Palladium (Pd) atomic layer deposition (ALD) can be performed with Pd(hfac)(2) (hfac = hexafluoroacetylacetone) and formalin as the reactants. For Pd ALD on oxide surfaces, the nucleation of Pd ALD has been observed to require between 20 and 100 ALD cycles. To understand the long nucleation periods, this study explored the surface reactions occurring during Pd ALD nucleation and growth on hydroxylated Al2O3 substrates. In situ Fourier transform infrared (FUR) spectroscopy on high surface area nanopowders was used to observe the surface species. The adsorption of Pd(hfac)(2) on hydroxylated Al2O3 substrates was found to yield both Pd(hfac)* and Al(hfac)* surface species. The identity of the Al(hfac)* species was confirmed by separate FTIR studies of hfacH adsorption on the hydroxylated Al2O3 substrates. Isothermal loss of the Al(hfac)* species revealed second-order kinetics at 448-523 K with an activation barrier of E-d = 39.4 kcal/mol. The lack of correlation between Al(hfac)* and AlOH* species during the loss of Al(hfac)* species suggested that the Al( hfac)* species may desorb as Al(hfac)(3). After Pd(hfac)(2) exposure and the subsequent formalin exposure on hydroxylated Al2O3 substrates, only hfac ligands from Pd( hfac)* species were removed from the surface. In addition, the formalin exposure added formate species. The Al(hfac)* species was identified as the cause of the long nucleation period because Al(hfac)* behaves as a site blocker. The surface poisoning by Al(hfac) species was corroborated by adsorbing hfacH prior to the Pd(hfac)(2) exposures. The amount of Pd( hfac)* species after Pd(hfac)2 exposures decreased progressively versus the previous hfacH exposure. Pd ALD occurred gradually during the subsequent Pd ALD cycles as the Al(hfac)* species were slowly removed from the Al2O3 surface. Ex situ transmission electron microscopy analysis revealed Pd nanoclusters that grew in size and dispersion with increasing number of Pd ALD cycles. These nanoclusters eventually coalesced to form a continuous Pd ALD film. Surface poisoning by the hfac ligands may help to explain the nucleation difficulties for metal ALD on oxide substrates using beta-diketonate reactants. (C) 2011 Elsevier B.V. All rights reserved.