SEARCH · Engineering Papers
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Here, nanomechanical measurements of platinum–carbon 3D nanoscale architectures grown via focused electron beam induced deposition (FEBID) were performed using a nanoindentation system in a scanning electron microscope (SEM) for simultaneous in situ imaging.
Elucidating energetic particle-precursor gas–solid interactions is critical to many atomic and nanoscale synthesis approaches. Focused ion beam sputtering and gas-assisted etching are among the more commonly used direct-write nanomachining techniques that have been developed. Here, we demonstrate a method to simulate gas-assisted focused ion beam (FIB) induced etching for editing/machining materials at the nanoscale. The method consists of an ion–solid Monte Carlo simulation, to which we have added additional routines to emulate detailed gas precursor–solid interactions, including the gas flux, adsorption, and desorption. Furthermore, for the reactive etching component, a model is presented by which energetic ions/target atoms, and secondary electrons, transfer energy to adsorbed gas molecules. The simulation is described in detail, and is validated using analytical and experimental data for surface gas adsorption, and etching yields. The method is used to study XeF 2 assisted FIB induced etching of nanoscale vias, using both a 35 keV Ga + , and a 10 keV Ne + beam. Remarkable agreement between experimental and simulated nanoscale vias is demonstrated over a range of experimental conditions. Importantly, we demonstrate that the resolution depends strongly on the XeF 2 gas flux, with optimal resolution obtained for either pure sputtering, or saturated gas coverage; saturated gas coverage has the clear advantage of lower overall dose, and thus lower implant damage, and much faster processing.
We report the excited-state behavior of a structurally simple bis -sulfoxide complex, cis -S,S-[Ru(bpy) 2 (dmso) 2 ] 2+ , as investigated by femtosecond pump–probe spectroscopy. The results reveal that a single photon prompts phototriggered isomerization of one or both dmso ligands to yield a mixture of cis -S,O-[Ru(bpy) 2 (dmso) 2 ] 2+ and cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ . The quantum yields of isomerization of each product and relative product distribution are dependent upon the excitation wavelength, with longer wavelengths favoring the double isomerization product, cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ . Transient absorption measurements on cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ do not reveal an excited-state isomerization pathway to produce either the S,O or S,S isomers. Femtosecond pulse shaping experiments reveal no change in the product distribution. Pump–repump–probe transient absorption spectroscopy of cis -S,S-[Ru(bpy) 2 (dmso) 2 ] 2+ shows that a pump–repump time delay of 3 ps dramatically alters the S,O:O,O product ratio; pump–repump–probe transient absorption spectroscopy of cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ with a time delay of 3 ps uncovers an excited-state isomerization pathway to produce the S,O isomer. In conjunction with low-temperature steady-state emission spectroscopy, these results are interpreted in the context of an excited-state bifurcating pathway, in which the isomerization product distribution is determined not by thermodynamics, but rather as a dynamics driven reaction.
Magnetoelectric (ME) heterostructures can exhibit higher magnetic and ferroelectric ordering temperatures along with large ME coupling compared to single-phase multiferroic materials. We synthesized Pb(Fe 0.5 Nb 0.5 )O 3 (PFN)/Ni 0.65 Zn 0.35 Fe 2 O 4 (NZFO)/Pb(Fe 0.5 Nb 0.5 )O 3 (PFN)/Ni 0.65 Zn 0.35 Fe 2 O 4 (NZFO)/Pb(Fe 0.5 Nb 0.5 )O 3 (PFN) multilayer heterostructures having dimensions of 40/10/40/10/40 nm. High quality epitaxial growth of these heterostructures was confirmed via X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns. These nanostructures show well saturated polarization (~52 μC cm -2 ) and magnetization (~62 emu cm -3 ) at room temperature (RT). The magnetic and ferroelectric transitions occur well above RT. These heterostructures exhibit relaxor behavior and undergo 2nd order ferroelectric phase transition. Magnetodielectric measurements show significant coupling between the magnetic and electrical order parameters at RT. These characteristics of the heterostructures make them suitable as potential candidates for ultra-low power memory, spintronics, and different multifunctional (micro)nanoscale device applications.
Abuse testing of lithium-ion batteries is widely performed in order to develop new safety standards and strategies. However, testing methodologies are not standardised across the research community, especially with failure mechanisms being inherently difficult to reproduce. High-speed X-ray radiography is proven to be a valuable tool to capture events occurring during cell failure, but the observations made remain largely qualitative. We have therefore developed a robust image processing toolbox that can quantify, for the first time, the rate of propagation of battery failure mechanisms revealed by high-speed X-ray radiography. Using Gabor filter, the toolbox selectively tracks the electrode structure at the onset of failure. This facilitated the estimation of the displacement of electrodes undergoing abuse via nail penetration, and also the tracking of objects, such as the nail, as it propagates through a cell. Further, by cross-correlating the Gabor signals, we have produced practical, illustrative spatiotemporal maps of the failure events. From these, we can quantify the propagation rates of electrode displacement prior to the onset of thermal runaway. The highest recorded acceleration (≈514 mm s -2 ) was when a nail penetrated a cell radially (perpendicular to the electrodes) as opposed to axially (parallel to the electrodes). The initiation of thermal runaway was also resolved in combination with electrode displacement, which occurred at a lower acceleration (≈108 mm s -2 ). Our assistive toolbox can also be used to study other types of failure mechanisms, extracting otherwise unattainable kinetic data. Ultimately, this tool can be used to not only validate existing theoretical mechanical models, but also standardise battery failure testing procedures.
Thermodynamic instabilities driven by temperature and irradiation in a nanocrystalline highly-concentrated alloy promote the nucleation and growth of FeCo-rich “nanomagnets”.
Magnetoelectric (ME) materials exhibit interesting physics with cross coupling between ferroelectric and magnetic order parameters and thus strong potential to be utilized in memory, spintronics and other multifunctional electronic/magnetic devices. Doping of suitable transition metals in ferroelectrics can induce magnetism and ME coupling and modify the physical properties. Here, we report the structural, electronic, magnetic and ME coupling of 3.5, 5 and 7.5 mol% cobalt doped BaTiO 3 (BTO) ceramics. X-ray diffraction and Raman spectroscopy indicate that the samples are single phase having a tetragonal crystal structure with P4mm symmetry. The tetragonality ratio is found to decrease with increasing cobalt content. We observed a Fano-like asymmetric peak in the [A 1 (LO 1 )] Raman mode at ~173 cm -1 in all the cobalt doped BTO samples. The cobalt dopants are shown to be uniformly distributed throughout the surface of the samples. We observed a lowering of the ferroelectric transition temperature and increasing diffusivity parameter with increasing cobalt concentration. The electrical properties of all the samples have been investigated in detail by impedance spectroscopy and ac conductivity studies before and after the ferroelectric phase transitions. All the samples show hysteretic ferroelectric behavior with a clear saturation state that decreases with increasing cobalt content. The observed ferroelectricity in these samples is intrinsic in nature. The 3.5% cobalt doped BTO sample exhibits paramagnetic behavior whereas the 5 and 7.5% cobalt doped BTO samples show ferromagnetic ordering below 43 K. The 7.5% cobalt doped BTO samples show significant ME coupling.
Five bismuth(III)-organic phases that consist of supramolecular assemblies of Bi-2,6-pyridinedicarboxylate structural units and substituted 1,10-phenanthroline molecules (R-Phen; R = H, 5-methyl, 5-chloro, 2,9-dimethyl, and 2,9-dicholoro) were synthesized. All five compounds exhibited solid-state photoluminescence. Whereas the phases containing 2,9-dimethylphenanthroline (Me 2 Phen) and 2,9-dichlorophenanthroline (Cl 2 Phen) displayed solely phosphorescence, the structures built from 5-methylphenanthroline and 5-chlorophenanthroline showed exclusively fluorescence. The remaining phase, consisting of phenanthrolinium, exhibited both fluorescence and phosphoresence. It was determined that phosphorescence arises from triplet state emission (T 1 → S 0 ) of substituted R-Phen units while fluorescence originates from Bi(III) coordinated pyrdinedicarboxylate ligands. Bismuth induces spin–orbit coupling for triplet state population and additionally acts as a heavy metal attenuator for X-ray luminescence (radioluminescence). The electronic structure was mapped and excitation pathway investigated via density functional theory calculations. Computational findings indicate favorable conditions for triplet energy transfer from donor Bi(III)-organic units to acceptor R-Phen derivatives. It is proposed that for the phosphorescent compounds, strong π–π interactions promote electron transfer, whereas the compounds that exhibit purely fluorescence lack any such π–π interactions and undergo triplet energy transfer. In conclusion, these results provide a useful platform for probing structure–property relationships of luminescent bismuth-organic compounds, and specifically highlights the role of noncovalent interactions in achieving room temperature phosphorescence and radioluminescence.
Focused electron beam induced etching (FEBIE) of Nb films produced a maximum etching yield of 3 Nb atoms/e − while varying beam energy, beam current, dwell time, and XeF 2 precursor working pressure. An optimized etch resolution of 17 nm was achieved.
We present a double multilayer monochromator (DMM) design which has been realized for the BAMline(BESSY-II light source, Germany) as well as in an updated version for the TopoTomo beamline (ANKA light source. Germany)[1-4]. The latter contains two pairs of multilayer stripes in order to avoid absorption edges of the coating material. For both DMMs, the second multilayer offers a meridional bending option for beam compression to increase the available photon flux density. Each multilayer mirror is equipped with a vertical stage for height adjustments allowing for compensation of varying incoming beam heights and giving a certain flexibility choosing the offset. The second multilayer can be moved in the beam direction in order to cover the full energy range available. Furthermore, a white beam option is available.
The behavior of a 50 nm Cu-Ni alloy film on Si in a process of reactive solid-state dewetting is presented. The films were annealed at a range of temperatures (300-700 deg. C) in 1%H{sub 2} 99%N{sub 2} reducing atmosphere. The resulting alloy and silicide particles formed by film dewetting and film reaction with the substrate were distinguished by selective wet etching and examined by scanning electron microscopy and spectroscopy. After potassium hydroxide etch, regions that etch slower than silicon substrate have distribution statistics similar to the alloy and silicide particles prior to their removal, indicating strong coupling between mass transport across the interface and along the surface.
For the new ITER-like wall at JET, two new infrared diagnostics (KL9B, KL3B) have been installed. These diagnostics can operate between 3.5 and 5 {mu}m and up to sampling frequencies of {approx}20 kHz. KL9B and KL3B image the horizontal and vertical tiles of the divertor. The divertor tiles are tungsten coated carbon fiber composite except the central tile which is bulk tungsten and consists of lamella segments. The thermal emission between lamellae affects the surface temperature measurement and therefore KL9A has been upgraded to achieve a higher spatial resolution (by a factor of 2). A technical description of KL9A, KL9B, and KL3B and cross correlation with a near infrared camera and a two-color pyrometer is presented.
When imaging soft tissues with hard X-rays, phase contrast is often preferred over conventional attenuation contrast due its superior sensitivity. However, it is unclear which of the numerous phase tomography methods yields the optimized results at given experimental conditions. Therefore, we quantitatively compared the three phase tomography methods implemented at the beamline ID19 of the European Synchrotron Radiation Facility: X-ray grating interferometry (XGI), and propagation-based phase tomography, i.e., single-distance phase retrieval (SDPR) and holotomography (HT), using cancerous tissue from a mouse model and an entire heart of a rat. We show that for both specimens, the spatial resolution derived from the characteristic morphological features is about a factor of two better for HT and SDPR compared to XGI, whereas the XGI data generally exhibit much better contrast-to-noise ratios for the anatomical features. Moreover, XGI excels in fidelity of the density measurements, and is also more robust against low-frequency artifacts than HT, but it might suffer from phase-wrapping artifacts. Thus, we can regard the three phase tomography methods discussed as complementary. The application will decide which spatial and density resolutions are desired, for the imaging task and dose requirements, and, in addition, the applicant must choose between the complexity of the experimental setup and the one of data processing.
We report on the implementation and characterization of grating interferometry operating at an x-ray energy of 183 keV. With the possibility to use this technique at high x-ray energies, bigger specimens could be studied in a quantitative way. Also, imaging strongly absorbing specimens will benefit from the advantages of the phase and dark-field signals provided by grating interferometry. However, especially at these high photon energies the performance of the absorption grating becomes a key point on the quality of the system, because the grating lines need to keep their small width of a couple of micrometers and exhibit a greater height of hundreds of micrometers. The performance of high aspect ratio absorption gratings fabricated with different techniques is discussed. Further, a dark-field image of an alkaline multicell battery highlights the potential of high energy x-ray grating based imaging.
Grating-based X-ray computed tomography allows for simultaneous and nondestructive determination of the full X-ray complex index of refraction and the scattering coefficient distribution inside an object in three dimensions. Its multi-contrast capabilities combined with a high resolution of a few micrometers make it a suitable tool for assessing multiple phases inside porous and composite materials such as concrete. Here, we present quantitative results of a proof-of-principle experiment performed on a concrete sample. Thanks to the complementarity of the contrast channels, more concrete phases could be distinguished than in conventional attenuation-based imaging. The phase-contrast reconstruction shows high contrast between the hardened cement paste and the aggregates and thus allows easy 3D segmentation. Thanks to the dark-field image, micro-cracks inside the coarse aggregates are visible. We believe that these results are extremely interesting in the field of porous and composite materials studies because of unique information provided by grating interferometry in a non-destructive way.
X-ray mirrors are needed for beam shaping and monochromatization at advanced research light sources, for instance, free-electron lasers and synchrotron sources. Such mirrors consist of a substrate and a coating. The shape accuracy of the substrate and the layer precision of the coating are the crucial parameters that determine the beam properties required for various applications. In principal, the selection of the layer materials determines the mirror reflectivity. A single layer mirror offers high reflectivity in the range of total external reflection, whereas the reflectivity is reduced considerably above the critical angle. A periodic multilayer can enhance the reflectivity at higher angles due to Bragg reflection. Here, the selection of a suitable combination of layer materials is essential to achieve a high flux at distinct photon energies, which is often required for applications such as microtomography, diffraction, or protein crystallography. This contribution presents the current development of a Ru/C multilayer mirror prepared by magnetron sputtering with a sputtering facility that was designed in-house at the Helmholtz-Zentrum Geesthacht. The deposition conditions were optimized in order to achieve ultra-high precision and high flux in future mirrors. Input for the improved deposition parameters came from investigations by transmission electron microscopy. The X-ray optical properties were investigated by means of X-ray reflectometry using Cu- and Mo-radiation. The change of the multilayer d-spacing over the mirror dimensions and the variation of the Bragg angles were determined. The results demonstrate the ability to precisely control the variation in thickness over the whole mirror length of 500 mm thus achieving picometer-precision in the meter-range.
The original monochromator design we present consists in a high-vacuum vessel comprising three monochromators mounted side-by-side: a Lauë/Lauë, a Bragg/Bragg, and a double-multilayer monochromator. The selection of one monochromator type is done remotely by sliding laterally the crystal support in the monochromator vessel. In this way, exotic combinations such as Lauë/Bragg are also possible. Installation and commissioning of the new monochromator at ESRF beamline ID19 was carried out 2013-2014 (the multilayers not being installed yet). Beamline ID19 offers not only superb beam characteristics for phase-contrast imaging with a high level of sensitivity but also compared to other synchrotron X-ray imaging facilities a large beam of currently up to 7 cm × 1.3 cm. A wide energy range can be accessed in a fixed-exit mode (depending on the optics chosen the accessible energy range is between 10 keV and 200 keV). A beryllium exit window (10 cm × 10 cm active opening) completes the monochromator assembly.
Multilayer mirrors present an attractive alternative for reflective hard X-ray monochromators due to their increased bandwidth compared with crystal-based systems. An issue remains the strong modulations in the reflected beam profile, i.e. an irregular stripe pattern. This is a major problem for micro-imaging applications, where multilayer-based monochromators are frequently employed to deliver higher photon flux density. A subject of particular interest is how to overcome beam profile modifications, namely the stripe patterns, induced by the reflection on a multilayer. For multilayer coatings in general it is known that the substrate and its surface quality significantly influence the performance of such kind of mirrors as the coating reproduces to a certain degree roughness and shape of the substrate. Our studies have shown that modified coatings can significantly change the impact of the multilayer reflection on the beam profile. We will present recent results as well as a critical review.