Insights into the decomposition of zirconium acetylacetonate using synchrotron radiation: Routes to the formation of volatile Zr-intermediates

Abstract

The thermal decomposition of Zr(acac)₄  is studied in a SiC-microreactor on the micro-second time scale. By utilizing synchrotron radiation and photoelectron photoion coincidence spectroscopy, six important zirconium-intermediates, as for instance Zr(C₅H₇O₂)₂(C₅H₆O₂), and Zr(C₅H₆O₂)₂, are identified in the gas phase for the first time. The adiabatic ionization thresholds of intermediately formed zirconium species are estimated and the main products of their thermal decomposition, actylacetone, acetylallene and acetone are characterized unambiguously and isomer-selectively. Based on all detected intermediates, we deduce the predominant pyrolysis pathways of the precursor in the temperature range from 400 to 900 K. Our findings are complemented by numerical simulations of the flow field in the microreactor, which show that the choice of seed gas significantly influences the temperature profile and residence times in the microreactor, such that helium provides a more uniform flow field than argon and should preferentially be used.