Atomic layer deposition and chemical vapor deposition precursor selection method application to strontium and barium...

A new selection method for atomic layer deposition (ALD) or chemical vapor deposition (CVD) precursors is proposed and tested. Density functional theory was used to simulate Sr and Ba precursors, and several precursors were selected and used to grow films via ALD as test cases for the precursor selection method. The precursors studied were M(x)2 (M = Sr, Ba; x = tetramethylheptanedionate (tmhd), acetylacetonate (acac), hexafluoroacetylacetonate (hfac), cyclopentadienyl (H(5)C(5)), pentamethylcyclopentadienyl (Me(5)C(5)), n-propyltetramethylcyclopentadienyl (PrMe(4)C(5)), tris(isopropylcyclopentadienyl) (Pr(3)(i)H(2)C(5)), tris(isopropylcyclopentadienyl)(THF) (Pr(3)(i)H(2)C(5))(OC(4)H(8)), tris(isopropylcyclopentadienyl)(THF)2 (Pr(3)(i)H(2)C(5))(OC(4)H(8))2, tris(tert-butylcyclopentadienyl) (Bu(3)(t)H(2)C(5)), tris(tert-butylcyclopentadienyl)(THF) (Bu(3)(t)H(2)C(5))(OC(4)H(8)), heptafluoro-2,2-dimethyl-3,5-octanedionate (fod)). The energy required to break bonds between the metal atom and the ligands was calculated to find which precursors react most readily. In the case of tmhd and Cp precursors, the energy required to break bonds in the precursor ligand was studied to evaluate the most likely mechanism of carbon incorporation into the film. Trends for Ba and Sr followed each other closely, reflecting the similar chemistry among alkaline earth metals. The diketonate precursors have stronger bonds to the metals than the Cp precursors, but weaker bonds within the ligand, explaining the carbon contamination found in experimentally grown films. Atomic layer deposition of SrO was tested with Sr(tmhd)2 and Sr(PrMe(4)Cp)2 and oxygen, ozone, and water as oxygen sources. No deposition was measured with tmhd precursors, and SrO films were deposited with PrMe(4)Cp with a source temperature of 200 degrees C and at substrate temperatures between 250 and 350 degrees C with growth rates increasing for oxygen sources in this order: O2 < H2O < O2 + H2O. The experimental results support the predictions based upon calculations: PrMe(4)Cp and Me(5)Cp precursors are expected to be the best precursors among those studied for Ba and Sr film growth.