ToF-SIMS Li Depth Profiling of Pure and Methylated Amorphous Silicon Electrodes After Their Partial Lithiation.

Pure (a-Si:H) and methylated [a-Si0.95(CH3)0.05:H] amorphous silicon thin films were analyzed by time-of-flight secondary ion mass spectrometry after partial lithiation. Depth profiling gives insights into the lithiation mechanism of the material, enabling us to study the detailed biphasic process in the first lithiation process. Lithiation induces swelling and roughening of the active layer. In both a-Si:H and a-Si0.95(CH3)0.05:H, no measurable Li diffusion was observed after stopping current-induced lithiation. After applying the same lithiation charges, distinct Li profiles were observed for these two materials. Unlike a-Si:H, the Li concentration drops slowly from the heavily lithiated region to the non-lithiated region in a-Si0.95(CH3)0.05:H. This apparent progressive transition between the lithiated and lithium-free regions is attributed to the presence of nanovoids inside the material. When their concentration is high enough, these nanovoids constitute favorable quasi-percolating paths for lithium during the first lithiation. A specific model was developed to simulate the Li depth profiles, fully supporting this hypothesis.

Influence of Carbonate Solvents on Solid Electrolyte Interphase Composition over Si Electrodes Monitored by In Situ and Ex Situ Spectroscopies.

A solid electrolyte interphase (SEI) layer on Si-based anodes should have high mechanical properties to adapt the volume changes of Si with low thickness and good ionic conductivity. To better understand the influence of carbonate solvents on the SEI composition and mechanism of formation, systematic studies were performed using dimethyl carbonate (DMC) or propylene carbonate (PC) solvent and LiPF6 as a salt. A 1 M LiPF6/EC-DMC was used for comparison. The surface chemical composition of the Si electrode was analyzed at different potentials of lithiation/delithiation and after a few cycles. Ex situ X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results demonstrate that a thinner and more stable SEI layer is formed in LiPF6/DMC. The in situ Fourier transform infrared spectroscopy proves that the coordination between Li+ and DMC is weaker, and fewer DMC molecules take part in the formation of the SEI layer. The higher capacity retention during 60 cycles and less significant morphological modifications of the Si electrode in 1 M LiPF6/DMC compared to other electrolytes were demonstrated, confirming a good and stable interfacial layer. The possible surface reactions are discussed, and the difference in the mechanisms of formation of SEI in these three various electrolytes is proposed.

Early stage of marine biofilm formation on duplex stainless steel.

The aim of this work was to investigate the bacteria-surface interactions occurring during the first hour of adhesion of marine Pseudoalteromonas NCIMB 2021 at the surface of 2304 lean duplex stainless steel in artificial seawater. A complete characterization of the biofilm and the passive film was performed coupling epifluorescence microscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and time of flight secondary ion mass spectrometry (ToF-SIMS). The coupling of XPS and ToF-SIMS analyses revealed that (1) protein and polysaccharide contents in the biofilm are similar in the presence or absence of nutrients, (2) the biofilm is mainly composed of proteins and the protein content is similar to the one of Tightly Bound EPS, (3) increased bacterial activity due to nutrients leads to chromium enrichment in the passive film in close vicinity to the bacteria.

Fast electrical modulation of strong near-field interactions between erbium emitters and graphene.

Combining the quantum optical properties of single-photon emitters with the strong near-field interactions available in nanophotonic and plasmonic systems is a powerful way of creating quantum manipulation and metrological functionalities. The ability to actively and dynamically modulate emitter-environment interactions is of particular interest in this regard. While thermal, mechanical and optical modulation have been demonstrated, electrical modulation has remained an outstanding challenge. Here we realize fast, all-electrical modulation of the near-field interactions between a nanolayer of erbium emitters and graphene, by in-situ tuning the Fermi energy of graphene. We demonstrate strong interactions with a  >1000-fold increased decay rate for  ~25% of the emitters, and electrically modulate these interactions with frequencies up to 300 kHz - orders of magnitude faster than the emitter's radiative decay (~100 Hz). This constitutes an enabling platform for integrated quantum technologies, opening routes to quantum entanglement generation by collective plasmon emission or photon emission with controlled waveform.

Local Degradation Mechanisms by Tarnishing of Protected Silver Mirror Layers Studied by Combined Surface Analysis.

In this work, we addressed the local degradation mechanisms limiting the prelaunch environmental durability of thin-layered silver stacks for demanding space mirror applications. Local initiation and propagation of tarnishing were studied by combined surface and interface analysis on model stack samples consisting of thin silver layers supported on lightweight SiC substrates and protected by thin SiO2 overcoats, deposited by cathodic magnetron sputtering and submitted to accelerated aging in gaseous H2S. The results show that tarnishing is locally initiated by the formation of Ag2S columns erupting above the stack surface. Ag2S growth is promoted at high aspect ratio defects (surface pores) of the SiC substrate as a result of an imperfect protection by the SiO2 overcoat. Channels most likely connect the silver layer to its environment through the protection layer, which enables local H2S entry and Ag2S growth. The silver sulfide columns grow in number and size eventually leading to coalescence with increasing H2S exposure. In more advanced stages, tarnishing slows down owing to saturation of all pre-existing imperfectly protected sites of preferential sulfidation. However, it progresses radially at the basis of the Ag2S columns underneath the protection layer, consuming the metallic silver layer and deteriorating the protecting overcoat.

Effects of molybdenum on the composition and nanoscale morphology of passivated austenitic stainless steel surfaces.

Surface analysis by time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy and scanning tunnelling microscopy has been applied to provide new insight on Mo effects on the composition and nanostructure of the passive films grown in sulfuric acid on well-controlled Fe-17Cr-14.5Ni-2.3Mo(100) austenitic stainless steel single crystal surfaces. A duplex hydroxylated oxide matrix, 1.8-1.9 nm thick, is formed with a strong partition between Cr(iii) and Fe(iii) in the inner and outer layers, respectively. Cr(iii) is increasingly enriched by preferential iron oxide dissolution upon passivation and ageing. Ni, only present as oxide traces in the film, is enriched in the alloy underneath. Mo, mostly present as Mo(iv) in the Cr-rich inner layer prior to anodic polarisation, becomes increasingly enriched (up to 16% of cations) mostly as Mo(vi) in the Fe-rich outer layer of the passive film, with ageing promoting this effect. Metallic Mo is not significantly enriched below the passive film produced from the native oxide covered surface. Mo does not markedly impact the nanogranular morphology of the native oxide film nor its local thickness variations assigned to substrate site effects on Cr(iii) enrichment. Site specific preferential passivation still takes place at the (native) oxide-covered step edges of the alloy surface, and transient dissolution remains preferentially located on the terraces. Nanostructures, possibly Mo-containing, and healing local depressions formed by transient dissolution during passivation, appear as a specific effect of the Mo presence. Another Mo effect, observed even after 20 h of passivation, is to prevent crystallisation at least in the Fe-rich outer part of the passive film where it is concentrated mostly as Mo(vi) (i.e. molybdate) species.

Nanometre-scale evidence for interfacial dissolution-reprecipitation control of silicate glass corrosion.

Silicate glasses are durable solids, and yet they are chemically unstable in contact with aqueous fluids-this has important implications for numerous industrial applications related to the corrosion resistance of glasses, or the biogeochemical weathering of volcanic glasses in seawater. The aqueous dissolution of synthetic and natural glasses results in the formation of a hydrated, cation-depleted near-surface alteration zone and, depending on alteration conditions, secondary crystalline phases on the surface. The long-standing accepted model of glass corrosion is based on diffusion-coupled hydration and selective cation release, producing a surface-altered zone. However, using a combination of advanced atomic-resolution analytical techniques, our data for the first time reveal that the structural and chemical interface between the pristine glass and altered zone is always extremely sharp, with gradients in the nanometre to sub-nanometre range. These findings support a new corrosion mechanism, interfacial dissolution-reprecipitation. Moreover, they also highlight the importance of using analytical methods with very high spatial and mass resolution for deciphering the nanometre-scale processes controlling corrosion. Our findings provide evidence that interfacial dissolution-reprecipitation may be a universal reaction mechanism that controls both silicate glass corrosion and mineral weathering.

The influence of the electrolyte on chemical and morphological modifications of an iron sulfide thin film negative electrode.

The chemical and morphological modifications of FeS thin film as anode material for LiBs have been studied in detail in two classical electrolytes usually used in Li-ion batteries: 1 M LiClO4-PC and 1 M LiPF6-EC/DMC. The X-ray photoelectron spectroscopic (XPS) analysis evidenced the formation of a solid electrolyte interphase (SEI) that contains a more significant amount of inorganic salt residues formed in LiPF6-EC/DMC than in LiClO4-PC, which is likely to increase the ionic resistivity of the SEI, thus impeding the lithiation-delithiation in the first cycles while improving its reversibility. Ion depth profiles performed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) show volume expansion-shrinkage of the thin film leading to cracking and pulverization of the electrode material, which is also confirmed by scanning electron microscopy (SEM) analysis. The prolonged cycling results in penetration and accumulation of the electrolyte in a bulk electrode with accumulation of the inorganic species in the inner part of the SEI enhanced in a fluoride-containing electrolyte. Cycling in these two different electrolytes leads also to formation of two different electrode morphologies: with a compact electrode structure formed in LiClO4-PC and a foam-like, porous structure in LiPF6-EC/DMC. A model of this conversion-type thin film electrode modification based on these thorough spectroscopic and microscopic analyses induced by cycling in two different electrolytes is proposed.

Effect of lithiation potential and cycling on chemical and morphological evolution of Si thin film electrode studied by ToF-SIMS.

Si thin films obtained by plasma enhanced chemical vapor deposition (PECVD) were used to investigate chemical and morphological modifications induced by lithiation potential and cycling. These modifications were thoughtfully analyzed by time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth profiling, which allows to distinguish the surface and bulk processes related to the formation of the solid electrolyte interphase (SEI) layer, and Li-Si alloying, respectively. The main results are a volume expansion/shrinkage and a dynamic behavior of the SEI layer during the single lithiation/delithiation process and multicycling. Trapping of lithium and other ions corresponding to products of electrolyte decomposition are the major reasons of electrode modifications. It is shown that the SEI layer contributes to 60% of the total volume variation of Si electrodes (100 nm). The apparent diffusion coefficient of lithium (DLi) calculated from the Fick's second law directly from Li-ion ToF-SIMS profiles is of the order of ∼5.9 × 10(-15) cm(2).s(-1). This quite low value can be explained by Li trapping in the bulk of electrode material, at the interfaces, continuous growth of the SEI layer and increase of SiO2 quantity. These modifications can result in limitation the ionic transport of Li.

Aging-induced chemical and morphological modifications of thin film iron oxide electrodes for lithium-ion batteries.

Spectroscopic (XPS, ToF-SIMS) and microscopic (SEM, AFM) analytical methods have been applied to iron oxide (∼Fe2O3) using a thin film approach to bring new insight into the aging mechanisms of conversion-type anode materials for lithium-ion batteries. The results show that repeated lithiation/delithiation causes both chemical and morphological modifications affecting the electrochemical performance. The SEI layer formed by reductive decomposition of the electrolyte remains stable in composition (mostly Li2CO3) but irreversibly thickens upon multicycling. Irreversible swelling of the material accompanied by penetration of the SEI layer and accumulation of non-deconverted material in the bulk of the oxide thin film occurs upon repeated conversion/deconversion. After initial pulverization of the thin film microstructure, grain growth and aggregation are promoted by multicycling. This leads to capacity increase in the first few cycles, but upon further cycling volume expansion and accumulation of non-deconverted material lead to deterioration of the electrode performances.

Interface stability of a TiO2/3-methoxypropionitrile-based electrolyte: first evidence for solid electrolyte interphase formation and implications.

We report an in-depth study focusing on the stability of a benchmark electrolyte composition based on a low-volatile 3-methoxypropionitrile (MPN) solvent employed in dye-sensitized solar cells. In the presence of TiO2, the semi-conductor surface plays a catalytic role in the thermal degradation of the electrolyte, which induces, among other effects, the nucleation and growth of a uniform solid electrolyte interphase (SEI) layer that wraps TiO2. On the basis of our actual understanding, we argue that SEI formation is responsible for triiodide depletion in the electrolyte during ageing and also has a simultaneous impact on TiO2 optoelectronic properties through the onset of a visible-light absorption tail, energy modification of intraband trap states, and the induction of an increase in both electron lifetime and transport time in TiO2. In-depth characterization of this layer by using XPS and ToF-SIMS indicates that the chemical composition of this SEI results from solvent and additive degradation, that is, iodide, sulfur, cyano, nitrogen, carbon, and imidazolium rings. The SEI thickness, its content, and the concentration profile strongly vary depending on the ageing conditions. The outcome of this new finding is discussed in comparison with literature observations and stresses the difficulties in reaching long-term stability at 85 °C by using MPN-based electrolytes unless new interfacial engineering is accomplished to impede pinholes between dye molecules on TiO2.

Sealing of hard CrN and DLC coatings with atomic layer deposition.

Atomic layer deposition (ALD) is a thin film deposition technique that is based on alternating and saturating surface reactions of two or more gaseous precursors. The excellent conformality of ALD thin films can be exploited for sealing defects in coatings made by other techniques. Here the corrosion protection properties of hard CrN and diamond-like carbon (DLC) coatings on low alloy steel were improved by ALD sealing with 50 nm thick layers consisting of Al2O3 and Ta2O5 nanolaminates or mixtures. In cross sectional images the ALD layers were found to follow the surface morphology of the CrN coatings uniformly. Furthermore, ALD growth into the pinholes of the CrN coating was verified. In electrochemical measurements the ALD sealing was found to decrease the current density of the CrN coated steel by over 2 orders of magnitude. The neutral salt spray (NSS) durability was also improved: on the best samples the appearance of corrosion spots was delayed from 2 to 168 h. On DLC coatings the adhesion of the ALD sealing layers was weaker, but still clear improvement in NSS durability was achieved indicating sealing of the pinholes.

Effect of protein adsorption on the corrosion behavior of 70Cu-30Ni alloy in artificial seawater.

Copper alloys often used in cooling circuits of industrial plants can be affected by biocorrosion induced by biofilm formation. The objective of this work was to study the influence of protein adsorption, which is the first step in biofilm formation, on the electrochemical behavior of 70Cu-30Ni (wt.%) alloy in static artificial seawater and on the chemical composition of oxide layers. For that purpose, electrochemical measurements performed after 1h of immersion were combined to surface analyses. A model is proposed to analyze impedance data. In the presence of bovine serum albumin (BSA, model protein), the anodic charge transfer resistance deduced from EIS data at Ecorr is slightly higher, corresponding to lower corrosion current. Without BSA, two oxidized layers are shown by XPS and ToF-SIMS: an outer layer mainly composed of copper oxide (Cu2O redeposited layer) and an inner layer mainly composed of oxidized nickel, with a global thickness of ~30nm. The presence of BSA leads to a mixed oxide layer (CuO, Cu2O, Ni(OH)2) with a lower thickness (~10nm). Thus, the protein induces a decrease of the dissolution rate at Ecorr and hence a decrease of the amount of redeposited Cu2O and of the oxide layer thickness.

(2-Thienylmethyl)ammonium trichlorostannate(II): a hybrid salt.

The structure of the title hybrid salt, (C(5)H(8)NS)[SnCl(3)], is built up from segregated layers of organic cations and Sn polyhedra. [SnCl(3)](-) groups are linked together by weak Sn...Cl interactions to form a one-dimensional polymeric chain of anions.