is a powerful extension of atomic force microscopy (AFM), which mostly uses nano-probes with functional coatings for studying magnetic surface features. Although well established, additional layers inherently increase apex radii, which reduce lateral resolution and also contain the risk of delamination, rendering such nano-probes doubtful or even useless. To overcome these limitations, we now introduce the additive direct-write fabrication of magnetic nano-cones via focused electron beam-induced deposition (FEBID) using an HCo3Fe(CO)12 precursor. The study first identifies a proper 3D design, confines the most relevant process parameters by means of primary electron energy and beam currents, and evaluates post-growth procedures as well. That way, highly crystalline nano-tips with minimal surface contamination and apex radii in the sub-15 nm regime are fabricated and benchmarked against commercial products. The results not only reveal a very high performance during MFM operation but in particular demonstrate virtually loss-free behavior after almost 8 h of continuous operation, thanks to the all-metal character. Even after more than 12 months of storage in ambient conditions, no performance loss is observed, which underlines the high overall performance of the here-introduced FEBID-based Co3Fe MFM nano-probes.
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The charging of nanoporous carbon via electrodeposition of solid iodine from iodide-based electrolyte is an efficient and ecofriendly method to produce battery cathodes. Here, the interactions at the carbon/iodine interface from first contact with the aqueous electrolyte to the electrochemical polarization conditions in a hybrid cell are investigated by a combination of in situ and ex situ methods. EQCM investigations confirm the flushing out of water from the pores during iodine formation at the positive electrode. XPS of the carbon surface shows irreversible oxidation at the initial electrolyte immersion and to a larger extent during the first few charge/discharge cycles. This leads to the creation of functional groups at the surface while further reactive sites are consumed by iodine, causing a kind of passivation during a stable cycling regime. Two sources of carbon electrode structural modifications during iodine formation in the nanopores have been revealed by in situ Raman spectroscopy, (i) charge transfer and (ii) mechanical strain, both causing reversible changes and thus preventing performance deterioration during the long-term cycling of energy storage devices that use iodine-charged carbon electrodes.
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Electron-induced fragmentation of the HFeCo3(CO)12 precursor allows direct-write fabrication of 3D nanostructures with metallic contents of up to >95 at %. While microstructure and composition determine the physical and functional properties of focused electron beam-induced deposits, they also provide fundamental insights into the decomposition process of precursors, as elaborated in this study based on EDX and TEM. The results provide solid information suggesting that different dominant fragmentation channels are active in single-spot growth processes for pillar formation. The use of the single source precursor provides a unique insight into high- and low-energy fragmentation channels being active in the same deposit formation process.
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Tailoring vacancies is a feasible way to improve the mechanical properties of ceramics. However, high concentrations of vacancies usually compromise the strength (or hardness). We show that a high elasticity and flexural strength could be achieved simultaneously using a nitride superlattice architecture with disordered anion vacancies up to 50%. Enhanced mechanical properties primarily result from a distinctive deformation mechanism in superlattice ceramics, i.e., unit-cell disturbances. Such a disturbance substantially relieves local high-stress concentration, thus enhancing deformability. No dislocation activity involved also rationalizes its high strength. The work renders a unique understanding of the deformation and strengthening/toughening mechanism in nitride ceramics.
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In this paper, it is shown that high vacuum conditions are not sufficient to completely remove water and oxygen from the ionic liquid 1-ethyl-3-methylimidazolium chloride. Complete removal of water demands heating above 150 °C under reduced pressure, as proven by Nuclear Reaction Analysis (NRA). Dissolved oxygen gas can only be removed by the use of an oxygen scavenger such as hydroquinone, despite the fact that calculations show that oxygen should be removed completely by the applied vacuum conditions. After applying a strict drying procedure and scavenging of molecular oxygen, it was possible to deposit copper directly on tantalum without the presence of an intervening oxide layer.