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At least 955 records · Page 53

New frontiers in atom probe tomography: a review of research enabled by cryo and/or vacuum transfer systems

There has been a recent surge in the use of cryo and/or vacuum specimen preparation and transfer systems that are broadening the scope of research enabled by the microscopy technique of atom probe tomography. This is driven by the fact that, like for many microscopes, the application of atom probe to air and temperature sensitive materials or wet biological specimens has previously been limited by through-air-transfer and through-vacuum-transfer at room temperature. Here we provide an overview of the critical areas of research that require these new transfer and analysis protocols, as well as a review of current advances in transfer devices, environmental cells and glove boxes for controlled sample manipulation. This includes the study of catalysis and corrosion, the application of atom probe to biological samples, the study of liquid-solid interfaces, natural ageing investigations and the analysis of hydrogen in metals.

36 MATERIALS SCIENCE↗

Time-Resolved Electrical Scanning Probe Microscopy of Layered Perovskites Reveals Spatial Variations in Photoinduced Ionic and Electronic Carrier Motion

We study light-induced dynamics in thin films comprising Ruddlesden–Popper phases of the layered 2D perovskite (C 4 H 9 NH 3 ) 2 PbI 4 . We probe ionic and electronic carrier dynamics using two complementary scanning probe methods, time-resolved G-mode Kelvin probe force microscopy and fast free time-resolved electrostatic force microscopy, as a function of position, time, and illumination. Here, we show that the average surface photovoltage sign is dominated by the band bending at the buried perovskite–substrate interface. However, the film exhibits substantial variations in the spatial and temporal response of the photovoltage. Under illumination, the photovoltage equilibrates over hundreds of microseconds, a time scale associated with ionic motion and trapped electronic carriers. Surprisingly, we observe that the surface photovoltage of the 2D grain centers evolves more rapidly in time than at the grain boundaries. We propose that the slower evolution at grain boundaries is due to a combination of ion migration occurring between PbI 4 planes, as well as electronic carriers traversing grain boundary traps, thereby changing the time-dependent band unbending at grain boundaries. These results provide a model for the photoinduced dynamics in 2D perovskites and are a useful basis for interpreting photovoltage dynamics on hybrid 2D/3D structures.

14 SOLAR ENERGY↗

Time-resolved probing of laser-induced nanostructuring processes in liquids

Laser synthesis and processing of colloids (LSPC) in liquids has gained widespread applications in producing nanomaterials of different classes of solids. While the technical processes in different cases of ablation, fragmentation or colloidal fusion may look macroscopically different in each application, the underlying fundamental mechanisms are always the same cascade of laser interaction with matter, non-thermal or thermal energy deposition, phase transitions, and the subsequent structure formation processes. Disentangling these mechanisms represents a veritable challenge, as ultrafast and structurally sensitive experimental methods are required. This review presents a discussion of how state-of-the-art experimental protocols using ultrafast lasers and sensitive structural probes, such as electrons or X-rays are able to address this challenge. In particular, it is possible to investigate LSPC on single objects using single probe pulses and avoid accumulation effects in a heterogeneous sample. The presented results capture structure formation with femtosecond and atomic scale resolution. Ultrafast time-resolved probing approaches are key to revealing the transient states and pathways that govern material transformation in LSPC.

X-ray scattering↗

Van Allen Probes, THEMIS, GOES, and cluster observations of EMIC waves, ULF pulsations, and an electron flux dropout

We examined an electron flux dropout during the 12–14 November 2012 geomagnetic storm using observations from seven spacecraft: the two Van Allen Probes, Time History of Events and Macroscale Interactions during Substorms (THEMIS)-A (P5), Cluster 2, and Geostationary Operational Environmental Satellites (GOES) 13, 14, and 15. The electron fluxes for energies greater than 2.0 MeV observed by GOES 13, 14, and 15 at geosynchronous orbit and by the Van Allen Probes remained at or near instrumental background levels for more than 24 h from 12 to 14 November. For energies of 0.8 MeV, the GOES satellites observed two shorter intervals of reduced electron fluxes. The first interval of reduced 0.8 MeV electron fluxes on 12–13 November was associated with an interplanetary shock and a sudden impulse. Cluster, THEMIS, and GOES observed intense He + electromagnetic ion cyclotron (EMIC) waves from just inside geosynchronous orbit out to the magnetopause across the dayside to the dusk flank. The second interval of reduced 0.8 MeV electron fluxes on 13–14 November was associated with a solar sector boundary crossing and development of a geomagnetic storm with Dst <–100 nT. At the start of the recovery phase, both the 0.8 and 2.0 MeV electron fluxes finally returned to near prestorm values, possibly in response to strong ultralow frequency (ULF) waves observed by the Van Allen Probes near dawn. A combination of adiabatic effects, losses to the magnetopause, scattering by EMIC waves, and acceleration by ULF waves can explain the observed electron behavior.

58 GEOSCIENCES↗

The occurrence and wave properties of H⁺-, He⁺-, and O⁺-band EMIC waves observed by the Van Allen Probes

We perform a statistical study of electromagnetic ion cyclotron (EMIC) waves detected by the Van Allen Probes mission to investigate the spatial distribution of their occurrence, wave power, ellipticity, and normal angle. The Van Allen Probes have been used which allow us to explore the inner magnetosphere (1.1 to 5.8 RE). Magnetic field measurements from the Electric and Magnetic Field Instrument Suite and Integrated Science on board the Van Allen Probes are used to identify EMIC wave events for the first 22 months of the mission operation (8 September 2012 to 30 June 2014). EMIC waves are examined in H⁺-, He⁺-, and O⁺-bands. Over 700 EMIC wave events have been identified over the three different wave bands (265 H⁺-band events, 438 He⁺-band events, and 68 O⁺-band events). EMIC wave events are observed between L = 2 – 8, with over 140 EMIC wave events observed below L = 4. The results show that H⁺-band EMIC waves have two peak magnetic local time (MLT) occurrence regions: pre-noon (09:00 < MLT ≤ 12:00) and afternoon (15:00 < MLT ≤ 17:00) sectors. He⁺-band EMIC waves feature an overall stronger dayside occurrence. O⁺-band EMIC waves have one peak region located in the morning sector at lower L shells (L < 4). He⁺-band EMIC waves average the highest wave power overall (>0.1 nT²/Hz), especially in the afternoon sector. Ellipticity observations reveal that linearly polarized EMIC waves dominate in lower L shells.

58 GEOSCIENCES↗

Multifunctional Biomedical Imaging in Physiological and Pathological Conditions Using a NIR-II Probe

Contrasted with imaging in the visible (400–650 nm) and near-infrared window I (NIR-I, 650–900 nm) regions, imaging in near-infrared window II (NIR-II, 1000–1700 nm) is a highly promising in vivo imaging modality with improved resolution and deeper tissue penetration. Here, a small molecule NIR-II dye,5,5'-(1H,5H-benzo[1,2-c:4,5-c'] bis[1,2,5]thiadiazole)-4,8-diyl)bis(N,N-bis(4-(3-((tert-butyldimethylsilyl)oxy)propyl)phenyl) thiophen-2-amine), is successfully encapsulated into phospholipid vesicles to prepare a probe CQS1000. The novel NIR-II probe is studied for in vivo multifunctional biological imaging. The results of this study indicate that the NIR-II vesicle CQS1000 can noninvasively and dynamically visualize and monitor many physiological and pathological conditions of circulatory systems, including lymphatic drainage and routing, angiogenesis of tumor, and vascular deformity such as arterial thrombus formation and ischemia with high spatial and temporal resolution. More importantly, by virtue of the favorable half-life of blood circulation of CQS1000, NIR-II imaging is capable of aiding precise resection of tumor such as osteosarcoma and accelerating the process of lymph node dissection to complete sentinel lymph node biopsy for better decision making during the tumor surgery. Overall, CQS1000 is a highly promising NIR-II probe for multifunctional biomedical imaging in physiological and pathological conditions, surpassing traditional NIR-I imaging modality and pathologic assessments for clinical diagnosis and treatment.

36 MATERIALS SCIENCE↗

Labeling of Phosphatidylinositol Lipid Products in Cells through Metabolic Engineering by Using a Clickable myo -Inositol Probe

Phosphatidylinositol (PI) lipids control critical biological processes, so aberrant biosynthesis often leads to disease. As a result, the capability to track the production and localization of these compounds in cells is vital for elucidating their complex roles. In this paper, we report the design, synthesis, and application of clickable myo -inositol probe 1 a for bioorthogonal labeling of PI products. To validate this platform, we initially conducted PI synthase assays to show that 1 a inhibits PI production in vitro. Fluorescence microscopy experiments next showed probe-dependent imaging in T-24 human bladder cancer and Candida albicans cells. Growth studies in the latter showed that replacement of myo -inositol with probe 1 a led to an enhancement in cell growth. Lastly, fluorescence-based TLC analysis and mass spectrometry experiments support the labeling of PI lipids. This approach provides a promising means for tracking the complex biosynthesis and trafficking of these lipids in cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New Colorimetric and Fluorometric Fluoride Ion Probe Based on Anthra[1,9-cd]pyrazol-6(2H)-one

New colorimetric and fluorometric fluoride ion probe, anthra[1,9-cd]pyrazol- 6(2H)-one (1), was synthesized by one-step condensation. The probe 1 shows F{sup −}-selective color change from colorless to pink and appearance of red fluorescence. The fluorescence quantum yield of free probe 1 in DMSO was calculated to be 0.03. After addition of 15 equiv. of F{sup −}, its fluorescence quantum yield can be increased to 0.37. The analytical detection limit for F{sup −} was 2.8 × 10{sup − 7} M. {sup 1}H NMR analysis and DFT calculation show that the F{sup −}-induced colorimetric and fluorometric responses of 1 are driven by deprotonation process. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Demonstration of femtosecond broadband X-rays from laser wakefield acceleration as a source for pump-probe X-ray absorption studies

Here, we present X-ray absorption measurements near the K-edge of laser heated aluminum in a pump-probe configuration using X-rays generated in a laser wakefield accelerator. A 30 fs duration laser pulse from the Hercules laser system was split into two beamlines, with one used to heat a 4 $μ$m thickness Al foil and the second to drive a laser wakefield accelerator. The laser-heated plasma was probed at various pump- probe delays using the femtosecond duration X-rays generated by betatron oscillations of the electrons in the wakefield. We observe an apparent blue-shift of the K-edge occurring on a sub-picosecond timescale in the transmission spectra.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Comparing simulated and observed EMIC wave amplitudes using in situ Van Allen Probes’ measurements

In this study, we perform a statistical study calculating electromagnetic ion cyclotron (EMIC) wave amplitudes based off in situ plasma measurements taken by the Van Allen Probes’ (1.1–5.8 R e ) Helium, Oxygen, Proton, Electron (HOPE) instrument. Calculated wave amplitudes are compared to EMIC waves observed by the Electric and Magnetic Field Instrument Suite and Integrated Science on board the Van Allen Probes during the same period. The survey covers a 22-month period (1 November 2012 to 31 August 2014), a full Van Allen Probe magnetic local time (MLT) precession. The linear theory proxy was used to identify EMIC wave events with plasma conditions favorable for EMIC wave excitation. Two hundred and thirty-two EMIC wave events (103 H + -band and 129 He + -band) were selected for this comparison. Nearly all events selected are observed beyond L = 4. Results show that calculated wave amplitudes exclusively using the in situ HOPE measurements produce amplitudes too low compared to the observed EMIC wave amplitudes. Hot proton anisotropy (Ahp) distributions are asymmetric in MLT within the inner (L < 7) magnetosphere with peak (minimum) A hp , ~0.81 to 1.00 (~0.62), observed in the dawn (dusk), 0000 < MLT ≤ 1200 (1200 < MLT ≤ 2400), sectors. Measurements of A hp are found to decrease in the presence of EMIC wave activity. A hp amplification factors are determined and vary with respect to EMIC wave-band and MLT. Lastly, He + -band events generally require double (quadruple) the measured A hp for the dawn (dusk) sector to reproduce the observed EMIC wave amplitudes.

58 GEOSCIENCES↗

Community-Driven Methods for Open and Reproducible Software Tools for Analyzing Datasets from Atom Probe Microscopy

Atom probe tomography, and related methods, probe the three-dimensional architecture of a material. The software tools that microscopists use, and how these tools are connected into workflows, makes a substantial contribution to the accuracy and precision of such a material characterization experiment. Typically, we adapt methods from other communities like mathematics, data science, computational geometry, artificial intelligence, or scientific computing. We also realize that improving on research data management is a challenge when it comes to align with the FAIR data stewardship principles. Faced with this global challenge, we are convinced that collaborating is useful. Here, we report the results and challenges with an inter-laboratory call for developing test cases for several types of atom probe software tools. The results support why defining detailed recipes of software workflows and sharing these recipes is necessary and rewarding: Open source tools and (meta)data exchange can help to make our day-to-day data processing tasks become more efficient, the training of new users and knowledge transfer become easier, and assist us with automated quantification of uncertainties to gain access to substantiated results.

36 MATERIALS SCIENCE↗

Light-Dependent Impedance Spectra and Transient Photoconductivity in a Ruddlesden–Popper 2D Lead–Halide Perovskite Revealed by Electrical Scanned Probe Microscopy and Accompanying Theory

Electric force microscopy was used to record the light-dependent impedance spectrum and the probe transient photoconductivity of a film of butylammonium lead iodide, BA 2 PbI 4 , a 2D Ruddlesden–Popper perovskite semiconductor. The impedance spectrum of BA 2 PbI 4 showed modest changes as the illumination intensity was varied up to 1400 mW cm –2 , in contrast with the comparatively dramatic changes seen for 3D lead–halide perovskites under similar conditions. BA 2 PbI 4 ’s light-induced conductivity had a rise time and decay time of ~100 μs, 10 4 slower than expected from direct electron–hole recombination yet 10 5 faster than the conductivity-recovery times recently observed in 3D lead–halide perovskites and attributed to the relaxation of photogenerated vacancies. What sample properties are probed by electric force microscope measurements remains an open question. A Lagrangian-mechanics treatment of the electric force microscope experiment was recently introduced by Dwyer, Harrell, and Marohn which enabled the calculation of steady-state electric force microscope signals in terms of a complex sample impedance. Here this impedance treatment of the tip–sample interaction is extended, through the introduction of a time-dependent transfer function, to include time-resolved electrical scanned probe measurements. Here, it is shown that the signal in a phase-kick electric force microscope experiment, and therefore also the signal in a time-resolved electrostatic force microscope experiment, can be written explicitly in terms of the sample’s time-dependent resistance (i.e., conductivity).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Differentiation of surface and bulk conductivities in topological insulator via four-probe spectroscopy

Topological insulators, with characteristic topological surface states, have emerged as a new state of matter with rich potentials for both fundamental physics and device applications. However, the experimental detection of the surface transport has been hampered by the unavoidable extrinsic conductivity associated with the bulk crystals. Here we show that a four-probe transport spectroscopy in a multi-probe scanning tunneling microscopy system can be used to differentiate conductivities from the surface states and the coexisting bulk states in topological insulators. We derive a scaling relation of measured resistance with respect to varying inter-probe spacing for two interconnected conduction channels, which allows quantitative determination of conductivities from both channels. Using this method, we demonstrate the separation of 2D and 3D conduction in topological insulators by comparing the conductance scaling of Bi 2 Se 3 , Bi 2 Te 2 Se, and Sb-doped Bi 2 Se 3 with that of a pure 2D conductance of graphene on SiC substrate. We also report the 2D conductance enhancement due to the surface doping effect in topological insulators. This technique can be applied to reveal 2D to 3D crossover of conductance in other complex systems.

36 MATERIALS SCIENCE↗

Direct Four-Probe Measurement of Grain-Boundary Resistivity and Mobility in Millimeter-Sized Graphene

Grain boundaries (GBs) in polycrystalline graphene scatter charge carriers, which reduces carrier mobility and limits graphene applications in high-speed electronics. Here we report the extraction of the resistivity of GBs and the effect of GBs on carrier mobility by direct four-probe measurements on millimeter-sized graphene bicrystals grown by chemical vapor deposition (CVD). To extract the GB resistivity and carrier mobility from direct four-probe intragrain and intergrain measurements, an electronically equivalent extended 2D GB region is defined based on Ohm’s law. Measurements on seven representative GBs find that the maximum resistivities are in the range of several kΩ·μm to more than 100 kΩ·μm. Furthermore, the mobility in these defective regions is reduced to 0.4–5.9‰ of the mobility of single-crystal, pristine graphene. Similarly, the effect of wrinkles on carrier transport can also be derived. We report the present approach provides a reliable way to directly probe charge-carrier scattering at GBs and can be further applied to evaluate the GB effect of other two-dimensional polycrystalline materials, such as transition-metal dichalcogenides (TMDCs).

36 MATERIALS SCIENCE↗

Quantitative Comparison of Dye and Ultrasmall Fluorescent Silica Core–Shell Nanoparticle Probes for Optical Super-Resolution Imaging of Model Block Copolymer Thin Film Surfaces

In recent years, high-resolution optical imaging in the far field has provided opportunities for alternative approaches to nanocharacterization traditionally dominated by electron and scanning probe microscopies. Here in this paper, we report the optical super-resolution imaging of model block copolymer (BCP) thin film surface nanostructures through stochastic optical reconstruction microscopy (STORM). We compare a set of surface-functionalized fluorescent core–shell silica nanoparticles encapsulating two different organic dyes, Cy3 and Cy5, with the corresponding free dyes in STORM. Using various click-type chemistries, these probes are covalently attached to the surface of specific blocks of BCP thin films, enabling selective block labeling and optical visualization. We demonstrate that the enhanced brightness of these particle probes offers distinct advantages over conventional dye labeling, outperforming one of the best STORM dyes available (Cy5).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous Observations of Electromagnetic Ion Cyclotron (EMIC) Waves and Pitch Angle Scattering During a Van Allen Probes Conjunction

On 22 December 2015, the two Van Allen Probes observed two sets of electromagnetic ion cyclotron (EMIC) wave bursts during a close conjunction when both Probe A and Probe B were separated by 0.57 to 0.68 R E . Here, the EMIC waves occurred during an active period in the recovery phase of a coronal mass ejection-driven geomagnetic storm. Both spacecraft observed EMIC wave bursts that had similar spatial structure within a 1–2 min time delay. The EMIC waves occurred outside the plasmasphere, within ΔL ≈ 1–2 of the plasmapause and within a few degrees in magnetic latitude of the equatorial plane. The spatial structure of the EMIC wave bursts may have been related to the proton drift paths outside the plasmasphere and influenced by total magnetic field strength variations associated with solar wind pressure enhancements. The EMIC waves were observed in a narrow L shell region from L ≈ 4.55–5.32 between 10 and 11 magnetic local time (MLT) on the outbound halves of the spacecraft orbits and from L ≈ 4.82–5.51 between 13 and 14 MLT on the inbound halves of the spacecraft orbits. However, Pc1 pulsations were observed on the ground over a broad range of local times. The anisotropy of the proton pitch angle distributions was enhanced when the EMIC waves were observed. Although the overall radiation belt response during this storm was dominated by acceleration and transport processes, the EMIC waves produced local pitch angle scattering of 13–15 keV protons and 2.1–2.6 MeV electrons, consistent with calculations of the expected resonant energies.

79 ASTRONOMY AND ASTROPHYSICS↗

Probing topological quantum matter with scanning tunnelling microscopy

The search for topological phases of matter is evolving towards strongly interacting systems, including magnets and superconductors, where exotic effects emerge from the quantum-level interplay between geometry, correlation and topology. Over the past decade or so, scanning tunnelling microscopy has become a powerful tool to probe and discover emergent topological matter, because of its unprecedented spatial resolution, high-precision electronic detection and magnetic tunability. Scanning tunnelling microscopy can be used to probe various topological phenomena, as well as complement results from other techniques. We discuss some of these proof-of-principle methodologies applied to probe topology, with particular attention to studies performed under a tunable vector magnetic field, which is a relatively new direction of recent focus. Finally, we then project the future possibilities for atomic-resolution tunnelling methods in providing new insights into topological matter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ionization and dissociation dynamics of vinyl bromide probed by femtosecond extreme ultraviolet transient absorption spectroscopy

Strong-field induced ionization and dissociation dynamics of vinyl bromide, CH{sub 2}=CHBr, are probed using femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy. Strong-field ionization is initiated with an intense femtosecond, near infrared (NIR, 775 nm) laser field. Femtosecond XUV pulses covering the photon energy range of 50-72 eV probe the subsequent dynamics by measuring the time-dependent spectroscopic features associated with transitions of the Br (3d) inner-shell electrons to vacancies in molecular and atomic valence orbitals. Spectral signatures are observed for the depletion of neutral C{sub 2}H{sub 3}Br, the formation of C{sub 2}H{sub 3}Br{sup +} ions in their ground (X{sup ~}) and first excited (A{sup ~}) states, the production of C{sub 2}H{sub 3}Br{sup ++} ions, and the appearance of neutral Br ({sup 2}P{sub 3/2}) atoms by dissociative ionization. The formation of free Br ({sup 2}P{sub 3/2}) atoms occurs on a timescale of 330 ± 150 fs. The ionic A{sup ~} state exhibits a time-dependent XUV absorption energy shift of ∼0.4 eV within the time window of the atomic Br formation. The yield of Br atoms correlates with the yield of parent ions in the A{sup ~} state as a function of NIR peak intensity. The observations suggest that a fraction of vibrationally excited C{sub 2}H{sub 3}Br{sup +} (A{sup ~}) ions undergoes intramolecular vibrational energy redistribution followed by the C–Br bond dissociation. The C{sub 2}H{sub 3}Br{sup +} (X{sup ~}) products and the majority of the C{sub 2}H{sub 3}Br{sup ++} ions are relatively stable due to a deeper potential well and a high dissociation barrier, respectively. The results offer powerful new insights about orbital-specific electronic processes in high field ionization, coupled vibrational relaxation and dissociation dynamics, and the correlation of valence hole-state location and dissociation in polyatomic molecules, all probed simultaneously by ultrafast table-top XUV spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗