Thermochimica Acta, Vol.452, No.2, 128-134, 2007
Combined experiments to measure low sublimation pressures and diffusion coefficients of organometallic compounds
Vapor pressures and sublimation pressures of organometallic (metalorganic) compounds are needed in several processes like chemical vapor deposition (CVD). Thermobalances at ambient pressures are often used to study the evaporation of such compounds. At least three strategies are found in the literature to evaluate the results using different theoretical approaches. In some of the frequently used approaches the diffusion out of a crucible is neglected. We present a simple theoretical approach which describes the interrelation between the observed mass transfer rate and the physical variables of typical TGA set-ups. It turns out that the mass transfer rate at a given total pressure and temperature is mainly a function of the diffusion coefficient and the vapor pressure of the sublimating substance. The vapor pressures may be determined from an independent measurement using the Knudsen cell and combined with the TGA to obtain the diffusion coefficients. Experiments have been performed with two well studied substances naphthalene and phenanthrene to check the present strategy. Further measurements were then performed for the metal organic CVD relevant compounds: ferrocene and Tris(2,2,6,6-tetramethyl-3,5-heptanedianato)cobalt III [Co(tmhd)(3)]. (C) 2006 Elsevier B.V. All rights reserved.
Keywords:vapor pressure;metalorganic compounds;ferrocene;cobalt salts;diffusion coefficients;naphthalene;phenanthrene