XPS on Li-Battery-Related Compounds: Analysis of Inorganic SEI Phases and a Methodology for Charge Correction

Accurate identification of chemical phases associated with the electrode and solid electrolyte interphase (SEI) is critical for understanding and controlling interfacial degradation mechanisms in lithium containing battery systems. To study these critical battery materials and interfaces X ray photoelectron spectroscopy (XPS) is a widely used technique that provides quantitative chemical insights. However, due to the fact that a majority of chemical phases relevant to battery interfaces are poor electronic conductors, phase identification that relies primarily on absolute XPS core level binding-energies (BEs) can be problematic. Charging during XPS measurements leads to BE shifts that can be difficult to correct. These difficulties are often exacerbated by the coexistence of multiple Li containing phases in the SEI with overlapping XPS core levels. To facilitate accurate phase identification of battery relevant phases, we propose a straightforward approach for removing charging effects from XPS data sets. We apply this approach to XPS data sets acquired from six battery relevant inorganic phases including lithium metal (Li0), lithium oxide (Li2O), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium carbonate (Li2CO3), and lithium nitride (Li3N). Specifically, we demonstrate that BE separations between core levels present in a particular phase (e.g. BE separation between the O 1s and Li 1s core levels in Li2O) provide an additional constraint that can significantly improve reliability of phase identification. Finally, as an exemplary case we apply the charge-correction methodology to XPS data acquired from a symmetric cell based on a Li2S P2S5 solid electrolyte. This analysis demonstrates that accurately accounting for XPS BE shifts as a function of current-bias conditions can provide a direct probe of ionic conductivities associated with battery materials

A study of Pt-/alpha-Fe2O3 nanocomposites by XPS

alpha-Fe2O3 matrices were deposited on Fluorine-doped Tin Oxide (FTO) substrates by Plasma Enhanced- Chemical Vapor Deposition (PE-CVD) from Fe(hfa)_2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N’,N’-tetramethylethylenediamine). The obtained nanosystems were subsequently functionalized by platinum nanoparticles (NPs) via Radio Frequency (RF)-sputtering, exposing samples either to a pre- or post-sputtering thermal treatment at 650°C for one hour in air. Interestingly, Pt oxidation state in the final composite systems strongly depended on the adopted processing conditions. In this work, a detailed X-ray Photoelectron Spectroscopy (XPS) analysis was carried out in order to investigate the material chemical composition, with particular regard to the relative Pt(0)/Pt(II)/Pt(IV) content. The obtained results evidenced that, when annealing is performed prior to sputtering, only PtO and PtO2 are revealed in the final Pt/alpha-Fe2O3 nanocomposite. In a different way, annealing after sputtering results in the co-presence of Pt(0), Pt(II) and Pt(IV) species, the former arising from the thermal decomposition of PtO2 to metallic platinum

Effect of 3d-doping on the electronic structure of BaFe2As2

The electronic structure of BaFe2As2 doped with Co, Ni, and Cu has been studied by a variety of experimental and theoretical methods, but a clear picture of the dopant 3d states has not yet emerged. Herein we provide experimental evidence of the distribution of Co, Ni, and Cu 3d states in the valence band. We conclude that the Co and Ni 3d states provide additional free carriers to the Fermi level, while the Cu 3d states are found at the bottom of the valence band in a localized 3d10 shell. These findings help shed light on why superconductivity can occur in BaFe2As2 doped with Co and Ni but not Cu.Comment: 18 pages, 8 figure

Search for an Near-IR Counterpart to the Cas A X-ray Point Source

We report deep near-infrared and optical observations of the X-ray point source in the Cassiopeia A supernova remnant, CXO J232327.9+584842. We have identified a J=21.4 +/- 0.3 mag and Ks=20.5 +/- 0.3 mag source within the 1-sigma error circle, but we believe this source is a foreground Pop II star with Teff=2600-2800 K at a distance of ~2 kpc, which could not be the X-ray point source. We do not detect any sources in this direction at the distance of Cas A, and therefore place 3-sigma limits of R >~ 25 mag, F675W >~ 27.3 mag, J >~ 22.5 mag and Ks >~ 21.2 mag (and roughly H >~ 20 mag) on emission from the X-ray point source, corresponding to M_{R} >~ 8.2 mag, M_{F675W} >~ 10.7 mag, M_{J} >~ 8.5 mag, M_{H} >~ 6.5 mag, and M_{Ks} >~ 8.0 mag, assuming a distance of 3.4 kpc and an extinction A_{V}=5 mag.Comment: 14 pages, 7 figures. Accepted by Ap

A photoelectron spectroscopy study of the electronic structure evolution in CuInSe2-related compounds at changing copper content

Evolution of the valence-band structure at gradually increasing copper content has been analysed by x-ray photoelectron spectroscopy (XPS) in In2Se3, CuIn5Se8, CuIn3Se5, and CuInSe2 single crystals. A comparison of these spectra with calculated total and angular-momentum resolved density-of-states (DOS) revealed the main trends of this evolution. The formation of the theoretically predicted gap between the bonding and non-bonding states has been observed in both experimental XPS spectra and theoretical DOS

Site-specific probing of charge transfer dynamics in organic photovoltaics

We report the site-specific probing of charge-transfer dynamics in a prototype system for organic photovoltaics (OPV) by picosecond time-resolved X-ray photoelectron spectroscopy. A layered system consisting of approximately two monolayers of C$_{60}$ deposited on top of a thin film of Copper-Phthalocyanine (CuPC) is excited by an optical pump pulse and the induced electronic dynamics are probed with 590 eV X-ray pulses. Charge transfer from the electron donor (CuPC) to the acceptor (C$_{60}$) and subsequent charge carrier dynamics are monitored by recording the time-dependent C 1$s$ core level photoemission spectrum of the system. The arrival of electrons in the C$_{60}$ layer is readily observed as a completely reversible, transient shift of the C$_{60}$ associated C 1$s$ core level, while the C 1$s$ level of the CuPC remains unchanged. The capability to probe charge transfer and recombination dynamics in OPV assemblies directly in the time domain and from the perspective of well-defined domains is expected to open additional pathways to better understand and optimize the performance of this emerging technology

Gravitational Lensing by Wormholes

Gravitational lensing by traversable Lorentzian wormholes is a ew possibility which is analyzed here in the strong field limit. Wormhole solutions are considered in the Einstein minimally coupled theory and in the brane world model. The observables in both the theories show significant differences from those arising in the Schwarzschild black hole lensing. As a corollary, it follows that wormholes with zero Keplerian mass exhibit lensing properties which are qualitatively (though not quantitatively) the same as those of a Schwarzschild black hole. Some special features of the considered solutions are pointed out.Comment: 20 pages, no figure