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High-resolution imaging of Cu/low-k on-chip interconnect stacks in advanced microelectronic products is demonstrated using full-field transmission X-ray microscopy (TXM). The comparison of two lens-based laboratory X-ray microscopes that are operated at two different photon energies, 8.0 keV and 9.2 keV, shows a contrast enhancement for imaging of copper nanostructures embedded in insulating organosilicate glass of a factor of 5 if 9.2 keV photons are used. Photons with this energy (Ga-Kα radiation) are generated from a Ga-containing target of a laboratory X-ray source applying the liquid-metal-jet technology. The 5 times higher contrast compared to the use of Cu-Kα radiation (8.0 keV photon energy) from a rotating anode X-ray source is caused by the fact that the energy of the Ga-Kα emission line is slightly higher than that of the Cu-K absorption edge (9.0 keV photon energy). The use of Ga-Kα radiation is of particular advantage for imaging of copper interconnects with dimensions from several 100 nm down to several 10 nm in a Cu/SiO 2 or Cu/low-k backend-of-line stack. Physical failure analysis and reliability engineering in the semiconductor industry will benefit from high-contrast X-ray images of sub-μm copper structures in microchips.

High-resolution imaging of buried metal interconnect structures in advanced microelectronic products with full-field X-ray microscopy is demonstrated in the hard X-ray regime, i.e., at photon energies > 10 keV. The combination of two multilayer optics-a side-by-side Montel (or nested Kirkpatrick-Baez) condenser optic and a high aspect-ratio multilayer Laue lens-results in an asymmetric optical path in the transmission X-ray microscope. This optics arrangement allows the imaging of 3D nanostructures in opaque objects at a photon energy of 24.2 keV (In-Kα X-ray line). Using a Siemens star test pattern with a minimal feature size of 150 nm, it was proven that features < 150 nm can be resolved. In-Kα radiation is generated from a Ga-In alloy target using a laboratory X-ray source that employs the liquid-metal-jet technology. Since the penetration depth of X-rays into the samples is significantly larger compared to 8 keV photons used in state-of-the-art laboratory X-ray microscopes (Cu-Kα radiation), 3D-nanopattered materials and structures can be imaged nondestructively in mm to cm thick samples. This means that destructive de-processing, thinning or cross-sectioning of the samples are not needed for the visualization of interconnect structures in microelectronic products manufactured using advanced packaging technologies. The application of laboratory transmission X-ray microscopy in the hard X-ray regime is demonstrated for Cu/Cu 6 Sn 5 /Cu microbump interconnects fabricated using solid-liquid interdiffusion (SLID) bonding.

We used high-throughput sequencing and multivariate analyses to describe soil microbial community composition in two four-year field plant-soil feedback (PSF) experiments in Minnesota, USA and Jena, Germany. In descending order of variation explained, microbial community composition differed between the two study sites, among years, between bulk and rhizosphere soils, and among rhizosphere soils cultivated by different plant species. To try to identify soil organisms or communities that may cause PSF, we correlated plant growth responses with the microbial community composition associated with different plants. We found that plant biomass was correlated with values on two multivariate axes. These multivariate axes weighted dozens of soil organisms, suggesting that PSF was not caused by individual pathogens or symbionts but instead was caused by 'many weak' plant-microbe interactions. Taken together, the results suggest that PSFs result from complex interactions that occur within the context of a much larger soil microbial community whose composition is determined by factors associated with 'site' or year, such as soil pH, soil type, and weather. The results suggest that PSFs may be highly variable and difficult to reproduce because they result from complex interactions that occur in the context of a larger soil microbial community.

Plant productivity often increases with species richness, but the mechanisms explaining this diversity-productivity relationship are not fully understood. We tested if plant-soil feedbacks (PSF) can help to explain how biomass production changes with species richness. Using a greenhouse experiment, we measured all 240 possible PSFs for 16 plant species. At the same time, 49 plant communities with diversities ranging from one to 16 species were grown in replicated pots. A suite of plant community growth models, parameterized with (PSF) or without PSF (Null) effects, was used to predict plant growth observed in the communities. Selection effects and complementarity effects in modeled and observed data were separated. Plants created soils that increased or decreased subsequent plant growth by 25% ± 10%, but because PSFs were negative for C 3 and C 4 grasses, neutral for forbs, and positive for legumes, the net effect of all PSFs was a 2% ± 17% decrease in plant growth. Experimental plant communities with 16 species produced 37% more biomass than monocultures due to complementarity. Null models incorrectly predicted that 16-species communities would overyield due to selection effects. Adding PSF effects to Null models decreased selection effects, increased complementarity effects, and improved correlations between observed and predicted community biomass. PSF models predicted 26% of overyielding caused by complementarity observed in experimental communities. Relative to Null models, PSF models improved the predictions of the magnitude and mechanism of the diversity-productivity relationship. Results provide clear support for PSFs as one of several mechanisms that determine diversity-productivity relationships and help close the gap in understanding how biodiversity enhances ecosystem services such as biomass production., (© 2022 The Ecological Society of America.)

Plant-soil feedback (PSF) has gained attention as a mechanism promoting plant growth and coexistence. However, most PSF research has measured monoculture growth in greenhouse conditions. Translating PSFs into effects on plant growth in field communities remains an important frontier for PSF research. Using a 4-year, factorial field experiment in Jena, Germany, we measured the growth of nine grassland species on soils conditioned by each of the target species (i.e., 72 PSFs). Plant community models were parameterized with or without these PSF effects, and model predictions were compared to plant biomass production in diversity-productivity experiments. Plants created soils that changed subsequent plant biomass by 40%. However, because they were both positive and negative, the average PSF effect was 14% less growth on "home" than on "away" soils. Nine-species plant communities produced 29 to 37% more biomass for polycultures than for monocultures due primarily to selection effects. With or without PSF, plant community models predicted 28%-29% more biomass for polycultures than for monocultures, again due primarily to selection effects. Synthesis : Despite causing 40% changes in plant biomass, PSFs had little effect on model predictions of plant community biomass across a range of species richness. While somewhat surprising, a lack of a PSF effect was appropriate in this site because species richness effects in this study were caused by selection effects and not complementarity effects (PSFs are a complementarity mechanism). Our plant community models helped us describe several reasons that even large PSF may not affect plant productivity. Notably, we found that dominant species demonstrated small PSF, suggesting there may be selective pressure for plants to create neutral PSF. Broadly, testing PSFs in plant communities in field conditions provided a more realistic understanding of how PSFs affect plant growth in communities in the context of other species traits., Competing Interests: None declared., (© 2021 The Authors. Ecology and Evolution published by John Wiley & Sons Ltd.)

Species-rich plant communities can produce twice as much aboveground biomass as monocultures, but the mechanisms remain unresolved. We tested whether plant-soil feedbacks (PSFs) can help explain these biodiversity-productivity relationships. Using a 16-species, factorial field experiment we found that plants created soils that changed subsequent plant growth by 27% and that this effect increased over time. When incorporated into simulation models, these PSFs improved predictions of plant community growth and explained 14% of overyielding. Here we show quantitative, field-based evidence that diversity maintains productivity by suppressing plant disease. Though this effect alone was modest, it helps constrain the role of factors, such as niche partitioning, that have been difficult to quantify. This improved understanding of biodiversity-productivity relationships has implications for agriculture, biofuel production and conservation.

We present results from the SPring-8 Angstrom Compact free electron LAser facility, where we used a high intensity (∼10^{20}  W/cm^{2}) x-ray pump x-ray probe scheme to observe changes in the ionic structure of silicon induced by x-ray heating of the electrons. By avoiding Laue spots in the scattering signal from a single crystalline sample, we observe a rapid rise in diffuse scattering and a transition to a disordered, liquidlike state with a structure significantly different from liquid silicon. The disordering occurs within 100 fs of irradiation, a timescale that agrees well with first principles simulations, and is faster than that predicted by purely inertial behavior, suggesting that both the phase change and disordered state reached are dominated by Coulomb forces. This method is capable of observing liquid scattering without masking signal from the ambient solid, allowing the liquid structure to be measured throughout and beyond the phase change.

Small angle x-ray scattering (SAXS) is a well established technique to detect nanometer scale structures in matter. In a typical setup, this diagnostic uses a detector with a direct line of sight to the scattering target. However, in the harsh environment of high intensity laser interaction, intense secondary radiation and high-energy particles are generated. Such a setup would therefore suffer a significant increase of noise due to this background, which could eventually prevent such measurements. In this paper, we present a novel tool consisting of a mosaic graphite crystal that works as a mirror for the SAXS signal and allows us to position the detector behind appropriate shielding. This paper studies the performance of this mirror both by experiment at the European XFEL (X-Ray Free-Electron Laser Facility) laboratory and by simulations.

The preparation of non-oxidized Ge quantum dot (QD) lattices embedded in Al 2 O 3 , Si 3 N 4 , SiC matrices by self-assembled growth was studied. The materials were produced by magnetron sputtering deposition, using different substrate temperatures. The deposition regimes leading to the self-assembled growth type and the formation of three-dimensionally ordered Ge QD lattices in different matrices were investigated and determined. The oxidation of the Ge QDs in different matrices was monitored and the best conditions for the production of non-oxidized Ge QDs were found. The optical properties of the Ge QD lattices in different matrices show a strong dependence on the Ge oxidation and the matrix type.

The realisation of photonic devices for different energy ranges demands materials with different bandgaps, sometimes even within the same device. The optimal solution in terms of integration, device performance and device economics would be a simple material system with widely tunable bandgap and compatible with the mainstream silicon technology. Here, we show that gallium arsenide nanowires grown epitaxially on silicon substrates exhibit a sizeable reduction of their bandgap by up to 40% when overgrown with lattice-mismatched indium gallium arsenide or indium aluminium arsenide shells. Specifically, we demonstrate that the gallium arsenide core sustains unusually large tensile strain with hydrostatic character and its magnitude can be engineered via the composition and the thickness of the shell. The resulted bandgap reduction renders gallium arsenide nanowires suitable for photonic devices across the near-infrared range, including telecom photonics at 1.3 and potentially 1.55 μm, with the additional possibility of monolithic integration in silicon-CMOS chips.

Gratings, one of the most important energy dispersive devices, are the fundamental building blocks for the majority of optical and optoelectronic systems. The grating period is the key parameter that limits the dispersion and resolution of the system. With the rapid development of large X-ray science facilities, gratings with periodicities below 50 nm are in urgent need for the development of ultrahigh-resolution X-ray spectroscopy. However, the wafer-scale fabrication of nanogratings through conventional patterning methods is difficult. Herein, we report a maskless and high-throughput method to generate wafer-scale, multilayer gratings with period in the sub-50 nm range. They are fabricated by a vacancy epitaxy process and coated with X-ray multilayers, which demonstrate extremely large angular dispersion at approximately 90 eV and 270 eV. The developed new method has great potential to produce ultrahigh line density multilayer gratings that can pave the way to cutting edge high-resolution spectroscopy and other X-ray applications.

Three-dimensional nanocomposite networks consisting of percolated Si nanowires in a SiO2 matrix, Si:SiO2, were studied. The structures were obtained by reactive ion beam sputter deposition of SiOx (x ≈ 0.6) thin films at 450 ∘C and subsequent crystallization using conventional oven, as well as millisecond line focus laser treatment. Rutherford backscattering spectrometry, Raman spectroscopy, X-ray diffraction, cross-sectional and energy-filtered transmission electron microscopy were applied for sample characterization. While oven treatment resulted in a mean Si wire diameter of 10 nm and a crystallinity of 72% within the Si volume, almost single-domain Si structures of 30 nm in diameter and almost free of amorphous Si were obtained by millisecond laser application. The structural differences are attributed to the different crystallization processes: conventional oven tempering proceeds via solid state and millisecond laser application via liquid phase crystallization of Si. The five orders of magnitude larger diffusion constant in the liquid phase is responsible for the three-times larger Si nanostructure diameter. In conclusion, laser treatment offers not only significantly shorter process times, but moreover, a superior structural order of nano-Si compared to conventional heating.

For Kupferschiefer mining established pyrometallurgical and acidic bioleaching methods face numerous problems. This is due to the finely grained and dispersed distribution of the copper minerals, the complex mineralogy, comparably low copper content, and the possibly high carbonate and organic content in this ore. Leaching at neutral pH seemed worth a try: At neutral pH the abundant carbonates do not need to be dissolved and therewith would not consume excessive amounts of provided acids. Certainly, copper solubility at neutral pH is reduced compared to an acidic environment; however, if copper complexing ligands would be supplied abundantly, copper contents in the mobile phase could easily reach the required economic level. We set up a model system to study the effect of parameters such as pH, microorganisms, microbial metabolites, and organic ligands on covellite leaching to get a better understanding of the processes in copper leaching at pH ≥ 6. With this model system we could show that glutamic acid and the microbial siderophore desferrioxamine B promote covellite dissolution. Both experimental and modeling data showed that pH is an important parameter in covellite dissolution. An increase of pH from 6 to 9 could elevate copper extraction in the presence of glutamic acid by a factor of five. These results have implications for both development of a biotechnological process regarding metal extraction from Kupferschiefer, and for the interaction of bacterial metabolites with the lithosphere and potential mobilization of heavy metals in alkaline environments., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

We report a simple one-pot method for the rapid preparation of sub-10 nm pure hexagonal (β-phase) NaYF 4 -based upconverting nanoparticles (UCNPs). Using Therminol ®  66 as a co-solvent, monodisperse UCNPs could be obtained in unusually short reaction times. By varying the reaction time and reaction temperature, it was possible to control precisely the particle size and crystalline phase of the UCNPs. The upconversion (UC) luminescence properties of the nanocrystals were tuned by varying the concentrations of the dopants (Nd 3+ and Yb 3+ sensitizer ions and Er 3+ activator ions). The size and phase-purity of the as-synthesized core and core-shell nanocrystals were assessed by using complementary transmission electron microscopy, dynamic light scattering, X-ray diffraction, and small-angle X-ray scattering studies. In-depth photophysical evaluation of the UCNPs was pursued by using steady-state and time-resolved luminescence spectroscopy. An enhancement in the UC intensity was observed if the nanocrystals, doped with optimized concentrations of lanthanide sensitizer/activator ions, were further coated with an inert/active shell. This was attributed to the suppression of surface-related luminescence quenching effects.

Plant soil feedbacks (PSFs) are thought to be important to plant growth and species coexistence, but most support for these hypotheses is derived from short-term greenhouse experiments. Here we use a seven-year, common garden experiment to measure PSFs for seven native and six nonnative species common to the western United States. We use these long-term, field-based estimates to test correlations between PSF and plant landscape abundance, species origin, functional type, and lifespan. To assess potential PSF mechanisms, we also measured soil microbial community composition, root biomass, nitrogen cycling, bulk density, penetration resistance, and shear strength. Plant abundance on the landscape and plant lifespan were positively correlated with PSFs, though this effect was due to the relationships for native plants. PSFs were correlated with indices of soil microbial community composition. Soil nutrient and physical traits and root biomass differed among species but were not correlated with PSF. While results must be taken with caution because only 13 species were examined, these species represent most of the dominant plant species in the system. Results suggest that native plant abundance is associated with the ability of long-lived plants to create positive plant-soil microbe interactions, while short-lived nonnative plants maintain dominance by avoiding soil-borne antagonists, increasing nitrogen cycling and dedicating resources to aboveground growth and reproduction rather than to belowground growth. Broadly, results suggest that PSFs are correlated with a suite of traits that determine plant abundance., (© 2017 by the Ecological Society of America.)

It has become clear that plants can create soils that affect subsequent plant growth. However, because plant-soil feedbacks (PSFs) are typically measured in monoculture experiments, it remains unclear to what extent PSFs affect plant growth in communities. Here we used data from a factorial PSF experiment to predict the biomass of 12 species grown in 162 plant community combinations. Five different plant growth models were parameterized with either monoculture biomass data (Null) or with PSF data (PSF) and model predictions were compared to plant growth observed in communities. For each of the five models, PSF model predictions were closer to observed species biomass in communities than Null model predictions. PSFs, which were associated with a 28% difference in plant biomass across soil types, explained 10% more variance than Null models. Results provided strong support for a small role for PSFs in predicting plant growth in communities and suggest several reasons that PSFs, as traditionally measured in monoculture experiments, may overestimate PSF effects in communities. First, monoculture data used in Null models inherently includes "self " PSF effects. Second, PSFs must be large relative to differences in intrinsic growth rates among species to change competitive outcomes. Third, PSFs must vary among species to change species relative abundances., (© 2016 by the Ecological Society of America.)

Semiconductor quantum dots and wires are important building blocks for future electronic and optoelectronic devices. The common way of producing semiconductor nanostructures is by molecular beam epitaxy (MBE). In this additive growth process atoms are deposited onto crystalline surfaces and self-assemble into 3D structures. Here we present a subtractive process, in which surface vacancies are created by ion impacts. On terraces of crystalline surfaces their nucleation forms depressions which coarsen and finally lead to a self-organized 3D morphology. It is shown that this kind of spontaneous pattern formation is inherent to the ion induced erosion process on crystalline surfaces and is analogous to 3D growth by MBE. However, novel facets are found due to slightly different energetics and kinetics of ad-atoms and surface vacancies, especially at Ehrlich-Schwoebel step-edge barriers. Depending on the crystal orientation, three-fold, four-fold, six-fold symmetry, as well as extremely regular periodic nanogrooves can be produced on different orientations of group IV (Si, Ge) and III-V (GaAs, InAs) semiconductors.

We report on the formation of Ge/Si quantum dots with core/shell structure that are arranged in a three-dimensional body centered tetragonal quantum dot lattice in an amorphous alumina matrix. The material is prepared by magnetron sputtering deposition of Al2O3/Ge/Si multilayer. The inversion of Ge and Si in the deposition sequence results in the formation of thin Si/Ge layers instead of the dots. Both materials show an atomically sharp interface between the Ge and Si parts of the dots and layers. They have an amorphous internal structure that can be crystallized by an annealing treatment. The light absorption properties of these complex materials are significantly different compared to films that form quantum dot lattices of the pure Ge, Si or a solid solution of GeSi. They show a strong narrow absorption peak that characterizes a type II confinement in accordance with theoretical predictions. The prepared materials are promising for application in quantum dot solar cells.

In this work, the influence of air pressure during the annealing of Ge quantum dot (QD) lattices embedded in an amorphous Al(2)O(3) matrix on the structural, morphological and compositional properties of the film is studied. The formation of a regularly ordered void lattice after performing a thermal annealing process is explored. Our results show that both the Ge desorption from the film and the regular ordering of the QDs are very sensitive to the annealing parameters. The conditions for the formation of a void lattice, a crystalline Ge QD lattice and a disordered QD lattice are presented. The observed effects are explained in terms of oxygen interaction with the Ge present in the film.

A pentathiophene-based swivel cruciform, which allows rotation between the cruciform arms, was synthesized. Homogeneous microcrystalline films were processed from solution, and field-effect transistors utilizing this dimer gave hole mobilities up to 0.012 cm2/V.s.

A detailed structural analysis of a Langmuir-Blodgett (LB) multilayer composed of a polyelectrolyte-amphiphile complex (PAC) is presented. The PAC is self-assembled from metal ions, ditopic bis-terpyridines, and amphiphiles. The vertical structure of the LB multilayer is investigated by X-ray reflectometry. The multilayer has a periodicity of 57 A, which corresponds to an architecture of flat lying metallo-supramolecular coordination polyelectrolyte (MEPE) rods and upright-standing amphiphiles (dihexadecyl phosphate, DHP). In-plane diffraction reveals hexagonal packing of the DHP molecules. Using extended X-ray absorption fine structure (EXAFS) experiments, we prove that the central metal ion is coordinated to the terpyridine moieties in a pseudo-octahedral coordination environment. The Fe-N bond distances are 1.82 and 2.0 A, respectively. Temperature resolved measurements indicate a reversible phase transition in a temperature range up to 55 degrees C. EXAFS measurements indicate a lengthening of the average Fe-N bond distance from 1.91 to 1.95 A. The widening of the coordination cage upon heating is expected to lower the ligand field stabilization, thus giving rise to spin transitions in these composite materials.

A basic understanding of the properties of thin polymer films is of fundamental importance for developing applications in nanotechnology. Results of energy and angle dispersive x-ray reflectivity measurements on polymer thin films as a function of temperature exhibit reversible negative thermal expansion below the glass transition temperature T(g). Above T(g), the thickness expansion becomes almost equal to the expected bulk volume expansion. These results could be explained on the basis of evolution of disorder with temperature at the interfaces, chain entanglement and associated entropy changes.

Multilayers of an Fe(II)-polyelectrolyte-amphiphile complex (Fe-PAC) were investigated simultaneously by energy-dispersive X-ray reflectivity and in-plane diffraction at the bending-magnet beamline at BESSY II. By recording spectra between room temperature and about 348 K with a time resolution of about 60 s, two phase transitions were identified and the respective activation energies were determined. Owing to a fixed geometrical set-up, an energy-dispersive experiment is suitable for measuring X-ray reflectivity and in-plane X-ray diffraction of thin organic films simultaneously. Installed at a bending magnet at BESSY II and using an energy range of 4 < E < 25 keV, both reflectivity and diffraction spectra can be collected within about 60 s. The performance is demonstrated by temperature- and time-resolved measurements of the phase transition behaviour of multilayers of an Fe-PAC deposited on a silicon support by means of the Langmuir-Blodgett (LB) technique. By measuring the X-ray reflectivity while increasing the temperature, it is shown that the original LB phase is not stable and transforms irreversibly into a liquid-crystalline (LC)-like phase at about 318 K. At the same temperature the in-plane diffraction signal vanishes reversibly, reflecting rotational disorder of the hexagonal arrangement of amphiphilic chains. Its activation energy is determined to be about 1.3 eV. At about 338 K a second irreversible phase transition occurs to another LC phase with smaller vertical layer spacing. This transition is reversible between 329 K and 338 K.