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Rare-earth elements are vital to advanced technological applications ranging from spintronic devices to quantum information science. Here, the authors formed charged rare-earth complexes on a material surface and demonstrated atomically precise control on their rotational dynamics.

Synchrotron X-ray Scanning Tunneling Microscopy (SX-STM) is a novel imaging technique capable of providing real space chemically specific mapping with a potential of reaching atomic resolution. Determination of chemical composition along with ultra-high resolution imaging by SX-STM can be realized through excitation of core electrons by incident X-rays when their energy is tuned to an absorption edge of a particular atom during raster scanning, as is done in the conventional STM experiments. In this work, we provide a brief summary and the current status of SX-STM and discuss its applications for material science. In particular, we discuss instrumentation challenges associated with the SX-STM technique and present early experiments on Cu doped ZrTe3 single crystals.

The nanoscale distribution of elements within fly ash and the aluminosilicate gel products of its alkaline activation (“fly ash geopolymers”) are analyzed by means of synchrotron X-ray fluorescence using a hard X-ray Nanoprobe instrument. The distribution of calcium within a hydroxide-activated (fly ash/KOH solution) geopolymer gel is seen to be highly heterogeneous, with these data providing for the first time direct evidence of the formation of discrete high-calcium particles within the binder structure of a geopolymer synthesized from a low-calcium (<2 wt % as oxides) fly ash. The silicate-activated (fly ash/potassium silicate solution) sample, by contrast, shows a much more homogeneous geopolymer gel binder structure surrounding the unreacted fly ash particles. This has important implications for the understanding of calcium chemistry within aluminosilicate geopolymer gel phases. Additionally, chromium and iron are seen to be very closely correlated within the structures of both fly ash and the geopolymer product and remain within the regions of the geopolymer which can be identified as unreacted fly ash particles. Given that the potential for chromium release has been one of the queries surrounding the widespread utilization of construction materials derived from fly ash, the observation that this element appears to be localized within the fly ash rather than dispersed throughout the gel binder indicates that it is unlikely to be released problematically into the environment. [ABSTRACT FROM AUTHOR]

Researchers at North Carolina State University have developed a stretchable strain sensor that can detect even minor changes in strain with a greater range of motion than previous technologies. The sensor consists of a silver nanowire network embedded in an elastic polymer, and it measures strain by measuring changes in electrical resistance. The researchers have demonstrated the sensor's utility in wearable devices for monitoring motion in physical therapy and in human-machine interface devices for controlling video games. The sensor can be easily incorporated into existing wearable materials and has potential for a range of additional applications. [Extracted from the article]

An ultra‐high‐vacuum compatible X‐ray chopper system has been designed, constructed and integrated into the XTIP beamline at the Advanced Photon Source at Argonne National Laboratory. The XTIP beamline can operate at soft X‐ray energies from 400 eV to 1900 eV while providing a focused beam down to about 10 µm × 10 µm into the synchrotron X‐ray scanning tunneling microscopy (SX‐STM) endstation instrument. The X‐ray chopper is a critical component for separating topographic information from chemical information in SX‐STM through phase‐sensitive current detection. Depending on the experimental needs, the modulation frequency can be controlled from 100 Hz to 10 kHz. In addition, the chopper system is fully bakeable and can achieve a base pressure of 10−10 mbar. Facilities for active water cooling have been designed, but passive cooling through copper braids has been shown to be sufficient at standard chopping frequencies. Using an Fe/Al2O3/CoAl(111) sample, the separation of the SX‐STM current into a chemical component and a stable feedback signal is demonstrated. [ABSTRACT FROM AUTHOR]

Lead halide perovskites have emerged as promising absorber materials over the last decade to increase the efficiency of photovoltaics beyond its current limits. However, to further optimize the performance of perovskites more detailed studies need to be performed, which allow for the correlation of film morphology and local electronic properties at the nanoscale. Here, we present a scanning tunneling microscopy (STM) approach to probe the effect of an applied electric field of a methylammonium formamidinium lead triiodide perovskite thin film on the film response by current–voltage spectroscopy, current imaging tunneling spectroscopy, differential conductance mapping, and x-ray absorption spectroscopy by means of synchrotron x-ray STM. We find a strong correlation between the measurement conditions and the obtained current–voltage characteristics when imaging under opposite bias polarities. In particular, we find similarities to already observed poling effects for lead halide perovskites, which result in either a positively or negatively charged interface due to ion and vacancy migration. Our results provide insight into the influence of measurement conditions such as bias polarity on the performance assessment of perovskite thin films by STM. [ABSTRACT FROM AUTHOR]

On page 2646 Volker Rose and co‐workers present a smart tip for synchrotron X‐ray scanning tunneling microscopy that is entirely coated by an insulating oxide, except at the tip apex. The tip is only sensitive to X‐ray‐excited tunnel currents and not to photoejected electrons caused by classical photo emission, which would degrade the spatial resolution. The bright light in the image, coming in from the right, that hits the tip apex schematically represents the synchrotron beam during an experiment. [ABSTRACT FROM AUTHOR]

Complexes containing rare-earth ions attract great attention for their technological applications ranging from spintronic devices to quantum information science. While charged rare-earth coordination complexes are ubiquitous in solution, they are challenging to form on materials surfaces that would allow investigations for potential solid-state applications. Here we report formation and atomically precise manipulation of rare-earth complexes on a gold surface. Although they are composed of multiple units held together by electrostatic interactions, the entire complex rotates as a single unit when electrical energy is supplied from a scanning tunneling microscope tip. Despite the hexagonal symmetry of the gold surface, a counterion at the side of the complex guides precise three-fold rotations and 100% control of their rotational directions is achieved using a negative electric field from the scanning probe tip. This work demonstrates that counterions can be used to control dynamics of rare-earth complexes on materials surfaces for quantum and nanomechanical applications. Rare-earth elements are vital to advanced technological applications ranging from spintronic devices to quantum information science. Here, the authors formed charged rare-earth complexes on a material surface and demonstrated atomically precise control on their rotational dynamics. [ABSTRACT FROM AUTHOR]

The effect of a local external electric field on the barrier potential of a tunneling gap is studied utilizing an emerging technique, synchrotron x-ray scanning tunneling microscopy. Here, we demonstrate that the shape of the potential barrier in the tunneling gap can be altered by a localized external electric field, generated by voltages placed on the metallic outer shield of a nanofabricated coaxial metal-insulator-metal tip, resulting in a controlled linear modulation of the tunneling current. Experiments at hard and soft x-ray synchrotron beamlines reveal that both the chemical contrast and magnetic contrast signals measured by the tip can be drastically enhanced, resulting in improved local detection of chemistry and magnetization at the surface. [ABSTRACT FROM AUTHOR]

Nanoparticle formation by dopant exsolution (migration) from bulk host lattices is a promising approach to generate highly stable nanoparticles with tunable size, shape, and distribution. We investigated Ni dopant migration from strontium titanate (STO) lattices, forming metallic Ni nanoparticles at STO surfaces. Ex situ scanning probe measurements confirmed the presence of nanoparticles at the H2 treated surface. In situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) revealed reduction from Ni2+ to Ni0 as Ni dopants migrated to the surface during heating treatments in H2. During Ni migration and reduction, the Sr and Ti chemical states were mostly unchanged, indicating the selective reduction of Ni during treatment. At the same time, we used in situ ambient pressure grazing incidence X-ray scattering (GIXS) to monitor the particle morphology. As Ni migrated to the surface, it nucleated and grew into compressed spheroidal nanoparticles partially embedded in the STO perovskite surface. These findings provide a detailed picture of the evolution of the nanoparticle surface and subsurface chemical state and morphology as the nanoparticles grow beyond the initial nucleation and growth stages. [ABSTRACT FROM AUTHOR]

X‐ray microscopy can provide unique chemical, electronic, and structural insights into perovskite materials and devices leveraging bright, tunable synchrotron X‐ray sources. Over the last decade, fundamental understanding of halide perovskites and their impressive performance in optoelectronic devices has been furthered by rigorous research regarding their structural and chemical properties. Herein, studies of perovskites are reviewed that have used X‐ray imaging, spectroscopy, and scattering microscopies that have proven valuable tools toward understanding the role of defects, impurities, and processing on perovskite material properties and device performance. Together these microscopic investigations have augmented the understanding of the internal workings of perovskites and have helped to steer the perovskite community toward promising directions. In many ways, X‐ray microscopy of perovskites is still in its infancy, which leaves many exciting paths unexplored including new ptychographic, multimodal, in situ, and operando experiments. To explore possibilities, pioneering X‐ray microscopy along these lines is briefly highlighted from other semiconductor systems including silicon, CdTe, GaAs, CuInxGa1−xSe2, and organic photovoltaics. An overview is provided on the progress made in utilizing X‐ray microscopy for perovskites and present opportunities and challenges for future work. [ABSTRACT FROM AUTHOR]

In recent years, there have been numerous efforts worldwide to develop the synchrotron X‐ray scanning tunneling microscopy (SX‐STM) technique. Here, the inauguration of XTIP, the world's first beamline fully dedicated to SX‐STM, is reported. The XTIP beamline is located at Sector 4 of the Advanced Photon Source at Argonne National Laboratory. It features an insertion device that can provide left‐ or right‐circular as well as horizontal‐ and vertical‐linear polarization. XTIP delivers monochromatic soft X‐rays of between 400 and 1900 eV focused into an environmental enclosure that houses the endstation instrument. This article discusses the beamline system design and its performance. [ABSTRACT FROM AUTHOR]

Since the X-ray signal was detected only when the probe was placed extremely close to the atom, X-ray excitation resonance tunneling is dominant, confirming the detection of atom localization in the tunneling region. As with the previous sample, STM imaging was performed and the synchrotron radiation energy was varied near the M SB 4,5 sb absorption edge of terbium under the same conditions and a single atom was detected. The research sample is a supramolecular assembly with a ring structure consisting of seven terpyridine-metal-terpyridine bridges, with six ruthenium atoms and one iron atom on the metal. [Extracted from the article]

We use a nanofabricated scanning tunneling microscope tip as a detector to investigate local X-ray induced tunneling and electron emission from a single cobalt nanocluster on a Au(111) surface. The tip-detector is positioned a few angstroms above the nanocluster, and ramping the incident X-ray energy across the Co photoabsorption K-edge enables the detection of element specific electrons. Atomic-scale spatial dependent changes in the X-ray absorption cross section are directly measured by taking the X-ray induced current as a function of X-ray energy. From the measured sample and tip currents, element specific X-ray induced current components can be separated and thereby the corresponding yields for the X-ray induced processes of the single cobalt nanocluster can be determined. The detection of element specific synchrotron X-ray induced electrons of a single nanocluster opens an avenue for materials characterization on a one particle at-a-time basis. [ABSTRACT FROM AUTHOR]

In situ and operando measurement techniques combined with nanoscale resolution have proven invaluable in multiple fields of study. We argue that evaluating device performance as well as material behavior by correlative X-ray microscopy with <100 nm resolution can radically change the approach for optimizing absorbers, interfaces and full devices in solar cell research. In this article, we thoroughly discuss the measurement technique of X-ray beam induced current and point out fundamental differences between measurements of wafer-based silicon and thin-film solar cells. Based on reports of the last years, we showcase the potential that X-ray microscopy measurements have in combination with in situ and operando approaches throughout the solar cell lifecycle: from the growth of individual layers to the performance under operating conditions and degradation mechanisms. Enabled by new developments in synchrotron beamlines, the combination of high spatial resolution with high brilliance and a safe working distance allows for the insertion of measurement equipment that can pave the way for a new class of experiments. Applied to photovoltaics research, we highlight today’s opportunities and challenges in the field of nanoscale X-ray microscopy, and give an outlook on future developments. [ABSTRACT FROM AUTHOR]

The study of a multilayered and multicomponent system by spatially resolved X-ray fluorescence microscopy poses unique challenges in achieving accurate quantification of elemental distributions. This is particularly true for the quantification of materials with high X-ray attenuation coefficients, depth-dependent composition variations and thickness variations. A widely applicable procedure for use after spectrum fitting and quantification is described. This procedure corrects the elemental distribution from the measured fluorescence signal, taking into account attenuation of the incident beam and generated fluorescence from multiple layers, and accounts for sample thickness variations. Deriving from Beer-Lambert's law, formulae are presented in a general integral form and numerically applicable framework. The procedure is applied using experimental data from a solar cell with a Cu(In,Ga)Se2 absorber layer, measured at two separate synchrotron beamlines with varied measurement geometries. This example shows the importance of these corrections in real material systems, which can change the interpretation of the measured distributions dramatically. [ABSTRACT FROM AUTHOR]

Objective The maturation of adult-born granule cells and their functional integration into the network is thought to play a key role in the proper functioning of the dentate gyrus. In temporal lobe epilepsy, adult-born granule cells in the dentate gyrus develop abnormally and possess a hilar basal dendrite (HBD). Although morphological studies have shown that these HBDs have synapses, little is known about the functional properties of these HBDs or the intrinsic and network properties of the granule cells that possess these aberrant dendrites. Methods We performed patch-clamp recordings of granule cells within the granule cell layer 'normotopic' from sham-control and status epilepticus (SE) animals. Normotopic granule cells from SE animals possessed an HBD (SE+HBD+ cells) or not (SE+HBD− cells). Apical and basal dendrites were stimulated using multiphoton uncaging of glutamate. Two-photon Ca2+ imaging was used to measure Ca2+ transients associated with back-propagating action potentials (bAPs). Results Near-synchronous synaptic input integrated linearly in apical dendrites from sham-control animals and was not significantly different in apical dendrites of SE+HBD− cells. The majority of HBDs integrated input linearly, similar to apical dendrites. However, 2 of 11 HBDs were capable of supralinear integration mediated by a dendritic spike. Furthermore, the bAP-evoked Ca2+ transients were relatively well maintained along HBDs, compared with apical dendrites. This further suggests an enhanced electrogenesis in HBDs. In addition, the output of granule cells from epileptic tissue was enhanced, with both SE+HBD− and SE+HBD+ cells displaying increased high-frequency (>100 Hz) burst-firing. Finally, both SE+HBD− and SE+HBD+ cells received recurrent excitatory input that was capable of generating APs, especially in the absence of feedback inhibition. Significance Taken together, these data suggest that the enhanced excitability of HBDs combined with the altered intrinsic and network properties of granule cells collude to promote excitability and synchrony in the epileptic dentate gyrus. [ABSTRACT FROM AUTHOR]

Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain. [ABSTRACT FROM AUTHOR]

Multi-technique characterisation of sodium carbonate-activated blast furnace slag binders was conducted in order to determine the influence of the carbonate groups on the structural and chemical evolution of these materials. At early age (<4 days) there is a preferential reaction of Ca with the CO from the activator, forming calcium carbonates and gaylussite, while the aluminosilicate component of the slag reacts separately with the sodium from the activator to form zeolite NaA. These phases do not give the high degree of cohesion necessary for development of high early mechanical strength, and the reaction is relatively gradual due to the slow dissolution of the slag under the moderate pH conditions introduced by the NaCO as activator. Once the CO is exhausted, the activation reaction proceeds in similar way to an NaOH-activated slag binder, forming the typical binder phases calcium aluminium silicate hydrate and hydrotalcite, along with Ca-heulandite as a further (Ca,Al)-rich product. This is consistent with the significant gain in compressive strength and reduced porosity observed after 3 days of curing. The high mechanical strength and reduced permeability developed in these materials beyond 4 days of curing elucidate that NaCO-activated slag can develop desirable properties for use as a building material, although the slow early strength development is likely to be an issue in some applications. These results suggest that the inclusion of additions which could control the preferential consumption of Ca by the CO might accelerate the reaction kinetics of NaCO-activated slag at early times of curing, enhancing the use of these materials in engineering applications. [ABSTRACT FROM AUTHOR]

The Advanced Photon Source is developing a suite of new X-ray beamlines to study materials and devices across many length scales and under real conditions. One of the flagship beamlines of the APS upgrade is the In Situ Nanoprobe (ISN) beamline, which will provide in situ and operando characterization of advanced energy materials and devices under varying temperatures, gas ambients, and applied fields, at previously unavailable spatial resolution and throughput. Examples of materials systems include inorganic and organic photovoltaic systems, advanced battery systems, fuel cell components, nanoelectronic devices, advanced building materials and other scientifically and technologically relevant systems. To characterize these systems at very high spatial resolution and trace sensitivity, the ISN will use both nanofocusing mirrors and diffractive optics to achieve spots sizes as small as 20 nm. Nanofocusing mirrors in Kirkpatrick-Baez geometry will provide several orders of magnitude increase in photon flux at a spatial resolution of 50 nm. Diffractive optics such as zone plates and/or multilayer Laue lenses will provide a highest spatial resolution of 20 nm. Coherent diffraction methods will be used to study even small specimen features with sub-10 nm relevant length scale. A high-throughput data acquisition system will be employed to significantly increase operations efficiency and usability of the instrument. The ISN will provide full spectroscopy capabilities to study the chemical state of most materials in the periodic table, and enable X-ray fluorescence tomography. In situ electrical characterization will enable operando studies of energy and electronic devices such as photovoltaic systems and batteries. We describe the optical concept for the ISN beamline, the technical design, and the approach for enabling a broad variety of in situ studies. We furthermore discuss the application of hard X-ray microscopy to study defects in multi-crystalline solar cells, one of the lines of inquiries for which the ISN is being developed. [ABSTRACT FROM AUTHOR]

The combination of the high spatial resolution of scanning tunneling microscopy with the chemical and magnetic contrast provided by synchrotron X-rays has the potential to allow a unique characterization of advanced functional materials. While the scanning probe provides the high spatial resolution, synchrotron X-rays that produce photo-excitations of core electrons add chemical and magnetic contrast. However, in order to realize the method's full potential it is essential to maintain tunneling conditions, even while high brilliance X-rays irradiate the sample surface. Different from conventional scanning tunneling microscopy, X-rays can cause a transition of the tip out of the tunneling regime. Monitoring the reaction of the z-piezo (the element that controls the tip to sample separation) alone is not sufficient, because a continuous tip current is obtained. As a solution, an unambiguous and direct way of fingerprinting such near to far field transitions of the tip that relies on the simultaneous analysis of the X-ray-induced tip and sample current is presented. This result is of considerable importance because it opens the path to the ultimate resolution in X-ray enhanced scanning tunneling microscopy. [ABSTRACT FROM AUTHOR]

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The effect of the activator concentration on the structure of alkali silicate-activated slag/metakaolin pastes is assessed through synchrotron radiation-based X-ray techniques. As main reaction products, both calcium aluminosilicate hydrate ( C- A- S- H) and sodium/calcium aluminosilicate hydrate [( C, N)- A- S- H] type gels are formed in activated binders solely based on slag, along with the zeolitic products gismondine and garronite. In activated blended pastes, the inclusion of metakaolin in the binder hinders the formation of zeolite products, instead favoring the formation of a ( C, N)- A- S- H type gel consistent with the activation of metakaolin in the presence of high concentrations of Ca. The formation of the two distinct binding products is confirmed by high-resolution X-ray fluorescence microscopy, where the 'inner' products and the 'outer' products have compositions consistent with ( C, N)- A- S- H and C- A- S- H type gels, respectively. These results provide important new insights into the gel chemistry and micro/nanostructure of blended alkali-activated binder systems. [ABSTRACT FROM AUTHOR]

Here for the first time we describe the use of high resolution nanoprobe X-ray fluorescence (XRF) mapping for the analysis of artists' paints, hierarchically complex materials typically composed of binder, pigments, fillers, and other additives. The work undertaken at the nanoprobe sought to obtain highly spatially resolved, highly sensitive mapping of metal impurities (Pb, Cd, Fe, and other metals) in submicron particles of zinc oxide pigments used in early 20th century artists' tube paints and enamel paints, with particular emphasis on Ripolin, a popular brand of French house paint used extensively by Pablo Picasso and some of his contemporaries. Analysis revealed that the Zn oxide particles only contain a little Fe, proving that the highest quality Zn oxide pigment, free of Pb and Cd, was used for Ripolin house paints as well as artists' paints. Nanoprobe XRF mapping also demonstrated that artists' tube paints generally have more abundant fillers and additional whites (based on Pb, Ti, Ca) than Ripolin paints, which contain mostly pure zinc oxide. The chemical characterization of paints at the nanoscale opens the path to a better understanding of their fabrication and chemical reactivity. [ABSTRACT FROM AUTHOR]

The Hard X-ray Nanoprobe Beamline (or Nanoprobe Beamline) is an X-ray microscopy facility incorporating diffraction, fluorescence and full-field imaging capabilities designed and operated by the Center for Nanoscale Materials and the Advanced Photon Source at Sector 26 of the Advanced Photon Source at Argonne National Laboratory. This facility was constructed to probe the nanoscale structure of biological, environmental and material sciences samples. The beamline provides intense focused X-rays to the Hard X-ray Nanoprobe (or Nanoprobe) which incorporates Fresnel zone plate optics and a precision laser sensing and control system. The beamline operates over X-ray energies from 3 to 30 keV, enabling studies of most elements in the periodic table, with a particular emphasis on imaging transition metals. [ABSTRACT FROM AUTHOR]

Synchrotron X-ray Scanning Tunneling Microscopy (SX-STM) is a novel imaging technique capable of providing real space chemically specific mapping with a potential of reaching atomic resolution. Determination of chemical composition along with ultra-high resolution imaging by SX-STM can be realized through excitation of core electrons by incident X-rays when their energy is tuned to an absorption edge of a particular atom during raster scanning, as is done in the conventional STM experiments. In this work, we provide a brief summary and the current status of SX-STM and discuss its applications for material science. In particular, we discuss instrumentation challenges associated with the SX-STM technique and present early experiments on Cu doped ZrTe3 single crystals. [ABSTRACT FROM AUTHOR]