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The inorganic perovskite CsPbI3 shows promising photophysical properties for a range of potential optoelectronic applications but is metastable at room temperature. To address this, Br can be alloyed into the X-site to create compositions such as CsPbI2Br that are stable at room temperature but have bandgaps >1.9 eV - severely limiting solar applications. Herein, in an effort to achieve phase stable films with bandgaps

An improved understanding of the degradation pathways under external stimuli is needed to address stability challenges in two-dimensional (2D) perovskite semiconductor materials. In this study, in situ synchrotron nanoprobe X-ray fluorescence (nano-XRF) is used to investigate the evolution of halide redistribution within various 2D halide perovskite (n = 1–3) lateral heterostructures under ultraviolet (UV) exposure. The results show that iodine (I) experiences a loss in all cases, with the rate of change following the perovskite dimensionality monotonically. In contrast, bromine (Br) is relatively more stable than I in n = 2 and 3 heterostructures, with no significant change in the total Br concentration but a visible amount of Br diffusion to the previously I-rich regime. Combining nano-XRF and X-ray absorption spectroscopy (XAS), we found a reduction of dimensionality in crystals with n > 1 after UV exposure, indicating significant structural reconfiguration beyond ion migration.

Glioblastoma (GBM) is one of the most difficult cancers to effectively treat, in part because of the lack of precision therapies and limited therapeutic access to intracranial tumor sites due to the presence of the blood-brain and blood-tumor barriers. We have developed a precision medicine approach for GBM treatment that involves the use of brain-penetrant RNA interference-based spherical nucleic acids (SNAs), which consist of gold nanoparticle cores covalently conjugated with radially oriented and densely packed small interfering RNA (siRNA) oligonucleotides. On the basis of previous preclinical evaluation, we conducted toxicology and toxicokinetic studies in nonhuman primates and a single-arm, open-label phase 0 first-in-human trial (NCT03020017) to determine safety, pharmacokinetics, intratumoral accumulation and gene-suppressive activity of systemically administered SNAs carrying siRNA specific for the GBM oncogene Bcl2Like12 (Bcl2L12). Patients with recurrent GBM were treated with intravenous administration of siBcl2L12-SNAs (drug moniker: NU-0129), at a dose corresponding to 1/50th of the no-observed-adverse-event level, followed by tumor resection. Safety assessment revealed no grade 4 or 5 treatment-related toxicities. Inductively coupled plasma mass spectrometry, x-ray fluorescence microscopy, and silver staining of resected GBM tissue demonstrated that intravenously administered SNAs reached patient tumors, with gold enrichment observed in the tumor-associated endothelium, macrophages, and tumor cells. NU-0129 uptake into glioma cells correlated with a reduction in tumor-associated Bcl2L12 protein expression, as indicated by comparison of matched primary tumor and NU-0129-treated recurrent tumor. Our results establish SNA nanoconjugates as a potential brain-penetrant precision medicine approach for the systemic treatment of GBM.

The role of the alkali metal cations in halide perovskite solar cells is not well understood. Using synchrotron-based nano-x-ray fluorescence and complementary measurements, we found that the halide distribution becomes homogenized upon addition of cesium iodide, either alone or with rubidium iodide, for substoichiometric, stoichiometric, and overstoichiometric preparations, where the lead halide is varied with respect to organic halide precursors. Halide homogenization coincides with long-lived charge carrier decays, spatially homogeneous carrier dynamics (as visualized by ultrafast microscopy), and improved photovoltaic device performance. We found that rubidium and potassium phase-segregate in highly concentrated clusters. Alkali metals are beneficial at low concentrations, where they homogenize the halide distribution, but at higher concentrations, they form recombination-active second-phase clusters.

Perovskite solar cells have shown remarkable efficiencies beyond 22%, throughorganic and inorganic cation alloying. However, the role of alkali-metalcations is not well-understood. By using synchrotron-based nano-X-rayfluorescence and complementary measurements, we show that when adding RbIand/or CsI the halide distribution becomes homogenous. This homogenizationtranslates into long-lived charge carrier decays, spatially homogenous carrierdynamics visualized by ultrafast microscopy, as well as improved photovoltaicdevice performance. We find that Rb and K phase-segregate in highlyconcentrated aggregates. Synchrotron-based X-ray-beam-induced current andelectron-beam-induced current of solar cells show that Rb clusters do notcontribute to the current and are recombination active. Our findings bringlight to the beneficial effects of alkali metal halides in perovskites, andpoint at areas of weakness in the elemental composition of these complexperovskites, paving the way to improved performance in this rapidly growingfamily of materials for solar cell applications.

Solar cells based on n-type multicrystalline silicon (mc-Si) wafers are a promising path to reduce the cost per kWh of photovoltaics; however, the full potential of the material and how to optimally process it are still unknown. Process optimization requires knowledge of the response of the metal-silicide precipitate distribution to processing, which has yet to be directly measured and quantified. To supply this missing piece, we use synchrotron-based micro-X-ray fluorescence (μ-XRF) to quantitatively map >250 metal-rich particles in n-type mc-Si wafers before and after phosphorus diffusion gettering (PDG). We find that 820 °C PDG is sufficient to remove precipitates of fast-diffusing impurities and that 920 °C PDG can eliminate precipitated Fe to below the detection limit of μ-XRF. Thus, the evolution of precipitated metal impurities during PDG is observed to be similar for n- and p-type mc-Si, an observation consistent with calculations of the driving forces for precipitate dissolution and segregation gettering. Measurements show that minority-carrier lifetime increases with increasing precipitate dissolution from 820 °C to 880 °C PDG, and that the lifetime after PDG at 920 °C is between the lifetimes achieved after 820 °C and 880 °C PDG.

Chromium (Cr) can degrade silicon wafer-based solar cell efficiencies at concentrations as low as 1010cm-3. In this contribution, we employ synchrotron-based X-ray fluorescence microscopy to study chromium distributions in multicrystalline silicon in as-grown material and after phosphorous diffusion. We complement quantified precipitate size and spatial distribution with interstitial Cr concentration and minority carrier lifetime measurements to provide insight into chromium gettering kinetics and offer suggestions for minimizing the device impacts of chromium. We observe that Cr-rich precipitates in as-grown material are generally smaller than iron-rich precipitates and that Cri point defects account for only one-half of the total Cr in the as-grown material. This observation is consistent with previous hypotheses that Cr transport and CrSi2 growth are more strongly diffusion-limited during ingot cooling. We apply two phosphorous diffusion gettering profiles that both increase minority carrier lifetime by two orders of magnitude and reduce [Cri] by three orders of magnitude to 1010cm-3. Some Cr-rich precipitates persist after both processes, and locally high [Cri] after the high-temperature process indicates that further optimization of the chromium gettering profile is possible.

Although the input of desert dust as a key source of trace metals in the Southern Ocean (SO) has been previously studied, the dissolution process of metals in surface waters, particularly iron (Fe), remain poorly understood. Given the crucial role of Fe in primary production and the biological carbon pump in the SO, we focused on experimental estimations of Fe dissolution from Patagonian dust, the primary natural dust source in the SO. Our study considered both current and projected future conditions, encompassing sea-surface warming, acidification, increased photosynthetically active radiation, and doubled dust inputs. Through controlled laboratory experiments using filtered SO seawater, conducted over 7 days, we assessed changes in particulate Fe (pFe) concentrations, Fe redox speciation (Fe(II)/Fe(III)), and in the mineralogy of Fe-bearing dust in abiotic condition. The predominant minerals in the dust included quartz and aluminosilicates, with silicon (Si), aluminum (Al), and Fe as the major elements. No significant alterations in the mineralogy and the elemental composition of the dust were recorded during the dissolution experiments, neither under present nor under projected future conditions. The particulate Fe(II)/Fe(III) ratio remained consistently at 0.25 during the experiments, unaffected by changed conditions. Consequently, changes in environmental conditions in the SO would therefore not significantly alter the mineralogy and redox speciation of pFe in the Patagonian dust. On the contrary, pFe exhibited a dissolution rate of 3.8% and 1.6% per day under present and future conditions, respectively. The environmental changes anticipated for 2100 in the SO will likely to result in a decrease in the dissolution rate of pFe. Thus, even though a doubling of dust input by 2100 is anticipated, it will unlikely provide significantly more dissolved Fe (dFe) in seawater in the SO. Consequently, the future intensification of Patagonian dust inputs may not alleviate the Fe limitation in the SO. [ABSTRACT FROM AUTHOR]

Synchrotron-based microprobe techniques have been applied to study the distribution, size, chemical state, and recombination activity of Fe clusters in two types of mc-Si materials: block cast mc-Si, and AstroPower Silicon Film(TM) sheet material. In sheet material, high concentrations of metals were found at recombination-active, micron-sized intragranular clusters consisting of micron and sub-micron sized particles. In addition, Fe nanoparticles were located in densities of ~;2'107 cm-2 along recombination-active grain boundaries. In cast mc-Si, two types of particles were identified at grain boundaries: (1) micron-sized oxidized Fe particles accompanied by other metals (Cr, Mn, Ca, Ti), and (2) a higher number of sub-micron FeSi2 precipitates that exhibited a preferred orientation along the crystal growth direction. In both materials, it is believed that the larger Fe clusters are inclusions of foreign particles, from which Fe dissolves in the melt to form the smaller FeSi2 nanoprecipitates, which by virtue of their more homogeneous distribution are deemed more dangerous to solar cell device performance. Based on this understanding, strategies proposed to reduce the impact of Fe on mc-Si electrical properties include gettering, passivation, and limiting the dissolution of foreign Fe-rich particles in the melt.

In this study, synchrotron-based x-ray absorption microspectroscopy (mu-XAS) is applied to identifying the chemical states of copper-rich clusters within a variety of silicon materials, including as-grown cast multicrystalline silicon solar cell material with high oxygen concentration and other silicon materials with varying degrees of oxygen concentration and copper contamination pathways. In all samples, copper silicide (Cu3Si) is the only phase of copper identified. It is noted from thermodynamic considerations that unlike certain metal species, copper tends to form a silicide and not an oxidized compound because of the strong silicon-oxygen bonding energy; consequently the likelihood of encountering an oxidized copper particle in silicon is small, in agreement with experimental data. In light of these results, the effectiveness of aluminum gettering for the removal of copper from bulk silicon is quantified via x-ray fluorescence microscopy (mu-XRF), and a segregation coefficient is determined from experimental data to be at least (1-2)'103. Additionally, mu-XAS data directly demonstrates that the segregation mechanism of Cu in Al is the higher solubility of Cu in the liquid phase. In light of these results, possible limitations for the complete removal of Cu from bulk mc-Si are discussed.

Synchrotron-based microprobe techniques were used to obtain precise and systematic information about the size distribution, spatial distribution, shape, electrical activity, and chemical states of iron-rich impurity clusters in multicrystalline silicon materials used for cost-effective solar cells. These experimentally observed properties of iron-rich clusters allow one to derive conclusions about the origins of iron contamination, the mechanisms for incorporating large amounts of Fe into mc-Si, quantitative information about the distribution of Fe in mc-Si and the impacts of such contamination on solar cell performance. Two distinct groups of iron-rich clusters have been identified in both materials: (a) the occasional large (diameter greater than or equal to 1 mu-m) particles, either oxidized and/or present with multiple other metal species reminiscent of stainless steels or ceramics, which are believed to originate from a foreign source such as the growth surfaces, production equipment, or feedstock, and (b) the more numerous, homogeneously distributed, and smaller iron silicide precipitates (dia. less than or equal to 800 nm, often < 100 nm), originating from a variety of possible formation mechanisms involving atomically dissolved iron in the melt or in the crystal. It was found that iron silicide nanoprecipitates account for bulk Fe concentrations as high as 1014-15 cm-3 and can have a large negative impact on device performance because of their homogeneous distribution along structural defects. The large (dia. greater than or equal to 1 mu-m) particles, while containing elevated amounts of metals, are low in spatial density and thus deemed to have a low direct impact on device performance, although they may have a large indirect impact via the dissolution of Fe, thus assisting the formation of iron silicide nanoprecipitates. These results demonstrate that it is not necessarily the total Fe content that limits mc-Si device performance, but the distribution of Fe within the material.

AbstractIn the following review we discuss several types of nanoparticles (such as TiO2, quantum dots, and gold nanoparticles) and their impact on the ability to image biological components in fixed cells. The review also discusses factors influencing nanoparticle imaging and uptake in live cells in vitro. Due to their unique size-dependent properties nanoparticles offer numerous advantages over traditional dyes and proteins. For example, the photostability, narrow emission peak, and ability to rationally modify both the size and surface chemistry of Quantum Dots allow for simultaneous analyses of multiple targets within the same cell. On the other hand, the surface characteristics of nanometer sized TiO2allow efficient conjugation to nucleic acids which enables their retention in specific subcellular compartments. We discuss cellular uptake mechanisms for the internalization of nanoparticles and studies showing the influence of nanoparticle size and charge and the cell type targeted on nanoparticle uptake. The predominant nanoparticle uptake mechanisms include clathrin-dependent mechanisms, macropinocytosis, and phagocytosis.

Understanding the optoelectronic properties of optically active materials at the nanoscale often proves challenging due to the diffraction-limited resolution of visible light probes and the dose sensitivity of many optically active materials to high-energy electron probes. In this study, we demonstrate correlative synchrotron-based scanning x-ray excited optical luminescence (XEOL) and x-ray fluorescence (XRF) to simultaneously probe local composition and optoelectronic properties of halide perovskite thin films of interest for photovoltaic and optoelectronic devices. We find that perovskite XEOL stability, emission redshifting, and peak broadening under hard x-ray irradiation correlates with trends seen in photoluminescence measurements under continuous visible light laser irradiation. The XEOL stability is sufficient under the intense x-ray probe irradiation to permit proof-of-concept correlative mapping. Typical synchrotron XRF and nano-diffraction measurements use acquisition times 10–100 x shorter than the 5-second acquisition employed for XEOL scans in this study, suggesting that improving luminescence detection should allow correlative XEOL measurements to be performed successfully with minimal material degradation. Analysis of the XEOL emission from the quartz substrate beneath the perovskite reveals its promise for use as a real-time in-situ x-ray dosimeter, which could provide quantitative metrics for future optimization of XEOL data collection for perovskites and other beam-sensitive materials. Overall, the data suggest that XEOL represents a promising route towards improved resolution in the characterization of nanoscale heterogeneities and defects in optically active materials that may be implemented into x-ray nanoprobes to complement existing x-ray modalities. [ABSTRACT FROM AUTHOR]

Understanding the optoelectronic properties of optically active materials at the nanoscale often proves challenging due to the diffraction-limited resolution of visible light probes and the dose sensitivity of many optically active materials to high-energy electron probes. In this study, we demonstrate correlative synchrotron-based scanning x-ray excited optical luminescence (XEOL) and x-ray fluorescence (XRF) to simultaneously probe local composition and optoelectronic properties of halide perovskite thin films of interest for photovoltaic and optoelectronic devices. We find that perovskite XEOL stability, emission redshifting, and peak broadening under hard x-ray irradiation correlates with trends seen in photoluminescence measurements under continuous visible light laser irradiation. The XEOL stability is sufficient under the intense x-ray probe irradiation to permit proof-of-concept correlative mapping. Typical synchrotron XRF and nano-diffraction measurements use acquisition times 10–100 x shorter than the 5-second acquisition employed for XEOL scans in this study, suggesting that improving luminescence detection should allow correlative XEOL measurements to be performed successfully with minimal material degradation. Analysis of the XEOL emission from the quartz substrate beneath the perovskite reveals its promise for use as a real-time in-situ x-ray dosimeter, which could provide quantitative metrics for future optimization of XEOL data collection for perovskites and other beam-sensitive materials. Overall, the data suggest that XEOL represents a promising route towards improved resolution in the characterization of nanoscale heterogeneities and defects in optically active materials that may be implemented into x-ray nanoprobes to complement existing x-ray modalities. [ABSTRACT FROM AUTHOR]