Spatially Resolved Dynamics of Cobalt Color Centers in ZnO Nanowires.

The dynamics of color centers, being a promising quantum technology, is strongly dependent on the local environment. A synergistic approach of X-ray fluorescence analysis and X-ray excited optical luminescence (XEOL) using a hard X-ray nanoprobe is applied. The simultaneous acquisition provides insights into compositional and functional variations at the nanoscale demonstrating the extraordinary capabilities of these combined techniques. The findings on cobalt doped zinc oxide nanowires show an anticorrelation between the band edge emission of the zinc oxide host and the intra-3d cobalt luminescence, indicating two competing recombination paths. Moreover, time-resolved XEOL measurements reveal two exponential decays of the cobalt luminescence. The fast and newly observed one can be attributed to a recombination cascade within the cobalt atom, resulting from direct excitation. Thus, this opens a new fast timescale for potential devices based on cobalt color centers in ZnO nanowires in photonic circuits.

Spatially and Time-Resolved Carrier Dynamics in Core-Shell InGaN/GaN Multiple-Quantum Wells on GaN Wire.

Time-resolved cathodoluminescence is a key tool with high temporal and spatial resolution. However, optical spectroscopic information can be also extracted using synchrotron pulses in a hard X-ray nanoprobe, exploiting a phenomenon called X-ray excited optical luminescence. Here, with 20 ps time resolution and 80 nm lateral resolution, we applied this time-resolved X-ray microscopy technique to individual core-shell InGaN/GaN multiple quantum well heterostructures deposited on GaN wires. Our findings suggest that the m-plane related multiple quantum well states govern the carrier dynamics. Likewise, our observations support not only the influence of In incorporation in the recombination rates, but also carrier localization phenomena at the hexagon wire apex. In addition, our experiment calls for further investigations of the spatiotemporal domain on the underlying mechanisms of optoelectronic nanodevices. Its great potential becomes more valuable when time-resolved X-ray excited optical luminescence microscopy is used in operando with other methods, such as X-ray absorption spectroscopy.

In-Operando Nanoscale X-ray Analysis Revealing the Local Electrical Properties of Rubidium-Enriched Grain Boundaries in Cu(In,Ga)Se2 Solar Cells.

Chalcogenide Cu(In,Ga)Se2 solar cells yield one of the highest efficiencies among all thin-film photovoltaics. However, the variability of the absorber compositions and incorporated alkali elements strongly affect the conversion efficiency. Thus, effective strategies for spatially resolved tracking of the alkali concentration and composition during operation are needed to alleviate this limitation. Here, using a hard X-ray nanoprobe, we apply a synergistic approach of X-ray fluorescence analysis and X-ray beam-induced current techniques under operando conditions. The simultaneous monitoring of both compositional and functional properties in complete solar cells illustrates the exceptional capabilities of this combination of techniques in top-view geometry, where high spatial resolution resulted even underneath the electrical contacts. Our observations reveal Rb agglomerations in selected areas and compositional variations between different grains and their boundaries. The concurrent detection of the functionality exhibits negligible effects on the collection efficiency for Rb-enriched grain boundaries in comparison to their neighboring grains, which indicates the passivation of detrimental defects.

Hot electrons in a nanowire hard X-ray detector.

Nanowire chip-based electrical and optical devices such as biochemical sensors, physical detectors, or light emitters combine outstanding functionality with a small footprint, reducing expensive material and energy consumption. The core functionality of many nanowire-based devices is embedded in their p-n junctions. To fully unleash their potential, such nanowire-based devices require - besides a high performance - stability and reliability. Here, we report on an axial p-n junction GaAs nanowire X-ray detector that enables ultra-high spatial resolution (~200 nm) compared to micron scale conventional ones. In-operando X-ray analytical techniques based on a focused synchrotron X-ray nanobeam allow probing the internal electrical field and observing hot electron effects at the nanoscale. Finally, we study device stability and find a selective hot electron induced oxidization in the n-doped segment of the p-n junction. Our findings demonstrate capabilities and limitations of p-n junction nanowires, providing insight for further improvement and eventual integration into on-chip devices.

A helium mini-cryostat for the nanoprobe beamline ID16B at ESRF: characteristics and performance.

A helium mini-cryostat has been developed for the hard X-ray nanoprobe ID16B of the European Synchrotron to collect X-ray excited optical luminescence and X-ray fluorescence at low temperature (<10 K). The mini-cryostat has been specifically designed to fit within the strong space restrictions and high-demanding mechanical constraints imposed by the beamline to provide vibration-free operation and maximal thermal stability. This paper reports the detailed design, architecture and technical requirements of the mini-cryostat, and presents the first experimental data measured using the cryogenic equipment. The resulting cryo-system features ultimate thermal stability, fast cool-down and ultra-low vibrations. The simultaneous X-ray fluorescence and X-ray excited optical luminescence data acquired from bulk GaN and core/shell InGaN/GaN multi-quantum wells validated the excellent performance of the cryostat with ultimate resolution, stability and sensitivity.

Elemental Distribution and Structural Characterization of GaN/InGaN Core-Shell Single Nanowires by Hard X-ray Synchrotron Nanoprobes.

Improvements in the spatial resolution of synchrotron-based X-ray probes have reached the nano-scale and they, nowadays, constitute a powerful platform for the study of semiconductor nanostructures and nanodevices that provides high sensitivity without destroying the material. Three complementary hard X-ray synchrotron techniques at the nanoscale have been applied to the study of individual nanowires (NWs) containing non-polar GaN/InGaN multi-quantum-wells. The trace elemental sensitivity of X-ray fluorescence allows one to determine the In concentration of the quantum wells and their inhomogeneities along the NW. It is also possible to rule out any contamination from the gold nanoparticle catalyst employed during the NW growth. X-ray diffraction and X-ray absorption near edge-structure probe long- and short-range order, respectively, and lead us to the conclusion that while the GaN core and barriers are fully relaxed, there is an induced strain in InGaN layers corresponding to a perfect lattice matching with the GaN core. The photoluminescence spectrum of non-polar InGaN quntum wells is affected by strain and the inhomogeneous alloy distribution but still exhibits a reasonable 20% relative internal quantum efficiency.

In operando x-ray imaging of nanoscale devices: Composition, valence, and internal electrical fields.

We introduce a method for directly imaging depletion layers in operando with elemental specificity and chemical speciation at sub-100 nm spatial resolution applicable to today's three-dimensional electronic architectures. These typically contain complex, multicomponent designs consisting of epitaxial heterostructures, buried domains, or nanostructures with different shapes and sizes. Although the variety of devices is immense, they commonly rely on carrier separation in a built-in potential induced by composition or strain gradients. To image these, we scanned a focused synchrotron x-ray nanobeam over a single semiconductor nanowire heterostructure and simultaneously measured the current through the device and the emitted characteristic x-rays as a function of the incoming hard x-ray energy. With these results, it is possible to identify the compositional and molecular structure as well as localize the electrical fields present under typical working conditions. This information allows us to draw an energy band diagram consistent with the elemental distribution and a high-resolution chemical speciation map.

Synergistic Toxicity of Copper and Gold Compounds in Cupriavidus metallidurans.

The bacterium Cupriavidus metallidurans can reduce toxic gold(I/III) complexes and biomineralize them into metallic gold (Au) nanoparticles, thereby mediating the (trans)formation of Au nuggets. In Au-rich soils, most transition metals do not interfere with the resistance of this bacterium to toxic mobile Au complexes and can be removed from the cell by plasmid-encoded metal efflux systems. Copper is a noticeable exception: the presence of Au complexes and Cu ions results in synergistic toxicity, which is accompanied by an increased cytoplasmic Cu content and formation of Au nanoparticles in the periplasm. The periplasmic Cu-oxidase CopA was not essential for formation of the periplasmic Au nanoparticles. As shown with the purified and reconstituted Cu efflux system CupA, Au complexes block Cu-dependent release of phosphate from ATP by CupA, indicating inhibition of Cu transport. Moreover, Cu resistance of Au-inhibited cells was similar to that of mutants carrying deletions in the genes for the Cu-exporting PIB1-type ATPases. Consequently, Au complexes inhibit export of cytoplasmic Cu ions, leading to an increased cellular Cu content and decreased Cu and Au resistance. Uncovering the biochemical mechanisms of synergistic Au and Cu toxicity in C. metallidurans explains the issues this bacterium has to face in auriferous environments, where it is an important contributor to the environmental Au cycle.IMPORTANCEC. metallidurans lives in metal-rich environments, including auriferous soils that contain a mixture of toxic transition metal cations. We demonstrate here that copper ions and gold complexes exert synergistic toxicity because gold ions inhibit the copper-exporting P-type ATPase CupA, which is central to copper resistance in this bacterium. Such a situation should occur in soils overlying Au deposits, in which Cu/Au ratios usually are ≫1. Appreciating how C. metallidurans solves the problem of living in environments that contain both Au and Cu is a prerequisite to understand the molecular mechanisms underlying gold cycling in the environment, and the significance and opportunities of microbiota for specific targeting to Au in mineral exploration and ore processing.

Silane-Induced N-Polarity in Wires Probed by a Synchrotron Nanobeam.

Noncentrosymmetric one-dimensional structures are key driving forces behind advanced nanodevices. Owing to the critical role of silane injection in creating nanosized architectures, it has become a challenge to investigate the induced local lattice polarity in single GaN wires. Thus, if axial and radial structures are well-grown by a silane-mediated approach, an ideal model to study their polar orientations is formed. By combining synchrotron X-ray fluorescence and X-ray excited optical luminescence, we show here experimental evidence of the role of silane to promote the N-polarity, light emission, and elemental incorporation within single wires. In addition, our experiment demonstrates the ability to spatially examine carrier diffusion phenomena without electrical contacts, opening new avenues for further studies with simultaneous optical and elemental sensitivity at the nanoscale.

Direct-Write X-ray Nanopatterning: A Proof of Concept Josephson Device on Bi2Sr2CaCu2O8+δ Superconducting Oxide.

We describe the first use of a novel photoresist-free X-ray nanopatterning technique to fabricate an electronic device. We have produced a proof-of-concept device consisting of a few Josephson junctions by irradiating microcrystals of the Bi2Sr2CaCu2O8+δ (Bi-2212) superconducting oxide with a 17.6 keV synchrotron nanobeam. Fully functional devices have been obtained by locally turning the material into a nonsuperconducting state by means of hard X-ray exposure. Nano-XRD patterns reveal that the crystallinity is substantially preserved in the irradiated areas that there is no evidence of macroscopic crystal disruption. Indications are that O ions have been removed from the crystals, which could make this technique interesting also for other oxide materials. Direct-write X-ray nanopatterning represents a promising fabrication method exploiting material/material rather than vacuum/material interfaces, with the potential for nanometric resolution, improved mechanical stability, enhanced depth of patterning, and absence of chemical contamination with respect to traditional lithographic techniques.

ID16B: a hard X-ray nanoprobe beamline at the ESRF for nano-analysis.

Within the framework of the ESRF Phase I Upgrade Programme, a new state-of-the-art synchrotron beamline ID16B has been recently developed for hard X-ray nano-analysis. The construction of ID16B was driven by research areas with major scientific and societal impact such as nanotechnology, earth and environmental sciences, and bio-medical research. Based on a canted undulator source, this long beamline provides hard X-ray nanobeams optimized mainly for spectroscopic applications, including the combination of X-ray fluorescence, X-ray diffraction, X-ray excited optical luminescence, X-ray absorption spectroscopy and 2D/3D X-ray imaging techniques. Its end-station re-uses part of the apparatus of the earlier ID22 beamline, while improving and enlarging the spectroscopic capabilities: for example, the experimental arrangement offers improved lateral spatial resolution (∼50 nm), a larger and more flexible capability for in situ experiments, and monochromatic nanobeams tunable over a wider energy range which now includes the hard X-ray regime (5-70 keV). This paper describes the characteristics of this new facility, short-term technical developments and the first scientific results.

Analysis of platinum and trace metals in treated glioma rat cells by X-ray fluorescence emission.

So far, reports in the literature indicate a superior effectiveness of anticancer treatments using drug liposome-encapsulated. In this work, the influence of cisplatin associated with lipid vesicles (liposomes) is studied. Possible induced changes in the elemental composition, distribution, and concentration inside F98 glioma cells are investigated by synchrotron X-ray fluorescence (SXRF) and particle-induced X-ray emission (PIXE), combined with backscattering spectrometry (BS). SXRF at nanometer spatial resolution provides information on the two-dimension variation of elements inside the cells, while PIXE and BS allow the determination of the elemental concentration at µg g(-1) level. In comparison with dead cells, the elemental analysis shows that both platinum and zinc contents decrease in surviving samples. Moreover, higher levels of calcium and lower levels of potassium are revealed in dead cells, especially in those treated with liposomal cisplatin. These findings would mean that liposome-treated cells died mainly by apoptosis. Although further analyses are still necessary, the results presented in this work suggest that the lipid vesicles could provide, thus, a methodology for an effective platinum administration.

Nanoscopic X-ray fluorescence imaging of meteoritic particles and diamond inclusions.

The new ESRF ID16B-NA Nanoanalysis beamline has been applied for the first time for XRF imaging with a resolution level down to a few tens of nanometers on rare geological materials: meteoritic fragments from achondrite NWA 6693 and diamond inclusions. The instrument proved to be an extremely valuable tool for mapping samples containing submicrometer heterogeneities. It was discovered that the track of bubblelike inclusions in NWA 6693 consists mainly of Cr-rich phases. Some inclusions containing Ni and Ca were also detected. In diamond SL05, originating from the Juina region in Brazil, multiple inclusions were analyzed with dimensions smaller than 1 µm. Raman spectrometry measurements indicated the presence of a ringwoodite inclusion in this diamond; the detection of several iron-rich inclusions justifies further investigation of this material.

Crossed Ga2O3/SnO2 multiwire architecture: a local structure study with nanometer resolution.

Crossed nanowire structures are the basis for high-density integration of a variety of nanodevices. Owing to the critical role of nanowires intersections in creating hybrid architectures, it has become a challenge to investigate the local structure in crossing points in metal oxide nanowires. Thus, if intentionally grown crossed nanowires are well-patterned, an ideal model to study the junction is formed. By combining electron and synchrotron beam nanoprobes, we show here experimental evidence of the role of impurities in the coupling formation, structural modifications, and atomic site configuration based on crossed Ga2O3/SnO2 nanowires. Our experiment opens new avenues for further local structure studies with both nanometer resolution and elemental sensitivity.

Exploring single semiconductor nanowires with a multimodal hard X-ray nanoprobe.

Semiconductor nanowires offer new opportunities for optoelectronic and spintronic nanodevices. However, their full potential is ultimately dictated by our ability to control multiple property-function relationships taking place at the nanoscale in the spatial and time domains. Only a combination of high-resolution analytical techniques can provide a comprehensive understanding of their complex functionalities. Here we describe how a multimodal hard X-ray nanoprobe addresses fundamental questions in nanowire research. Selected topics ranging from cluster formation, dopant segregation, and phase separations to quantum confinement effects are investigated with sub-100 nm spatial resolution and sub-50 ps temporal resolution. This approach opens new avenues for structural, composition and optical studies with broad applicability in materials science.

Doping change in the Bi-2212 superconductor directly induced by a hard X-ray nanobeam.

We describe the controlled use of a 17 keV X-ray synchrotron nanobeam to progressively change the oxygen doping level in Bi-2212 superconducting whisker-like single crystals. Our data combine structural and electrical information collected on the same crystals, showing a maximum change in the critical temperature Tc of 1.3 K and a maximum elongation of ∼1 Šin the c-axis length, compared to the as-grown conditions. Simulations of our experimental conditions by means of a finite element model exclude local heating induced by the X-ray nanobeam as a possible cause for the change in the doping level and suggest an important role of secondary electrons. These findings support the possible use of hard X-rays as a novel direct-writing, photoresist-free lithographic process for the fabrication of superconducting devices, with potential nanometric resolution and 3D capability.

Probing quantum confinement within single core-multishell nanowires.

Theoretically core-multishell nanowires under a cross-section of hexagonal geometry should exhibit peculiar confinement effects. Using a hard X-ray nanobeam, here we show experimental evidence for carrier localization phenomena at the hexagon corners by combining synchrotron excited optical luminescence with simultaneous X-ray fluorescence spectroscopy. Applied to single coaxial n-GaN/InGaN multiquantum-well/p-GaN nanowires, our experiment narrows the gap between optical microscopy and high-resolution X-ray imaging and calls for further studies on the underlying mechanisms of optoelectronic nanodevices.

Synchrotron microanalysis techniques applied to potential photovoltaic materials.

X-ray synchrotron radiation techniques are used to characterize photovoltaic-related semiconductors. Micro-X-ray-fluorescence and X-ray beam induced current mapping of multicrystalline silicon photovoltaic cells show metallic impurities accumulating at the interface of crystallographic defects, and current variations over the cell that are attributed to bulk defects and structural variation of the silicon. Similarly, studies on a single-crystal GaAs using X-ray fluorescence and X-ray excited optical luminescence show an inhomogeneous As distribution correlated with the photoluminescence signal, with higher As concentration regions having stronger photoluminescence signal. Both examples show how the combination of synchrotron microanalysis techniques can contribute to a better understanding of the optical properties of photovoltaic materials.

Status of the hard X-ray microprobe beamline ID22 of the European Synchrotron Radiation Facility.

The ESRF synchrotron beamline ID22, dedicated to hard X-ray microanalysis and consisting of the combination of X-ray fluorescence, X-ray absorption spectroscopy, diffraction and 2D/3D X-ray imaging techniques, is one of the most versatile instruments in hard X-ray microscopy science. This paper describes the present beamline characteristics, recent technical developments, as well as a few scientific examples from recent years of the beamline operation. The upgrade plans to adapt the beamline to the growing needs of the user community are briefly discussed.

µ-EXAFS, µ-XRF, and µ-PL characterization of a multi-quantum-well electroabsorption modulated laser realized via selective area growth.

In the past few years, strong efforts have been devoted to improving the frequency of optical-fiber communications. In particular, the use of a special kind of integrated optoelectronic device called an electroabsorption modulated laser (EML) allows communication at 10 Gb s(-1) or higher over long propagation spans (up to 80 km). Such devices are realized using the selective area growth (SAG) technique and are based on a multiple quantum well (MQW) distributed-feedback laser (DFB) monolithically integrated with a MQW electroabsorption modulator (EAM). Since the variation in the chemical composition between these two structures takes place on the micrometer scale, in order to study the spatial variation of the relevant parameters of the MQW EML structures, the X-ray microbeam available at the ESRF ID22 beamline is used. The effectiveness of the SAG technique in modulating the chemical composition of the quaternary alloy is proven by a micrometer-resolved X-ray fluorescence (µ-XRF) map. Here, reported micrometer-resolved extended X-ray absorption fine structure (µ-EXAFS) spectra represent the state of the art of µ-EXAFS achievable at third-generation synchrotron radiation sources. The results are in qualitative agreement with X-ray diffraction (XRD) and micrometer-resolved photoluminescence (µ-PL) data, but a technical improvement is still crucial in order to make µ-EXAFS really quantitative on such complex heterostructures.