Search Results
Lithium metal penetration induced by electrodeposition through solid electrolytes: Example in single-crystal Li6La3ZrTaO12 garnet
Solid electrolytes potentially enable rechargeable batteries with lithium metal anodes possessing higher energy densities than today’s lithium ion batteries. To do so the solid electrolyte must suppress instabilities that lead to poor coulombic efficiency and short circuits. In this work, lithium electrodeposition was performed on single-crystal Li6La3ZrTaO12 garnets to investigate factors governing lithium penetration through brittle electrolytes. In single crystals, grain boundaries are excluded as paths for lithium metal propagation. Vickers microindentation was used to introduce surface flaws of known size. However, operando optical microscopy revealed that lithium metal penetration propagates preferentially from a different, second class of flaws. At the perimeter of surface current collectors smaller in size than the lithium source electrode, an enhanced electrodeposition current density causes lithium filled cracks to initiate and grow to penetration, even when large Vickers defects are in proximity. Modeling the electric field distribution in the experimental cell revealed that a 5-fold enhancement in field occurs within 10 micrometers of the electrode edge and generates high local electrochemomechanical stress. This may determine the initiation sites for lithium propagation, overriding the presence of larger defects elsewhere.
On the Impact of Strained PECVD Nitride Layers on Oxide Precipitate Nucleation in Silicon
PECVD nitride layers with different layer stress ranging from about 315 MPa to −1735 MPa were deposited on silicon wafers with similar concentration of interstitial oxygen. After a thermal treatment consisting of nucleation at 650°C for 4 h or 8 h followed annealing 780°C 3 h + 1000°C 16 h in nitrogen, the profiles of the oxide precipitate density were investigated. The binding states of hydrogen in the layers was investigated by FTIR. There is a clear effect of the layer stress on oxide precipitate nucleation. The higher the compressive layer stress is the higher is a BMD peak below the front surface. If the nitride layer is removed after the nucleation anneal the BMD peak below the front surface becomes lower. It is possible to model the BMD peak below the surface by vacancy in-diffusion from the silicon/nitride interface. With increasing duration of the nucleation anneal the vacancy injection from the silicon/nitride interface decreases and with increasing compressive layer stress it increases. © The Author(s) 2019.
The influence of partial replacement of Cu with Ga on the corrosion behavior of Ti40Zr10Cu36PD14 metallic glasses
TiZrCuPdGa metallic glasses are under consideration for small dental biomedical implants. There is interest in replacing some of the Cu with Ga to improve the glass-forming ability and biocompatibility. Ti40Zr10Cu36-xPd14Gax (x = 0, 1, 2, 4, 8 and 10 at.%) metallic glasses in rod and ribbon forms were fabricated by mould casting and melt spinning, respectively, and electrochemically tested in a 0.9wt.% NaCl (0.154 M) solution. It has been shown that for both rod and ribbon samples Ga levels up to 8% have no significant effect on passive current density, pitting potential or cathodic reactivity in 0.9% NaCl at 37°C. Different pitting potential and corrosion potential values were found when ribbon and rod samples of the same composition were compared for all compositions apart from the one containing the highest Ga level (10%). This was attributed to structural relaxation occurring as a result of the slower cooling rates during casting rods compared with melt-spinning ribbons. Substitution of Ga for Cu in these metallic glasses therefore expected to have no significant effect on corrosion susceptibility. © The Author(s) 2019.
Static Dielectric Constant of β-Ga2O3 Perpendicular to the Principal Planes (100), (010), and (001)
The relative static dielectric constant ℇr of β-Ga2O3 perpendicular to the planes (100), (010), and (001) is determined in the temperature range from 25 K to 500 K by measuring the AC capacitance of correspondingly oriented plate capacitor structures using test frequencies of up to 1 MHz. This allows a direct quantification of the static dielectric constant and a unique direction assignment of the obtained values. At room temperature, ℇr perpendicular to the planes (100), (010), and (001) amounts to 10.2 ± 0.2, 10.87 ± 0.08, and 12.4 ± 0.4, respectively, which clearly evidence the anisotropy expected for β-Ga2O3 due to its monoclinic crystal structure. An increase of ℇr by about 0.5 with increasing temperature from 25 K to 450 K was found for all orientations. Our ℇr data resolve the inconsistencies in the previously available literature data with regard to absolute values and their directional assignment and therefore provide a reliable basis for the simulation and design of devices. © The Author(s) 2019.
Boundary conditions for electrochemical interfaces
Consistent boundary conditions for electrochemical interfaces, which cover double layer charging, pseudo-capacitive effects and transfer reactions, are of high demand in electrochemistry and adjacent disciplines. Mathematical modeling and optimization of electrochemical systems is a strongly emerging approach to reduce cost and increase efficiency of super-capacitors, batteries, fuel cells, and electro-catalysis. However, many mathematical models which are used to describe such systems lack a real predictive value. Origin of this shortcoming is the usage of oversimplified boundary conditions. In this work we derive the boundary conditions for some general electrode-electrolyte interface based on non-equilibrium thermodynamics for volumes and surfaces. The resulting equations are widely applicable and cover also tangential transport. The general framework is then applied to a specific material model which allows the deduction of a current-voltage relation and thus a comparison to experimental data. Some simplified 1D examples show the range of applicability of the new approach.
On the Impact of Strained PECVD Oxide Layers on Oxide Precipitation in Silicon
PECVD oxide layers with different layer stress ranging from about −305.2 MPa to 39.9 MPa were deposited on silicon wafers with similar concentration of interstitial oxygen. After a thermal treatment consisting of rapid thermal annealing (RTA) and furnace annealing 780°C 3 h + 1000°C 16 h in nitrogen the profiles of the oxide precipitate density were investigated. Supersaturations of self-interstitials as function of layer stress were determined by adjusting modelling results to measured depth profiles of bulk microdefects. The self-interstitial supersaturation generated by RTA at 1250°C and 1175°C at the silicon/oxide interface is increasing linearly with increasing layer stress. Values for self-interstitial supersaturation determined on deposited oxide layers after RTA at 1250°C and 1175°C are very similar to values published for RTO by Sudo et al. An RTA at 1175°C with a PECVD oxide on top of the wafer is a method to effectively suppress oxygen precipitation in silicon wafers. Nucleation anneals carried out at 650°C for 4 h and 8 h did not show any effect of PECVD oxide layers on oxide precipitate nucleation. © The Author(s) 2019.