Advanced Lithium Ion Battery Materials Prepared with Atomic Layer Deposition

As the world consumes the dwindling supply of fossil fuels, an alternative to gasoline powered vehicles will become necessary. Lithium ion batteries (LIBs) are emerging as the dominant power source for portable electronics, and are seen as a promising energy source in the development of electric vehicles. Current LIB technology is not well suited for vehicles, increases in the energy density, power density and durability are needed before LIB are ready for widespread use in electric vehicles. LiCoO2 and graphite are the dominant cathode and anode active materials, respectively in LIBs. On the cathode side, instabilities in LiCoO2 can lead to the deterioration of the LIB. Decomposition of electrolyte on the graphite anode surface to form a solid-electrolyte interphase (SEI) consumes lithium from the cathode resulting in a lower battery capacity. Instabilities in the in the SEI can result in catastrophic battery failure. Previous studies have employed metal oxides films, typically grown with wet chemical techniques, to stabilize LiCoO2 and mitigate the formation of the SEI on graphite. The thicknesses of films grown with wet chemical techniques was typically ∼50-1000 Å. In order to achieve higher power densities, the particle size of LIB active materials is being scaled down. As active materials get smaller the mass contribution of a protective film can become a significant fraction of the total mass. Atomic layer deposition (ALD) has been used to grow ultra thin films of Al2O3 on LiCoO2 and graphite. By altering the interaction between the active material and the battery electrolyte it was possible to improve the stability of both LiCoO2 and graphite electrodes in LIBs. In the case of graphite, the Al2O3 film may be thought of as an artificial SEI. During the initial charge-discharge cycle of a LIB, the electrolyte decomposes on the anode to form the SEI. The formation of the SEI is believed to prevent further decomposition of the electrolyte on the anode surface. The SEI contains electrolyte decomposition products including Li2CO3, Li2O, LiOH, LiF and R-OLi. In order to grow a truly artificial SEI on the graphite anode, i.e. grow a film that mimics the SEI that forms during charge-discharge cycling, new ALD chemistries for the growth of Li2CO3 and LiOH have been developed. The ALD of an artificial SEI layer may limit lithium loss and improve the capacity stability during charge-discharge cycles

Thermal atomic layer etching of germanium-rich SiGe using an oxidation and "conversion-etch" mechanism

The thermal atomic layer etching (ALE) of germanium-rich SiGe was demonstrated using an oxidation and "conversion-etch" mechanism with oxygen (O-2) or ozone (O-3), hydrofluoric acid (HF), and trimethylaluminum [TMA, Al(CH3)(3)] as the reactants. The crystalline germanium-rich SiGe film was prepared using physical vapor deposition and had a composition of Si0.15Ge0.85. In situ spectroscopic ellipsometry was employed to monitor the thickness of both the SiGe film and the surface oxide layer on the SiGe film during thermal ALE. Using a reactant sequence of O-2-HF-TMA, the etch rate of the SiGe film increased progressively with temperatures from 225 to 290 degrees C. At 290 degrees C, the SiGe film thickness decreased linearly at a rate of 0.57 angstrom /cycle with a surface oxide thickness of 18-19 angstrom. This etch rate was obtained using reactant pressures of 25, 0.2, and 0.4Torr and doses of 1.5, 1.0, and 1.0s for O-2, HF, and TMA, respectively. The TMA and HF reactions were self-limiting and the O-2 reaction was reasonably self-limiting at 290 degrees C. Using an O-3-HF-TMA reaction sequence, the SiGe ALE etch rate was 0.42 angstrom /cycle at 290 degrees C. This etch rate was obtained using reactant pressures of 15, 0.2, and 0.4Torr and dose times of 0.5, 1.0, and 1.0s for O-3, HF, and TMA, respectively. The O-3, TMA, and HF reactions were all self-limiting at 290 degrees C. Atomic force microscopy images revealed that thermal ALE with the O-2-HF-TMA or O-3-HF-TMA reaction sequences did not roughen the surface of the SiGe film. The SiGe film was etched selectively compared with Si or Si3N4 at 290 degrees C using an O-2-HF-TMA reaction sequence. The etch rate for the SiGe film was >10 times faster than Si(100) or Si3N4 that was prepared using low-pressure chemical vapor deposition. This selectivity for the SiGe film will be useful to fabricate Si nanowires and nanosheets using SiGe as the sacrificial layer.Peer reviewe

Ultrathin Oxide Films by Atomic Layer Deposition on Graphene

In this paper, a method is presented to create and characterize mechanically robust, free standing, ultrathin, oxide films with controlled, nanometer-scale thickness using Atomic Layer Deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 \pm 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes and flexible electronics.Comment: Nano Letters (just accepted

A guide to photosynthetic gas exchange measurements:Fundamental principles, best practice and potential pitfalls

Gas exchange measurements enable mechanistic insights into the processes that underpin carbon and water fluxes in plant leaves which in turn inform understanding of related processes at a range of scales from individual cells to entire ecosytems. Given the importance of photosynthesis for the global climate discussion it is important to (a) foster a basic understanding of the fundamental principles underpinning the experimental methods used by the broad community, and (b) ensure best practice and correct data interpretation within the research community. In this review, we outline the biochemical and biophysical parameters of photosynthesis that can be investigated with gas exchange measurements and we provide step‐by‐step guidance on how to reliably measure them. We advise on best practices for using gas exchange equipment and highlight potential pitfalls in experimental design and data interpretation. The Supporting Information contains exemplary data sets, experimental protocols and data‐modelling routines. This review is a community effort to equip both the experimental researcher and the data modeller with a solid understanding of the theoretical basis of gas‐exchange measurements, the rationale behind different experimental protocols and the approaches to data interpretation

Centre of pressure characteristics in normal, planus and cavus feet

Background The aim of this study was to compare centre of pressure (COP) characteristics between healthy adults with normal, planus or cavus feet who were allocated to groups based on reliable foot posture measurement techniques. Methods Ninety-two healthy adult participants (aged 18 to 45) were recruited and classified as either normal (n = 35), pes planus (n = 31) or pes cavus (n = 26) based on Foot Posture Index, Arch Index and normalised navicular height truncated measurements. Barefoot walking trials were conducted using an emed®-x 400 plantar pressure system (Novel GmbH, Munich, Germany). Average, maximum, minimum and range (difference between maximum and minimum) values were calculated for COP velocity and lateral-medial force index during loading response, midstance, terminal stance and pre-swing phases of stance. The COP excursion index was also calculated. One-way analyses of variance were used to compare the three foot posture groups. Results The cavus foot exhibited the slowest average and minimum COP velocity during terminal stance, but this pattern was reversed during pre-swing, when the cavus foot exhibited the fastest maximum COP velocity. The planus foot exhibited the smallest lateral medial force index range during terminal stance. There were no differences between the groups for COP excursion index. Conclusion These findings indicate that there are differences in COP characteristics between foot postures, which may represent different mechanisms for generating force to facilitate forward progression of the body during the propulsive phases of gait

Structural brain correlates of serum and epigenetic markers of inflammation in major depressive disorder

Funding Information: Generation Scotland received core support from the Chief Scientist Office of the Scottish Government Health Directorates [CZD/16/6] and the Scottish Funding Council [HR03006] and is currently supported by the Wellcome Trust [216767/Z/19/Z]. Genotyping of the GS:SFHS samples was carried out by the Genetics Core Laboratory at the Edinburgh Clinical Research Facility, University of Edinburgh, Scotland and was funded by the Medical Research Council UK and the Wellcome Trust (Wellcome Trust Strategic Award “STratifying Resilience and Depression Longitudinally” (STRADL) Reference 104036/Z/14/Z). CG is supported by The Medical Research Council and The University of Edinburgh through the Precision Medicine Doctoral Training program. SRC is supported by the UK Medical Research Council [MR/R024065/1] and a National Institutes of Health (NIH) research grant R01AG054628. Acknowledgements The authors thank all of the STRADL and Generation Scotland participants for their time and effort taking part in this study. We would also like to thank all of the research assistants, clinicians and technicians for their help in the collecting this data.Peer reviewedPublisher PD

A Major Determinant of Cyclophilin Dependence and Cyclosporine Susceptibility of Hepatitis C Virus Identified by a Genetic Approach

Since the advent of genome-wide small interfering RNA screening, large numbers of cellular cofactors important for viral infection have been discovered at a rapid pace, but the viral targets and the mechanism of action for many of these cofactors remain undefined. One such cofactor is cyclophilin A (CyPA), upon which hepatitis C virus (HCV) replication critically depends. Here we report a new genetic selection scheme that identified a major viral determinant of HCV's dependence on CyPA and susceptibility to cyclosporine A. We selected mutant viruses that were able to infect CyPA-knockdown cells which were refractory to infection by wild-type HCV produced in cell culture. Five independent selections revealed related mutations in a single dipeptide motif (D316 and Y317) located in a proline-rich region of NS5A domain II, which has been implicated in CyPA binding. Engineering the mutations into wild-type HCV fully recapitulated the CyPA-independent and CsA-resistant phenotype and four putative proline substrates of CyPA were mapped to the vicinity of the DY motif. Circular dichroism analysis of wild-type and mutant NS5A peptides indicated that the D316E/Y317N mutations (DEYN) induced a conformational change at a major CyPA-binding site. Furthermore, nuclear magnetic resonance experiments suggested that NS5A with DEYN mutations adopts a more extended, functional conformation in the putative CyPA substrate site in domain II. Finally, the importance of this major CsA-sensitivity determinant was confirmed in additional genotypes (GT) other than GT 2a. This study describes a new genetic approach to identifying viral targets of cellular cofactors and identifies a major regulator of HCV's susceptibility to CsA and its derivatives that are currently in clinical trials

Genome-Wide Association Study of Circadian Rhythmicity in 71,500 UK Biobank Participants and Polygenic Association with Mood Instability

Background: Circadian rhythms are fundamental to health and are particularly important for mental wellbeing. Disrupted rhythms of rest and activity are recognised as risk factors for major depressive disorder and bipolar disorder. Methods: We conducted a genome-wide association study (GWAS) of low relative amplitude (RA), an objective measure of rest-activity cycles derived from the accelerometer data of 71,500 UK Biobank participants. Polygenic risk scores (PRS) for low RA were used to investigate potential associations with psychiatric phenotypes. Outcomes: Two independent genetic loci were associated with low RA, within genomic regions for Neurofascin (NFASC) and Solute Carrier Family 25 Member 17 (SLC25A17). A secondary GWAS of RA as a continuous measure identified a locus within Meis Homeobox 1 (MEIS1). There were no significant genetic correlations between low RA and any of the psychiatric phenotypes assessed. However, PRS for low RA was significantly associated with mood instability across multiple PRS thresholds (at PRS threshold 0·05: OR = 1·02, 95% CI = 1·01–1·02, p = 9·6 × 10−5), and with major depressive disorder (at PRS threshold 0·1: OR = 1·03, 95% CI = 1·01–1·05, p = 0·025) and neuroticism (at PRS threshold 0·5: Beta = 0·02, 95% CI = 0·007–0·04, p = 0·021). Interpretation: Overall, our findings contribute new knowledge on the complex genetic architecture of circadian rhythmicity and suggest a putative biological link between disrupted circadian function and mood disorder phenotypes, particularly mood instability, but also major depressive disorder and neuroticism. Funding: Medical Research Council (MR/K501335/1)