Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering

Recent advances in battery science and technology have triggered both the challenges and opportunities on studying the materials and interfaces in batteries. Here, we review the recent demonstrations of soft X-ray spectroscopy for studying the interfaces and electrode materials. The focus of this review is on the recently developed mapping of resonant inelastic X-ray scattering (mRIXS) as a powerful probe of battery chemistry with superior sensitivity. Six different channels of soft X-ray absorption spectroscopy (sXAS) are introduced for different experimental purposes. Although conventional sXAS channels remain effective tools for quantitative analysis of the transition-metal states and surface chemistry, we elaborate the limitations of sXAS in both cationic and anionic redox studies. Particularly, based on experimental findings in various electrodes, we show that sXAS is unreliable for studying oxygen redox. We then demonstrate the mRIXS as a reliable technique for fingerprinting oxygen redox and summarize several crucial observations. We conclude that mRIXS is the tool-of-choice to study both the practical issue on reversibility of oxygen redox and the fundamental nature of bulk oxygen states. We hope this review clarifies the popular misunderstanding on oxygen sXAS results of oxide electrodes, and establishes a reliable technique for detecting oxygen redox through mRIXS

Two-terminal write-once-read-many-times memory device based on charging-controlled current modulation in Al/Al-Rich Al 2O 3/p-Si diode

A write-once-read-many-times (WORM) memory device was realized based on the charging-controlled modulation in the current conduction of Al/Al-rich Al 2O 3/p-type Si diode. A large increase in the reverse current of the diode could be achieved with a negative charging voltage, e.g., charging at -25 V for 1 ms results in a current increase by about four orders. Memory states of the WORM device could be altered by changing the current conduction with charge trapping in the Al-rich Al 2O 3 layer. The memory exhibited good reading endurance and retention characteristics. © 2011 IEEE.published_or_final_versio

Holographic colour prints for enhanced optical security by combined phase and amplitude control.

Conventional optical security devices provide authentication by manipulating a specific property of light to produce a distinctive optical signature. For instance, microscopic colour prints modulate the amplitude, whereas holograms typically modulate the phase of light. However, their relatively simple structure and behaviour is easily imitated. We designed a pixel that overlays a structural colour element onto a phase plate to control both the phase and amplitude of light, and arrayed these pixels into monolithic prints that exhibit complex behaviour. Our fabricated prints appear as colour images under white light, while projecting up to three different holograms under red, green, or blue laser illumination. These holographic colour prints are readily verified but challenging to emulate, and can provide enhanced security in anti-counterfeiting applications. As the prints encode information only in the surface relief of a single polymeric material, nanoscale 3D printing of customised masters may enable their mass-manufacture by nanoimprint lithography

Capacitance switching in SiO 2 thin film embedded with Ge nanocrystals caused by ultraviolet illumination

A structure of indium tin oxide/ SiO 2 embedded with Ge nanocrystal (nc-Ge) /p-Si substrate was fabricated. The capacitance of the structure can be switched to a high-capacitance or low-capacitance state by an ultraviolet (UV) illumination. The increase (or decrease) in the capacitance is accompanied with the decrease (or increase) in the oxide resistance. The capacitance switching is explained in terms of the UV illumination-induced charging and discharging in the nc-Ge. © 2009 American Institute of Physics.published_or_final_versio

Resistive switching in aluminum/anodized aluminum film structure without forming process

Metal-insulator-metal (MIM) structure was fabricated by partially anodizing aluminum film followed by deposition of another aluminum film. Unipolar resistive switching between a high-resistance state and a low-resistance state with a high resistance ratio (> ∼ 10 4) was observed from the structure. The switching occurred without the requirement of a forming process, which was attributed to the pre-existing conductive filaments in the Al-rich Al x O y layer formed by the anodization. Each resistance state exhibited Ohmic behavior which could be explained by the metallic conduction and electron hopping from one isolated state to the next in the Al-rich Al x O y layer. The MIM structure showed good memory characteristics. © 2009 American Institute of Physics.published_or_final_versio

Charging-induced changes in reverse current-voltage characteristics of Al/Al-Rich Al 2O 3/p-Si Diodes

An Al-rich Al 2O 3 thin film was deposited on a p-type silicon substrate by radio frequency sputtering to form Al/ Al-rich Al 2O 3/p-Si diodes. The current-voltage (I-V) characteristics of the diodes were determined by carrier injection from either the Si substrate or the Al gate and by carrier transport along the tunneling paths formed by Al nanocrystals distributed in the oxide layer. The reverse I-V characteristics were greatly affected by the charge trapping in the oxide layer, i.e., the electron trapping significantly reduced the reverse current while the hole trapping enhanced the current significantly. However, the charge trapping did not produce a large change in the forward I-V characteristic. © 2009 IEEE.published_or_final_versio

Temperature dependence of current transport in Al/Al 2O 3 nanocomposite thin films

In this work, Al/Al 2O 3 nanocomposite thin film is deposited on Si substrate by radio frequency sputtering to form a metal-insulator-semiconductor structure. It is found that the current conduction at low fields is greatly enhanced with temperature. The current increase can be attributed to the decrease in the tunneling resistance and/or the formation of some tunneling paths due to the release of some measurement-induced charges trapped in the thin film as a result of increase in the temperature. The current conduction evolves with a trend toward a three-dimensional transport as the temperature increases. © 2011 American Institute of Physics.published_or_final_versio

Vps13-like proteins provide phosphatidylethanolamine for GPI anchor synthesis in the ER

Glycosylphosphatidylinositol (GPI) is a glycolipid membrane anchor found on surface proteins in all eukaryotes. It is synthesized in the ER membrane. Each GPI anchor requires three molecules of ethanolamine phosphate (P-Etn), which are derived from phosphatidylethanolamine (PE). We found that efficient GPI anchor synthesis in Saccharomyces cerevisiae requires Csf1; cells lacking Csf1 accumulate GPI precursors lacking P-Etn. Structure predictions suggest Csf1 is a tube-forming lipid transport protein like Vps13. Csf1 is found at contact sites between the ER and other organelles. It interacts with the ER protein Mcd4, an enzyme that adds P-Etn to nascent GPI anchors, suggesting Csf1 channels PE to Mcd4 in the ER at contact sites to support GPI anchor biosynthesis. CSF1 has orthologues in Caenorhabditis elegans (lpd-3) and humans (KIAA1109/TWEEK); mutations in KIAA1109 cause the autosomal recessive neurodevelopmental disorder Alkuraya-Kučinskas syndrome. Knockout of lpd-3 and knockdown of KIAA1109 reduced GPI-anchored proteins on the surface of cells, suggesting Csf1 orthologues in human cells support GPI anchor biosynthesis

Mammalian cell growth dynamics in mitosis

The extent and dynamics of animal cell biomass accumulation during mitosis are unknown, primarily because growth has not been quantified with sufficient precision and temporal resolution. Using the suspended microchannel resonator and protein synthesis assays, we quantify mass accumulation and translation rates between mitotic stages on a single-cell level. For various animal cell types, growth rates in prophase are commensurate with or higher than interphase growth rates. Growth is only stopped as cells approach metaphase-to-anaphase transition and growth resumes in late cytokinesis. Mitotic arrests stop growth independently of arresting mechanism. For mouse lymphoblast cells, growth in prophase is promoted by CDK1 through increased phosphorylation of 4E-BP1 and cap-dependent protein synthesis. Inhibition of CDK1-driven mitotic translation reduces daughter cell growth. Overall, our measurements counter the traditional dogma that growth during mitosis is negligible and provide insight into antimitotic cancer chemotherapies

Momentum-resolved resonant inelastic soft X-ray scattering (qRIXS) endstation at the ALS

A momentum resolved resonant inelastic X-ray scattering (qRIXS) experimental station with continuously rotatable spectrometers and parallel detection is designed to operate at different beamlines at synchrotron and free electron laser (FEL) facilities. This endstation, currently located at the Advanced Light Source (ALS), has five emission ports on the experimental chamber for mounting the high-throughput modular soft X-ray spectrometers (MXS) [24]. Coupled to the rotation from the supporting hexapod, the scattered X-rays from 27.5° (forward scattering) to 152.5° (backward scattering) relative to the incident photon beam can be recorded, enabling the momentum-resolved RIXS spectroscopy. The components of this endstation are described in details, and the preliminary RIXS measurements on highly oriented pyrolytic graphite (HOPG) reveal the low energy vibronic excitations from the strong electron-phonon coupling at C K edge around σ* band. The grating upgrade option to enhance the performance at low photon energies is presented and the potential of this spectroscopy is discussed in summary