Knudsen effusion mass spectrometry: Current and future approaches.

RATIONALE: Knudsen effusion mass spectrometry (KEMS) has been a powerful tool in physical chemistry since 1954. There are many excellent reviews of the basic principles of KEMS in the literature. In this review, we focus on the current status and potential growth areas for this instrumental technique. METHODS: We discuss (1) instrumentation, (2) measurement techniques, and (3) selected novel applications of the technique. Improved heating methods and temperature measurement allow for better control of the Knudsen cell effusive source. Accurate computer models of the effusive beam and its introduction to the ionizer allow optimization of such parameters as sensitivity and removal of background signals. Computer models of the ionizer allow for optimized sensitivity and resolution. Additionally, data acquisition systems specifically tailored to a KEMS system permit improved quantity and quality of data. RESULTS: KEMS is traditionally utilized for thermodynamic measurements of pure compounds and solutions. These measurements can now be strengthened using first principles and model-based computational thermochemistry. First principles can be used to calculate accurate Gibbs energy functions (gefs) for improving third law calculations. Calculated enthalpies of formation and dissociation energies from ab initio methods can be compared to those measured using KEMS. For model-based thermochemistry, solution parameters can be derived from measured thermochemical data on metallic and nonmetallic solutions. Beyond thermodynamic measurements, KEMS has been used for many specific applications. We select examples for discussion: measurements of phase changes, measurement/control of low-oxygen potential systems, thermochemistry of ultrahigh-temperature ceramics, geological applications, nuclear applications, applications to organic and organometallic compounds, and thermochemistry of functional room temperature materials, such as lithium ion batteries. CONCLUSIONS: We present an overview of the current status of KEMS and discuss ideas for improving KEMS instrumentation and measurements. We discuss selected KEMS studies to illustrate future directions of KEMS.

Integration of epitaxial LiNbO3thin films with silicon technology.

Development of bulk acoustic wave filters with ultra-wide pass bands and operating at high frequencies for 5thand 6thgeneration telecommunication applications and micro-scale actuators, energy harvesters and sensors requires lead-free piezoelectric thin films with high electromechanical coupling and compatible with Si technology. In this paper, the epitaxial growth of 36°Y-X and 30°X-Y LiNbO3films by direct liquid injection chemical vapour deposition on Si substrates by using epitaxial SrTiO3layers, grown by molecular beam epitaxy, has been demonstrated. The stability of the interfaces and chemical interactions between SrTiO3, LiNbO3and Si were studied experimentally and by thermodynamical calculations. The experimental conditions for pure 36°Y-X orientation growth have been optimized. The piezoelectricity of epitaxial 36°Y-X LiNbO3/SrTiO3/Si films was confirmed by means of piezoelectric force microscopy measurements and the ferroelectric domain inversion was attained at 85 kV.cm-1as expected for the nearly stoichiometric LiNbO3. According to the theoretical calculations, 36°Y-X LiNbO3films on Si could offer an electromechanical coupling of 24.4% for thickness extension excitation of bulk acoustic waves and a comparable figure of merit of actuators and vibrational energy harvesters to that of standard PbZr1-xTixO3films.

Knudsen cell mass spectrometry using restricted molecular beam collimation. I. Optimization of the beam from the vaporizing surface.

RATIONALE: This study analyzes molecular beam sampling by mass spectrometry by the Knudsen method using the so-called " restricted collimation device" . This device, defined by the field and source apertures, was proposed in order to eliminate any additional contribution to the genuine molecular beam of surface vaporizations coming from the vicinity of the effusion orifice as usually detected by the ion source of a mass spectrometer. METHODS: The molecular transmission of the " restricted collimation device" was calculated using a vaporization law under vacuum taking into account the real surface where the molecules are emitted, i.e., the sample evaporation surface in the Knudsen cell or the effusion orifice section, towards the ion source inlet by integration of elementary solid angles. RESULTS: An optimum is observed depending on the pair of selected apertures that define the restricted collimation device, i.e., the field and source apertures. This optimum is different from that previously calculated when taking into account only the solid angle, as defined by the restricted collimation device. CONCLUSIONS: This difference is attributed to the previously approximate assumption that optimizing the restricted collimation solid angle automatically optimizes the sampling of the effused beam included in the restricted collimation angle. Moreover, the location of the evaporating surface for molecules traveling through the collimation device towards the ionization chamber remains an important factor: the distance between the sample evaporation surface and the field aperture is of paramount importance as it changes the molecular transmission to the mass spectrometer or to any target collection device in the conventional Knudsen method.

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.

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.

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).