342 research outputs found
Orgin of Subgap Features in Transparent Amorphous Oxide Semiconductors
Amorphous indium gallium zinc oxide (a-IGZO) is a transparent amorphous oxide semiconductor (TAOS) that has shown promise as transparent thin film transistors (TTFTs) in various display applications. Within a-IGZO films, states can form in the band gap that hinder TTFT performance. In order to elucidate the origin of these states, we examined the formation of the subgap states for a-IGZO thin films with various compositions. We observed a positive correlation between the subgap formation and the percentage of oxygen ruling out oxygen deficiencies as a factor in the formation of subgap states. Furthermore, metallic indium crystallites were observed to form for samples grown in oxygen deficient conditions. Our studies reveal that subgap states are due to oxygen with few surrounding metal neighbors and indium with few surrounding oxygen neighbors. The subgap states can be suppressed in a-IGZO (and other TAOS) by careful choice of composition
NF-protocadherin and TAF1 regulate retinal axon initiation and elongation in vivo
NF-protocadherin (NFPC)-mediated cell–cell adhesion plays a critical role in vertebrate neural tube formation. NFPC is also expressed during the period of axon tract formation, but little is known about its function in axonogenesis. Here we have tested the role of NFPC and its cytosolic cofactor template-activating factor 1 (TAF1) in the emergence of the Xenopus retinotectal projection. NFPC is expressed in the developing retina and optic pathway and is abundant in growing retinal axons. Inhibition of NFPC function in developing retinal ganglion cells (RGCs) severely reduces axon initiation and elongation and suppresses dendrite genesis. Furthermore, an identical phenotype occurs when TAF1 function is blocked. These data provide evidence that NFPC regulates axon initiation and elongation and indicate a conserved role for TAF1, a transcriptional regulator, as a downstream cytosolic effector of NFPC in RGCs
X-Ray Spectroscopy of Ultra-Thin Oxide/Oxide Heteroepitaxial Films: A Case Study of Single-Nanometer VO2/TiO2
Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically \u3c 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe a low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Our results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. More generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions
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Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes.
The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na0.6[Li0.2Mn0.8]O2 and compare it with Na2/3[Mg1/3Mn2/3]O2. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na0.6[Li0.2Mn0.8]O2 stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na2/3[Mg1/3Mn2/3]O2. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes
Visible light-driven H2 production over highly dispersed Ruthenia on Rutile TiO2 nanorods
The immobilization of miniscule quantities of RuO2 (~0.1%) onto one-dimensional (1D) TiO2 nanorods (NRs) allows H2 evolution from water under visible light irradiation. Rod-like rutile TiO2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO2(110) grown as 1D nanowires on rutile TiO2(110), which occurs only at extremely low loads of RuO2, leads to the formation of a heterointerface that efficiently adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.Peer ReviewedPostprint (published version
The Anode Challenge for Lithium-Ion Batteries: A Mechanochemically Synthesized Sn-Fe-C Composite Anode Surpasses Graphitic Carbon
Carbon-based anodes are the key limiting factor in increasing the volumetric capacity of lithium-ion batteries. Tin-based composites are one alternative approach. Nanosized Sn-Fe-C anode materials are mechanochemically synthesized by reducing SnO with Ti in the presence of carbon. The optimum synthesis conditions are found to be 1:0.25:10 for initial ratio of SnO, Ti, and graphite with a total grinding time of 8 h. This optimized composite shows excellent extended cycling at the C/10 rate, delivering a first charge capacity as high as 740 mAh g(-1) and 60% of which still remained after 170 cycles. The calculated volumetric capacity significantly exceeds that of carbon. It also exhibits excellent rate capability, delivering volumetric capacity higher than 1.6 Ah cc(-1) over 140 cycles at the 1 C rate
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How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode-Electrolyte Interface when Addressing Oxygen Redox.
Sensitivity to the "bulk" oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes-Li2MnO3, Li-rich NMC, and NMC 442-that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer
High Reversibility of Lattice Oxygen Redox in Na-ion and Li-ion Batteries Quantified by Direct Bulk Probes of both Anionic and Cationic Redox Reactions
The reversibility and cyclability of anionic redox in battery electrodes hold
the key to its practical employments. Here, through mapping of resonant
inelastic X-ray scattering (mRIXS), we have independently quantified the
evolving redox states of both cations and anions in Na2/3Mg1/3Mn2/3O2. The
bulk-Mn redox emerges from initial discharge and is quantified by
inverse-partial fluorescence yield (iPFY) from Mn-L mRIXS. Bulk and surface Mn
activities likely lead to the voltage fade. O-K super-partial fluorescence
yield (sPFY) analysis of mRIXS shows 79% lattice oxygen-redox reversibility
during initial cycle, with 87% capacity sustained after 100 cycles. In
Li1.17Ni0.21Co0.08Mn0.54O2, lattice-oxygen redox is 76% initial-cycle
reversible but with only 44% capacity retention after 500 cycles. These results
unambiguously show the high reversibility of lattice-oxygen redox in both
Li-ion and Na-ion systems. The contrast between Na2/3Mg1/3Mn2/3O2 and
Li1.17Ni0.21Co0.08Mn0.54O2 systems suggests the importance of distinguishing
lattice-oxygen redox from other oxygen activities for clarifying its intrinsic
properties.Comment: 33 pages, 8 Figures. Plus 14 pages of Supplementary Materials with 12
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Oxygen hole formation controls stability in LiNiO2 cathodes
Ni-rich lithium-ion cathode materials achieve both high voltages and capacities but are prone to structural instabilities and oxygen loss. The origin of the instability lies in the pronounced oxidation of O during delithiation: for LiNiO2, NiO2, and the rock salt NiO, density functional theory and dynamical mean-field theory calculations based on maximally localized Wannier functions yield a Ni charge state of ca. +2, with O varying between −2 (NiO), −1.5 (LiNiO2), and −1 (NiO2). Calculated X-ray spectroscopy Ni K and O K-edge spectra agree well with experimental spectra. Using ab initio molecular dynamics simulations, we observe loss of oxygen from the (012) surface of delithiated LiNiO2, two surface O⋅− radicals combining to form a peroxide ion, and the peroxide ion being oxidized to form O2, leaving behind two O vacancies and two O2− ions. Preferential release of 1O2 is dictated via the singlet ground state of the peroxide ion and spin conservation
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