Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium–manganese rich cathode material of composition Li1 + xM1 – xO2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface

Interface Engineering for Atomic Layer Deposited Alumina Gate Dielectric on SiGe Substrates.

Optimization of the interface between high-k dielectrics and SiGe substrates is a challenging topic due to the complexity arising from the coexistence of Si and Ge interfacial oxides. Defective high-k/SiGe interfaces limit future applications of SiGe as a channel material for electronic devices. In this paper, we identify the surface layer structure of as-received SiGe and Al2O3/SiGe structures based on soft and hard X-ray photoelectron spectroscopy. As-received SiGe substrates have native SiOx/GeOx surface layers, where the GeOx-rich layer is beneath a SiOx-rich surface. Silicon oxide regrows on the SiGe surface during Al2O3 atomic layer deposition, and both SiOx and GeOx regrow during forming gas anneal in the presence of a Pt gate metal. The resulting mixed SiOx-GeOx interface layer causes large interface trap densities (Dit) due to distorted Ge-O bonds across the interface. In contrast, we observe that oxygen-scavenging Al top gates decompose the underlying SiOx/GeOx, in a selective fashion, leaving an ultrathin SiOx interfacial layer that exhibits dramatically reduced Dit

Interface Engineering for Atomic Layer Deposited Alumina Gate Dielectric on SiGe Substrates.

Optimization of the interface between high-k dielectrics and SiGe substrates is a challenging topic due to the complexity arising from the coexistence of Si and Ge interfacial oxides. Defective high-k/SiGe interfaces limit future applications of SiGe as a channel material for electronic devices. In this paper, we identify the surface layer structure of as-received SiGe and Al2O3/SiGe structures based on soft and hard X-ray photoelectron spectroscopy. As-received SiGe substrates have native SiOx/GeOx surface layers, where the GeOx-rich layer is beneath a SiOx-rich surface. Silicon oxide regrows on the SiGe surface during Al2O3 atomic layer deposition, and both SiOx and GeOx regrow during forming gas anneal in the presence of a Pt gate metal. The resulting mixed SiOx-GeOx interface layer causes large interface trap densities (Dit) due to distorted Ge-O bonds across the interface. In contrast, we observe that oxygen-scavenging Al top gates decompose the underlying SiOx/GeOx, in a selective fashion, leaving an ultrathin SiOx interfacial layer that exhibits dramatically reduced Dit

Photocathode device using diamondoid and cesium bromide films

A photocathode structure is presented that shows promise for use in high brightness electron sources. The structure consists of a metal substrate, a monolayer of a diamondoid derivative, and a thin film of cesium bromide. Diamondoid monolayers reduce the energy spread of electron emitters, while cesium bromide increases the yield and stability of cathodes. We demonstrate that the combined structure retains these properties, producing an emitter with lower energy spread than the corresponding cesium bromide emitter (1.06?eV versus 1.45?eV) and higher yield and stability than un-coated diamondoid emitters

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

Boron Reconstructed Si(111) Surfaces Produced by B2O3 Decomposition

Scanning tunneling microscopy has been used to study the growth of boron on the Si(111) surface. Boron was deposited in the form of B2O3 which was decomposed by heating the substrate. With this technique, it is possible to control the B coverage, and also to produce the well known √3 x √3 reconstruction at annealing temperatures as low as 600°C. The optimal conditions for the formation of the √3 x √3 surface by B2O3 decomposition are given. In addition, the nature of the √3 x √3 surface over a range of B coverages and annealing temperatures is described

Subspace Modeling for Fast and High-sensitivity X-ray Chemical Imaging

Resolving morphological chemical phase transformations at the nanoscale is ofvital importance to many scientific and industrial applications across variousdisciplines. The TXM-XANES imaging technique, by combining full fieldtransmission X-ray microscopy (TXM) and X-ray absorption near edge structure(XANES), has been an emerging tool which operates by acquiring a series ofmicroscopy images with multi-energy X-rays and fitting to obtain the chemicalmap. Its capability, however, is limited by the poor signal-to-noise ratios dueto the system errors and low exposure illuminations for fast acquisition. Inthis work, by exploiting the intrinsic properties and subspace modeling of theTXM-XANES imaging data, we introduce a simple and robust denoising approach toimprove the image quality, which enables fast and high-sensitivity chemicalimaging. Extensive experiments on both synthetic and real datasets demonstratethe superior performance of the proposed method.<br