20 research outputs found
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Surface-to-Bulk Redox Coupling through Thermally Driven Li Redistribution in Li- and Mn-Rich Layered Cathode Materials.
Li- and Mn-rich (LMR) layered cathode materials have demonstrated impressive capacity and specific energy density thanks to their intertwined redox centers including transition metal cations and oxygen anions. Although tremendous efforts have been devoted to the investigation of the electrochemically driven redox evolution in LMR cathode at ambient temperature, their behavior under a mildly elevated temperature (up to ∼100 °C), with or without electrochemical driving force, remains largely unexplored. Here we show a systematic study of the thermally driven surface-to-bulk redox coupling effect in charged Li1.2Ni0.15Co0.1Mn0.55O2. We for the first time observed a charge transfer between the bulk oxygen anions and the surface transition metal cations under ∼100 °C, which is attributed to the thermally driven redistribution of Li ions. This finding highlights the nonequilibrium state and dynamic nature of the LMR material at deeply delithiated state upon a mild temperature perturbation
Absolute Energy Measurements with Superconducting Transition-Edge Sensors for Muonic X-ray Spectroscopy at 44 keV
Superconducting transition-edge sensor (TES) microcalorimeters have great
utility in x-ray applications owing to their high energy resolution, good
collecting efficiency and the feasibility of being multiplexed into large
arrays. In this work, we develop hard x-ray TESs to measure the absolute
energies of muonic-argon (-Ar) transition lines around 44 keV and 20 keV.
TESs with sidecar absorbers of different heat capacities were fabricated and
characterized for their energy resolution and calibration uncertainty. We
achieved ~ 1 eV absolute energy measurement accuracy at 44 keV, and < 12 eV
energy resolution at 17.5 keV
A Tabletop X-Ray Tomography Instrument for Nanometer-Scale Imaging: Integration of a Scanning Electron Microscope with a Transition-Edge Sensor Spectrometer
X-ray nanotomography is a powerful tool for the characterization of nanoscale
materials and structures, but is difficult to implement due to competing
requirements on X-ray flux and spot size. Due to this constraint,
state-of-the-art nanotomography is predominantly performed at large synchrotron
facilities. Compact X-ray nanotomography tools operated in standard analysis
laboratories exist, but are limited by X-ray optics and destructive sample
preparation techniques. We present a laboratory-scale nanotomography instrument
that achieves nanoscale spatial resolution while changing the limitations of
conventional tomography tools. The instrument combines the electron beam of a
scanning electron microscope (SEM) with the precise, broadband X-ray detection
of a superconducting transition-edge sensor (TES) microcalorimeter. The
electron beam generates a highly focused X-ray spot in a metal target, while
the TES spectrometer isolates target photons with high signal-to-noise. This
combination of a focused X-ray spot, energy-resolved X-ray detection, and
unique system geometry enable nanoscale, element-specific X-ray imaging in a
compact footprint. The proof-of-concept for this approach to X-ray
nanotomography is demonstrated by imaging 160 nm features in three dimensions
in a Cu-SiO2 integrated circuit, and a path towards finer resolution and
enhanced imaging capabilities is discussed.Comment: The following article has been submitted to Physical Review Applie
A tabletop x-ray tomography instrument for nanometer-scale imaging: demonstration of the 1,000-element transition-edge sensor subarray
We report on the 1,000-element transition-edge sensor (TES) x-ray
spectrometer implementation of the TOMographic Circuit Analysis Tool (TOMCAT).
TOMCAT combines a high spatial resolution scanning electron microscope (SEM)
with a highly efficient and pixelated TES spectrometer to reconstruct
three-dimensional maps of nanoscale integrated circuits (ICs). A 240-pixel
prototype spectrometer was recently used to reconstruct ICs at the 130 nm
technology node, but to increase imaging speed to more practical levels, the
detector efficiency needs to be improved. For this reason, we are building a
spectrometer that will eventually contain 3,000 TES microcalorimeters read out
with microwave superconducting quantum interference device (SQUID)
multiplexing, and we currently have commissioned a 1,000 TES subarray. This
still represents a significant improvement from the 240-pixel system and allows
us to begin characterizing the full spectrometer performance. Of the 992
maximimum available readout channels, we have yielded 818 devices, representing
the largest number of TES x-ray microcalorimeters simultaneously read out to
date. These microcalorimeters have been optimized for pulse speed rather than
purely energy resolution, and we measure a FWHM energy resolution of 14 eV at
the 8.0 keV Cu K line.Comment: 5 pages, 4 figures, submitted to IEEE Transactions on Applied
Superconductivit
Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers
Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)(4)(2,2 '-bipyridine)](2-) (1), [Fe(CN)(4)(2,3-bis(2-pyridyl)pyrazine)](2-) (2) and [Fe(CN)(4)(2,2 '-bipyrimidine)](2-) (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the (MLCT)-M-1 vertical energy to be varied from 1.64 eV to 2.64 eV and the (MLCT)-M-3 lifetime to range from 180 fs to 67 ps. The (MLCT)-M-3 lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred ((MC)-M-3) excited state, as established by the Tanabe-Sugano analysis of the Fe 2p3d RIXS data. In contrast, the (MLCT)-M-3 lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing (MLCT)-M-3 -> ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The (MLCT)-M-3 -> GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (h nu = 1530 cm(-1)), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the (MLCT)-M-3 and the (MC)-M-3 states and suppression of the intramolecular distortion of the acceptor ligand in the (MLCT)-M-3 excited state
X-ray Spectrometer
An x-ray spectrometer includes: an x-ray plasma source that produces first x-rays; an x-ray optic in optical communication with the x-ray plasma source and that: receives the first x-rays from the x-ray plasma source; focuses the first x-rays to produce second x-rays; and communicates the second x-rays to a sample that produces product x-rays in response to receipt of the second x-rays and second light; and a microcalorimeter array detector in optical communication with the sample and that receives the product x-rays from the sample