Study of the initial stage of solid electrolyte interphase formation upon chemical reaction of lithium metal and N-Methyl-N-Propyl-Pyrrolidinium-Bis (Fluorosulfonyl) Imide

Chemical reaction studies of N-methyl-N-propyl-pyrrolidinium-bis(fluorosulfonyl)imide-based ionic liquid with the lithium metal surface were performed using ab initio molecular dynamics (aMD) simulations and X-ray Photoelectron Spectroscopy (XPS). The molecular dynamics simulations showed rapid and spontaneous decomposition of the ionic liquid anion, with subsequent formation of long-lived species such as lithium fluoride. The simulations also revealed the cation to retain its structure by generally moving away from the lithium surface. The XPS experiments showed evidence of decomposition of the anion, consistent with the aMD simulations and also of cation decomposition and it is envisaged that this is due to the longer time scale for the XPS experiment compared to the time scale of the aMD simulation. Overall experimental results confirm the majority of species suggested by the simulation. The rapid chemical decomposition of the ionic liquid was shown to form a solid electrolyte interphase composed of the breakdown products of the ionic liquid components in the absence of an applied voltage.

Effect of Imidazolium-based Ionic Liquids on the nanoscale morphology of CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane) metal-organic semiconductors

We demonstrate for the first time the ionic-liquid-mediated synthesis of nanostructured CuTCNQ by the simple immersion of copper in a solution of TCNQ where the viscosity of the medium significantly impacts the corrosion–crystallization process and the final morphology of the material.

Plasma-controlled metal catalyst saturation and the initial stage of carbon nanostructure array growth

The kinetics of the nucleation and growth of carbon nanotube and nanocone arrays on Ni catalyst nanoparticles on a silicon surface exposed to a low-temperature plasma are investigated numerically, using a complex model that includes surface diffusion and ion motion equations. It is found that the degree of ionization of the carbon flux strongly affects the kinetics of nanotube and nanocone nucleation on partially saturated catalyst patterns. The use of highly ionized carbon flux allows formation of a nanotube array with a very narrow height distribution of half-width 7 nm. Similar results are obtained for carbon nanocone arrays, with an even narrower height distribution, using a highly ionized carbon flux. As the deposition time increases, nanostructure arrays develop without widening the height distribution when the flux ionization degree is high, in contrast to the fairly broad nanostructure height distributions obtained when the degree of ionization is low.

Growth of carbon nanocone arrays on a metal catalyst: The effect of carbon flux ionization

The growth of carbon nanocone arrays on metal catalyst particles by deposition from a low-temperature plasma is studied by multiscale Monte Carlo/surface diffusion numerical simulation. It is demonstrated that the variation in the degree of ionization of the carbon flux provides an effective control of the growth kinetics of the carbon nanocones, and leads to the formation of more uniform arrays of nanostructures. In the case of zero degree of ionization (neutral gas process), a width of the distribution of nanocone heights reaches 360 nm with the nanocone mean height of 150 nm. When the carbon flux of 75% ionization is used, the width of the distribution of nanocone heights decreases to 100 nm, i.e., by a factor of 3.6. A higher degree of ionization leads to a better uniformity of the metal catalyst saturation and the nanocone growth, thus contributing to the formation of more height-uniform arrays of carbon nanostructures.

CFD simulations of flow and heat transfer through the porous interface of a metal foam heat exchanger

This paper offers numerical modelling of a waste heat recovery system. A thin layer of metal foam is attached to a cold plate to absorb heat from hot gases leaving the system. The heat transferred from the exhaust gas is then transferred to a cold liquid flowing in a secondary loop. Two different foam PPI (Pores Per Inch) values are examined over a range of fluid velocities. Numerical results are then compared to both experimental data and theoretical results available in the literature. Challenges in getting the simulation results to match those of the experiments are addressed and discussed in detail. In particular, interface boundary conditions specified between a porous layer and a fluid layer are investigated. While physically one expects much lower fluid velocity in the pores compared to that of free flow, capturing this sharp gradient at the interface can add to the difficulties of numerical simulation. The existing models in the literature are modified by considering the pressure gradient inside and outside the foam. Comparisons against the numerical modelling are presented. Finally, based on experimentally-validated numerical results, thermo-hydraulic performance of foam heat exchangers as waste heat recovery units is discussed with the main goal of reducing the excess pressure drop and maximising the amount of heat that can be recovered from the hot gas stream.

Nanocrystalline Janus films of inorganic materials prepared at the liquid-liquid interface

The interface between toluene and water has been employed to prepare ultrathin Janus nanocrystalline films of metal oxides, metal chalcogenides and gold, wherein the surface on the organic-side is hydrophobic and the aqueous-side is hydrophilic. We have changed the nature of the metal precursor or capping agent in the organic layer to increase the hydrophobicity. The strategy employed for this purpose is to increase the length of the alkane chain in the precursor or use a perfluroalkane derivative as precursor or as a capping agent. The hydrophobicity and hydrophilicity of the Janus films have been determined by contact angle measurements. The morphology of hydrophobic and hydrophilic sides of the film have been examined by field emission scanning electron microscopy.

Distribution of phosphorus and oxygen between liquid steel and basic oxygen steelmaking slag

The efficiency of dephosphorisation is governed by the thermodynamic behaviour of phosphorus and oxygen in molten metal, and P2O5 and FeO in slag. The equilibrium distribution of phosphorus and oxygen, for a wide range of chemical compositions simulating the evolution of slag composition during a typical BOF blow, has been experimentally determined. A mathematical model for estimation of the activity coefficients, as a function of the chemical composition, was also attempted.

Doping Dependence of Semiconductor-Metal Transition in InP at High Pressures

The resistivity of selenium-doped n-InP single crystal layers grown by liquid-phase epitaxy with electron concentrations varying from 6.7 x 10$^18$ to 1.8 x 10$^20$ cm$^{-3}$ has been measured as a function of hydrostatic pressure up to 10 GPa. Semiconductor-metal transitions were observed in each case with a change in resistivity by two to three orders of magnitude. The transition pressure p$_c$ decreased monotonically from 7.24 to 5.90 GPa with increasing doping concentration n according to the relation $p_c = p_o [1 - k(n/n_m)^a]$, where n$_m$ is the concentration (per cubic centimetre) of phosphorus donor sites in InP atoms, p$_o$ is the transition pressure at low doping concentrations, k is a constant and $\alpha$ is an exponent found experimentally to be 0.637. The decrease in p$_c$ is considered to be due to increasing internal stress developed at high concentrations of ionized donors. The high-pressure metallic phase had a resistivity (2.02-6.47) x 10$^{-7}$ $\Omega$ cm, with a positive temperature coefficient dependent on doping.

Permeation of gases through liquid films

Permeation of gases through single surfactant stabilized aqueous films has previously been studied in view of the potentiality of foam to separate gaseous mixtures. The earlier analysis assumed that the gas phase was well mixed and that the mass-transfer process was completely controlled by the liquid film. Permeabilities evaluated from single film data based on such analysis failed to predict the mass-transfer data obtained on permeation through two films. It is shown that the neglect of gas-phase resistance and the effect of film movement is the reason for the failure of the well-mixed gas models. An exact analysis of diffusion through two films is presented. It successfully predicts the experimental data on two films based on parameters evaluated from single film data.

ESR evidence for 2 coexisting liquid phases in deeply supercooled bulk water

Using electron spin resonance spectroscopy (ESR), we measure the rotational mobility of probe molecules highly diluted in deeply supercooled bulk water and negligibly constrained by the possible ice fraction. The mobility increases above the putative glass transition temperature of water, T-g = 136 K, and smoothly connects to the thermodynamically stable region by traversing the so called "no man's land" (the range 150-235 K), where it is believed that the homogeneous nucleation of ice suppresses the liquid water. Two coexisting fractions of the probe molecules are evidenced. The 2 fractions exhibit different mobility and fragility; the slower one is thermally activated (low fragility) and is larger at low temperatures below a fragile-to-strong dynamic cross-over at approximate to 225 K. The reorientation of the probe molecules decouples from the viscosity below approximate to 225 K. The translational diffusion of water exhibits a corresponding decoupling at the same temperature [Chen S-H, et al. (2006) The violation of the Stokes-Einstein relation in supercooled water. Proc Natl Acad Sci USA 103:12974-12978]. The present findings are consistent with key issues concerning both the statics and the dynamics of supercooled water, namely the large structural fluctuations [Poole PH, Sciortino F, Essmann U, Stanley HE (1992) Phase behavior of metastable water. Nature 360: 324-328] and the fragile-to-strong dynamic cross-over at approximate to 228 K [Ito K, Moynihan CT, Angell CA (1999) Thermodynamic determination of fragility in liquids and a fragile-tostrong liquid transition in water. Nature 398: 492-494].

Copper Diffusion Barrier Deposition on Integrated Circuit Devices by Atomic Layer Deposition Technique

Transfer from aluminum to copper metallization and decreasing feature size of integrated circuit devices generated a need for new diffusion barrier process. Copper metallization comprised entirely new process flow with new materials such as low-k insulators and etch stoppers, which made the diffusion barrier integration demanding. Atomic Layer Deposition technique was seen as one of the most promising techniques to deposit copper diffusion barrier for future devices. Atomic Layer Deposition technique was utilized to deposit titanium nitride, tungsten nitride, and tungsten nitride carbide diffusion barriers. Titanium nitride was deposited with a conventional process, and also with new in situ reduction process where titanium metal was used as a reducing agent. Tungsten nitride was deposited with a well-known process from tungsten hexafluoride and ammonia, but tungsten nitride carbide as a new material required a new process chemistry. In addition to material properties, the process integration for the copper metallization was studied making compatibility experiments on different surface materials. Based on these studies, titanium nitride and tungsten nitride processes were found to be incompatible with copper metal. However, tungsten nitride carbide film was compatible with copper and exhibited the most promising properties to be integrated for the copper metallization scheme. The process scale-up on 300 mm wafer comprised extensive film uniformity studies, which improved understanding of non-uniformity sources of the ALD growth and the process-specific requirements for the ALD reactor design. Based on these studies, it was discovered that the TiN process from titanium tetrachloride and ammonia required the reactor design of perpendicular flow for successful scale-up. The copper metallization scheme also includes process steps of the copper oxide reduction prior to the barrier deposition and the copper seed deposition prior to the copper metal deposition. Easy and simple copper oxide reduction process was developed, where the substrate was exposed gaseous reducing agent under vacuum and at elevated temperature. Because the reduction was observed efficient enough to reduce thick copper oxide film, the process was considered also as an alternative method to make the copper seed film via copper oxide reduction.

Viscoelastic Properties of Nanocrystalline Films of Semiconducting Chalcogenides at Liquid/Liquid Interface

The interfacial shear rheological properties of a continuous single-crystalline film of CuS and a 3D particulate gel of CdS nanoparticles (3−5 nm in diameter) formed at toluene−water interfaces have been studied. The ultrathin films (50 nm in thickness) are formed in situ in the shear cell through a reaction at the toluene−water interface between a metal−organic compound in the organic layer and an appropriate reagent for sulfidation in the aqueous layer. Linear viscoelastic spectra of the nanofilms reveal solid-like rheological behavior with the storage modulus higher than the loss modulus over the range of angular frequencies probed. Large strain amplitude sweep measurements on the CdS nanofilms formed at different reactant concentrations suggest that they form a weakly flocculated gel. Under steady shear, the films exhibit a yield stress, followed by a steady shear thinning at high shear rates. The viscoelastic and flow behavior of these films that are in common with those of many 3D “soft” materials like gels, foams, and concentrated colloidal suspensions can be described by the “soft” glassy rheology model.

A Convenient Route for the Synthesis of Complex Metal Oxides Employing Solid-Solution Precursors

Synthesis of complex metal oxides by the thermal decomposition of solid-solution precursors (formed by isomorphous compounds of component metals) has been investigated since the method enables mixing of cations on an atomic scale and drastically reduces diffusion distances to a few angstroms. Several interesting oxides such as Ca2Fe03,5C, aCoz04,C a2C0205a, nd Ca,FeCo05 have been prepared by this technique starting from carbonate solid solutions of the type Ca,-,Fe,C03, Cal-,Co,C03, and Ca,-,,M,M'yC03 (M, M' = Mn, Fe, Co). The method has been extended to oxalate solid-solution precursors, and the possibility of making use of other kinds of precursor solid solutions is indicated.

Low-frequency resistance fluctuations in metal films under current stressing at low temperature (T<0.3Tmelting)

In this paper, we report a systematic study of low frequency 1∕fα resistance fluctuation in thin metal films (Ag on Si) at different stages of damage process when the film is subjected to high current stressing. The resistance fluctuation (noise) measurement was carried out in situ using a small ac bias that has been mixed with the dc stressing current. The experiment has been carried out as a function of temperature in the range of 150–350 K. The experiment establishes that the current stressed film, as it undergoes damage due to various migration forces, develops an additional low-frequency noise spectral power that does not have the usual 1∕f spectral shape. The magnitude of extra term has an activated temperature dependence (activation energy of ≈0.1 eV) and has a 1∕f1.5 spectral dependence. The activation energy is the same as seen from the temperature dependence of the lifetime of the film. The extra 1∕f1.5 spectral power changes the spectral shape of the noise power as the damage process progress. The extra term likely arising from diffusion starts in the early stage of the migration process during current stressing and is noticeable much before any change can be detected in simultaneous resistance measurements. The experiment carried out over a large temperature range establish a strong correlation between the evolution of the migration process in a current stressed film and the low-frequency noise component that is not a 1∕f noise.

The Use of Liquid-Liquid Interface (Biphasic) for the Preparation of Benzenetricarboxylate Complexes of Cobalt and Nickel

New metal-organic frameworks (MOFs) [Ni(C12N2H10)(H2O)][C6H3(COO)2(COOH)] (I), [Co2(H2O)6][C6H3(COO)3]2·(C4N2H12)(H2O)2 (II), [Ni2(H2O)6][C6H3(COO)3]2·(C4N2H12)(H2O)2 (III), [Ni(C13N2H14)(H2O)][C6H3(COO)2(COOH)] (IV), [Ni3(H2O)8][C6H3(COO)3] (V) and [Co(C4N2H4)(H2O)][C6H3(COO)3] (VI) {C6H3(COOH)3 = trimesic acid, C12N2H10 = 1,10-phenanthroline, C4N2H12 = piperazine dication, C13N2H14 = 1,3-bis(4-pyridyl)propane and C4N2H4 = pyrazine} have been synthesized by using an interface between two immiscible solvents, water and cyclohexanol. The compounds are constructed from the connectivity between the octahedral M2+ (M = Ni, Co) ions coordinated by oxygen atoms of carboxylate groups and water molecules and/or by nitrogen atoms of the ligand amines and the carboxylate units to form a variety of structures of different dimensionality. Strong hydrogen bonds of the type O-H···O are present in all the compounds, which give rise to supramolecularly organized higher-dimensional structures. In some cases ··· interactions are also observed. Magnetic studies indicate weak ferromagnetic interactions in I, IV and V and weak antiferromagnetic interactions in the other compounds (II, III and VI). All the compounds have been characterized by a variety of techniques.