Gas-phase aluminium acetylacetonate decomposition: revision of the current mechanism by VUV synchrotron radiation
Sebastian Grimm, Seung-Jin Baik, Patrick Hemberger, András Bödi, Andreas Kempf, Tina Kasper, Burak Atakan
Abstract
Although aluminium acetylacetonate, Al(C5H7O2)3, is a common precursor for chemical vapor deposition (CVD) of aluminium oxide, its gas-phase decomposition is not well-known. Here, we studied its thermal decomposition in a microreactor by double imaging photoelectron photoion coincidence spectroscopy (i2PEPICO) between 325 and 1273 K. The reactor flow field was characterized by CFD. Quantum chemical calculations were used for the assignment of certain species. The dissociative ionization of the room temperature precursor molecule starts at a photon energy of 8.5 eV by the rupture of the bond to an acetylacetonate ligand leading to the formation of the Al(C5H7O2)2+ ion. In pyrolysis experiments, up to 49 species were detected and identified in the gas-phase, including reactive intermediates and isomeric/isobaric hydrocarbons, oxygenated species as well as aluminium containing molecules. We detected aluminium bis(diketo)acetylacetonate-H, Al(C5H7O2)C5H6O2, at m/z 224 together with acetylacetone (C5H8O2) as the major initial products formed at temperatures above 600 K. A second decomposition channel affords Al(OH)2(C5H7O2) along with the formation of a substituted pentalene ring species (C10H12O2) as assigned by Franck-Condon simulations and quantum chemical calculations. Acetylallene (C5H6O), acetone (C3H6O) and ketene (C2H2O) were major secondary decomposition products, formed upon decomposition of the primary products. Three gas-phase aromatic hydrocarbons were also detected and partially assigned for the first time: m/z 210, m/z 186 (C14H18 or C12H10O2) and m/z 146 (C11H14 or C9H6O2) and their formation mechanism is discussed. Finally, Arrhenius parameters are presented on the gas-phase decomposition kinetics of Al(C5H7O2)3, aided by numerical simulation of the flow field.