Ioana Nuta

High temperature NMR study of aluminum metal influence on speciation in molten NaF-AlF3 fluorides.

In situ high temperature NMR spectroscopy has been used to characterize the interactions between aluminum metal and cryolitic melts. (27)Al, (23)Na, and (19)F NMR spectra have been acquired in NaF-AlF(3) and NaF-AlF(3)-Al melts over a wide range of compositions. The evolution of the signals evidence a chemical reaction between the metal and the salt. The different samples have been also described after solidification at room temperature by Environmental Scanning Electronic Microscopy, high resolution solid state NMR, and X-ray diffraction. The combination of in situ high temperature NMR characterization of the melts, with experimental description of solidified samples after cooling, evidence an enrichment of the melts with AlF(3) and different reactions with metallic aluminum depending on the initial bath composition.

A special reactor coupled with a high‐temperature mass spectrometer for the investigation of the vaporization and cracking of organometallic compounds

A special reactor coupled to a high-temperature mass spectrometer was specifically designed for the study of vaporization and thermal cracking of organometallic precursors. This reactor has two kinds of settings. One is a single Knudsen effusion cell which enables the analysis of the composition of saturated vapors and the determination of the partial pressure of each gaseous molecule in equilibrium with its condensed phase. This cell is an evaporation/sublimation cell (operating from 243 to 473 K), which can be tightly closed--like a vacuum chamber--in order to protect organometallic compounds against moisture and atmospheric components. This cell can be independently weighed usefully to evaluate the equilibrium vapor pressures of the sample using the mass-loss method. During experiments, the effusion aperture is externally opened for direct mass spectrometric measurements. The other setting dedicated to the study of thermal decomposition of gaseous molecules consists of a set of tandem cells: the previously described Knudsen cell and a cracking cell (operating from 293 to 973 K).

Cracking study of pentakis(dimethylamino)tantalum vapors by Knudsen cell mass spectrometry

Organometallic molecules are commonly used as gaseous precursors in Atomic Layer Deposition/Chemical Vapor Deposition (ALD/CVD) processes. However, the use of these molecules, which are generally thermally unstable at temperatures close to the deposition temperature, requires an understanding of their gas-phase chemical behavior. The thermal cracking of the gaseous precursor, pentakis(dimethylamino) tantalum (PDMAT), generally adopted in the ALD/CVD TaN deposition processes, has been studied in the temperature range from 343 to 723K using a specific reactor coupled with a high-temperature mass spectrometer. This reactor - built as tandem Knudsen cells - consists of two superimposed cells. The first stage reactor - an evaporation cell - provides an input saturated vapor flow operating from room temperature to 333K. The second stage cell, named the cracking cell, operated from 333 to 723K in the present study. Experiments showed the appearance of many gaseous species when the cracking temperature increased and, in particular, dimethylamine, corresponding to the saturated organic branches of PDMAT. Decomposition products of the HNC(2)H(6) branch were observed at relatively high temperature, namely above 633K. This gas-phase study - as for the preceding saturated one - shows the presence of oxygen-containing molecules in PDMAT cracked vapor. Thus, it explains the systematic presence of oxygen contamination in the deposited TaN films observed in ALD/CVD industrial processes.

CFD Modeling of Boron Removal from Liquid Silicon with Cold Gases and Plasma

The present study focuses on a specific step of the metallurgical path of purification to provide solar-grade silicon: the removal of boron through the injection of H2O(g)-H2(g)-Ar(g) (cold gas process) or of Ar-H2-O2 plasma (plasma process) on stirred liquid silicon. We propose a way to predict silicon and boron flows from the liquid silicon surface by using a CFD model (©Ansys Fluent) combined with some results on one-dimensional diffusive-reactive models to consider the formation of silica aerosols in a layer above the liquid silicon. The comparison of the model with experimental results on cold gas processes provided satisfying results for cases with low and high concentrations of oxidants. This confirms that the choices of thermodynamic data of HBO(g) and the activity coefficient of boron in liquid silicon are suitable and that the hypotheses regarding similar diffusion mechanisms at the surface for HBO(g) and SiO(g) are appropriate. The reasons for similar diffusion mechanisms need further enquiry. We also studied the effect of pressure and geometric variations in the cold gas process. For some cases with high injection flows, the model slightly overestimates the boron extraction rate, and the overestimation increases with increasing injection flow. A single plasma experiment from SIMaP (France) was modeled, and the model results fit the experimental data on purification if we suppose that aerosols form, but it is not enough to draw conclusions about the formation of aerosols for plasma experiments.