| CPC C23C 16/45529 (2013.01) [C23C 16/402 (2013.01); C23C 16/405 (2013.01); C23C 16/4554 (2013.01); C23C 16/45544 (2013.01); H01L 21/76837 (2013.01)] | 34 Claims |

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1. A method of filling a gap formed on a substrate using atomic layer deposition (ALD), the method comprising:
forming a first reaction inhibition layer by adsorbing a reaction inhibitor onto a side wall of the gap, the reaction inhibitor including a precursor material that does not react with a second reactant, and the first reaction inhibition layer having a density gradient in which a density of the reaction inhibitor decreases toward a bottom of the gap;
forming a first precursor layer by adsorbing a first reactant onto the bottom of the gap and the side wall of the gap around the bottom of the gap; and
forming a first atomic layer on the bottom of the gap and the side wall of the gap around the bottom of the gap, the forming the first atomic layer including adsorbing the second reactant onto the first precursor layer, wherein the reaction inhibitor includes a center metal and a cyclopentadienyl (Cp) ligand, the center metal and a pentamethyl cyclopentadienyl (Cp*) ligand, Hf(tBuO)4, Hf(OiPr)4, or Hf(OtBu)(NEtMe)3.
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